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Novel application of biochar from biomass pyrolysis for low temperature

selective catalytic reduction

Article  in  Journal of the Energy Institute · November 2012

DOI: 10.1179/1743967112z.00000000033

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 Novel application of biochar from biomass
pyrolysis for low temperature selective
catalytic reduction
C. F. Wu*1, M. A. Nahil1, X. Sun2, S. Singh1, J. H. Chen2, B. X. Shen2 and
P. T. Williams1
Biomass pyrolysis is regarded as a promising technology to produce bio-oils for future energy.
Biochar generated from the biomass pyrolysis is normally combusted to provide extra heat to the
pyrolysis process. In this work, the novel application of the biochar in the field of low temperature
selective catalytic reduction (SCR) of NOx has been investigated in order to increase the
economic value of the biochar. Biochar produced from the pyrolysis of cotton stalk agriculture
waste was steam activated and used as a catalyst support for Ce–Mn. The influence of the steam
Published by Maney Publishing (c) Energy Institute

activation on SCR experiment was investigated. The results show that there are two temperature
windows during the SCR. The first is between 180 and 240uC, where the material (Ce–Mn–AC1)
with less mesoporous shows the highest NO conversion (y20%). The second is after 260uC,
where the catalysts with more mesopores and higher acidity show better NO conversion (y55%).
Keywords: Pyrolysis, Activated carbon, SCR, Biochar, Biomass

Introduction avoiding poisoning from the pollutants, e.g. SOx; in

Biomass is recognised as a carbon neutral resource for
future energy use to cope with the problem of climate
change caused by the utilisation of fossil fuels. Through
pyrolysis of biomass, bio-oil can be produced for
transportation and chemical feedstock production.
Therefore, there are extensive research and policy studies
in the field of biomass pyrolysis.1–3 Biochar is the solid
residue after the pyrolysis of biomass. The biochar is
usually combusted to provide extra heat for the pyrolysis
process. In order to make the pyrolysis process more
economically feasible, biochar should be used as a more
high value product such as activated carbon.4,5 However,
the applications of the activated carbon derived from
biochar are few.
At present, selective catalytic reduction (SCR) has
attracted much attention to reduce the production of
NOx in the flue gas stream from a number of industrial
processes as more stringent regulation of NOx emission
is implemented around the world, for example for power
plants and motor vehicles.6,7 Carbon materials have
been tested as supports for the SCR catalyst due to the
low cost of the materials and its particular surface
properties such as high surface area and pore volume.8,9
Low temperature SCR (around or below 250uC) is
drawing special interest since the SCR catalyst could be
located downstream of the desulphurisation device,
1
Energy Research Institute, The University of Leeds, Leeds LS2 9JT, UK
2
College of Environmental Science and Engineering, Nankai University,
Tianjin 300071, China
*Corresponding author, email wcf1314@gmail.com
addition, the middle temperature performance (300–
400uC) of SCR has been well established in the
industry.10
Most low temperature SCR catalysts contain transi-
tional metals, such as Fe, V, Cr, Cu and Mn.11 Among
them, Mn based SCR catalysts have been studied
extensively because of their excellent performance at low
temperature.10,12 Additionally, CeO2 has been widely used
as a promoter to the SCR catalyst due to its unique redox
and acid base properties.13,14 Therefore, MnOx–CeO2
based catalysts are interesting for the investigation of the
SCR process.
In this paper, we examined the performance of
biochar as a MnOx–CeO2 catalyst support during the
SCR of NO in a laboratory scale reaction system. The
influence of the physical properties of the biochar on
the efficiency of the NO reduction was studied.
Experimental
Biochar and catalyst preparation
Biochar was produced from the pyrolysis of cotton stalk
agriculture waste using a fixed bed reactor.15 The raw
biomass sample (10 g) was placed in a crucible, which
was placed in a tubular reactor. The reactor was heated
to 600uC at a heating rate of 5uC min21 and held for 1 h.
N2 gas was used as a carrier gas during the pyrolysis.
The obtained char product was further activated using
steam (water injection rate of 7?59 g h21) at tempera-
tures of 600, 700 or 800uC for 1 or 2 h.
Char and steam activated char [activated carbon
(AC)] products were supported with Mn and Ce by

