Atmospheric Environment Vol. 27A, No, 3, pp. 443 447, 1993. 0004 6981/93 $6.00+0.

00
Printed in Great Britain, ~ 1993 Pergamon Press Ltd

CATALYST FOR NOx REMOVAL IN NITRIC-ACID PLANT

GASEOUS EFFLUENTS
P. AVlLA,* C. BARTHELEMY,t A. BAHAMONDE* a n d J. BLANCO*
*Instituto de Cat/tlisis y Petroleoquimica, CSIC, Serrano 119, 28006 Madrid, Spain and tUniversidad
Nacional de EducaciOn a Distancia, Madrid, Spain

(First received 8 March 1991 and in final form 30 Auoust 1991)

Abstract--The behaviour of a VzOs-WOa-TiO 2 phosphorated catalyst, in the Selective Catalytic

Reduction (SCR) of equimolar N O + NO2 mixtures, is studied in order to analyse the possibility of its
industrial utilization for the treatment of nitric-acid plant stack gases. With this new catalyst, an NOx
conversion higher than 90% molar can be achieved, the ammonia concentration at the exit gas being lower
than that required to form ammonium salts, throughout the temperature range of commercial interest:
250-450°C, at a relatively high space velocity (GHSV~<40000 h - t NC). The effect of several operating
variables such as oxygen concentration and NOg/NO molar ratio in the feed is also discussed.

Key word index: Nitrogen oxides, Selective Catalytic Reduction (SCR), De-NOx, nitric-acid plant, NO x
removal.

INTRODUCTION
The recognition of the direct participation of the
nitrogen oxides in the formation of "acid rain" and
"photochemical smog" phenomena raised great inter-
est in the development of N O x abatement methods.
The main anthropogenic non-combustion source
of NOx is the chemical industry, where nitric-acid
plants deserve special consideration owing to the high
concentrations of nitrogen oxides in their stack gases
(20(R)~000 ppm), which cause severe damage to the
factory surroundings.
Several processes have been developed to reduce the
nitrogen-oxide content of industrial effluent. Argu-
ments for and against such processes have been dis-
cussed in the extensive review of Bosch and Janssen
(1988). Among them, Selective Catalytic Reduction
(SCR) processes are being considered as offering the
best technical and economical advantages not only for
power plants (Ando, 1983) but also for the treatment
of the nitric-acid plant stack gases (Ritzert, 1987).
In SCR processes, ammonia, used as a selective
reducing agent, is injected directly into the flue gas
stream to convert NOx to nitrogen and water over a
catalyst in the presence of oxygen.
The removal of N O x from nitric-acid plants by SCR
presents significant differences with respect to the
removal of these contaminants from power plants,
mainly owing to the different composition of the
treated gases (Table 1).
The high N O 2 concentration in the tail gases of
nitric-acid plants (molar ratio N O E / N O ~ 1) signific-
antly affects the catalyst behaviour, in some cases
improving its performance ( C u O - N i O / A l 2 0 3 ) (Avila
et al., 1984) and in others causing a negative effect
(Pt/A12Oa) (Blanco and Avila, 1984).
The catalysts available for SCR processes cover a
wide range of metals and oxides, standing out

Table 1. Comparison of the composition and conditions of tail gases of

nitric-acid plants and power plants

Power plant
Composition and conditions H N Q 3 plant (coal)
NO x (ppm) 2000-4000 200-1200
NO/NO 2 ratio 1/1 10/1
0 2 (% vol.) 2 3 1-5
HzO (% vol.) 1-5 10-20
SOx (ppm) -- 300-3000
CO 2 (% mol) 10-15
Ash (mgNm -3) 10000-20000
Pressure (atm) 3-7 1
Temperature (°C) 200-500 350
Flow gases (Nm 3 h - 1) (20-100) x 103 (1-20) × l05

443
444 P. AVILAet al.

