Fuel 79 (2000) 651658

www.elsevier.com/locate/fuel

Adsorption and reduction of NO over activated coke at low temperature

Zhenping Zhu*, Zhenyu Liu, Shoujun Liu, Hongxian Niu
The State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, Peoples Republic of China
Accepted 10 August 1999

Abstract
NO adsorption and reduction with NH3 over activated coke at low temperatures were studied by temperature-programmed desoption
(TPD) and step-response experiments. NO adsorption is inhibited by competitive adsorption of NH3 in the absence of oxygen, and is
significantly increased in the presence of oxygen. This phenomenon cannot be explained by either the oxidation of NO in the gas phase, nor
the creation of oxidized surface on the activated coke. A hypothesis is proposed to interpret the phenomenon, which suggests that on the
surface of the activated coke there are at least two types of adsorption sites, one of them adsorbs NO2 and/or the oxidized NO species rather
than NO. NONH3 O2 reaction proceeds via both the ED mechanism and the LH mechanism. NO conversion decreases with increasing
temperature in the range of 302508C, which suggests that the adsorption of reactants, especially NH3, is the rate-limiting step. q 2000
Elsevier Science Ltd. All rights reserved.
Keywords: Nitric oxide; Reduction; Activated coke; Adsorption

1. Introduction 2. Experimental

Carbonaceous materials, such as activated coke, activated
carbon, and activated carbon fibre, can be used as effective
catalysts for selective catalytic reduction (SCR) of NO with
NH3 at low temperatures (,2008C) [19]. Among them,
activated coke (AC), with characteristics of low cost and
high mechanical strength, has been applied to commercial
coal-fired boilers for combined removal of NOx and SOx [9].
Mechanisms of the SCR reaction over activated carbon
have previously been discussed [2,5]. However, little infor-
mation is available in the literature about the interaction
between NOx molecules and the carbon surface. Although
the conception that gas-phase oxygen significantly increases
NO adsorption and conversion has been well established,
the role of oxygen remains uncertain [3]. Further, it is not
clear whether the reaction proceeds via a Langmuir
Hinshelwood (LH) mechanism or an EleyRideal (ER)
mechanism. Those informations are important and need to
be elucidated.
In the present study, temperature-programmed desorption
(TPD) and step-response techniques were used to character-
ize the AC surface and to investigate the behavior of NO
adsorption, the role of O2, the competitive adsorption of
NH3 and, therefore, the reaction mechanism.
* Corresponding author.
0016-2361/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00192-1
2.1. Activated coke and activity test
The AC was prepared from a commercial coal-derived
semicoke (Datong Coal Gas Co., China) through steam acti-
vation at about 9008C. It has a BET surface area of
647 m 2 g 21 and a pore volume of 0.338 ml g 21 measured
by N2 adsorption at 77 K. Before being used, the AC was
crashed and sieved into 2860 mesh particles. The SCR
activity of the AC was measured in a conventional fixed-
bed quartz reactor of 10 mm i.d. and 350 mm in length.
Before entering the reactor, four feed gases (NO 1 Ar;
NH3 1 Ar; O2 1 Ar; and Ar) controlled separately by
mass flow controllers were mixed in a chamber filled with
glass wool. The compositions of the feed and the effluent of
the reactor were continuously analyzed using an online
Combustion Gas Analyser (KM9006 Quintox, Kane Inter-
national Limited) which is capable of monitoring NO, NO2,
O2 and CO simultaneously.
2.2. TPD procedure
For the TPD experiments, 0.5 g AC was loaded in the
reactor and was pretreated in situ in an Ar stream (20 ml/
min) at 3508C for 1 h, and then cooled to 308C in the same
stream. The pretreated AC was then exposed to a gas
mixture, containing NO 1 Ar or NO 1 O2 1 Ar or NO 1
NH3 1 Ar or NO 1 NH3 1 O2 1 Ar; at a flow rate of
652 Z. Zhu et al. / Fuel 79 (2000) 651658

