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NOx RemovalCatalysis
P. Forzatti, I. Nova, and L. Castoldi
Centro NEMAS – Nano Engineered MAterials and Surfaces Original scientific paper
Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta” Received: May 31, 2005
Politecnico di Milano; Piazza Leonardo da Vinci, 32 – 20133 Milano, Italy Accepted: November 10, 2005
This paper surveys the most important catalytic emission control technologies being
employed or near commercialization for the removal of nitrogen oxides (NOx) from the
exhausts of mobile sources under lean conditions. Urea/Ammonia-SCR systems and NOx
Storage/Reduction (NSR) catalysts will be addressed, with particular attention to the spe-
cific demands related to the mobile applications.
In the first part of the paper the transient kinetics of standard de-NOx SCR reaction
over commercial V-W/Ti SCR catalysts and the dynamic model of the honeycomb reac-
tor will be addressed. Then the validation of the dynamic model with integral reactor
measurements and full-scale transients in vehicles will be illustrated.
The second part presents a complete and quantitative understanding of the NOx
storage chemistry of a Pt-Ba/Al2O3 “Lean NOx Trap” catalyst.
Keywords:
Catalysis, environment, deNOx, Urea SCR, NOx Storage/Reduction (NSR)
surements and full-scale transients in vehicles will As shown in Figure 1 the intrinsic first order
be illustrated. rate constant of NOx reduction increases linearly
In the second part of this review the chemistry with the vanadium content, whereas the intrinsic
involved in the storage of NOx over reference NSR first order rate constant for the oxidation of SO2 in-
catalysts will be presented and discussed and the creases more than linearly with the vanadia con-
open issues outlined. tent.3 This is consistent with the identification of
the active sites for NOx reduction with isolated V
sites as opposite to the active sites for SO2 oxida-
Ammonia/Urea SCR tion that are likely associated with dymeric (or
polymeric) sulphated vanadyls, in line with the con-
Ammonia-SCR fundamentals solidated picture of the active sites in commercial
sulphuric acid catalysts. Accordingly, high disper-
The SCR process is based on the reduction of sion of surface V-oxides must be realized during the
NOx with ammonia into water and nitrogen accord- impregnation of the tungsta-titania powders with
ing to the following main reaction: the solution of the vanadium salt, as indeed attained
4 NO + 4 NH3 + O2 ® 4 N2 + 6 H2O (1) in commercial catalysts, and the vanadia content
must be low in any case.
In fact NO accounts for 90–95 % of NOx in the
exhausts.
In the case of sulphur containing fuels (e.g.
coal), SO2 is produced during combustion in the
boiler along with minor fractions of SO3 (about 1 %
of total SOx): SO2 can further be oxidized to SO3
over the catalyst:
SO2 + 1/2 O2 ® SO3 (2)
This reaction is highly undesired because SO3
reacts with water present in the flue gas and with
ammonia to form ammonium sulphates. Ammonium
sulphates deposit and accumulate onto the catalyst if
the temperature is not high enough, leading to cata-
lyst deactivation that can be reversed upon heating.
Commercial SCR catalysts are made of homo- F i g . 1 – Dependence of the intrinsic kinetic constants of
geneous mixtures of titania, tungsta and vanadia. de-NOx and SO2 oxidation reactions on the cata-
Titania in the anatase form is used as high surface lyst vanadium content at T = 350 °C
and sulphur resistant carrier to support the active
components. Tungsta is employed in large amounts
(w = 10 %) to increase the surface acidity and the Besides, the reduction of NOx is a very fast re-
thermal stability of the catalyst. Vanadia is respon- action, and is controlled by external and internal
sible for the activity in the reduction of NOx, but it diffusion. On the opposite, the oxidation of SO2 is
is also very active in the oxidation of SO2. Accord- very slow and is controlled by the chemical kinet-
ingly its content is kept low, usually below w = ics. Accordingly the SCR activity is increased by
1–2 %. increasing the catalyst external surface area (i.e. the
The SCR catalysts are used in the form of hon- cell density) to favour inter-phase mass transfer,
eycomb monoliths or plates to guarantee low pres- while the activity in oxidation of SO2 is reduced by
sure drops in view of the large frontal area with par- decreasing the volume of the catalyst (i.e. the wall
allel channels, high external surface area per unit thickness); this does not affect negatively the activ-
volume of catalyst, high attrition resistance, and low ity in NOx removal because significant ammonia
tendency to fly ash plugging. The SCR monoliths concentrations are confined only near the external
and plates are assembled into standard modules and geometric surface of the catalyst. Besides a good
inserted into the reactor to form catalyst layers. balance between macro-pores, which guarantee fast
An important requirement of SCR catalysts, es- diffusion of reagents, and micro-pores, which en-
pecially for stationary applications and power sta- sure high activity by providing high catalyst spe-
tions, is to combine high activity in the de-NOx re- cific surface area, can lead to optimal catalyst per-
action and very low (almost negligible) activity in formances, in the limit, however, of the required
the oxidation of SO2 to SO3. mechanical specifications.4
P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005) 311
Mechanism and steady state kinetics nia, the following kinetic expression has been even-
of the ammonia-SCR reaction tually derived in the literature:1
Different proposals have been advanced in the k c K W p NH 3 p NO
literature for the mechanism of the SCR reaction rNO = (1)
(1+ K NH 3 p NH 3 + K H 2O p H 2O )
over vanadia-based catalysts.