amongst which are those prepared with vanadium
oxides supported on a TiO 2 carrier (Matsuda and
Kato, 1983). This type of catalyst presents high effici-
ency in the NOx reduction and severe resistance to the
SO2 deactivation.
Most of the published literature about this type of
SCR catalyst concerns N O reduction, but studies
where the NO2 reduction is also taken into account
(Tuenter et al., 1986; Andersson et al., 1989) are very
scarce.
This paper studies the performance of a
V 2 O s - W O 3 - T i O 2 phosphorated catalyst for the
selective catalytic reduction of equimolar N O + N O 2
mixtures.
It is important to point out that the catalyst utilized
in this study was prepared taking into account the
possibility of its industrial utilization for the treatment
of nitric-acid plant stack gases. F o r this reason phos-
phoric acid was included in its initial composition as
an agglomerating agent. The presence of phosphorus
compounds in the final composition of the catalyst
produces a significant improvement of the mechanical
properties of the pelletized solid at the expense of a
certain decrease in its catalytic activity (Bianco et al.,
1989).
EXPERIMENTAL
The catalyst used in this study was described previously
(Blanco et al., 1988). It was based on TiO2, V205, WO3, using
phosphoric acid as a binder. The atomic ratio was: Ti:V:W
= 87:5:8. An aqueous 3M phosphoric acid solution was used
to prepare a paste which was extruded in cylinders of 2.2 mm
dia. The extrudates were dried at ll0°C and treated, for 4 h,
at 700°C.
The catalytic activity tests were carried out in a pseudo-
adiabatic tubular fixed-bed reactor described previously
(Blanco et al., 1989).
The gas-feed composition was established to reproduce the
conditions of the tail gases of the nitric-acid plant, operating
in an integral regime as close as possible to the plug-flow
ideal model (see Table 2). The Gas Hourly Space Velocity
(GHSV) defined as:
mixed with oxygen in such a way that part of the NO was
converted to NO 2 in a homogeneous phase according to the
reaction:
NO+~O2~NO 2 . (1)
Controlling the concentration of NO and 0 2 as well as the
temperature and the contact time between the gases, the
molar ratio of NO2/NO can be maintained close to the test-
selected value.
Ammonia was fed directly to the entrance of the catalytic
reactor in order to avoid the formation of ammonia salts.
The NO and NO 2 concentrations were determined by a
Luminox 201A (BOC) chemiluminescence instrument before
and after passage through the reactor. NH 3 and N20
concentrations were determined by non-dispersive infrared
spectroscopy using a Miran 1A (Foxboro).
RESULTS AND DISCUSSION
The influence of the reaction temperature, the oxy-
gen concentration and the N O 2 / N O molar ratio in
the feed over the NOx conversion is discussed. More-
over the effect of space velocity and N H 3 / N O x molar
ratio over the NOx removal efficiency are studied in
order to analyse the possibility of using this catalyst to
clean the stack gases of the H N O 3 plant.
Influence o f reaction temperature
In Fig. 1 the conversion values obtained for each
reactant (NO, NO2 and NH3) and for the global NOx
is shown as a function of the reaction temperature at
the experimental condition shown in Table 1 as refer-
ence values.
Conversion has been defined as:
moles i (inlet) - moles i (outlet)
xi- x 100.
moles /(inlet)
M o r e o v e r results of conversion to N 2 0 are shown
at the bottom. This parameter has been defined as"
moles N 2 0 generated
y= x 100.
moles NOx in the feed

total gas flow at normal conditions (:h-1)

GHSV = As can be seen the conversion to N 2 0 was either
catalyst volume (:) equal to or lower than 5% in all cases, for this reason
In order to obtain the desired NO2/NO ratio at the the formation of N 2 0 was not considered significant
reactor inlet, nitrogen with 10% vol. NO was previously for kinetic effects.