ß 2012 Energy Institute

Published by Maney on behalf of the Institute
Received 6 February 2012; accepted 19 March 2012
236 DOI 10.1179/1743967112Z.00000000033 Journal of the Energy Institute 2012 VOL 85 NO 4

1: gas bottles; 2: gas regulators; 3: mass flow meters;
4: gas mixers; 5: preheater; 6: sample collection point;
7: SCR reactor; 8: catalytic bed; 9: gas analyser
1 Schematic diagram of SCR test system
coimpregnation methods, where Ce and Mn nitrates
(Ce/Mn molar ratio, 1 : 2; Mn/AC weight ratio, 4%) were
Published by Maney Publishing (c) Energy Institute
dissolved into deionised water and a certain amount of
activated carbon was added. The mixture of metal
nitrates and char was heated and stirred until the
precursor became semisolid. The precursor was dried in
an air atmosphere oven at 105uC overnight, and further
calcined under N2 atmosphere at 500uC for 5 h. The
catalyst was assigned to Ce–Mn–char (no steam activa-
tion to char), Ce–Mn–AC1, Ce–Mn–AC2, Ce–Mn–AC3
and Ce–Mn–AC4 respectively. Activation conditions of
the char are shown in Table 1.
Selective catalytic reduction reaction system
The SCR tests were carried out in a fixed bed reactor at
atmospheric pressure (Fig. 1). The main reactor for the
SCR test is a 10 mm diameter stainless steel tube. A
mesh support was placed inside the reactor for placing
the catalyst. The reactor was well temperature controlled
and insulated. During the experiment, a mixture of
model gas [N2–0?06NO–0?06NH3–3O2 (vol.-%)] with a
total flowrate of 300 mL min21 was mixed and then
introduced to the reaction system. In each experiment,
0?5 g of catalyst was used. Selective catalytic reduction
tests were carried out between 100 and 280uC. The
reaction system was stabilised at the desired temperature
for 2 h before the analysis of gas products.
NO concentration in the outlet gas was analysed by a
flue gas analyser (KM900; Kane International Ltd). The
NO conversion was calculated as follows
½NOinlet {½NOoutler
NO conversion (%)~ |100%
½NOinlet
Table 1 Surface property of the catalysts
Catalyst no. Ce–Mn–char
Char activation temperature/uC … 600
Char activation time/h … 2
Brunauer–Emmet–Teller surface area/m2 g21 156.0
Microvolume/cm3 g21 … 0.122
Average pore size/nm … 3.6
Wu et al. Application of biochar from biomass pyrolysis for SCR
where [NO]inlet is the introduced NO concentration
(vol.-%), and [NO]outlet is the NO concentration of the
exit of the reactor (vol.-%).
Catalyst characterisation
Textural parameters of the samples were determined by
N2 sorption at 77 K using a NOVA 2000 automated gas
sorption system (Quantachrome Instruments, USA).
The crystal structures of the selected catalysts were
determined by X-ray diffraction (XRD), using a D/Max-
2500 diffractometer (Rigaku Co., Japan) with mono-
chromatised Cu Ka radiation (l51?5405 Å).
Temperature programmed reduction (TPR) with H2
was also carried out with a thermogravimetric analyser
(TP5080). Samples (0?1 g) were loaded and pretreated at
550uC in the atmosphere of N2, and then the samples
were cooled to room temperature. After that, the
samples were reduced by H2 (5 vol.-%)/N2 with a
flowrate of 30 mL min21 from room temperature to
850uC at a heating rate of 10uC min21.
Total acidity and acid distribution of the catalysts
were measured by temperature programmed desorption
(TPD) of NH3 on a thermogravimetric analyser
(TP5080; XQ-instrument, Tianjin, China).
Results and discussion
Catalyst characterisation
Surface analysis of prepared biochar catalysts
Surface areas and pore volumes of the catalysts are
shown in Table 1. Brunauer–Emmet–Teller surface area
of the Ce–Mn–char was 156?0 m2 g21. The Brunauer–
Emmet–Teller surface area was increased to
293?0 m2 g21 when the catalyst support (biochar) was
activated with steam at 600uC for 2 h and was slightly
decreased to ,270 m2 g21 when the steam activation
temperature increased to 700 and 800uC. Pore volume
and size were shown to be increased when the biochar
was activated by steam and further increased with the