One of the first reaction scheme was proposed This equation is appropriate in the case of typi-
for the SCR reaction by Takagi et al.5 Their pro- cal stationary SCR applications where a sub-
posal is based on the reaction between co-adsorbed stoichiometric NH3/NO feed ratio is employed to
NH4+ (produced by ammonia adsorption over a V minimize the slip of unconverted ammonia. For
Brønsted acid site) and NO2 (coming from oxida- high water concentrations (above j = 5 % vol.) the
tion of NO) via a Langmuir-Hinshelwood mecha- dependence of water can be neglected and the fol-
nism to form nitrogen and water. lowing simplified rate equation can be adopted for
Inomata et al.6 proposed that ammonia is first practical purposes:
adsorbed at a Brøensted V site adjacent to a k c K NH 3 p NH 3 p NO
vanadyl and then it reacts with gas-phase NO ac- rNO = (2)
cording to an Eley-Rideal mechanism to form H2O 1+ K NH 3 p NH 3
and reduced V species [V(4+)–OH]. The reduced V
species is reoxidized by gaseous oxygen. which for KNH3 pNH3 > 1 (i.e. rNH3/NOx ³ 1, when full
coverage of the surface by NH3 is attained) reduces
Based primarily on FT-IR studies, Busca et al.7 to (eq. 3):
suggested that ammonia is adsorbed over Lewis
acid site and is activated to form an amide species. rNO = k c p NO (3)
The amide species then react with gas-phase NO
via a radical coupling to give a nitrosamide inter- Equations (2) and (3) have been successfully
mediate that is known to decompose easily and used by many authors for steady state modelling of
quantitatively to nitrogen and water. The catalytic the SCR monolith reactor operating with rNH3/NOx < 1
cycle is closed by re-oxidation of the reduced cata- and > 1 respectively.10,11,12
lyst by gaseous oxygen.
Steady state modelling of the SCR reactor
Topsøe et al.8,9 proposed that ammonia is ad-
sorbed at a V Brøensted acid site and is activated by The customary approach to the design and
a near-by vanadyl group that is then reduced. NO analysis of monolith SCR reactor, adopted in the
reacts from the gas-phase with the activated ammo- technical literature, is based on simple isothermal
nia species leading to the formation of an interme- pseudo-homogeneous single channel lD model that
diate, which finally decomposes to nitrogen and accounts only for the axial concentration gradients
water. The catalytic cycle is closed by the re-oxida- inside the channels, whereas the effects of
tion of the catalyst by means of gas-phase oxygen. inter-phase and intra-phase mass transfer limitations
It is worth noting that, both, mechanisms pro- are lumped into the overall effective pseudo-first
posed by Inomata et al. and by Topsøe et al. require order rate constant kNOx:
the participation of dymeric or polymeric vanadyl kNOx = – V ln (1 – cNOx) (4)
species. As an opposite, the mechanism proposed
by Busca et al. requires the participation of isolated In eq. (4) V is the superficial velocity, i.e. the
vanadyls, and this is consistent with the linear de- ratio of the volumetric flow rate to the overall geo-
pendence of the rate constant of NOx reduction on metric surface area of the monolith catalyst, cNOx
the vanadia loading shown in Figure 1. Whatever is represents the fractional conversion of NOx, and
the reaction mechanism a key step of the mecha- kNOx is given by
nism is represented by the formation of a reaction
intermediate that decomposes selectively and quan- 1/kNOx = 1/kc + 1/kg (5)
titatively to nitrogen and water. In fact, the reaction operates under combined
Considering that the Eley-Rideal mechanisms intra-particle and external diffusion control: kc is
discussed above imply the reaction between ad- the effective rate constant of the surface chemical
sorbed NH3 and gas-phase NO (rNO = k c c NO q NH 3 ) reaction incorporating the influence of mass trans-
and besides that the reaction is virtually independ- fer in catalyst pores (kc = h kSCR with h = catalyst
ent of the oxygen partial pressure and is slightly de- internal efficiency and kSCR = intrinsic kinetic coef-
pressed by water up to j = 5–10 %, due to competi- ficient of the SCR reaction) and kg represents the
tion for adsorption onto the active sites with ammo- inter-phase gas-solid mass transfer coefficient.
