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Fuel 79 (2000) 651658

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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 2.1. Activated coke and activity test
carbon, and activated carbon fibre, can be used as effective
catalysts for selective catalytic reduction (SCR) of NO with The AC was prepared from a commercial coal-derived
NH3 at low temperatures (,2008C) [19]. Among them, semicoke (Datong Coal Gas Co., China) through steam acti-
activated coke (AC), with characteristics of low cost and vation at about 9008C. It has a BET surface area of
high mechanical strength, has been applied to commercial 647 m 2 g 21 and a pore volume of 0.338 ml g 21 measured
coal-fired boilers for combined removal of NOx and SOx [9]. by N2 adsorption at 77 K. Before being used, the AC was
Mechanisms of the SCR reaction over activated carbon crashed and sieved into 2860 mesh particles. The SCR
have previously been discussed [2,5]. However, little infor- activity of the AC was measured in a conventional fixed-
mation is available in the literature about the interaction bed quartz reactor of 10 mm i.d. and 350 mm in length.
between NOx molecules and the carbon surface. Although Before entering the reactor, four feed gases (NO 1 Ar;
the conception that gas-phase oxygen significantly increases NH3 1 Ar; O2 1 Ar; and Ar) controlled separately by
NO adsorption and conversion has been well established, mass flow controllers were mixed in a chamber filled with
the role of oxygen remains uncertain [3]. Further, it is not glass wool. The compositions of the feed and the effluent of
clear whether the reaction proceeds via a Langmuir the reactor were continuously analyzed using an online
Hinshelwood (LH) mechanism or an EleyRideal (ER) Combustion Gas Analyser (KM9006 Quintox, Kane Inter-
mechanism. Those informations are important and need to national Limited) which is capable of monitoring NO, NO2,
be elucidated. O2 and CO simultaneously.
In the present study, temperature-programmed desorption
(TPD) and step-response techniques were used to character- 2.2. TPD procedure
ize the AC surface and to investigate the behavior of NO
For the TPD experiments, 0.5 g AC was loaded in the
adsorption, the role of O2, the competitive adsorption of
reactor and was pretreated in situ in an Ar stream (20 ml/
NH3 and, therefore, the reaction mechanism.
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
* Corresponding author. NH3 1 Ar or NO 1 NH3 1 O2 1 Ar; at a flow rate of
0016-2361/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00192-1
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 a new steady state. The above procedure was then reversed
was purged with Ar of 50 ml/min for 1 h to remove the by resuming the dismissed reactive gas to replace the make-
physically adsorbed species. Typically, TPD was carried up Ar.
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-
3. Results
ously monitored for NO and NO2 during the whole adsorp-
tion/desorption process.
3.1. Activity test
2.3. Step-response experiments
Fig. 1 shows the dependence of NO conversion on reac-
Step-response experiments were carried out at 308C tion time for NO reduction with NH3 over AC at 308C. The
according to the following procedure. A gas mixture NO conversion is about 90% at the initial stage, and then
containing 610 ppm NO, 700 ppm NH3, 3.5 vol% O2 and decreases to a steady-state value of 80% in about 180 min. A
balance Ar was fed, at a total flow rate of 300 ml/min, similar observation was reported by Mochida et al. [7,8] in
into the reactor containing 1.0 g AC for sufficient time the SCR reaction over the pitch-based active carbon fibre (p-
(about 6 h) to allow steady state NO conversion to be ACF). The higher conversion at the initial stage can be
reached. One of the three reactants, NO, NH3 and O2, was ascribed to simultaneous reaction and adsorption. The
then cut off separately from the feed stream and replaced by steady state conversion is resulted from the reaction only
a make-up Ar of the same flow rate to keep the feed concen- because the AC surface has reached adsorption equilibrium.
trations of the other two reactants constant. The new feed 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 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.
Fig. 4. The effluent NOx concentration during co-adsorption of NOO2 on The TPD patterns of NO and NO2 after adsorption of
AC at 308C. NO, 1000 ppm; O2, 3%; Ar, balance; AC, 0.5 g; total flow rate, NO 1 O2 are shown in Fig. 5, and the total desorbed NO
300 ml/min. and NO2 are presented in Table 1. The amount of NO
desorbed in this case is about eight times of that in the
from 30 to 1208C, and reaches an asymptotic value of 20% absence of O2 during adsorption. Two strong NO desorption
beyond 1208C. It is important to note that no NO2 was peaks were observed, with maximums at 115 and 1558C,
monitored in the entire process. which clearly link to the MT1 and MT2 peaks of NO in Fig.
