Ammonium Sulphate Deactivation of SCR DeNOx Catalysts

Christoffer Falk

Department of Chemical Engineering, Lund institute of Technology, January 2007

Abstract
When operating a reactor for selective catalytic reduction of NOx at low temperatures ammonium sulphate salts
may form on the catalyst and reduce catalytic activity. If the deposition of sulphate species could be predicted
from a theoretic model it would enlarge the temperature window of operation for the SCR process and render
additional income from NOx-credits. Activity measurements were performed on a commercial catalyst in an
attempt to verify the predictions. The specific surface area of the exposed catalyst samples were analysed to
study the effect of salt formation on the catalyst surface. From the results presented in this thesis it can be
concluded that ammonia salts deposit at the catalyst surface and that it affects the catalyst activity. The relations
derived theoretically show some concurrence with the experimental results, concerning the impact of changes in
operating temperature and condensation temperature in pores with different diameters. This indicates that the salt
equilibrium affects the condensation temperature and that the temperature where deactivation occurs is not
completely controlled by kinetics. It also indicates that capillary forces have a strong impact on the condensation
temperature in the catalyst pore, especially the pores in, or close to, the micropore range. The activity
measurements show that it is not possible to regenerate the catalyst at 350oC under apparent operating condition.
Even if some activity is restored it is still far from the initial activity. If the samples are degassed under vacuum
at temperatures above 300oC surface analysis shows that it is possible to evaporate the salt in the pores and
restore much of the blocked pore surface. This indicates that much of the initial activity could also be retrieved
with the same treatment.

Introduction catalyst activity. The salts would then decompose

Nitrogen oxides (NOx) emitted from combustion
sources are considered to be major pollutants in air.
The use of catalytic systems to reduce NOx
emissions has grown world wide in the last
decades. This development has been induced by
adoption of strict environmental regulations.
Selective catalytic reduction (SCR) of NOx by
ammonia is one of the most common methods of
reducing NOx emissions from power plants. In
today’s industrial application of the SCR-
technology the energy consumption sometimes
varies periodically during day and night or over a
season. As the boiler loads vary the flue gas
temperatures also vary and since the function of an
SCR application is sensitive to temperature this
could constitute a problem. At high temperatures
the sulphur dioxide oxidation increases and may
cause problems downstream, at low temperatures,
as mentioned in the previous section, ammonium
sulphate salts may form and reduce catalytic
activity. If the deposition of sulphate species could
be predicted from a theoretic model, which is
verified by experimental data, it would be possible
to improve process performance and lower the
temperature margin used today. This would enlarge
the temperature window of operation for the SCR
process and render additional income from NOx-
credits. Further it would be of interest to see if it is
possible to regenerate a catalyst deactivated by
sulphate salts under operating conditions. If that is
the case, a small amount of salt could be allowed to
deposit during low loads with minor impact on the
during high loads restoring the lost activity.
The Reduction of NOx in a SCR is achieved by
adding ammonia, NH3, or urea as the reducing
agent, to the gas flow and passing the gases over a
catalyst. The DeNOx process is based on the
following reactions 1 with ammonia
4NO + 4NH3 + O2 → 4N2 + 6H2O (1)
NO + NO2 + 2NH3 → 2N2 + 3H2O (2)
6NO2 + 8NH3 → 7N2 + 12H2O (3)
Typically more than 90 % of the nitrogen oxides
consist of nitrogen monoxide and reaction (1)
proceed very rapidly on the catalyst between 250 oC
and 450 oC in excess oxygen. Reaction (1) accounts
for the overall stoichiometry of the process, thus a
NH3/NO ratio off one is used.
If SO2 is present in the flue gases it can lead to the
undesired oxidation to SO3 over the catalyst,
according to reaction (4).
SO2 + ½ O2 → SO3 (4)
Even if the conversion rate is low it is highly
undesired because it causes deposition and
accumulation of ammonium sulphate salts and
sulphuric acid on the catalyst surface and/or the
downstream equipment. The SO2 content in the flue