increase in the activation temperature from 600 to 800uC
(Table 1). The table shows that steam activation was
effective to improve the pore volume and size; however,
the surface area could be reduced at high activation
temperature. From Table 1, surface area and pore
volume of the catalyst were increased slightly when the
activation time was increased from 1 to 2 h at the steam
activation temperature of 800uC.
N2 adsorption and desorption isotherms of the
catalysts are shown in Fig. 2. The adsorption/desorption
of N2 is a combination of type I and IV isotherms
indicating a mesostructured material.16 The adsorption
type seems similar for the investigated catalysts except
the Ce–Mn–char catalyst. In addition, the Ce–Mn–
CA1 catalyst shows low adsorption/desorption with
Ce–Mn–AC1 Ce–Mn–AC2 Ce–Mn–AC3 Ce–Mn–AC4
700 800 800
2 2 1
293.0 370.0 370.3 353.1
0.141 0.144 0.134
4.4 4.8 4.6
Journal of the Energy Institute 2012 VOL 85 NO 4 237
 Wu et al. Application of biochar from biomass pyrolysis for SCR
2 N2 adsorption and desorption of the biochar catalysts
mesopores; as shown in Fig. 2, most of the adsorption/
desorption occurred for micro- and macropores.
X-ray diffraction analysis of selected catalysts
The XRD analysis of the Ce–Mn–AC1 and Ce–Mn–
AC3 catalysts is shown in Fig. 3. Both samples show a
Published by Maney Publishing (c) Energy Institute
broad amorphous carbon peak at ,23u. CeO2 crystal
was found at ,29, 33, 47 and 56u.17 A MnO2 phase was
also identified from XRD analysis.18 Compared to the
Ce–Mn–AC3 catalyst, the intensity of the crystal phases
in the Ce–Mn–AC1 catalyst is stronger, demonstrating
that more CeO2 and MnO2 crystals were formed on the
surface of the biochar derived from the steam activation
at a temperature of 600uC. Additionally, more homo-
geneous dispersion of Ce and Mn is obtained for the Ce–
Mn–AC3 catalyst. The better dispersion of Ce and Mn
in the Ce–Mn–AC3 catalyst might be due to more
mesopores being available compared with the Ce–Mn–
AC1 catalyst (Table 1 and Fig. 2).
H2-TPR analysis of catalysts
As shown in Fig. 4, the prepared catalysts showed one
hydrogen reduction peak at ,600uC. The only one peak of
hydrogen reduction was regarded as the overlap of the
reduction of MnO2 and CeO2,19,20 which have been
identified in the XRD analysis (Fig. 3). Hydrogen gaining
was found after 650uC from Fig. 4; this might be due to the
release of hydrogen derived from the decomposition of the
carbon materials at the higher temperature (.650uC).
3 X-ray diffraction analysis of the selected catalysts
238 Journal of the Energy Institute 2012 VOL 85 NO
4 H2-TPR of prepared catalysts
Temperature programmed desorption of catalysts
Temperature programmed desorption analysis was
carried out to obtain the acid property of the prepared
catalysts (Fig. 5). Similar broad NH3 desorption (100–
400uC) was found for all the investigated catalysts. The
desorption peak ,150uC was assigned to weakly
adsorbed NH3.21 Moreover, Ce–Mn–AC3 showed the
highest NH3 adsorption, and the Ce–Mn–char showed
the lowest NH3 adsorption, indicating that the steam
activation of biochar results in an increase in the acidity
of the catalysts. Additionally, the reduction of the steam
activation time from 2 h (Ce–Mn–CA3) to 1 h (Ce–Mn–
CA4) reduced the acidity of the catalyst.
Selective catalytic reduction experiments with
biochar based catalysts
The prepared catalysts were tested for their NO reduction
between 100 and 280uC. The NO conversion is shown in
Fig. 6. Around 10% of NO conversion was obtained before
the SCR reaction temperature of 180uC; when the reaction
temperature increased to 280uC, more than 50% of NO
conversion was achieved for the biochar based catalysts.
From Fig. 6, there are two temperature windows for
the SCR test. One is between 180 and 240uC; the other is
between 260 and 280uC. The NO conversion is similar at
the other temperatures for all the studied catalysts.
Between the reaction temperature of 180 and 240uC,
5 NH3-TPD analysis of prepared catalysts
4