Fig. 1. NO reduction conversion versus time over AC at 308C. Reaction

condition: NO, 500 ppm; NH3, 560 ppm; O2, 3.5%; Ar, balance; AC,
1.78 g; total flow rate, 300 ml/min. Fig. 3. TPD profile of NO after adsorption on AC at 308C.

composition was maintained until NO concentration reaches

300 ml/min. After steady state was reached, the AC surface
was purged with Ar of 50 ml/min for 1 h to remove the
physically adsorbed species. Typically, TPD was carried
out in an Ar stream of 300 ml /min at a heating rate of
58C/min from 308C up to 3008C. The effluent was continu-
ously monitored for NO and NO2 during the whole adsorp-
tion/desorption process.
2.3. Step-response experiments
Step-response experiments were carried out at 308C
according to the following procedure. A gas mixture
containing 610 ppm NO, 700 ppm NH3, 3.5 vol% O2 and
balance Ar was fed, at a total flow rate of 300 ml/min,
into the reactor containing 1.0 g AC for sufficient time
(about 6 h) to allow steady state NO conversion to be
reached. One of the three reactants, NO, NH3 and O2, was
then cut off separately from the feed stream and replaced by
a make-up Ar of the same flow rate to keep the feed concen-
trations of the other two reactants constant. The new feed
a new steady state. The above procedure was then reversed
by resuming the dismissed reactive gas to replace the make-
up Ar.
3. Results
3.1. Activity test
Fig. 1 shows the dependence of NO conversion on reac-
tion time for NO reduction with NH3 over AC at 308C. The
NO conversion is about 90% at the initial stage, and then
decreases to a steady-state value of 80% in about 180 min. A
similar observation was reported by Mochida et al. [7,8] in
the SCR reaction over the pitch-based active carbon fibre (p-
ACF). The higher conversion at the initial stage can be
ascribed to simultaneous reaction and adsorption. The
steady state conversion is resulted from the reaction only
because the AC surface has reached adsorption equilibrium.
The effect of reaction temperature on NO conversion at
steady state is shown in Fig. 2. NO conversion decreases
from 80 to 30% when the reaction temperature increases

Table 1
Total desorbed NO and NO2 during TPD after adsorption or reaction on AC
at 308C

Adsorption gases and Desorption amount (mmol/g)

composition
NO NO2 NO2/NO

1000 ppmNO/Ar 0.057 ND b 0

(1000 ppm NO 1 3%O2)/Ar 0.465 0.191 0.41
1000 ppm NO/Ar after O2 a 0.075 ND b 0
(1000 ppm NO 1 1000 ppm 0.005 ND b 0
NH3)/Ar
(1000 ppm NO 1 1000 ppm 0.141 0.006 0.04
NH3 1 3%O2)/Ar