312 P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005)
It has been demonstrated that the gas-solid rameter: the effective diffusivities of NO and NH3
mass transfer coefficient can be estimated by anal- were estimated from the pore size distribution mea-
ogy with the Graetz-Nusselt problem governing surements and the intrinsic rate parameters were
heat transfer to a fluid in a duct with constant wall obtained from independent kinetic data collected
temperature (Sh = NuT), according to the expression over the same catalyst ground to very fine parti-
Sh = Nu¥T + 6.874 (1,000 z*) – 0.488 exp (–57.2 cles.12
z*),13 which accounts for the entrance effects.
Figure 2 compares the axial concentration pro- Dynamic modelling of ammonia-SCR
files of the 1D model with those of the rigorous The study of the dynamics of the ammo-
multidimensional model of the SCR monolith reac- nia-SCR reaction was addressed by investigating
tor in the case of square channels, that are most first the adsorption-desorption kinetics of NH3 and
common in industrial applications, and of NO and then the surface reaction.15
Eley-Rideal kinetics, which must be introduced in In the case of NH3 a typical result obtained
place of the first order kinetics (Eq.3) to comply upon a rectangular step feed in flowing He+O2 over
with industrial conditions for steady state applica- a ternary home-made V2O5–WO3/TiO2 catalyst at
tions (substoichiometric rNH3/NO feed ratio, i.e. 280 °C is presented in the Figure 3. The results of
rNH3/NO < 1). It is apparent that the 1D model is the TPD experiment obtained upon heating the cat-
equivalent to the rigorous multidimensional mo- alyst from RT up to 500 °C at the end of the ammo-
del.13 nia adsorption are also presented. Upon the NH3
step addition (at t = 0 s), the ammonia reactor outlet
concentration slowly increased with time, ap-
proaching the ammonia inlet molar fraction (c =
700 · 10–6) only after » 500 s. This clearly indi-
cates that ammonia is involved in adsorp-
tion-desorption processes at the catalyst surface.
Along similar lines, upon the ammonia shut-off (t =
1000 s) the reactor outlet NH3 concentration slowly
decreases with time due to the desorption of previ-
ously adsorbed ammonia. Complete desorption of
NH3 is not yet achieved after 2200 s, but could only
be achieved by heating the catalyst at high tempera-
ture. The results confirm that the adsorption of am-
monia is very fast and that ammonia is strongly ad-
sorbed onto the catalyst surface.
The NH3 dynamic adsorption-desorption ex-
F i g . 2 – Comparison between calculated axial concentra-
tion profiles of NO and NH3 obtained by the lD model and by a periments were also performed at different tempera-
rigorous multidimensional model of the SCR monolith reactor tures, in the range 220–400 °C. On increasing the
catalyst temperature, the variations in the ammonia value; again the N2 fraction trace is symmetrical to
outlet concentration during the adsorption step are that of NO. These data suggest that the rate of the
faster and the amount of ammonia adsorbed on the SCR reaction is unaffected by changes in the am-
catalyst surface is reduced, in line with the in- monia surface coverage at high ammonia coverage.
creased rates of the adsorption-desorption processes Similar results were obtained by performing the
and with the exothermicity of NH3 adsorption. NH3 step-feed experiments at higher temperatures
Similar experiments were performed for NO,15 (280 and 350 °C): the results were found in line
which indicated that it does not appreciably adsorb with, both, the exothermicity of the NH3 adsorption
onto the catalyst surface, in line with previous liter- and with the increased rate of the surface reaction,
ature indications. which result in lower ammonia surface coverage.