1(7)
gas depends on the composition of the fuel and in a
coal application a typical SO2 content is 30 ppm.
The geometric shape of commercial SCR catalysts
is generally honeycomb monoliths or plates.
Intraporous diffusion limitations restrict the DeNOx
reaction to a thin outer shell of the catalyst, hence
the geometric surface of the catalyst should be
maximised 2 .
The complex equilibrium concerning salt formation
from sulphur oxides, NH3 and H2O in flue gas has
not been fully investigated. In literature the general
position is that the sulphate salts are formed from
SO3 oxidized from SO2 over the vanadia catalyst.
Unfortunately no mechanism for the deposition in
the range of 260-350 oC was found in literature.
With the assumption that SO2 is oxidized before
deposition a number of different salts may form at
the catalyst surface under operating conditions.
Literature suggests (NH4)2SO4, NH4HSO4,
(NH4)2S2O7 among others 3,4 , but the main
compounds, if a V2O5 catalyst is used, will be
(NH4)2SO4 and NH4HSO4 5 . The two salts may form
through different reaction paths, reactions (5) and
(6) may be the sum of two or more reactions
depending on equilibrium and reaction kinetics.
SO3(g) + 2NH3(g) + H2O(g)↔ (NH4)2SO4 (5)
SO3(g) + NH3(g) + H2O(g)↔ NH4HSO4 (6)
The aim of this work was to predict the temperature
where the catalyst is deactivated by ammonium
sulphates under specific operating conditions using
equilibrium calculations. Since the catalyst is
porous the effect of capillary forces must be taken
into consideration when evaluating the equilibrium.
The calculations are to be verified by experimental
activity measurements on a commercial catalyst.
The specific surface area of the exposed catalyst
samples is to be analysed by nitrogen adsorption at
77 K (BET) to study the effect of salt formation on
the catalyst surface. Exposed catalyst samples
where a loss of activity is confirmed will also be
exposed at elevated operating temperatures to
evaluate if the activity can be restored under
operating conditions.
Experimental
Activity measurements and the salt depositions
were performed using a commercial honeycomb
catalyst placed in a heated gas stream inside a
heating cabinet. The inlet gas (atmospheric air) was
heated with an electric induction heater and reactant
gases were added to the hot stream, at 250-320 oC.
To control the gas composition with respect to NO,
NH3 and SO2 (oxidized to SO3 when introduced to
the main flow as described below), Brooks mass
flow controllers (model 5850E) were used. A pump
2(7)
with variable flow was applied to supply an
evaporator with a controlled amount of water. The
steam thus added to the flue gas was overheated by
approximately 50-100 oC to ensure that no liquid
water was introduced to the gas stream. During this
work SO3 and not SO2 was added in order to
maintain control of the SO3 content in the gas
stream above the catalyst and the SO3 content was
set to 30 ppm. The hypothesis was that all of the
SO2 is oxidized to SO3 (see below) and that the test
should be conducted as a worst case scenario. The
SO3 gas was generated by direct oxidation of SO2
with air, over a vanadium catalyst (VK-WSA)
provided by Haldor Topsøe A/S. The oxidation of
SO2 was performed in a packed bed reactor at 410
o
C..
The catalyst elements used during this study were
160 mm long 7x7 channels honeycomb monoliths,
cut down from a larger, 21x21 duct, commercial
monolith, provided by Cormetech Inc. The catalyst
used is designed for use in stationary coal boilers.
The chemical composition of the catalyst was TiO2
<85 wt%, SiO2 0-5 wt%, WO3 <24 wt% and V2O5
0-5 wt%. The pitch of the catalyst was 7.1 mm and
the channel opening was 6.4 mm. The catalyst was
placed in a square steel vessel, the reactor, with the
inner dimensions 80x80 mm. A perforated stainless
steel sheet at the inlet was applied to accomplish an
evenly distributed flow through the reactor. To
monitor the reduction of NO in the reactor the NO
content was measured at the inlet and outlet of the
reactor with a NDIR-analyser, a SICK MAIHAK
Sidor. Unfortunately only one NDIR instrument for
NO was available, hence only the outlet content
could be monitored continuously. Temperature was
monitored at several measuring points, at the inlet
and outlet of the reactor, in the heating cabinet, in
the SO2 oxidation reactor and the in the steam
added to the main gas flow. The data attained
during operation was logged and saved using an
INTAB PC-logger and the software EasyView 5 by
INTAB.
The NH3 content in the flue gas was measured with
a wet chemical method 6,7 . A small fraction of the
gas stream was redirected through a series of three
impingers. The temperature and volume of the
flow through the impingers was measured. The first
two impingers contained 100 ml 0.05 M H2SO4 and
the third one 100 ml deionised water. The liquid
from the first and the second impinger was diluted
with 0.05 M H2SO4 to a NH3 concentration suitable
for analysis. Sodium-pentacyannitroferrate and
sodium hypochlorite solutions were then added to
the diluted samples to from a coloured complex that
could be analysed in a spectrophotometer. This
method supplies a mean value of the NH3 content in
the flue gas over a time period in the magnitude of
hours.
 for about 7 h and some for another 7 h when
During the experiments the ambition was to have as attempting to regain the lost activity.
similar operating conditions as possible to a
commercial SCR application for coal fired boilers, Results and Discussion
Table 1 describes the operating conditions used in Since no kinetic expression for the formation of the
this study. The NO content in a SCR depend on salts found in literature was applicable in the
external conditions, boiler flame temperature etc., temperature range of interest, the focus of the
and the gas composition used during the theoretic study was to predict the condensation
experiments is typical for coal applications 8 . temperature of the ammonium sulphate salts. When
reviewing all of the results presented in this paper it
Table 1. Data for the SCR reactor
is important to consider that the DeNOx-reactions
Operating conditions are very fast and that reactions over a monolith
catalyst are strongly influenced by mass transfer
Pressure about 1.0 atm
-1
limitations2. Hence the concentration of ammonia in
Space Velocity 10 000 h the pores should be lower than in the bulk
concentration, especially in the smaller pores where
3
Flow (Qn) 8.23 Nm /h
the impact of diffusion limitations is greater. The
Gas Content calculations were however based on a worst case
NO 500 ppm scenario thus the bulk content of NH3 was used.
NH3 500 ppm
Table 1 shows the gas contents used for all of the
* equilibrium calculations in the following sections.
SO3 30 ppm
H2O 10 %
The fist consideration was if the sulphur in the flue
gas exists as SO3 or as sulphuric acid, see reaction
(Air 89,9 %) (7). The equilibrium favours the acid at
O2 18,9 % temperatures below 320°C, as illustrated in Figure
N2 71,0 % 1. Above 320oC SO3 is the dominating form but
H2SO4 is still abundant up to 350oC. The reaction
Temperature between H2O and SO3 is considered to be very fast,
Flue gas 280 - 320 °C
thus it was approximated that all of the SO3 was
converted to H2SO4.
Steam 150 - 200 °C
From SO2 reactor 410 °C
Considering the low partial pressure of the acid
* In the calculations where H2SO4 is the sulphur even if all of the SO3 is converted, only 3 Pa, and
containing reactant, a H2SO4 content of 30 ppm the temperature range, the acid is in a gaseous
is used state 9 .
The space velocity used should be considered high SO3(g) + H2O(g) ↔ H2SO4(g) (7)
in this context, but due to equipment limitations it
was problematic to achieve stable conditions at HSC Chemistry 10 was used to calculate a
lower space velocities. In a SCR application for condensation temperature for reaction 8 and 9,
coal the operating temperature is generally kept where the condensation occurs with gaseous acid.
above 350oC to avoid deactivation by sulphate salts. The conditions for the calculations were chosen to
imitate the operating conditions used during the
Initially the goal was to achieve a deposition experimental part, see Table 1.
sufficient to observe a measurable change in
activity and to investigate if that had any effect on
2 NH3(g) + H2SO4 (g) ↔ (NH4)2SO4 (8)
the catalyst BET surface area. To favour the
deposition the operating temperature was low,
NH3(g) + H2SO4 (g) ↔ NH4HSO4 (9)
250oC, and the SO3 content was high, 60 ppm,
when exposing these samples. The second step was
Table 2 show the thermodynamic data used to
to study the rate of deactivation at different
calculate the change in ΔGr for the reactions caused
temperatures, 280, 290 and 320oC. To facilitate the
by capillary forces in the pores.
comparison of the samples the operating
temperature was the only difference between the
tests. The final step was to evaluate if it is possible
to regain the initial activity of the exposed samples.
The samples exposed on stream at a temperature
that caused deactivation were exposed again at a
higher temperature to evaluate if it was possible to
restore the initial activity. All samples was exposed

