Accepted Manuscript

The combined promotive effect of SO2 and HCl on Pb-poisoned

commercial NH3-SCR V2O5-WO3/TiO2 catalysts

Jifa Miao, Huirong Li, Qingfa Su, Yanke Yu, Yanting Chen,
Jinsheng Chen, Jinxiu Wang

PII: S1566-7367(19)30108-6
DOI: https://doi.org/10.1016/j.catcom.2019.03.030
Reference: CATCOM 5668
To appear in: Catalysis Communications
Received date: 3 February 2019
Revised date: 26 March 2019
Accepted date: 30 March 2019

Please cite this article as: J. Miao, H. Li, Q. Su, et al., The combined promotive effect
of SO2 and HCl on Pb-poisoned commercial NH3-SCR V2O5-WO3/TiO2 catalysts,
Catalysis Communications, https://doi.org/10.1016/j.catcom.2019.03.030

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The Combined Promotive Effect of SO2 and HCl on Pb-Poisoned

Commercial NH3-SCR V2O5-WO3/TiO2 Catalysts

Jifa Miaoa,b,c, Huirong Lia,b,c, Qingfa Sua,b,c, Yanke Yud, Yanting Chena,b, Jinsheng

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Chena,b,*, Jinxiu Wanga,b,*

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a
Center for Excellence in Regional Atmospheric Environment, Institute of Urban
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Environment, Chinese Academy of Sciences, Xiamen 361021, PR China

b
Key Laboratory of Urban Environment and Health, Institute of Urban Environment,
Chinese Academy of Sciences, Xiamen 361021, PR China
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c
University of Chinese Academy of Sciences, Beijing 100049, PR China
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d
Department of Environmental Science and Engineering, School of Energy and
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Power Engineering, Xi'an Jiaotong University, Xi'an 710049, PR China

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Corresponding Authors

* Jinsheng Chen, Tel./Fax: +86 592 6190765, Email: jschen@iue.ac.cn

* Jinxiu Wang, Tel./Fax: +86 592 6190548, Email: jxwang@iue.ac.cn

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Abstract

In this study, the deactivation of commercial V2O5-WO3/TiO2 selective catalytic

reduction catalysts by Pb was discussed primarily, and the combined promotive
effects of SO2 and HCl on Pb-poisoned V2O5-WO3/TiO2 catalysts were studied. The
results show that the treatment with SO2 and HCl markedly improves the NOx
conversion of Pb-poisoned catalysts. SO2 and HCl react with Pb chemisorbed on V2O5,

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which increases effectively the ratio of V5+ and active oxygen species and the amount

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of acid sites.

Keywords: SCR catalysts, Pb-poisoned, SO2 promotive effect, HCl promotive effect.

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1.Introduction
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Nitrogen oxides (NOx) emitted from automobiles, coal-fired power plants and
municipal solid waste (MSW) incinerators, can cause a variety of environmentally
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harmful effects, such as acid rain, photochemical smog and ozone depletion [1].
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Incineration of MSW for generating electrical power has increased in recent years.
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V2O5-WO3/TiO2, as the main commercial catalyst used for the selective catalytic
reduction (SCR) of NOx with NH3, is commonly applied in MSW incinerators for
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abating NOx in flue gas to meet the strict emission standards [2-3].

The V2O5-WO3/TiO2 catalyst suffers severe poisoning because of the large amount
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of Pb contained in the flue gas. Tokarz et al. [4] measured 90 ppm Pb on the catalysts
used in a MSW incinerator with an operating time of 1840 h. Khodayari et al. [5]
found that Pb concentration reached 3350 ppm after running for 1900 h in a
high-dust municipal waste incinerator. Khodayari et al. [6-7] also investigated the Pb
deactivation of commercial SCR catalysts by applying chemical means, e.g. reaction
with the poisoned active sites, or by physically introducing a barrier between active
sites and the gas phase.
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Chen et al. [8] suggested that the poisoning effect of Pb (PbO) on the SCR activity
was between K2O and Na2O. Gao et al. [9] proposed that each Pb atom could
influence two active sites. Meanwhile, it should be stated that there are large amounts
of acid gas, like SO2 and HCl in the flue gas produced during the combustion of MSW
[10-11]. However, most previous studies examined the deactivation mechanism of Pb
on commercial SCR catalysts were conducted in the absence of HCl and SO2 which