The dynamics of the SCR reaction was in- The adsorption-desorption and reaction kinetic
vestigated upon performing step changes of the data were analyzed by means of a dynamic 1D iso-
ammonia reactor inlet concentration in flowing thermal heterogeneous PFR model of the laboratory
He + NO + O2, and step changes of the NO reactor microreactor and fitted by nonlinear regression to
inlet concentration in flowing He + NH3 + O2. provide the estimates of the relevant kinetic param-
Figure 4 shows typical results obtained over eters.15 The influence of both intra-particle and ex-
model V2O5-WO3/TiO2 sample upon performing ternal mass transfer limitations were estimated as
step changes of the NH3 inlet concentration (dashed negligible, on the basis of theoretical diagnostic cri-
line) at 220 °C in flowing He + NO (c = 700 · 10–6) teria.16 The complete unsteady state model for ad-
+ O2 (j = 1 · 10–2). The figure reports the evolution sorption-desorption and surface reactions was based
with time of NH3, N2, and NO molar fractions. on the following equations, with symbols defined in
the Notation section:
NH3 mass balance on the catalyst surface:
¶q NH 3
= ra - rd - rNO - rOX (6)
¶t
NH3, NO and N2 mass balances on the gas stream:
¶c NH 3 ¶c NH 3
=- v + C NH 3 ×( ra - rd - rNO- r0X ) (7)
¶t ¶z
¶c NO ¶c NO
=-v + W NH 3 × rNO (8)
¶t ¶z
¶c N 2 ¶c N 2
=-v . × r0X ) (9)
- W NH 3 × ( rNO + 05
¶t ¶z
F i g . 4 – Step feed and shut off of NH3 in He + O2 (r = 1 %)
+ NO (700 q 10–6) over a WO3-V2O5/TiO2 model catalyst rate expressions:
(wV2O5 = 1.47 ; wWO3 = 9 %) at 220 EC. Dashed lines: ideal
inlet NH3 concentration; symbols: outlet concentrations (trian- ra = k a0 × e -Ea RT
× c NH 3 × (1- q NH 3 ) (10)
gles: ammonia, squares: N2, circles: NO); solid lines: model
fits (Temkin-type coverage dependence and “modified kinetics”
Eq.(13)). rd = k d0 × e -Ed RT
× q NH 3 (11)
0
rax = k ax × e -Eax RT
× q NH 3 (12)
Upon the NH3 step feed the outlet reactor con-
centration decreases and that of N2 shows a sym- q NH 3 q*NH 3
metric change indicating the occurrence of a genu- rd = k d0 × e -Ed RT
× c N0 × q *NH 3 × (1- e ) (13)
ine SCR process. The ammonia fraction profile ex-
hibits a dead time and then increases with time to Thus, in addition to adsorption and desorption
the final steady state value that is consistent with of ammonia (ra and rd, respectively) and to its sur-
the occurrence of the SCR reaction. Upon the face reaction with NO to give nitrogen and water
shut-off of ammonia at the reactor inlet the ammo- (rNO), also ammonia oxidation (rox) was introduced
nia fraction at the reactor outlet rapidly dropped to in order to account for the direct oxidation of am-
zero, but the NO and nitrogen fraction signals were monia occurring at high temperatures. CNH3 in the
not affected for several minutes. Then the NO frac- equations represents the catalyst NH3 adsorption ca-
tion signal began to increase up to the inlet fraction pacity (mol m–3).