3(7)
 Table 2. Properties for AS and AHS used to the condensation temperature is as low as -28 oC.
calculate the energy change due to capillarity Experimental results found in literature 11 show that
the condensation temperature is significantly
Substance (NH4)2SO4 NH4HSO4 higher. Literature suggests that the equilibrium for
reaction (9) could be described by11:
3
Density 1770 1780 kg/m
Surface tension 0,15 0,15
11
N/m 12 ⎛ − 53 000 ⎞
PNH ⋅ PH SO = 1.41 ⋅ 10 exp⎜ ⎟ (Eq. 1)
Molecular weight 0,1321 0,1151 kg/mol 3 2 4
⎝ RT ⎠
Pore Diameter 150 150 A
or:
53 000
T = − (Eq. 2)
To further evaluate the deposition of AS the ⎛ PNH3 ⋅ PH 2SO 4 ⎞
condensation temperature for formation from SO3 R ⋅ ln⎜ ⎟
⎜ 1.41 ⋅ 1012 ⎟
and NH3 was also calculated. As seen in Table 3 the ⎝ ⎠
formation from acid is favoured in larger pores, where T is the temperature in K and -53 000
from a thermodynamic point of view even if the represents the enthalpy of reaction in kcal/mol for
differences are not very large. But as previously the reaction between ammonia and sulphuric acid.
stated the formation from acid is more likely. The Kelvin equation of capillary condensation is
mol-% File: C:\Program\HSC 5.1\Gibbs\TestSo3.OGI
applied to the relationship in Eq. 2. The
0.0030
H2SO4(g)
condensation temperatures calculated from this
SO3(g) relationship in pores with a diameter of 20, 60 and
0.0025
150 A are 355, 324 and 314 oC respectivly.
Corresponding temperatures from calculations with
HCS Chemistry for a pore diameter of 20 A is -28
o
0.0020
C and even lower for larger pore diameters. The
significant difference between the calculated value
0.0015 and the model based on empiric results indicate that
the data attained from equilibrium calculations with
0.0010 HSC Chemistry are not reliable.