3, respectively, within experimental errors. On the contrary,
3.2. TPD after NO adsorption the LT and HT peaks, as shown in Fig. 3 are very weak,
showing as shoulders. In addition, NO2 desorption was
Fig. 3 shows the TPD pattern of NO after the AC was clearly observed as two peaks of considerable amount
exposed to NO at 308C to a steady state. The total amount of which locate at temperatures similar to the desorption
desorbed NO is shown in Table 1. The NO adsorption is low peaks of NO.
with a value of 0.057 mmol/g, and no NO2 was detected Considering the importance of O2 for NO adsorption and
during both the adsorption and desorption. There are at reduction with NH3, it is interesting to understand the origin
least four distinct NO desorption peaks, centered at about of oxygen atoms. For this purpose, NOO2 reaction in the
708C (LT), 1108C (MT1), 1608C (MT2), and 2008C (HT). gas phase was carried out in an empty reactor at 308C, under
Among them, the MT2 peak is the strongest, and the MT1 the same conditions as that with the experiment for AC. It
peak exists as a shoulder. This result indicates that there are was found that NO oxidation in the gas phase was very low,
multiple adsorption sites and various adsorbed NO species with a NO conversion of less than 1%, which indicates that
on the AC surface. gas phase NO oxidation contributes only a small part of the
12% NO conversion shown in Fig. 4.
3.3. TPD after NOO2 co-adsorption To further elucidate the effect of O2 on the NO adsorp-
tion, an experiment was performed where O2 was introduced
To understand the effect of O2 on NO adsorption, NOO2 to the AC before NO adsorption. The O2 pre-adsorption on
co-adsorption and subsequent TPD experiments were the AC was conducted in situ using 10 vol% O2 in Ar
carried out. Fig. 4 shows the effluent NO and NO2 concen- (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


Fig. 5. TPD profiles of NO and NO2 after the co-adsorption of NOO2 at
308C as shown in Fig. 4. 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. Fig. 8. TPD profiles of NO and NO2 after NONH3 O2 reaction over AC 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 panied by a weak NO2 desorption peak, which is about
one sharp peak was found at 708C, which is clearly related to 3% (in desorbed amount) of that for NOO2 coadsorption
the LT peak shown in Fig. 3. The amount of the desorbed (see Table 1). Using p-ACF as a catalyst, Mochida et al. [7]
NO is listed in Table 1 and is about 10% less than that for showed that after a NONH3 O2 reaction at 258C there are
NO adsorption alone. It is important to note that the inten- two major peaks of NO desorption at about 95 and 2008C.
sities of the LT peaks in Figs. 3 and 7 are similar and
independent of the presence of NH3. It is also important to 3.6. Step-response results
note that NO2 was not detected during the adsorption/deso-
rption process, which is similar to the TPD behavior of NO Fig. 9 shows the step-response of NO in the NONH3 O2
adsorption in Fig. 3. 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
3.5. TPD after NONH3 O2 co-adsorption NO complexes are present on the surface under the reaction
conditions, otherwise the effluent NO concentration should
The amount of NO desorbed after the AC being exposed drop at once to zero upon the removal of NO from the feed.
to NONH3 O2 mixture at 308C is significantly more than This agrees well with the TPD after the reaction (see Fig. 8).
that after the co-adsorption of NONH3 but significantly On considering the low NO conversion of about 60% before
less than that after the co-adsorption of NOO2 (see Table the cut of NO, more interestingly, it also indicates that the
1). This tendency is also shown with the amount of the adsorbed NO complexes can participate in the SCR reac-
desorbed NO2. Fig. 8 illustrates the TPD patterns of NO tion. Upon re-introduction of NO into the feed stream, the
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. 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
Fig. 7. TPD profiles of NO after co-adsorption of NONH3 on AC at 308C. AC, flow rate of 300 ml/min.
Z. Zhu et al. / Fuel 79 (2000) 651658 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
Fig. 10. Step response to NH3 in the NONH3 O2 reaction over AC at NH3 and hence do not deactivate the AC catalyst, even at
308C. Initial reaction condition: 610 ppm NO, 700 ppm NH3, 3.5 vol% O2, a temperature as low as 308C. Almost undoubtedly, the slow
1.0 g AC, 300 ml/min flow rate. decrease of NO concentration, corresponding to increasing
rate of NO conversion, is due to the gradually increasing
signal of NO instantaneously appears and quickly reaches to coverage of NH3 on the surface, which suggests that the
its original level in a few minutes. This result suggests that adsorption of NH3 is necessary for the SCR reaction. The
the gas phase NO can react with the adsorbed NH3, because slight increase of NO concentration, right after the NH3
the AC surface is expected to be entirely occupied by NH3 resumption may result from the deficiency of the adsorbed
before the NO re-introduction, and because NO adsorption NH3 species for the SCR reaction, while NO oxidation is
is very limited upon the NO reintroduction. restrained by gas phase NH3 to a certain extent.