314 P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005)
Eq. (6)-(9) were solved by standard numerical rate of surface reaction, whereas ammonia desorp-
procedures17,18 and the data fit was performed on tion is much slower. Accordingly, the assumption of
the experimental results, as shown in the figures 4 equilibrated adsorption, which is usually assumed
and 5 for selected NH3 adsorption-desorption ex- in the kinetic studies available in the literature, may
periments, and runs with changes in the NH3 reac- be incorrect.
tor inlet concentration in flowing NO + O2. The More recently specific attention was paid to
data fit is reported as solid lines in the same figures: transient experiments in the low-T region: accord-
it appears that the goodness of fit is satisfactory. ingly dedicated dynamic experiments have been
The activation energy for NH3 adsorption was performed on a commercial V2O5-WO3/TiO2 cata-
found to be close to zero, and accordingly a non-ac- lyst.20
tivated ammonia adsorption process was considered
in the model (Ea » 0). Besides, a Temkin-type Figure 5 shows data recorded at 175 °C feed-
( E d = E d0 × (1- g × q NH 3 )) coverage dependence of ing NH3 step pulses (0 ® 1000 ® 0 ppmv) in flow-
the desorption energy had to be used to describe the ing He + NO (1000 ppmv) + O2 (2 % v/v) + H2O
adsorption desorption data; indeed a simple (l % v/v): the measured temporal evolutions of NH3
Langmuir approach (that considers a constant value (circles), NO (squares), and N2 (triangles) outlet
of the desorption activation energy) was not appro- fractions are plotted. It is worth noticing that at t =
priate. This is consistent with the presence of dis- 1500 s, when ammonia is removed from the feed
tinct types of acid sites (Lewis and/or Brøensted) stream, the NO concentration trace decreases, goes
characterized by different acid strengths at the cata- through a minimum and then begins to increase, re-
lyst surface.19 covering the inlet value when the reaction is de-
pleted. The symmetrical evolution of N2 confirmed
the occurrence of the SCR reaction. Similar effects,
always observed in transient experiments per-
formed under equivalent conditions and T < 250 °C
and reported in the past over different commercial
SCR catalysts for stationary applications,21,22 were
attributed to an inhibiting effect of excess NH3,
possibly caused by a competition between NO and
ammonia in adsorbing onto the catalyst. Such inhi-
bition effects are of limited interest for stationary
applications of the SCR technology, but may play a
considerable role in mobile applications, since they
become more significant at low temperatures, and
also affect the dynamic response of the SCR sys-
tems.
The peculiar dynamic effect attributed to the
F i g . 5 – Step feed and shut off of NH3 in He + O2 (r = 2 %) inhibition effect of ammonia, has been recently ac-
+ H2O (r = 1 %) + NO (1.0 q 10–3) over a WO3-V2O5/TiO2
commercial catalyst at 175 EC. Dashed lines: ideal inlet NH3 counted for by a dual-site modified Redox rate law
concentration; symbols: outlet concentrations (triangles: am- (MR)20
monia, squares: NO, circles: N2); solid thin lines: kinetic fit by
“modified kinetics” – Eq.(13); solid thick lines: kinetic fit by 0¢
æ E NO ö
modified Redox rate expression – Eq.(14). k ¢NO expç- ÷c q
p öb
è RT ø NO NH 3 æ ç O2 ÷ (14)
rNO = ç ÷
q NH 3 è 002
. ø
To describe quantitatively the reactivity data 1+ K ¢NH 3
a “modified qNH3 kinetics” Eley-Rideal (eq.(13)) 1- q NH 3
had to be adopted:15 this empiric expression as-
sumes that rNO is essentially independent of the am- that assumes competition between ammonia and
monia surface coverage above a critical NH3 cover- NO in adsorbing onto the catalyst. This model pro-
age (q *NH 3 ). This has been explained assuming that vides a much better description of the observed dy-
a “reservoir” of NH3 species, adsorbed on poorly namics than the previously employed Eley-Rideal
reactive and most abundant W and Ti sites, is pres- kinetics.
ent and available for the reaction upon ammonia In Figure 5 the fit results obtained by using ei-
desorption followed by re-adsorption at the active ther the MR rate expression, Eq. (14), (solid thick
V sites. Indeed, the analysis of the rate parameters lines) or the “modified qNH3 kinetics” ER kinetics,
estimated by fitting the dynamic data indicated that Eq. (13), (solid thin lines) are compared: it clearly
the rate of ammonia adsorption is comparable to the appears that the redox kinetics account better for
P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005) 315
Pt-Ba/Al2O3 (z = 1/x/100) samples with different without any dead time; large amounts of NOx are
barium loading (5–30 %) were prepared by impreg- stored at the end of the pulse, near 9E-04 mol gcat–1.