Table 2. Operating conditions of the catalytic activity tests

Reference
Feed composition and operating conditions Range value
NOx (ppm) 2000-4000 3000
NO2/NO (molar ratio) 0-1.4 1.0
NHa/NO x (molar ratio) 0.6-1.4 1.0
02 (% vol.) 0~5 3
GHSV (h- 1) 20,000-80,000 40,000
Total gas flow (:tNrP) min- 1) 3.0
Linear velocity (cm s- 1) 160
Temperature (°C) 250-450 350
Total pressure (kPa) 120
 Catalyst for NO x removal 445

Conversion, molar % y, molar % NOx conversion, molar %

100 - - - - ~ NO 50 IO0
9 ~ H I ~ 2
90 P ~ ~
NOx
90 ........
NO
40

70
80
QHSV - 40000 h -1

--
--
NO.
NO
30 60
50~~NO
+ NO,
80
40 ~~'~~ /NO ©
70 ~7¢ NH,

N20
20
30P
60 10 20~ IO --~3" 10
.? 10J [ 0 0.2 r 0.6 •

50
200 250 300
J
350
'
400
'
450
0
500
0
0 1
t
2
I I
3 4
I I
5 6 7

Reaction Temperature, o C Oxygen concentration, vol %

Fig. 1. Influence of the reaction temperature on the con- Fig. 2. Influence of oxygen concentration in the feed on the
version of NO (L]), NO 2 (©), NH 3 (V) and NOx (B) and NOx conversion at 350°C for NO2/NO molar ratios: 1.0
on the formation of N20 ( x ). (D), 0.6 (<>), 0.2 (V), 0.0 (6~).

It can be also be seen in this figure that NH3, N O

NOx conversion, molar %
and NO2 conversion values increase as the reaction IO0
temperature increases from 250 to 350°C, the stoi-
chiometry of the process according to reactions being: j.t f

4 N H 3 + 3 N O 2 ~ 7/2 N 2 + 6 H 2 0 (2) 80, / J

2 N H 3 + 3 N O ~ 5/2 N 2 + 3 H 2 0 . (3) 7o / /v"

/
Taking into account that this experimental activity 60
test was carried out with the same N O and N O 2
concentration in the inlet gas, from the experimental 50 - GHSV - 40000 h -1 /

results obtained it can be deduced that when the

• T • 250°C [] T • 350 °
S
40 ~ ~ ~ ~ _~ L
reaction temperature is lower than 350°C the process 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
can be described as follows: NO 2/NO molar ratio

2 NH3+NO+NO2 ~ 3 N2+3 H20.
At temperatures above 350°C, the N O molar con-
version drops as the reaction temperature increases,
while N O : and N H 3 conversions still continue to
increase. This behaviour leads to a maximum in the
NOx conversion curve close to 350°C.
In spite of the abundant studies carried out, the
mechanism of this reaction is under discussion (Jans-
sen et al., 1987; Nam, 1989; Janssen and Von der
Kerkhof, 1989), especially when a significant N O 2
concentration is in the middle of the reaction (Brandin
et al., 1989; Luck and Roiron, 1989). Taking into
account the results obtained by these authors with
C u O NiO/A120 3 (Avila et al., 1984) and Pt/A120 3
catalysts (Blanco and Avila, 1984), it can be considered
that the decreasing of the N O conversion is probably
due to an increase in the reaction rate o f N H 3 with O2
to form N 2, N 2 0 or even NO:
2 NH3 + 3/2 02 ~ N 2 + 3 H 2 0
2 N H 3 + 2 02--, N 2 0 + 3 H 2 0
2 NH3+5/2 O2~ 2 NO+3 H20.
These secondary reactions can produce a decrease
of the N H 3 available to reduce the NOx to N z. As the
NOz conversion increases with the temperature above
350°C, it can be considered that the competition only
(4) Fig. 3. Effect of NO2/NO molar ratio in the feed on the
catalytic activity at reaction temperatures: 250°C (B) and
350°C (D).
takes place between N O and 02 for the N H 3 adsorbed
on the surface of the catalyst. This hypothesis does not
rule out the possibility of a partial reduction of N O z to
NO:
2 N H 3 + 5NO2 ~ 7 N O + 3 H 2 0 . (8)
Influence of inlet N O 2 / N O molar ratio and of the
oxygen concentration in the feed
According to the results given in Fig. 2, oxygen
concentration is a significant parameter when the inlet
N O 2 / N O molar ratio is lower than 0.5, mainly at
concentrations below 2% vol. Nevertheless, catalytic
activity becomes independent of the O 2 feed content at
ratios of N O 2 / N O > 0 . 5 and I-O2] >~ 1% vol.
(5)
In Fig. 3 the values of NOx total conversion ob-
(6) tained with this catalyst at reaction temperatures of
250 and 350°C were plotted as a function of the
(7)
N O 2 / N O molar ratio in the feed. The maximum
activity is obtained when the N O 2 / N O ratio is close
to the unity.
These results are in accordance with the one ob-
tained by Luck and Roiron (1989) over a V 2 O s / A I 2 0 3
446 P. AVILAet al.