a
Fig. 2. Steady state conversion of NO versus temperature over AC. Reac- NO adsorption is preformed after 10%O2/Ar preadsorption for 3 h at
tion condition: NO, 500 ppm; NH3, 560 ppm; O2, 3.5%; Ar, balance; AC, 308C and followed Ar purge for 2 h.
b
1.78 g; total flow rate, 300 ml/min. NDno NO2 was detected.
 Z. Zhu et al. / Fuel 79 (2000) 651658
Fig. 4. The effluent NOx concentration during co-adsorption of NOO2 on
AC at 308C. NO, 1000 ppm; O2, 3%; Ar, balance; AC, 0.5 g; total flow rate,
300 ml/min.
from 30 to 1208C, and reaches an asymptotic value of 20%
beyond 1208C. It is important to note that no NO2 was
monitored in the entire process.
3.2. TPD after NO adsorption
Fig. 3 shows the TPD pattern of NO after the AC was
exposed to NO at 308C to a steady state. The total amount of
desorbed NO is shown in Table 1. The NO adsorption is low
with a value of 0.057 mmol/g, and no NO2 was detected
during both the adsorption and desorption. There are at
least four distinct NO desorption peaks, centered at about
708C (LT), 1108C (MT1), 1608C (MT2), and 2008C (HT).
Among them, the MT2 peak is the strongest, and the MT1
peak exists as a shoulder. This result indicates that there are
multiple adsorption sites and various adsorbed NO species
on the AC surface.
3.3. TPD after NOO2 co-adsorption
To understand the effect of O2 on NO adsorption, NOO2
co-adsorption and subsequent TPD experiments were
carried out. Fig. 4 shows the effluent NO and NO2 concen-
Fig. 5. TPD profiles of NO and NO2 after the co-adsorption of NOO2 at
308C as shown in Fig. 4.
653
trations during the adsorption at 308C. With increasing time,
the NO concentration increased from an initial value of
300 ppm to that of the feed (650 ppm) in 110 min. NO2
was not detected initially until 40 min, its concentration
then rose slowly with time and reached a steady state in
about 300 min. This shows that NO can be steadily oxidized
to NO2 by O2 over AC under the conditions used. Unlike NO
which releases at once with a considerable concentration in
the beginning of the co-adsorption (or oxidation), the
formed NO2 is completely adsorbed on the AC surface in
the initial 40 min and reaches the steady state much later
than NO does. It clearly indicates that there are surface sites
preferring NO2 adsorption to NO adsorption.
The TPD patterns of NO and NO2 after adsorption of
NO 1 O2 are shown in Fig. 5, and the total desorbed NO
and NO2 are presented in Table 1. The amount of NO
desorbed in this case is about eight times of that in the
absence of O2 during adsorption. Two strong NO desorption
peaks were observed, with maximums at 115 and 1558C,
which clearly link to the MT1 and MT2 peaks of NO in Fig.
3, respectively, within experimental errors. On the contrary,
the LT and HT peaks, as shown in Fig. 3 are very weak,
showing as shoulders. In addition, NO2 desorption was
clearly observed as two peaks of considerable amount
which locate at temperatures similar to the desorption
peaks of NO.
Considering the importance of O2 for NO adsorption and
reduction with NH3, it is interesting to understand the origin
of oxygen atoms. For this purpose, NOO2 reaction in the
gas phase was carried out in an empty reactor at 308C, under
the same conditions as that with the experiment for AC. It
was found that NO oxidation in the gas phase was very low,
with a NO conversion of less than 1%, which indicates that
gas phase NO oxidation contributes only a small part of the
12% NO conversion shown in Fig. 4.
To further elucidate the effect of O2 on the NO adsorp-
tion, an experiment was performed where O2 was introduced
to the AC before NO adsorption. The O2 pre-adsorption on
the AC was conducted in situ using 10 vol% O2 in Ar
(300 ml/min) for 3 h at 308C followed by purging with Ar
for 2 h at the same temperature to remove the physically
adsorbed O2, and by NO adsorption and TPD using the
standard adsorption/desorption procedure. Fig. 6 shows
the TPD pattern of NO and compared with that in Fig. 1.
O2 preadsorption clearly changed NO adsorption. The O2-
preadsorption significantly increased NO adsorption peak
MT1, but has only a little effect on the total amount of
NO adsorption (see Table 1). Moreover, unlike the situation