nation of calcined Pt/Al2O3 with different solutions FTIR spectra (Figure 7B) collected upon contacting
of barium acetate.31,37 the catalyst with NO2 show that only nitrates are
The adsorption of NOx under lean conditions formed. The nitrate species adsorbed over
has been investigated by performing transient ex- Ba/g-Al2O3 show high thermal stability; as a matter
periments where a step change of NO and NO2 was of fact, during the subsequent TPD experiment,
imposed in the presence and absence of oxygen at NO2 desorption was observed starting from 370 °C
350 °C over reference catalysts and analyzing the with a maximum at 470 °C, while NO and oxygen
transient response in the outlet concentrations of re- show peaks at higher temperature (with maxima
actants and products (Transient Response Method); close to 560 °C).
the stored NOx species were then removed from the In agreement with literature2,27,31 the nitrates are
catalyst surface by performing a TPD run up to primarily formed through a NO2 disproportionation
600 °C. FT-IR was used as a complementary tech- reaction, following the overall stoichiometry:
nique to investigate the nature of the stored NOx BaO + 3 NO2 ® Ba(NO3)2 + NO (3)
species.
The adsorption of NO2 over the Ba(16)/g-Al2O3 that also accounts for the evolution of NO.
sample has been investigated at first. In fact, NO2 It is worth noting, that over the supported Ba
has been suggested as intermediate in the NO ad- sample the Integral Molar Ratio of NO evolved to
sorption in the presence of oxygen.24 As shown NO2 consumed (Figure 8), that is equal to 1/3 ac-
in Figure 7A, the storage of NO2 over the cording to the disproportionation reaction, is ini-
Ba(16)/g-Al2O3 sample is accompanied by the evo- tially lower than the stoichiometric value. This indi-
lution of NO in the gas phase, which is observed cates that the NO2 uptake at the beginning of the
F i g . 7 – Results of NO2 adsorption TRM experiments in He at 350 °C and subsequent TPD in terms of NO, NO2, NOx, O2 outlet
concentrations and NO2 inlet concentration over A) Ba/g-Al2O3; C) Pt-Ba/g-Al2O3 catalysts. Results of NO2 adsorption
FT-IR experiments over B) Ba/g-Al2O3, D) Pt-Ba/g-Al2O3 catalysts. Spectra are reported after 1 and 10 min of exposure
to 5 mbar of NO2 at 350 °C. Each spectrum is reported as difference from the spectrum before NO2 admission.
318 P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005)
F i g . 9 – Results of NO adsorption TRM experiments at 350 °C in He+O2 and subsequent TPD in He in terms of NO, NO2, NOx, O2
outlet fraction and NO inlet fraction over A) Ba/g-Al2O3, C) Pt-Ba/g-Al2O3 catalysts. Results of NO/O2 adsorption FT-IR experiments
over B) Ba/g-Al2O3, D) Pt-Ba/g-Al2O3 catalysts. Spectra are reported after 1, 3, 5, 10, 15 and 20 min of exposure to NO/O2 mixtures
(1:4, pNO = 5 mbar) at 350 °C. Each spectrum is reported as difference from the spectrum before NO/O2 admission.
into nitrates over Pt. Notably, the rate of, both, ni-
trite formation and their oxidation to nitrates are
higher on Pt-Ba/g-Al2O3 than on Ba/g-Al2O3, point-
ing out a catalytic role of Pt. This situation was also
confirmed by DRIFT data (Figure 10) collected un-
der operando conditions equal to those used in the
TRM experiments, showing that during the initial
NOx uptake nitrites are more abundant than nitrates:
the nitrite band intensity showed a broad maximum
and then decreased with time on stream, while the
nitrate bands presented a monotonous increase dur-
ing the entire storage phase, so that at the end of the
experiment (at ca. 700 s) nitrates are the most abun-
dant adsorbed species. Thus, in line with FTIR data, F i g . 1 0 – Results of NO/O2 adsorption DRIFT experiment
in the adsorption process nitrites are intermediate over Pt-Ba/Al2O3 plots of band maxims vs. time
species which then evolve leading to the formation
of nitrates. Notably, the maximum in the nitrite storage of NOx over Pt-Ba/alumina catalysts. In the
band intensity corresponded roughly to the NO presence of oxygen NO is effectively stored
breakthrough observed by TRM experiments and through a stepwise oxidation at a Pt site followed
confirmed by the analysis of data collected with the by adsorption at a neighboring Ba site to form
quadrupole mass-spectrometer interfaced with the Ba-nitrites at first and Ba-nitrates later on. The
DRIFT cell. proximity of Pt and Ba sites likely results in the sta-
All the previous data led to the proposal of the bilization of nitrites against further oxidation to ni-
following reaction pathways (Figure 11) for the trates. This is referred to as the nitrite route.