0.0005
The formation of AS has an additional option, it
could be formed when AHS reacts with ammonia,
Temper
according to reaction 10. Calculations with HSC
0.0000
200 250 300 350 400 C Chemistry show that from a thermodynamic point
of view this is definitely a spontaneous reaction
Figure 1. Equilibrium composition of H2SO4 even at low ammonia pressures. However, literature
and SO3 in the flue gas in the temperature range suggests that the reaction should proceed in the
of 200 to 400 oC. Input composition according to other direction in the temperature range of
Table 1. interest 12 .
Table 3. Calculated condensation temperatures
for AS when forming from Sulphuric acid and NH4HSO4 + NH3(g) ↔ (NH4)2SO4 (10)
sulphur trioxide. The gas concentrations used
for the calculations was according to Table 1. The liquid state of AS and AHS is not very well
defined and the value used for the surface tension of
Formation Pore diameter Condensation T AS and AHS should be considered as very
from A ºC uncertain. The referred article, reference 11, has
approximated the surface tension of AHS to 0.15
H2SO4 10 322
N/m and since no other source of data was found,
H2SO4 20 287 the same approximation has been used during this
H2SO4 60 265 study. To assess the affect of this source of error a
H2SO4 150 <260 brief sensitivity analysis was undertaken. If the
SO3 10 321 value of the surface tension is too high and the
SO3 20 294 actual value is lower, 0.015 N/m, it will only have
SO3 60 275 minor impact on the condensation temperature. But
SO3 150 270 if the value is to low and the actual surface tension
is 1.5 N/m the calculated condensation temperature
The calculated temperatures for formation of AHS is much to low. A surface tension of 1.5 N/m gives
from acid, not shown, are unreasonably low and a condensation temperature of over 100oC higher
even if a pore diameter of 20 A is used to calculate compared to when a surface tension of 0.15 N/m in