of NO 1 O2 adsorption/desorption process, no NO2 release
was detected during this process. Therefore, neither gas
phase oxygen, nor preadsorbed oxygen contributes to the
significant increase of NO adsorption in the presence of O2.
3.4. TPD after NONH3 co-adsorption
To understand the NONH3 reaction, it is necessary to
654 Z. Zhu et al. / Fuel 79 (2000) 651658
Fig. 6. TPD patterns of NO adsorbed on clean (solid) and O2 covered
(dotted) AC surface at 308C.
study the effect of NH3 on NO adsorption. Fig. 7 shows the
TPD profile of NO after co-adsorption of NO and NH3. Only
one sharp peak was found at 708C, which is clearly related to
the LT peak shown in Fig. 3. The amount of the desorbed
NO is listed in Table 1 and is about 10% less than that for
NO adsorption alone. It is important to note that the inten-
sities of the LT peaks in Figs. 3 and 7 are similar and
independent of the presence of NH3. It is also important to
note that NO2 was not detected during the adsorption/deso-
rption process, which is similar to the TPD behavior of NO
adsorption in Fig. 3.
3.5. TPD after NONH3 O2 co-adsorption
The amount of NO desorbed after the AC being exposed
to NONH3 O2 mixture at 308C is significantly more than
that after the co-adsorption of NONH3 but significantly
less than that after the co-adsorption of NOO2 (see Table
1). This tendency is also shown with the amount of the
desorbed NO2. Fig. 8 illustrates the TPD patterns of NO
and NO2 in this case. Two distinct peaks can be observed
for NO desorption, one centered at 708C (similar to the LT
peak), and another at about 1308C. The latter is accom-
Fig. 7. TPD profiles of NO after co-adsorption of NONH3 on AC at 308C.
Fig. 8. TPD profiles of NO and NO2 after NONH3 O2 reaction over AC at
308C.
panied by a weak NO2 desorption peak, which is about
3% (in desorbed amount) of that for NOO2 coadsorption
(see Table 1). Using p-ACF as a catalyst, Mochida et al. [7]
showed that after a NONH3 O2 reaction at 258C there are
two major peaks of NO desorption at about 95 and 2008C.
3.6. Step-response results
Fig. 9 shows the step-response of NO in the NONH3 O2
reaction. The NO concentration in the effluent drops sharply
in the initial 2 min and reaches almost zero in 12 min after
the feed of NO was discontinued. This indicates that some
NO complexes are present on the surface under the reaction
conditions, otherwise the effluent NO concentration should
drop at once to zero upon the removal of NO from the feed.
This agrees well with the TPD after the reaction (see Fig. 8).
On considering the low NO conversion of about 60% before
the cut of NO, more interestingly, it also indicates that the
adsorbed NO complexes can participate in the SCR reac-
tion. Upon re-introduction of NO into the feed stream, the
Fig. 9. Step-response to NO in the NONH3 O2 reaction over AC at 308C.
Initial reaction condition: 610 ppm NO, 700 ppm NH3, 3.5 vol% O2, 1.0 g
AC, flow rate of 300 ml/min.
 Z. Zhu et al. / Fuel 79 (2000) 651658
Fig. 10. Step response to NH3 in the NONH3 O2 reaction over AC at
308C. Initial reaction condition: 610 ppm NO, 700 ppm NH3, 3.5 vol% O2,
1.0 g AC, 300 ml/min flow rate.
signal of NO instantaneously appears and quickly reaches to
its original level in a few minutes. This result suggests that
the gas phase NO can react with the adsorbed NH3, because
the AC surface is expected to be entirely occupied by NH3
before the NO re-introduction, and because NO adsorption
is very limited upon the NO reintroduction.
Upon the removal of NH3 from the feed stream, the efflu-
ent NO concentration gradually increases and reaches a
maximum of about 470 ppm corresponding to a NO removal
of about 23% in 18 min, and then decreases to a new steady
state of 320 ppm in 16 min (Fig. 10). During the new steady
state, hardly any NO2 is detected. This observation indicates
that the adsorbed NH3 species are able to react with NO and
O2. After depletion of the adsorbed NH3, the AC surface is
virtually similar to that in NOO2 coadsorption described in
Fig. 4, where NO oxidation occurs. During the 50 min of the
new steady state, the formed NO2 is completely adsorbed on