320 P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005)
In the case of the Pt-Ba/alumina the dead time The effect of the Pt-Ba interaction, that repre-
in the NOx breakthrough upon a step change of NO sents a key feature of the nitrite route, has been in-
in the presence of oxygen is reasonably well pre- vestigated by preparing Pt-Ba/alumina catalysts
dicted by the model (see Figure 12B), but the oxi- with different Ba loading.40
dation of NO to NO2 is markedly overestimated. The existence of Pt-Ba proximity over the ter-
The Pt dispersion in the model must be low- nary Pt-Ba(16)/g-Al2O3 sample was investigated by
ered to describe properly the oxidation of NO to CO chemisorption.32 The intensity of the FTIR
NO2 but in this case the time delay in the break- band of CO linearly adsorbed on Pt (observed at
through of NOx is no longer predicted (Figure 12C). 2070 cm–1) decreases on increasing the Ba loading
Therefore, the literature model is not able to and is progressively shifted towards higher frequen-
describe at the same time the oxidation of NO cies due to the increasing basic character of the cat-
to NO2 and the storage of NO2 over the ternary alysts. This indicates that the interaction between Pt
Pt-Ba/g-Al2O3 system. and Ba increases on increasing the Ba loading.
As a matter of fact these two catalyst properties The effect of the Ba loading on the mechanism
are strictly interrelated within the nitrate route. Ac- of NOx adsorption has been studied by performing
cordingly, the nitrate route cannot account for the TRM experiments with rNO/O2 mixtures at 350 °C
storage of NOx under conditions of industrial inter- over the various samples.
est (presence of NO in excess of oxygen). Upon a step change of NO at the inlet in the
From data presented so far, it seems evident presence of oxygen the dead time in the break-
that the nitrite route requires not only the co-pres- through of NOx (i.e. the NOx storage capacity) in-
ence of Pt and Ba components, but also a coopera- creases with the Ba mass fraction and is maximum
tive effect between Pt and Ba. This cooperation im- at w = 23 % Ba, as shown in Figure 13. Besides the
plies a sort of interaction between these two cata- rNO2/NO molar ratio (which can be related to the oxi-
lyst components. dizing capacity of the system) is almost constant up
F i g . 1 3– NO, NO2 outlet molar fraction and NO inlet fraction vs time upon NO addition on the Pt-Ba(x)/g-Al2O3 catalysts at
350°C: Ba(0); Ba(5); Ba(10); Ba(16); Ba(23) and Ba(30) catalysts
322 P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005)
to 16 % Ba, but it is markedly lower at very high v) The presence of Pt-Ba couples enhances the ex-
Ba loading (i.e. w = 30 % Ba). ploitation of the Ba component in the storage of NOx.
Considering the fraction of Ba that participates vi) The nitrite route is most effective under
in the storage process (“active” Ba), i.e. the molar conditions of industrial interest.
ratio (%) of Ba involved in the storage with respect
to the total amount of Ba present in the catalyst ACKNOWLEDGMENT
sample, it appears that the fraction of Ba involved
up to NOx breakthrough is low (about 4 %) for Fruitful discussion with Professor Luca Lietti
Pt-Ba(5) sample, and then increases linearly with and Professor Enrico Tronconi is gratefully ac-
the catalyst Ba content, and up to the maximum knowledged.