4(7)
a pore with a diameter of 150 A is used. It should
also be noted that at smaller pore diameters the To be able to compare the activity at different
impact of an error in the estimation of the surface temperatures the ratio of kapp/k0app was used. The
tension will have an even greater affect. initial activity was measured at different
temperatures to attain values for k0app. From these
Experimental results data the apparent activation energy, Ea, for the
Due to equipment control limitations it was not DeNOx reaction was obtained using the Arrhenius
possible to apply unsupervised operation wherefore equation, Eq 3, and linear regression.
the experiments where both deposition and Ea
regeneration was applied had to be divided into ln k O, app = ln A − (Eq. 3)
separate experiments. In between the experiments RT
the catalyst was stored in the reactor under Activity Sample 6
moderate heating, at 150-190oC.
1.2
It was necessary to attain a simple tool to compare
the deactivation rates at different operating 1.0
temperatures. The data are presented in Table 4.
The values in the column “Slope” represents the 0.8
quota of the change in activity during the exposure

Activity [k/k0]
and the exposure time which provides a simple tool 0.6
to compare the deactivation rates at different
temperatures. 0.4

0.2
Table 4. The deactivation per hour at different
operating temperatures. Operating conditions
0.0
for the samples was according to Table 1. 00:00 02:24 04:48 07:12 09:36 12:00 14:24
Deposition temperature Slope d(kapp/k0app)/dt Time
o -1
Sample C h
3 280 -0.0521 Figure 2. Measured activity during exposure of
6 290 -0.0365 Sample 6. The operating conditions for Sample 4
5 320 -0.0150 were according to Table 1.
The calculated activation energy is 18.6 kJ/mol, or
The deactivation rate increases by a factor 2 when
4.4 kcal/mol, which indicates that the reaction is
the temperature is lowered from 320oC to 290oC
limited by external mass transport.
and it increases even more rapidly with temperature
when lowered to 280oC. This indicates that the
When analyzing the exposed sample with nitrogen
deactivation rate varies more than linearly with
adsorption some precaution has to be observed.
temperature. It should be noted that the deactivation
Since ammonium sulphate salts are volatile it is
rate is probably affected by mass transportation
important that the temperature used for degassing
limitations since the DeNOx-reaction proceed
the exposed catalyst is not sufficient to evaporate
simultaneously with the deposition of the salts and
the salt. However, if the temperature is to low the
there will be concentration gradients above the
atmospheric water condensed in the catalyst pore
surface of the catalyst and in the catalyst pores.
will not be evaporated and the nitrogen adsorption
measurement of the catalyst will not measure the
Sample 6 was exposed at 280oC for approximately
actual surface area. To satisfy both of these criteria
6.5 h and a change in activity was verified. The
the degassing temperature was set to 130 oC. Due to
temperature was then raised to 350oC to see if the
reasons discussed in the following sections some
initial activity could be retrieved. The activity
samples where degassed at higher temperatures.
change for sample 6 is illustrated in Figure 2, where
The sample glass containers used for degassing at
the first 7 h are exposure at 280°C and the
200 oC and higher was covered with a white-beige
remaining 7 h are exposure at 320°C. The first 3 h
coating, verifying that something was evaporated
of exposure at 320°C the activity increases but after
from these samples. The coating was not present for
3 h the affect subsides and activity start to decrease
samples degassed at 130 oC suggesting that salts are
again. It should be noted that different k0’s are used
not evaporated at this temperature
for the different temperatures to compensate for the
relation between activity and temperature. The
The pore volume distribution of the fresh catalyst
result from Sample 6 shows that 350oC is not a
shows a wide range of pores, from micropores up to
sufficient temperature to the regenerate the catalyst
macropores with a diameter of 500 A. Since the
at operating conditions.
capillary force strongly depend on the pore size,