Fig. 11. Step response to O2 in the NONH3 O2 reaction over AC at 308C.
Initial reaction condition: 610 ppm NO, 700 ppm NH3, 3.5 vol% O2, 1.0 g
AC, 300 ml/min flow rate.
655
some surface sites, which prefer NO2 adsorption to NO
adsorption, as observed in the initial 40 min of NOO2
co-adsorption experiment in Fig. 4 (note that the amount
of the AC used is in this experiment is 1.0 g, while in Fig.
4 it is 0.5 g). It should be pointed out that NO oxidation by
O2 and reduction by NH3 may occur simultaneously before
the exhaustion of NH3 and that some of the formed NO2 is
also possibly reduced by the adsorbed NH3.
Upon the re-introduction of NH3 into the feed stream, NO
concentration slightly increases in the first few minutes and,
subsequently, decreases slowly and reaches to a new steady
state after about 60 min. Interestingly, the NO conversion at
the new steady state is comparable to that before the NH3
removal. This phenomena means that the NO species,
formed in the absence of NH3, can react with adsorbed
NH3 and hence do not deactivate the AC catalyst, even at
a temperature as low as 308C. Almost undoubtedly, the slow
decrease of NO concentration, corresponding to increasing
rate of NO conversion, is due to the gradually increasing
coverage of NH3 on the surface, which suggests that the
adsorption of NH3 is necessary for the SCR reaction. The
slight increase of NO concentration, right after the NH3
resumption may result from the deficiency of the adsorbed
NH3 species for the SCR reaction, while NO oxidation is
restrained by gas phase NH3 to a certain extent.
The step-response for O2 is shown in Fig. 11. Upon the
removal of O2 from the feed stream NO concentration in the
effluent quickly increases and gradually reaches the feed
value in about 30 min. This suggests that O2 plays an impor-
tant role in the SCR reaction. The oxygen adsorbed on the
surface is able to participate in the SCR reaction, but its
contribution is rather smaller than that of O2 in the gas
phase. Upon the reintroduction of O2, NO concentration
quickly drops to the previous steady state value within
only 3 min, which further shows that the gas phase O2 is
the main oxygen source for the SCR reaction on the AC.
4. Discussion
4.1. Adsorbed NO species
There is little information about the nature of NO species
on the AC surface in the literature. For metal oxide cata-
lysts, however, infrared (IR) spectroscopy studies show that
the surface species of NO are mainly in the form of nitrosyl,
nitrite (linear, monodentate, and/or bridged), and nitrate
(monodentate, bidentate, and/or bridged) [1012]. Kijlstra
et al. [12] discussed thermal stability of the NO species
based on the results of TPD and IR studies over MnOx/
Al2O3, and suggested that the nitrate is the most stable
form, followed by nitrite and nitrosyl.
The TPD pattern of NO (Fig. 3) clearly shows that there
are multiple adsorption sites, which may correspond to
different NO species on the AC surface. This may result
from the complexity of the carbon structure of the AC.
656 Z. Zhu et al. / Fuel 79 (2000) 651658
Fig. 12. Simplified scheme of NO adsorption on AC in the presence of O2.
A: sites for both NO and NO2 adsorption; B: sites for NO2 adsorption only.
The LT peak at about 708C (Figs. 3, 58) exists in all the
TPD patterns of NO, and the peak areas are in the same
order of magnitude, independent of the adsorption gas
composition (the LT peak in Fig. 5 looks very weak because
of the strong MT1 peak.) This suggests that the surface
species corresponding to the LT peak is (or is similar to)
the nitrosyl, a physically (weakly) adsorbed species. The
MT1, MT2 and HT species of NO decompose at tempera-
tures higher than 1008C and therefore are relatively stable.
They may be chemically adsorbed species such as nitrites
and/or nitrates. The significant increase in desorption peaks
in the presence of oxygen, especially for the MT1 and MT2
species (see Fig. 5), supports this conjecture. It is worth-
while to point out that the formation of nitrites and/or
nitrates in the absence of O2 may possibly result from the
interaction between NO and the oxygen-containing func-
tional groups on the AC surface. The literature [3,4,13,14]