Upon the removal of NH3 from the feed stream, the efflu- The step-response for O2 is shown in Fig. 11. Upon the
ent NO concentration gradually increases and reaches a removal of O2 from the feed stream NO concentration in the
maximum of about 470 ppm corresponding to a NO removal effluent quickly increases and gradually reaches the feed
of about 23% in 18 min, and then decreases to a new steady value in about 30 min. This suggests that O2 plays an impor-
state of 320 ppm in 16 min (Fig. 10). During the new steady tant role in the SCR reaction. The oxygen adsorbed on the
state, hardly any NO2 is detected. This observation indicates surface is able to participate in the SCR reaction, but its
that the adsorbed NH3 species are able to react with NO and contribution is rather smaller than that of O2 in the gas
O2. After depletion of the adsorbed NH3, the AC surface is phase. Upon the reintroduction of O2, NO concentration
virtually similar to that in NOO2 coadsorption described in quickly drops to the previous steady state value within
Fig. 4, where NO oxidation occurs. During the 50 min of the only 3 min, which further shows that the gas phase O2 is
new steady state, the formed NO2 is completely adsorbed on 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
Fig. 11. Step response to O2 in the NONH3 O2 reaction over AC at 308C. are multiple adsorption sites, which may correspond to
Initial reaction condition: 610 ppm NO, 700 ppm NH3, 3.5 vol% O2, 1.0 g different NO species on the AC surface. This may result
AC, 300 ml/min flow rate. from the complexity of the carbon structure of the AC.
656 Z. Zhu et al. / Fuel 79 (2000) 651658

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 !
Fig. 12. Simplified scheme of NO adsorption on AC in the presence of O2. NO 1 CO and because of that the desorbed NO2 peaks
A: sites for both NO and NO2 adsorption; B: sites for NO2 adsorption only. occur at the same location as desorbed NO peaks and no
CO was detected during the TPD process.
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 4.2. Role of O2 in NO adsorption
order of magnitude, independent of the adsorption gas
composition (the LT peak in Fig. 5 looks very weak because It is of interest to consider the ways in which the presence
of the strong MT1 peak.) This suggests that the surface of O2 greatly enhances the NO adsorption as shown in Table
species corresponding to the LT peak is (or is similar to) 1 and Figs. 3 and 5. The first possibility as mentioned by
the nitrosyl, a physically (weakly) adsorbed species. The Ahmed et al. [3], is that NO is oxidized by O2 to NO2 in the
MT1, MT2 and HT species of NO decompose at tempera- gas phase and then NO2 is adsorbed onto the AC surface.
tures higher than 1008C and therefore are relatively stable. This interpretation is supported by the observation [3] that
They may be chemically adsorbed species such as nitrites the amount of NO2 adsorbed is nearly 50 times that of NO in
and/or nitrates. The significant increase in desorption peaks the absence of O2 at 1008C. However, at low temperatures
in the presence of oxygen, especially for the MT1 and MT2 and low NO and O2 concentrations, the oxidation of NO in
species (see Fig. 5), supports this conjecture. It is worth- the gas phase is very slow compared with that in the
while to point out that the formation of nitrites and/or presence of AC as mentioned above and reported by Rao
nitrates in the absence of O2 may possibly result from the and Hougen [15]. This suggests that NO oxidation in the gas
interaction between NO and the oxygen-containing func- phase plays only a minor role for the increased NO adsorp-
tional groups on the AC surface. The literature [3,4,13,14] tion on the AC surface in the presence of O2, at least at low
has shown that there are a large number of oxygen-contain- temperatures such as 308C.