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may limit the understanding of the mechanism of SCR catalysts deactivation under
the actual operating conditions. Recent studies found that HCl and SO2 could increase

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the activity of poisoned V2O5-WO3/TiO2 catalysts. More precisely, Lisi et al. [12]
found that HCl promoted the formation of new acid sites on the surface of SCR

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catalysts. Khodayari et al. [6-7] found that sulphation with SO2 resulted in higher
activities due to the formation of surface sulphate groups. Yu et al. [13] also suggested
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that SO2 regenerates active sites on the surface of K-poisoned catalysts in the
operating conditions with SO2 present in the flue gas. Our recent work also found the
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promotional effect of SO2 on the Pb-poisoned V2O5-WO3/TiO2 catalysts by forming

sulfates on the SCR catalyst surface [14].
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In this work, the poisoning effect of Pb on V2O5-WO3/TiO2 and the combined

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promotive effects of HCl and SO2 on the Pb-poisoned catalysts are presented and
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discussed.
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2. Experimental
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A commercial V2O5-WO3/TiO2 catalyst (named as Fresh, with 2.55 wt% V2O5 and
3.30 wt% WO3, Table S1) used in this study was ground and sieved to 60-80 mesh
particle size. The Pb element content in D-Pb catalyst (dried and calcined, see Section
2.1 in ESI) is 0.88 wt%. The catalytic activities of the samples were evaluated in a
simulated fixed bed microreactor, and the applied conditions are summarized in the
Electronic Supporting Information, ESI.

The catalysts were characterized by XRF, ICP-OES, BET, XRD, TPD-MS, XPS,
DRIFT and FTIR spectroscopy techniques and all related information is provided in
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the ESI.

3. Results and discussion

3.1. Catalytic activity

Fig. S1shows the SCR activity of the catalyst samples in the temperature range of
250-450 °C under a GHSV of 60,000 h−1. The NOx conversion of Fresh sample is 90%

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at the temperature range of 250-380 °C and decreases dramatically as the temperature
is higher than 400 °C. The poisoning effect of Pb on the V2O5-WO3/TiO2 catalyst

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obviously decreases the NOx conversion of D-Pb sample. However, the pretreatment

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with HCl of Pb-poisoned sample improves its catalytic activity to some degree.

Fig. 1 shows the influence of SO2 on the Fresh, D-Pb and D-Pb-Cl (treated with
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HCl, see Section 2.1, ESI) samples at 350 °C for 600 min. The above-mentioned
treated samples are correspondingly denoted as Fresh-S, D-Pb-S and D-Pb-Cl-S. As
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the SO2 is introduced into the system, the NOx conversion of poisoned samples
increases fast in about 60 min and gradually reaches stable value. The treatment with
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SO2 enhances the activity of D-Pb sample so largely, that D-Pb-S shows higher NOx
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conversion than Fresh-S sample when NOx conversion of samples is stable. Moreover,
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the D-Pb-Cl-S sample treated with HCl and SO2 exhibits the highest NOx conversion
values, exceeding Fresh-S sample by 7%-units, which indicates the combined
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promotive effect of HCl and SO2 on the activity of Pb-poisoned catalyst.

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3.2. Structure and surface acid sites

N2 adsorption-desorption isotherms of all samples are shown in Fig. S2 (ESI).

According to the IUPAC classification, the isotherms are type-IV nitrogen isotherm
corresponding to typical mesoporous materials. The specific surface area (SBET), pore
volume (VP) and pore radius (rA) of all samples are summarized in Table S2 (ESI). Pb
loading decreases the SBET of the catalyst [15], whereas treatment with HCl and SO2
decreases SBET and increases pore radius of samples. These results might be because
the product of reaction between acid component and deposited Pb results in a slight
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pore blocking.