has shown that there are a large number of oxygen-contain-
ing functional groups on the AC surface.
These chemically adsorbed species are rather susceptible
to the gas environment. In the presence of NH3, the MT1,
MT2 and HT desorption peaks disappear (see Fig. 7). It
most likely results from strong competitive adsorption of
NH3 at the corresponding sites, and/or from continuous
removal of the formed NO species by the reaction with
NH3 species. The latter seems to be inconsistent with the
fact that the NO 1 NH3 reaction hardly occurs in the
absence of O2 (see Fig. 11). On the contrary, the former is
supported by the obvious adsorption of NH3 shown in the
step-response experiment (see Fig. 10). Some studies [3,13]
showed recently that the surface oxygen-containing func-
tional groups significantly increase the acidity of carbon
surface and NH3 adsorption, which suggests that the major-
ity of NH3 is most likely to be adsorbed at the oxidative and
acidic sites. Therefore, it is reasonable to say that the forma-
tion of the chemically adsorbed species of NO is inhibited
by the competitive adsorption of NH3. On comparing the
results of NOO2 co-adsorption and NONH3 O2 co-
adsorption (see Table1 and Figs. 5 and 8), a similar deduc-
tion can be made on the basis of the obvious decrease of NO
and NO2 desorptions in the presence of NH3. It should be
pointed out that, in this case, the removal of the chemically
adsorbed species through the NONH3 reaction is also
possible due to the presence of O2 which greatly accelerates
this reaction as shown in Fig. 11.
In the presence of O2, two types of NO adsortion species
are clearly formed as shown in Fig. 5, they are likely to be
nitrite (may decompose into NO) and nitrate (may decom-
pose into NO2). Each of them exists in at least two forms,
such as linear, monodentate, bidentate or bridged ones [10
12], indicated by the strong double desorption peaks.
Although the TPD profiles in Fig. 5 may suggest that the
desorbed NO is formed via the reaction of NO2 1 C !
NO 1 CO and because of that the desorbed NO2 peaks
occur at the same location as desorbed NO peaks and no
CO was detected during the TPD process.
4.2. Role of O2 in NO adsorption
It is of interest to consider the ways in which the presence
of O2 greatly enhances the NO adsorption as shown in Table
1 and Figs. 3 and 5. The first possibility as mentioned by
Ahmed et al. [3], is that NO is oxidized by O2 to NO2 in the
gas phase and then NO2 is adsorbed onto the AC surface.
This interpretation is supported by the observation [3] that
the amount of NO2 adsorbed is nearly 50 times that of NO in
the absence of O2 at 1008C. However, at low temperatures
and low NO and O2 concentrations, the oxidation of NO in
the gas phase is very slow compared with that in the
presence of AC as mentioned above and reported by Rao
and Hougen [15]. This suggests that NO oxidation in the gas
phase plays only a minor role for the increased NO adsorp-
tion on the AC surface in the presence of O2, at least at low
temperatures such as 308C.
The second possibility, as proposed by Richter et al. [16],
is that a more oxidized surface, formed by the reaction
between gas phase O2 and the activated carbon, serves as
active sites for NO adsorption. This argument is in agree-
ment with the results obtained from metal oxides catalysts
[12,17]. However, the observations in this paper clearly
show that pre-adsorption of O2 on the AC surface has only
limited promoting effect on the NO adsorption, especially
compared to that of NOO2 co-adsorption (see Table 1 and
Figs. 5 and 6). In the latter case, a considerable amount of
NO2 is also desorbed. Additionally, the argument that NO
adsorption is favorable on an oxidized surface of AC
disagrees with the observation [3,13] that NO adsorption
decreases with the increasing amount of oxygen-containing
functional groups on the AC surface. Moreover, Mochida et
al. [7,18,19] have studied and discussed the NO oxidation
on p-ACF and showed that at room temperature, oxygen of
4% does not introduce any oxygen functional groups. There-
fore, surface oxidation of NO by both gas phase oxygen and
adsorbed oxygen may be the reason for the increased NO