5(7)
especially at small diameters (according to Kelvin’s Fresh 0.245
equation) this will greatly influence the
condensation temperature. The micro pore area is If the average pore diameter is studied (not shown)
relatively large, about 10% of the total surface area, for the same samples a correlation is also found.
hence it is likely that salt deposition in the The average pore diameter increases at lower
micropores will affect catalyst activity. operating temperatures which indicate that the
amount of smaller pores decrease due to salt
The results from the nitrogen adsorption analysis formation.
show that the deactivation has a correlation with the
loss of catalyst surface. All of the exposed samples As seen in Table 5, sample 2, exposed for 7 h at
have lost surface area compared to a fresh catalyst 250oC, has a significant difference in pore volume
but if the samples are compared with each other the compared to a fresh catalyst. The pore volume for
data are inconclusive. The measured surface areas sample 5, exposed for 7.5 h at 320oC, also deviates
of the exposed samples are illustrated in Figure 3. from a fresh catalyst but the difference is not as
Surface Area of exposed Samples and Fresh
pronounced. The same applies for sample 6,
Catalyst exposed for 6 h at 290oC then for 8 h at 350oC, and
for sample 3, exposed at 280oC for 7.5 h. If the
70 exposed samples are compared the data are
65 inconclusive. Sample 3 and 5 have a higher total
Surface Area [m²/g]

60
pore volume than sample 6 with a final exposure
temperature of 350 oC.
55

50 Figure 4 illustrates a differential desorption plot of

45 samples 2, 5, 6 and the fresh catalyst. In this figure
40 the samples has a good alignment above 200 A but
it is obvious that the fresh catalyst has more pore
t
h

ed

ys
,7

,7

,7

volume in the range of 50 – 100 A. The difference

at

al
°C

°C

°C

er

at
en

C
0

between Sample 5 and 6 is relatively small in the

25

28

32

h
eg

es
2,

3,

5,

Fr

range 50-100 A but sample 6 show a higher

e

6,
pl

pl

pl

e
m

pl
Sa

Sa

Sa

differential for all data points. It is hard to see any

m
Sa

general effect over the whole data range but the

exposed samples are shifted slightly towards larger
Figure 3. Surface area of samples exposed at pores.
different temperatures. Sample 6 was first
exposed for 6 h at 290 oC and then exposed at
350 oC for 8 h. The degassing conditions for all
of the samples were 130 oC for 20 h at vacuum.

As Figure 3 shows there is a weak correlation

between the exposure temperature and the surface
area. Sample 3 has a higher surface than Sample 5
which was exposed at a higher temperature, hence it
should be less affected by the deposition. Sample 3
had a surprisingly high activity, suggesting that
Sample 3 might not be representative. The analysis
of Sample 6 shows only minor difference in surface
area compared to Sample 3 and 5, which indicate
that 350 oC is not sufficient to evaporate the
deposited salts under operating conditions.
Table 5. The measured pore volume for sample
2, 3, 5, 6 and a fresh catalyst. Remaining
operating condition according to Table 1.
Sample T Time Pore volume
ºC h
2 250 7 0.211 Figure 4. Differential pore volume at different
3 280 7.5 0.234
pore diameters for Sample 2, exposed for 7 h at
250 oC, Sample 5, exposed for 7 at 320 oC,
5 320 7.5 0.232
Sample 6, exposed for 6 h at 290 oC then for 8 h
6 290/350 6/7.5 0.226
at 350 oC and for a fresh catalyst.