6 NO conversion at various reaction temperatures with
different catalysts
Ce–Mn–AC1 exhibits the highest NO conversion
(y20%) among the catalysts. It indicates that optimal
pore volume and surface area of the catalyst are important
during the SCR test at this temperature window (180–
240uC), since Ce–Mn–AC1 has higher surface area
Published by Maney Publishing (c) Energy Institute
compared with the non-activated biochar based catalyst
(Ce–Mn–char). However, Ce–Mn–AC1 has lower surface
area and pore volume compared with the Ce–Mn–AC2,
Ce–Mn–AC3 and Ce–Mn–AC4 catalysts, which present a
lower NO conversion (Table 1 and Fig. 6). Additionally,
as shown in Fig. 2, most of the pores of the Ce–Mn–AC1
are micropores when the other steam activated catalysts
(Ce–Mn–AC2, Ce–Mn–AC3 and Ce–Mn–AC4) are domi-
nated by mesopores. Therefore, it is suggested that
micropores of the biochar promote NO conversion at the
temperature window between 180 and 240uC.
For a higher temperature window (260–280uC), Ce–
Mn–AC1 shows the lowest NO conversion among the
studied catalysts. It is suggested that at the reaction
temperature above 260uC, the presence of mesopores in
the biochar materials benefit NO conversion. In addi-
tion, the Ce–Mn–AC1 catalyst has lower dispersion of
Ce and Mn metals (XRD results from Fig. 3) and lower
intensity of acidity, compared with the other steam
activated biochar based catalysts. Therefore, within the
temperature window (260–280uC) studied in this work,
higher dispersion of metals and catalyst acidity promote
NO reduction. Furthermore, the NO reduction effi-
ciency presented in this work is comparatively lower
compared with the literature.22,23 However, the perfor-
mance of the catalysts for the SCR depends significantly
on various conditions such as doped metals, metal
loading and the precursor carbon materials. The novelty
of this work is to apply the biochar derived from
biomass pyrolysis for NOx SCR and also to indentify the
influence of steam activation of the biochar on the NO
conversion. Through this work, we found the biochar
based catalyst is effective to reduce NO in the SCR
process. Future work will focus on the Ce–Mn–AC1
catalyst to increase the NO conversion in low tempera-
ture SCR by manipulating the metal loadings.
Conclusions
This wok investigated the novel application of biochar
derived from biomass pyrolysis in the process of SCR. Ce
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Wu et al. Application of biochar from biomass pyrolysis for SCR
and Mn oxides were loaded on the biochar, and the catalysts
were tested for NO reduction in a fixed bed reactor.
The surface area was increased by steam activation;
especially, the mesopores were increased with the increase
in the steam activation temperature from 600 to 800uC. In
addition, the XRD showed that high dispersion of metals
were obtained for the catalyst with more mesopores
(Ce–Mn–AC3) compared with Ce–Mn–AC1, and high
intensity of NH3-TPD absorption (high acidity) was also
obtained for the catalyst with higher surface area and
pore volume. The increased mesopores and high acidity
seem to promote the NO reduction at the temperature
window of 260–280uC. However, the Ce–Mn–AC1
catalyst with less mesopores shows the best NO conver-
sion at the temperature window of 180–240uC.
Acknowledgements
This work was supported by the UK Engineering and
Physical Sciences Research Council under EPSRC
grant no. EP/D053110/1, International Cooperation
and Exchange project no. 51150110155 and National
Natural Science Foundation of China grant nos.
51176077 and 50976050.
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Journal of the Energy Institute 2012 VOL 85 NO 4 239