adsorption.
It is possible that there are at least two types of adsorption
 Z. Zhu et al. / Fuel 79 (2000) 651658
sites on the AC surface, one adsorbs both NO and NO2, and
another only NO2. This assumption is supported by the
multiple adsorption sites on the AC surface as shown in
Fig. 3 and by the fact that the adsorption capacity of NO2
on AC is considerably larger than that of NO [3]. This can
give a good explanation for the difference in the break-
through curves of NO and NO2 during NOO2 coadsorption
(see Fig. 4).
Based on the above analysis, the NO adsorption in the
presence of O2 is likely to follow a pathway shown in Fig.
12, where oxidized NO species are firstly formed at A sites
either through NO adsorption and subsequent oxidation by
gas phase O2 or by direct adsorption of NO at oxidized sites.
The oxidized NO species then migrate from A to B sites
possibly through spillover and/or through desorption and re-
adsorption processes, which results in storage of the
oxidized NO species (nitrites and/or nitrates) on B sites
and vacancy of A sites for continued adsorption until both
A and B sites are saturated. In this procedure, the role of O2
is to make the formation, migration and subsequent storage
of the oxidized NO species possible. This explains well the
observations on NO adsorption in the presence or absence of
O2 both in this paper and in the literature.
4.3. NO reduction via LH or ED mechanism
There is a general agreement that the SCR reaction starts
with NH3 adsorption. On most SCR catalysts the NH3
adsorption is stronger than NO adsorption. For the AC cata-
lyst, this is also true as shown by the NH3 step-response
pattern in Fig. 10. The slow responses of NO concentration
to the removal and re-introduction of NH3 in the feed stream
suggest that the NH3 adsorption on the AC surface is neces-
sary for the SCR reaction. Two reaction mechanisms
proposed for SCR on metal oxides may, therefore, be used
to describe the SCR reaction on AC: (1) a reaction of gas
phase NO with adsorbed NH3 to form an active intermediate
species which is subsequently decomposed into N2 and H2O
(ED mechanism); (2) the adsorption of NO at sites adjacent
to that of NH3, followed by reaction between them to form
the products (LH mechanism).
The TPD results in Fig. 8 and Table 1 show that a large
number of adsorbed NO species exists on the AC surface
after NONH3 O2 co-adsorption (or reaction) and that most
of the adsorbed NO species are stable at temperatures lower
than 1008C. If the SCR reaction follows only the ED
mechanism, the surface coverage of the stable NO species
would reduce NH3 adsorption and result in low SCR activ-
ity. But this was not observed in Fig. 1, in which a high
steady state conversion of NO is obtained at 308C. This
indicates that the adsorbed NO species can be continuously
removed by the adsorbed NH3, which leads to the LH
mechanism. This is also supported by the step-response
experiment in Fig. 10. A similar mechanism was also
suggested by Mochida et al. [7] based on the SCR reaction
over p-ACF.
657
On the contrary, if the reaction proceeded exclusively
through the LH mechanism, upon NO introduction to the
AC surface saturated with NH3 (Ref. Fig. 9), it can be
suspected that few NO molecules would instantaneously
adsorb on the surface and the reaction would be only at a
slow rate at the moment, subsequently, the NO conversion is
expected to increase gradually with the increasing NO
coverage until it reaches a steady state. However, upon
NO being introduced into the reaction stream, its concentra-
tion quickly reaches a stationary value within a few minutes
without overshooting (see Fig. 9). This suggests that
the SCR reaction can proceed between gas phase NO and
the adsorbed NH3 via a ED mechanism. As a conclusion, the
SCR reaction on the AC surface proceeds either through a
considerable part of the ER pathway and also, to a certain
extent, via the LH mechanism.
Interestingly, NO conversion greatly declines with
increasing reaction temperature for the NONH3 O2 reac-
tion over AC as shown in Fig. 2. Similar observations were
also reported in the literature [3,7,16]. For a given catalytic