6(7)
To further evaluate the decomposition temperature
of the deposited sulphate species, a series of
samples from Sample 1 where analysed with
nitrogen adsorption using different degassing
temperatures. The surface area shows a strong
correlation with the degassing temperature and the
surface area increases at higher degassing
temperatures. This is in agreement with the
temperature dependence of the capillary forces and
its effect on the equilibrium. At 375 oC the surface
of the fresh catalyst is almost restored and it
indicates that it is possible to thermally decompose
all of the salt. However, since the degassing
preceding a nitrogen adsorption analysis takes place
under vacuum the temperatures in are not
representative for decomposition under operating
conditions. It is likely that a significantly higher
temperature is needed to evaporate the salts under
operating conditions.
Conclusions
From the results presented in this paper it can be
concluded that ammonium sulphate salts deposit at
the catalyst surface and that they affect the catalyst
activity. Exposed catalyst samples show changes in
BET surface area, pore volume and average pore
diameter compared with a fresh catalyst. However,
the results are not concurrent enough to make any
firm statements about the correlation between
exposure temperature, loss of surface area and the
activity. To produce such relations more
experimental data would be a necessity.
The relations derived theoretically show some
concurrence with the experimental results,
concerning the impact of changes in operating
temperature and condensation temperature in pores
with different diameters. This indicates that the salt
equilibrium affects the condensation temperature
and that the temperature where deactivation occurs
is not completely controlled by kinetics. It also
indicates that capillary forces have a strong impact
on the condensation temperature in the catalyst
pore, especially the pores in, or close to, the
micropore range. But the data are not
comprehensive enough to draw any conclusions
about the correlation between calculated
temperatures and the actual condensation
temperatures.
As mentioned it was not possible to perform the
experiments where the DeNOx-reaction is under
kinetic control. Thus it can neither be guaranteed
that the deposition takes place under kinetic control.
The available testing equipment offered no
possibility to measure the inlet and outlet
concentrations of SO3 or NH3 continuously, which
is necessary to determine kinetic relationships.
7(7)
The activity measurements during exposure of
Sample 6 show that it is not possible to regenerate
the catalyst at 350 oC under operating condition.
Even if some activity is restored it is still far from
the initial activity. The nitrogen adsorption analysis
shows that it is possible to evaporate the salt in the
pores and restore much of the blocked pore surface.
This indicates that much of the initial activity could
also be retrieved with the same treatment. During
degassing the pressure above the catalyst is very
low, basically vacuum, and to achieve the same
results under operating conditions the temperature
would have to be higher. The fact that the salts do
not decompose when the temperature is raised, at
least to 350 oC, indicates that the decomposition
proceeds through other reactions than the
formation, which is supported by results found in
literature, or that the decomposition is suppressed
by very slow kinetics.
Acknowledgements
The author thanks Prof. Ingemar Odenbrand and
Ph.d. Ann-Charlotte Larsson for their support and
guidance during this work and the personnel at
Alstom Power Environment in Växjö for their
assistance during the experimental part of this
work.
1 P. Forzatti, Applied Catalysis A: General 222
(2001) 221
2
P. Forzatti, Catalysis Today, 62 (2000) 51
3 K Nagai, Y Kamino, Internal Alstom document
4
H. Bosch, F. Janssen, Catalysis Today, 2 (1988)
369
5
K Nagai, Y Kamino, Internal Alstom document
6
Environmental Protection Agency (EPA)
document CTM 27
7
Swedish Standard Institute (SIS) document
028134
8 Discussion with Ann-Charlotte Larsson, Manger
Process Technology, Alstom Power Environment
9 Discussion with Ingemar Odenbrand, Professor at
Lund University, Faculty of Engineering,
Department of Chemical Engineering
10
Software, HSC Chemistry 5.0, Outokumpu
Reserch Oy
11
S. Matsuda, T. Kamo, A. Kato, F. Nakajima, T.
Kumura, H. Kuroda, Ind. Eng. Chem. Prod. Res.
Dev. 21 (1982) 48
12
R. Kiyoura, K. Urano, Ind. Chem. Process Des.
Develop., 9 (1970) 489