As shown in Fig. S3 (ESI), only anatase phase TiO2 is observed in all samples,
indicating that the presence of Pb does not affect the crystallinity of the commercial
catalyst. No powder diffraction peaks corresponding to any lead compound was
detected. It might be because the uniform distribution of Pb on the surface of TiO2 or
the content of Pb is lower than the detection limit of XRD.

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Based on the results of N2 adsorption and XRD patterns, the phase and textural
structure properties of D-Pb, D-Pb-Cl and D-Pb-Cl-S are insignificantly affected by

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the treatment with Pb, HCl or SO2. In order to investigate the reason(s) for the very

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different catalytic activity observed over of these samples, further characterizations
were conducted.
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It is recognized that the surface acid sites of the present catalysts play an important
role in the SCR reaction of NO with NH3 [2, 16]. Hence, NH3-TPD experiments were
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performed to investigate the combined effect of Pb, HCl and SO2 on the surface
acidity of V2O5-WO3/TiO2 catalysts, as shown in Fig. 2. All curves in the NH3-TPD
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profiles recorded from 100-600 °C are divided into two parts. The part below or
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around 300 °C which is attributed to NH3 desorption from surface weak acid sites,
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and the other part above 300 °C which is ascribed to NH3 desorption from surface
strong acid sites. After Pb poisoning, the NH3 signal from strong acid sites decreases
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remarkably, which implies that the reaction between strong acid sites and Pb atoms
contributes to catalyst deactivation effects imposed by the presence of Pb on the
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catalysts. The pretreatment with HCl increases the surface weak acid sites of
Pb-poisoned catalyst to some degree. The peak attributed to strong acid sites in the
NH3-TPD profile of D-Pb-Cl-S sample increases evidently in comparison with
D-Pb-Cl and D-Pb-S samples, which might be the main reason for the improved
activity after the combined treatment with HCl and SO2. The observed signal of
gaseous SO2 for the fresh catalyst was from the decomposition of sulphates in the
additives of the commercial V2O5–WO3/TiO2 SCR catalysts [22]. The increased signal
of SO2 on the D-Pb-S and D-Pb-Cl-S samples implies that some sulfates were
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produced during the SCR process in the presence of SO2, and previous studies proved
that sulfates could lead to the formation of Brønsted acid sites for the SCR reaction
[14]. Therefore, the effect of HCl and SO2 on the surface acidity and oxidation states
of elements, which are important factors for the SCR reaction, is further studied by in
situ DRIFTS and XPS.

Besides the surface concentration of acid sites, the chemical nature of acid sites is

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also important for the SCR catalysts [17]. Therefore, a set of in situ DRIFTS
experiments were conducted to obtain further understanding of the interaction

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between NH3 and the surface acid sites.

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As shown in the Fig. 3, for the spectra of fresh catalysts, IR bands at 1602 cm-1 and
in the 1150-1300 cm-1 range are ascribed to NH3 adsorbed on the Lewis acid sites [18].
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The IR bands at 1710 cm-1 and 1656 cm-1 are assigned to ionic ammonium species on
Brønsted acid sites [19-20]. The other IR band at 1505 cm-1 could be ascribed to the
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wagging vibration of -NH2 species, an important intermediate product in the

NH3-SCR reaction [21]. In Fig. 3, for the spectra of D-Pb sample, the intensity of IR
bands at 1656 cm-1 attributed to ionic ammonium on Brønsted acid sites decreases
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obviously. In addition, the IR band at 1232 cm-1 vanishes absolutely. The results imply
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that Pb could react with the Brønsted acid sites and Lewis acid sites of
V2O5-WO3/TiO2 catalyst.
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In Fig. 3, the spectra of D-Pb-Cl sample are similar to those of fresh catalyst. It
suggests that the pretreatment with HCl could restore large part of acid sites, thus
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reducing the poisoning impact of Pb. The intensity of detected IR bands on D-Pb-Cl-S
sample increases obviously. In addition, the new IR band recorded at 1438 cm-1 is
ascribed to ionic ammonium on Brønsted acid sites, which implies that new Brønsted
acid sites form in the presence of SO2.