value of about 25 % for the Pt-Ba(23) sample,
which accordingly exhibits the best exploitation of
the Ba component. Notation
On the basis of the evidence collected for the V – superficial velocity, m3 m–2 h–1, m h–1
Pt-Ba interaction, the results can be explained con- ci – gas-phase concentration of species i, mol m–3
sidering that at low Ba loading the interaction be- cw,i – concentration of species i at gas-solid interface,
tween Pt and Ba is low and the behaviour results mol m–3
from the superposition of that of the two single Deff,i – effective intraporous diffusivity of species i, m2/s
components: Pt oxidizes NO to NO2 and NO2 un- dh – hydraulic diameter of the monolith channels, m
dergoes disproportionation over Ba (and possibly Ea – activation energy for NH3 adsorption, kJ mol–1
alumina). In this case the storage of NOx proceeds Ed – activation energy for NH3 desorption, kJ mol–1
primarily through the nitrate route (see Figure 11)
Ed° – activation energy for NH3 desorption at
but notice that the NOx breakthrough occurs with a zero-coverage, kJ mol–1
short dead time.
ENO – activation energy for the DeNOx reaction, kJ mol–1
At high Ba content the interaction between the h – gas-solid heat transfer coefficient, J cm–2 s–1 K–1
two components is favoured by their proximity. In ka° – pre-exponential factor for NH3 adsorption rate,
this case the storage of NOx occurs primarily m3 mol–1 s–1
through the nitrite route: NO is oxidised over Pt kc – effective rate coefficient of the surface chemical
and is adsorbed at a neighbouring Ba site in the reaction, m3 mol–1 s–1
form of a nitrite species that is then oxidized to a kd° – pre-exponential constant for NH3 desorption rate, s–1
nitrate species. In this case the storage of NOx is
kg – the inter-phase gas-solid mass transfer coeffi-
characterised by a significant dead time in the NOx cient, m3 mol–1 s–1
breakthrough.
kmt – gas-solid mass transfer coefficient, m3 mol–3 s–1
KNH3 – quantity for NH3 inhibition, m3 mol–1
kNO – kinetic coefficient for the DeNOx reaction rate,
Conclusions m3 mol–1 s–1
The bulk of the information gained by the cur- kox – rate coefficient for ammonia oxidation, s–1
rent transient experiments, coupled with the FTIR kSCR – intrinsic kinetic coefficient of the SCR reaction, –
spectra, helped in clarifying reaction pathway for the L – monolith length, m
storage of NOx species over Pt-Ba/Al2O3 catalyst n – amount of substance, mol
from NO/O2. The most important features include: NuT – Nusselt number, –
i) On Pt-Ba/Al2O3 catalysts the storage of NOx p – partial pressure, bar
occurs through both a nitrite and a nitrate route. pO2 – oxygen partial pressure, bar
ii) The nitrite route implies a stepwise oxida- ra – rate of NH3 adsorption, s
tion of NO at Pt followed by adsorption at a neigh- rd – rate of desorption, s
bouring Ba site to form a nitrite ad-species that is reff,i – effective surface rate of formation of species j,
then oxidised to a nitrate species. mol m–2 s–1
iii) The nitrate pathway implies the oxidation ri – intrinsic volumetric rate of formation of species i,
of NO to NO2 at Pt followed by the adsorption in mol m–3 s–1
the form of nitrates through the disproportionation rNO – rate of NO consumption, s–1
reaction of NO2. rox – rate of ammonia oxidation, s–1
iv) On increasing the Ba loading, the nitrite rNH 3 NOx – molar ratio,
route is more favoured than the nitrate route due to Sh – Sherwood number
the higher number of Pt-Ba couples (Pt atoms in dw – half-thickness of monolith wall, m
close proximity to Ba atoms). T – temperature, K
P. FORZATTI et al., NOx Removal Catalysis, Chem. Biochem. Eng. Q. 19 (4) 309–323 (2005) 323
t – time, s 11. Beeckman, J. W., Hegedus, L. L., Ind. Eng. Chem. Res.,
Tg – gas temperature, K 30(5) (1991) 969.
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z – dimensionless reactor axial coordinate, –
16. Mears, D. E. Ind. Eng. Chem. Process Des. Develop,
DHf,i – enthalpy of formation of species i, J mol–1 10(4), (1971) 541.
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18. Hindmarsh, A. C., in “Odepack: a systematized collection
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r – volume fraction, %, 10–2
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qi – surface coverage of species i Bandl-Konrad, B., Burkhardt, T., “Modelling of an SCR
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q *NH 3 – parameter for the NH3 surface coverage dependence
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