ing functional groups on the AC surface. The second possibility, as proposed by Richter et al. [16],
These chemically adsorbed species are rather susceptible is that a more oxidized surface, formed by the reaction
to the gas environment. In the presence of NH3, the MT1, between gas phase O2 and the activated carbon, serves as
MT2 and HT desorption peaks disappear (see Fig. 7). It active sites for NO adsorption. This argument is in agree-
most likely results from strong competitive adsorption of ment with the results obtained from metal oxides catalysts
NH3 at the corresponding sites, and/or from continuous [12,17]. However, the observations in this paper clearly
removal of the formed NO species by the reaction with show that pre-adsorption of O2 on the AC surface has only
NH3 species. The latter seems to be inconsistent with the limited promoting effect on the NO adsorption, especially
fact that the NO 1 NH3 reaction hardly occurs in the compared to that of NOO2 co-adsorption (see Table 1 and
absence of O2 (see Fig. 11). On the contrary, the former is Figs. 5 and 6). In the latter case, a considerable amount of
supported by the obvious adsorption of NH3 shown in the NO2 is also desorbed. Additionally, the argument that NO
step-response experiment (see Fig. 10). Some studies [3,13] adsorption is favorable on an oxidized surface of AC
showed recently that the surface oxygen-containing func- disagrees with the observation [3,13] that NO adsorption
tional groups significantly increase the acidity of carbon decreases with the increasing amount of oxygen-containing
surface and NH3 adsorption, which suggests that the major- functional groups on the AC surface. Moreover, Mochida et
ity of NH3 is most likely to be adsorbed at the oxidative and al. [7,18,19] have studied and discussed the NO oxidation
acidic sites. Therefore, it is reasonable to say that the forma- on p-ACF and showed that at room temperature, oxygen of
tion of the chemically adsorbed species of NO is inhibited 4% does not introduce any oxygen functional groups. There-
by the competitive adsorption of NH3. On comparing the fore, surface oxidation of NO by both gas phase oxygen and
results of NOO2 co-adsorption and NONH3 O2 co- adsorbed oxygen may be the reason for the increased NO
adsorption (see Table1 and Figs. 5 and 8), a similar deduc- adsorption.
tion can be made on the basis of the obvious decrease of NO It is possible that there are at least two types of adsorption
Z. Zhu et al. / Fuel 79 (2000) 651658 657

sites on the AC surface, one adsorbs both NO and NO2, and On the contrary, if the reaction proceeded exclusively
another only NO2. This assumption is supported by the through the LH mechanism, upon NO introduction to the
multiple adsorption sites on the AC surface as shown in AC surface saturated with NH3 (Ref. Fig. 9), it can be
Fig. 3 and by the fact that the adsorption capacity of NO2 suspected that few NO molecules would instantaneously
on AC is considerably larger than that of NO [3]. This can adsorb on the surface and the reaction would be only at a
give a good explanation for the difference in the break- slow rate at the moment, subsequently, the NO conversion is
through curves of NO and NO2 during NOO2 coadsorption expected to increase gradually with the increasing NO
(see Fig. 4). coverage until it reaches a steady state. However, upon
Based on the above analysis, the NO adsorption in the NO being introduced into the reaction stream, its concentra-
presence of O2 is likely to follow a pathway shown in Fig. tion quickly reaches a stationary value within a few minutes
12, where oxidized NO species are firstly formed at A sites without overshooting (see Fig. 9). This suggests that
either through NO adsorption and subsequent oxidation by the SCR reaction can proceed between gas phase NO and
gas phase O2 or by direct adsorption of NO at oxidized sites. the adsorbed NH3 via a ED mechanism. As a conclusion, the
The oxidized NO species then migrate from A to B sites SCR reaction on the AC surface proceeds either through a
possibly through spillover and/or through desorption and re- considerable part of the ER pathway and also, to a certain
adsorption processes, which results in storage of the extent, via the LH mechanism.
oxidized NO species (nitrites and/or nitrates) on B sites Interestingly, NO conversion greatly declines with
and vacancy of A sites for continued adsorption until both increasing reaction temperature for the NONH3 O2 reac-
A and B sites are saturated. In this procedure, the role of O2 tion over AC as shown in Fig. 2. Similar observations were
is to make the formation, migration and subsequent storage also reported in the literature [3,7,16]. For a given catalytic
of the oxidized NO species possible. This explains well the reaction, generally speaking, temperature has a positive
observations on NO adsorption in the presence or absence of effect on the activation of reactants and the desorption of
O2 both in this paper and in the literature. products, and a negative effect on the adsorption of reac-
tants. Thus, for the SCR reaction over AC, at least at a low
4.3. NO reduction via LH or ED mechanism temperature, the adsorption kinetics of reactants may be rate
limiting. A similar proposition was presented in the litera-
There is a general agreement that the SCR reaction starts ture [3,7]. Additionally, among the reactants, NO, NH3 and
with NH3 adsorption. On most SCR catalysts the NH3 O2, NH3 adsorption is expected to be the rate-limiting step
adsorption is stronger than NO adsorption. For the AC cata- because only NH3 coverage seems to be related to the reac-
lyst, this is also true as shown by the NH3 step-response tion rate, as observed in Figs. 911. This suggestion is
pattern in Fig. 10. The slow responses of NO concentration supported by the following facts: (1) the increase of
to the removal and re-introduction of NH3 in the feed stream oxygen-containing functional groups on the AC surface
suggest that the NH3 adsorption on the AC surface is neces- increases NO conversion and NH3 adsorption capacity,
sary for the SCR reaction. Two reaction mechanisms and decreases the NO adsorption capacity [3,13]; (2) the
proposed for SCR on metal oxides may, therefore, be used presence of the basic surface N, either in the carbon struc-
to describe the SCR reaction on AC: (1) a reaction of gas ture or incorporated as an additive or surface modifier,
phase NO with adsorbed NH3 to form an active intermediate increases NO conversion [3,13,20]; (3) the SCR reaction
species which is subsequently decomposed into N2 and H2O can proceed via both the LH and ED mechanisms as
(ED mechanism); (2) the adsorption of NO at sites adjacent shown above, the NO adsorption being unnecessary in the
to that of NH3, followed by reaction between them to form latter way.