3.3. Surface functional groups and chemical states

To understand the functional groups changes after doping with Pb and exposing to
HCl and SO2, the samples are analyzed by FT-IR spectra, and results are presented in
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Fig. 4. As shown in the FT-IR spectra, the IR band at 1103 cm-1 is associated with
vibrational modes of the SO42- group, and the IR band at 1058 cm-1 is attributed to the
stretching vibrational mode of V5+-O. The IR band intensity of V5+-O in Pb-poisoned
catalysts decreases, but the treatment with HCl increases the V5+-O to some degree.
The band intensity of V5+-O also increases in the D-Pb-Cl-S sample. The IR band
assigned to SO42- increases obviously after exposure to SO2 during the SCR reaction.

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The sulfate groups may provide more active sites for the SCR reaction, which
promotes the activity of Pb-poisoned catalysts treated with SO2.

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The samples were also investigated by XPS to gain a better understanding about the

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oxidation state of surface-active species. Fig. 5 presents the O 1s and V 2p spectra of
all samples. The positions and concentrations of photoelectron peaks in the V 2p and
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O 1s spectra are displayed in Table S3 and Table S4 (ESI). The O 1s spectra are fitted
into three peaks corresponding to the lattice oxygen in the metal oxides (Oγ, 529.45
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eV-529.65 eV), the surface oxygen of hydroxyl species (Oβ), and the absorbed oxygen
or/and weakly bonded oxygen species (Oα) [14, 22]. The BE value of Oγ shifts from
529.48 to 529.41 eV after Pb-poisoning. This may be because Pb donates electrons to
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lattice oxygen.
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Several previous studies in the deactivation mechanism of Pb on vanadium-based

SCR catalysts indicated that Pb interacts mainly with the oxygens of the vanadium
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phase rather than with the oxygens of titania phase [14, 23]. After being exposed to
HCl and SO2, the BE value of Oγ shifts to higher position, result which was also
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observed by Xu et al. [24]. It could be explained as Cl- and SO42- reacted with Pb
chemisorbed on active sites. It is also well-known that surface adsorbed oxygen
species is more reactive to benefit the oxidation of NO to NO2 [17], and the hydroxyl
species on the surface are also important to adsorb NH3 [25], which are regarded as
active oxygen species as well. The population of Oβ seems more important during the
SCR process. The content of Oα+Oβ increases significantly in the D-Pb-Cl and
D-Pb-Cl-S compared with D-Pb, which indicates that exposing the sample to SO2 or
HCl increases the population of surface bound hydroxyl species and absorbed oxygen.
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The content of Oβ in the D-Pb-Cl-S sample is higher than that in the D-Pb-S, which is
in accordance with the results of activity test (Fig. 1).

Based on previous reports [26, 27], the SCR activity of catalyst is positively
correlated with the surface V5+/V4+ molar ratio. For all samples, the V 2p3/2 peak
could be fitted into V5+ and V4+ peaks. The atomic ratio of V5+/V4+ could be
determined according to the peaks area ratio of V5+/V4+ [26]. The atomic ratio of

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V5+/V4+ decreases from 1.19 to 0.86 after Pb poisoning, so Pb results in the
transformation of V5+ into V4+ in the V2O5-WO3/TiO2 catalysts [23]. The atom ratio of

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V5+/V4+ in D-Pb-Cl and D-Pb-S samples increases to 0.97 and 1.59 compared with

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that in the D-Pb sample (0.86). These results indicate that the HCl or SO2 can weaken
the poisoning effect of Pb. The surface V5+/V4+ ratio of D-Pb-Cl-S increases by a
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factor of 1.10, which is even higher than the sum of increased parts of D-Pb-Cl and
D-Pb-S compared with D-Pb sample. Therefore, the synergistic effect of HCl and SO2
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improves the V5+/V4+ ratio and in turn the activity of catalysts to a large extent.