reaction, generally speaking, temperature has a positive
effect on the activation of reactants and the desorption of
products, and a negative effect on the adsorption of reac-
tants. Thus, for the SCR reaction over AC, at least at a low
temperature, the adsorption kinetics of reactants may be rate
limiting. A similar proposition was presented in the litera-
ture [3,7]. Additionally, among the reactants, NO, NH3 and
O2, NH3 adsorption is expected to be the rate-limiting step
because only NH3 coverage seems to be related to the reac-
tion rate, as observed in Figs. 911. This suggestion is
supported by the following facts: (1) the increase of
oxygen-containing functional groups on the AC surface
increases NO conversion and NH3 adsorption capacity,
and decreases the NO adsorption capacity [3,13]; (2) the
presence of the basic surface N, either in the carbon struc-
ture or incorporated as an additive or surface modifier,
increases NO conversion [3,13,20]; (3) the SCR reaction
can proceed via both the LH and ED mechanisms as
shown above, the NO adsorption being unnecessary in the
latter way.
5. Conclusion
NO adsorption and reduction with NH3 over AC at low
temperatures were studied by TPD and step response experi-
ments. In the absence of oxygen, NO adsorption is restricted
by NH3 due to competitive adsorption. Significant increase
of NO adsorption in the presence of oxygen cannot be
simply explained by either NO oxidation in the gas phase
or the creation of an oxidized surface. A new explanation
was provided on the basis of experimental observation
which suggests that there are at least two types of adsorption
sites on the AC surface, one adsorbs both NO and NO2,
while another only NO2 and/or the oxidized NO species.
In the presence of O2, the adsorbed NO is oxidized and
658 Z. Zhu et al. / Fuel 79 (2000) 651658
subsequently migrate onto the adjacent sites by spillover
and/or desorption and readsorption processes.
Step response experiments show that NH3 adsorption is
necessary for the NONH3 O2 reaction. NH3 species can
react with both gas phase NO (EleyRideal mechanism) and
adsorbed NO species (LangmuirHinshelwood mechanism)
which are steadily formed in the presence of O2 and stable at
temperatures of less than 1008C. A rapid decrease of NO
conversion with increasing temperature was observed in the
range of 302508C, which suggests that the adsorption of
reactants, especially NH3, is the rate-limiting step.
Acknowledgements
The authors express their grateful acknowledgements to
the National Science Foundation of China, Shanxi Natural
Science Foundation, and The State Key Laboratory of Coal
Conversion for financial supports.
References
[1] Knoblauch K, Richter E, Juntgen H. Fuel 1981;60:832.
[2] Juntgen H, Richter E, Kuhl H. Fuel 1988;67:775.
[3] Ahmed SN, Baldwin R, Derbyshire F, McEnaney B, Stencel J. Fuel
1993;72:287.
[4] Singoredjo L, Kapteijn F, Moulijn JA, Martnez JM, Boehm HP.
Carbon 1993;31:213.
[5] Richter E. Catal Today 1990;7:93.
[6] Mochida I, Ogaki M, Fujitsu H, Komatsubara Y, Ida S. Fuel
1983;62:867.
[7] Mochida I, Kishino M, Kawano S, Iwaizono H, Yasutake A, Yoshi-
kawa M. Energy and Fuels 1997;11:307.
[8] Mochida I, Kawano S, Hironaka M, Kishino, Yatsunami S, Korai Y,
Yoshikawa M. Chem Lett 1995;385.
[9] Tsuji K, Shiraishi I. Fuel 1997;76:549.
[10] London JW, Bell AT. J Catal 1973;31:96.
[11] Pozdnyakov DV, Fillimonov VN. Kinet Catal 1973;14:655.
[12] Kijlstra WS, Brands DS, Poels EK, Bliek A. J Catal 1997;171:208.
[13] Ku BJ, Lee JK, Park D, Rhee HK. Ind Engng Chem Res
1994;33:2868.
[14] Fujitsu H, Mochida I, Verheyen TV, Perry GJ, Allardice DJ. Fuel
1993;72:109.
[15] Rao MN, Hougen OA. Chem Engng Prog Symp Ser 1952;(4):110.
[16] Richter E, Schmidt H, Schecker H. Chem Engng Technol
1990;13:332.
[17] Kapteijn F, Singoredjo L, Van Driel M, Andreini A, Moulijn JA,
Ramis G, Busca G. J Catal 1994;150:105.
[18] Mochida I, Kisamori S, Hironaka M, Kishino M, Kawano S, Matsu-
mura Y, Yoshikawa M. Energy and Fuels 1994;8:1341.
[19] Mochida I, Kawano S, Hironaka, Yatsunami S, Korai Y, Matsumura
Y. Energy and Fuels 1995;9:659.
[20] Kuhle H, Richter E, Knoblauch K, Juntgen H. Carbon86. Fourth
International Carbon Conference, Baden, 1986. p. 351.