catalyst and by Brandin et al. (1989). In line with these NOx Convereibn, molar % [NHe] outlet, ppm
100 r- __~ 1000
authors, the mechanism proposed for the NO reduc- , !
90 . . . . . . . . . 900
tion seems to involve the reaction of NO and NO 2
80 ...... .......... 800
(ads) to form bonded surface species. The absorbed
species react with NH 3 forming ammonium com- 70 ........ i .............. 7oo

60
plexes that decompose into N 2 and H20. -- 250 oc 600

Taking this overall mechanism into consideration,

the explanation of the results obtained is obvious
50

40
\
...... ......
j
..... , ......
-- aoo oe
~5o oc li 600

,oo

because if the rate-controlling step is the reaction of 30 , ............. 300

20
NO and 02 to form NO2 (ads), when NO2 is in the ......... N
i ...... ~. . . . . . . . . . . . . . . . . 200100
feed, the formation of part of NO2 (ads) takes place 10

from NO 2 (gas) and the global reaction rate becomes 0

0 1 2
0
3 4 5 6 7 8
faster as the molar ratio N O 2 / N O increases from 0 to WlF x 10 5 h

unity. Moreover the non-dependence of oxygen in this

case is also explained. Fig. 4. Influenceof the contact time on the NOx conversion
and on the NH 3 concentration at the reactor outlet at
several reaction temperatures.
Influence of the operating variables
The behaviour of the catalyst in the abatement of
NO x has been studied by analysing the effect of the
N O x Conversion, °k molar [NH a] outlet, ppm
space velocity (GHSV) and the N H 3 / N O x molar ratio 100 ~ ~ 1000
in the feed on the conversion values of NOx and on ,o l,.o.,.,.t j 1,oo
NH 3 residual concentration at the outlet of the re- so-l÷ ,ooo,o° / / . ~ ~ ~oo
actor.
In order to achieve the standards of NOx emission,
70