Based on the present NH3-TPD, DRIFTS and XPS spectra analysis, and previous
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studies, the interactions among Pb, HCl and SO2 on the surface of SCR catalysts
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could be concluded in Fig. 6. Each Pb atom reacts with two Brønsted acid sites and
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makes them inactive for the adsorption of NH3. HCl combines with chemisorbed Pb
and recovers hydroxyl groups. Further, the effect of SO2 generates more acid sites on
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the HCl-treated Pb-poisoned catalysts.

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4. Conclusions

In this study, it is confirmed that Pb present in the flue gas decreases the DeNOx
activity of commercial V2O5-WO3/TiO2 SCR catalysts by its reaction with surface
active sites. The NO conversion of Pb-poisoned catalysts is largely improved after the
combined treatment of the poisoned catalyst with HCl and SO2, which even exceeds
that of the fresh catalyst. HCl and SO2 do not change the crystalline phase and textural
structure of Pb-poisoned catalysts. Based on the NH3-TPD and in situ DRIFTS results,
it is believed that the combined treatment with HCl and SO2 recovers and further
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generates new active acid sites on the Pb-poisoned catalysts. Moreover, the synergistic
effect of HCl and SO2 can increase the ratio of V5+ and active oxygen species
contributing to the NOx conversion over the Pb-poisoned V2O5-WO3/TiO2 catalysts
after treated with HCl and SO2.

Acknowledgments

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This work is financially supported by the Natural Science Foundation of Fujian

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Province, China [grant number2016J05048], Bureau of Science and Technology,
Fujian Province, China [grant number2015H0043], National Natural Science

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Foundation of China [grant number21403210], and Fujian Institute of Innovation,
Chinese Academy of Sciences.
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Appendix A. Supplementary data

Supplementary data to this article can be found online.

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28. M. Kong, Q.C. Liu, L.J. Jiang, F.Q. Guo, S. Ren, L. Yao, J. Yang, Property
influence and poisoning mechanism of HgCl2 on V2O5-WO3/TiO2 SCR-DeNOx
catalysts, Catal. Commun. 85 (2016) 34-38.
https://doi.org/10.1016/j.catcom.2016.07.011

Figure captions

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Fig. 1. The effect of SO2 on Fresh (a), D-Pb-Cl (b) and D-Pb (c) sample at 350 °C.
Reaction conditions: catalyst amount = 1.2 cm3, [NO] = [NH3] = 550 ppm, [O2] = 4.5
vol%, [SO2] = 300 ppm, balance N2, GHSV = 60,000 h−1.

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Fig. 2. NH3-TPD profiles of Fresh, D-Pb, D-Pb-Cl, D-Pb-S and D-Pb-Cl-S catalyst

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samples.

Fig. 3. In situ DRIFTS spectra of Fresh, D-Pb, D-Pb-Cl, D-Pb-S and D-Pb-Cl-S
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pretreated with 2000 ppm NH3 in N2 at 350 °C for 30 min.

Fig. 4. FT-IR spectra of a) Fresh, b) D-Pb, c) D-Pb-Cl, d) D-Pb-S and e) D-Pb-Cl-S

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catalyst samples.

Fig. 5. XPS spectra of the O 1s and V 2p3/2 of Fresh, D-Pb, D-Pb-Cl, D-Pb-S and
D-Pb-Cl-S catalyst samples.
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Fig. 6. Schematic diagram of the combined effects of HCl and SO2 on the
Pb-poisoned V2O5-WO3/TiO2 SCR catalysts.
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Highlights:
 Pb-poisoned commercial SCR catalyst is reactivated by treatment with HCl and
SO2.
 XPS confirms the transformation of V5+ species into V4+ species after doping by
Pb.
 Active oxygen species are generated after the treatment with HCl and SO2.

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 V4+ transforms to V5+ in the catalyst after exposing to HCl and SO2.
 Results indicate the promotive effect of SO2 and HCl on Pb-poisoned catalysts.

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