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 5. Conclusion
after NONH3 O2 co-adsorption (or reaction) and that most
of the adsorbed NO species are stable at temperatures lower NO adsorption and reduction with NH3 over AC at low
than 1008C. If the SCR reaction follows only the ED temperatures were studied by TPD and step response experi-
mechanism, the surface coverage of the stable NO species ments. In the absence of oxygen, NO adsorption is restricted
would reduce NH3 adsorption and result in low SCR activ- by NH3 due to competitive adsorption. Significant increase
ity. But this was not observed in Fig. 1, in which a high of NO adsorption in the presence of oxygen cannot be
steady state conversion of NO is obtained at 308C. This simply explained by either NO oxidation in the gas phase
indicates that the adsorbed NO species can be continuously or the creation of an oxidized surface. A new explanation
removed by the adsorbed NH3, which leads to the LH was provided on the basis of experimental observation
mechanism. This is also supported by the step-response which suggests that there are at least two types of adsorption
experiment in Fig. 10. A similar mechanism was also sites on the AC surface, one adsorbs both NO and NO2,
suggested by Mochida et al. [7] based on the SCR reaction while another only NO2 and/or the oxidized NO species.
over p-ACF. 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 [4] Singoredjo L, Kapteijn F, Moulijn JA, Martnez JM, Boehm HP.
and/or desorption and readsorption processes. Carbon 1993;31:213.
[5] Richter E. Catal Today 1990;7:93.
Step response experiments show that NH3 adsorption is [6] Mochida I, Ogaki M, Fujitsu H, Komatsubara Y, Ida S. Fuel
necessary for the NONH3 O2 reaction. NH3 species can 1983;62:867.
react with both gas phase NO (EleyRideal mechanism) and [7] Mochida I, Kishino M, Kawano S, Iwaizono H, Yasutake A, Yoshi-
adsorbed NO species (LangmuirHinshelwood mechanism) kawa M. Energy and Fuels 1997;11:307.
which are steadily formed in the presence of O2 and stable at [8] Mochida I, Kawano S, Hironaka M, Kishino, Yatsunami S, Korai Y,
Yoshikawa M. Chem Lett 1995;385.
temperatures of less than 1008C. A rapid decrease of NO [9] Tsuji K, Shiraishi I. Fuel 1997;76:549.
conversion with increasing temperature was observed in the [10] London JW, Bell AT. J Catal 1973;31:96.
range of 302508C, which suggests that the adsorption of [11] Pozdnyakov DV, Fillimonov VN. Kinet Catal 1973;14:655.
reactants, especially NH3, is the rate-limiting step. [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.
Acknowledgements [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.
The authors express their grateful acknowledgements to [16] Richter E, Schmidt H, Schecker H. Chem Engng Technol
the National Science Foundation of China, Shanxi Natural 1990;13:332.
Science Foundation, and The State Key Laboratory of Coal [17] Kapteijn F, Singoredjo L, Van Driel M, Andreini A, Moulijn JA,
Conversion for financial supports. 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.
References [19] Mochida I, Kawano S, Hironaka, Yatsunami S, Korai Y, Matsumura
Y. Energy and Fuels 1995;9:659.
[1] Knoblauch K, Richter E, Juntgen H. Fuel 1981;60:832. [20] Kuhle H, Richter E, Knoblauch K, Juntgen H. Carbon86. Fourth
[2] Juntgen H, Richter E, Kuhl H. Fuel 1988;67:775. International Carbon Conference, Baden, 1986. p. 351.
[3] Ahmed SN, Baldwin R, Derbyshire F, McEnaney B, Stencel J. Fuel
1993;72:287.