oo-
~2- 4000 ppm
/
/ • .
/ i16oo
//
I 700

the concentration of these compounds in the tail gases 50 ./ // Iooo

has to be reduced from 2000-4000 to 200 ppm or 40 - • 400

lower; therefore the NOx conversion values have to be 30 300

higher than 90%. Moreover, in order to analyse the 20 200

possibility of using this catalyst at full scale, it is 10 ~00

necessary to consider the concentration of NH 3 at the
outlet as a very important parameter, because the
main problem over installing the SCR system in an
HNO 3 plant is to avoid the formation of ammonium
salts (Toering, 1982; Marzo et al., 1989).
From the data of Odembrand et al. (1986) it can be
considered that if the temperature of gases is higher
than 400 K, the minimum necessary concentration of
NH 3 to form NH4NO 3 is 100ppm. If the NH 3
concentration is lower than 100 ppm or the temper-
ature is higher than 400 K the formation of this salt is
not very likely.
Figure 4 shows the influence of the contact time
(W/F) expressed in h at normal conditions, on the
NOx global conversion and the [NH3]outletexpressed
in ppm.
From the data of this figure it can be considered that
the catalyst operates satisfactorily if the reaction tem-
perature is greater than 300°C and the contact time is
higher than 2.5 x 10 -5 h (GHSV~<40000 h-X).
If the reaction temperature is lower than 300°C,
even though at this space velocity (40000 h-~) the
NOx conversion is higher than 90%, in order to
achieve the proposed objectives it is necessary to
increase the contact time to a value near to 3.3
x 10 -5 h (GHSV=30000h 1) and to lower the
NH3/NO ~ ratio in the feed below the unity.
Figure 5 shows the results obtained using the
catalyst studied at GHSV=40000 h-1, reaction tem-
0 0.2 0.4 0.6 0.8 1 1.2 1.4
NH a / N O x , molar ratio
Fig. 5. Effect of NHa/NO x in the feed on the global
conversion of NO:, and on the NH 3 concentration at the
reactor outlet, at several NOx inlet concentrations. GHSV
= 40000 h- 1, reaction temperature = 350°C.
perature 350 °C, changing the NH3/NO x ratio at several
values of the concentration of NOx in the feed and Fig.
6 shows the same type of data obtained at 250°C and
GHSV = 30000 h - 1.
In these figures it can be seen that when the
NH3/NO x ratio in the feed is higher than unity, a very
great increase of the NH 3 concentration in the exit
gases is obtained. On the contrary, it is possible to
obtain a very small NH 3 residual concentration by
decreasing the NH3/NO x ratio in the feed below
unity.
For example, from the data shown in Fig. 5 it can be
observed that at 350°C, G H S V = 4 0 0 0 0 h -1 and a
molar ratio in the feed NH3/NO x in the range
0.93-1.0, the NOx conversion is higher than 90% and
the [-NH3] residual is lower than 100 ppm. On the
other hand, from the data of Fig. 6 it can be concluded
that these objectives can be achieved at 250°C and
GHSV ~<300(g) h - 1.
 Catalyst for NOx removal 447

NOx Conversion % molar [NH a] outlet, ppm REFERENCES

100 1000

90 [NOx] Inlet 1~ ~ / f 900

Andersson L. A. H., Brandin J. G. M. and Odenbrand I.
-- 2000 ppm ~,~
80
/ 800 (1989) Selective catalytic reduction of NOx over acid-
- e - 3000 ppm
70 ~" 4000 ppm j /-~"
700 leached. Catal. Today 4, 173-185.
60 600 Ando J. (1983) NOx abatement for stationary sources in
Japan. EPA report 600/7-83-027, order no. PB 83-207639.
50 500
Avila P., Blanco J. and Moreno M. (1984) Reducci6n cata-
40 400 litica de oxidos de nitr6geno a baja temperatura. Actas 9th
30
/'1//'~/ '.~/f 30O Simp. lberoamericano Catalysis, Lisboa, Vol. II, pp.
/
./ )
20O 817-827.
20
./ Blanco J. and Avila P. (1984) Comportamiento de un cata-
10 / 100
/ lizador de Pt/A120 3 en la.Reducci6n Catalitica Selectiva
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 de 6xidos de nitr6geno. A,n. Qulm. 80, 645-649.
NH a / N O x, molar ratio
Blanco J., Avila P., Barthelemy C. and Bahamonde A. (1988)
La Reducci6n Catalitica Selectiva de 6xidos de nitr6geno
en efluents industriales. Spanish patent no. ES 2009397.
Fig. 6. Effect of NHa/NOx in the feed on the global
Blanco J., Avila P., Barthelemy C., Bahamonde A., Odriozola
conversion of NO:, and on the NH 3 concentration at the
J. A., Garcia de la Banda J. F. and Heinemann H. (1989)
reactor outlet, at several NO:, inlet concentrations. GHSV
Influence of phosphorus in vanadium containing catalysts
= 30000 h - 1, reaction temperature = 250°C.
for NOx removal. Appl. Catal. 55, 151-164.
Bosch H. and Janssen F. (1988) Catalytic reduction of
nitrogen oxides. A review on the fundamentals and techno-
logy. Catal. Today 2, 1-531 (1988).
Brandin J. G. M., Andersson L. A. H. and Odenbrand I.
(1989) Catalytic reduction of nitrogen oxides on mor-
CONCLUSIONS
denite some aspect on the mechanism. Catal. Today 4,
187-203.
The results o b t a i n e d at l a b o r a t o r y scale with the Janssen F. J. J. G and Van der Kerkhof F. M. G. (1989)
catalyst studied show t h a t the presence of N O 2 in the Reply to the letter of In-Sink Nam concerning the paper
feed improves its performance, increasing the global "Preparation and performance of a silica supported V20 5
reaction rate of reduction of N O x by N H 3 a n d reduces on TiO 2 catalyst for the selective reduction of NO with
NH3". J. Catal. 119, 270 271.
its dependence on the oxygen in the feed. Janssen F. J. J. G., Van der Kerkhof F. M. G., Bosch H. and
F r o m a general p o i n t of view, the results o b t a i n e d Ross J. R. H. (1987) Mechanism of the reaction of nitric
with this catalyst can be considered satisfactory for oxide, ammonia, and oxygen over vanadia catalysts. 2.
removing the N O x emitted from a n H N O 3 p r o d u c t i o n Isotopic transient studies with oxygen- 18 and nitrogen- l 5.
plant. In fact what can be achieved is a n N O x conver-
J. phys. Chem. 91, 6633-6638.
Luck F. and Roiron J. (1989) Selective Catalytic Reduction of
sion greater t h a n 9 0 % m o l a r (the c o n c e n t r a t i o n of NOx emitted by nitric acid plants. Catal. Today4, 205-218.
N H 3 at the outlet being lower t h a n necessary to form Marzo L., Marzo J. and Solbes A. (1989) lnstalaci6n de
a m m o n i u m salts), t h r o u g h the whole t e m p e r a t u r e catalizadores para la destrucci6n de 6xidos de nitr6geno.
range of commercial interest: 250-450°C, at a rel- Ing. Quire.2, 93-96.
Matsuda S. and Kato A. (1983) Titanium oxide based
atively high space velocity ( G H S V ~<40000 h - l ) . catalysts a review. Appl. Catal. 8, 149-165.
T a k i n g into a c c o u n t t h a t most of the commercial Nam I. S. (1989) Stoichiometry for NO reduction by NH 3. J.
catalysts described in the literature operate at G H S V Catal. 119, 269.
in the range of 3000-10000 h - ~ (Ritzert, 1987; Luck et Odenbrand I., Andersson L. A. H., Brandin J. G. M. and
Lundin S. T. (1986) Catalytic reduction of nitrogen oxides.
al., 1989), these results indicate t h a t the a m o u n t of 2. The reduction of NO 2. Appl. Catal. 27, 363-377.
catalyst needed to o b t a i n a p p r o p r i a t e conversion val- Ritzert G. (1987) Current status of the development of
ues with this catalyst is four to ten times lower t h a n catalysts for NO~ abatement in flue gas. Tech. Mitt. 80,
c o n v e n t i o n a l catalysts. 602-608.
Toering W. (1982) Nitrogen oxides from nitric acid produc-
tion. Stud. envir. Sci. 21, 671-686.
Tuenter G., Van Leeuwen W. F. and Snepvangers I_,. J. M.
(1986) Kinetics and mechanism of the NOx reduction with
Acknowledgement--This work was supported by CICYT NH 3 on V20 5 WO3-TiO2 catalyst. Ind. Engng Chem.
(project no. 618/397). Prod. Res. Dev. 25, 633 636.