Fuel 160 (2015) 3542

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Fuel
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Utilization of sargassum based activated carbon as a potential waste

derived catalyst for low temperature selective catalytic reduction
of nitric oxides
Wei Li a,b, Shan Tan a,b, Yun Shi a,b, Sujing Li a,
a
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Institute of Industrial Ecology and Environment, College of Chemical and Biological Engineering,
Zhejiang University (Yuquan Campus), Hangzhou 310027, China
b
Institute of Environmental Engineering, College of Environmental Science and Resource, Zhejiang University (Zijingang Campus), Hangzhou 310058, China

h i g h l i g h t s
 N-doped sargassum based activated carbon is prepared via different techniques.
 NOx conversion of commercial AC is 50.84%.
 C/SAC-2/U-6 achieved a maximum NOx conversion of 87% at 150 C.
 The characterization of catalysts was determined by EA, BET, XPS and FTIR.
 C/SAC-2/U-6 has an excellent water-tolerance and sulfur-tolerance.

a r t i c l e

i n f o

Article history:
Received 6 February 2015
Received in revised form 19 June 2015
Accepted 14 July 2015
Available online 22 July 2015
Keywords:
Activated carbon
Novel sargassum-based catalysts
N-doped
Low temperature NH3-SCR
Water and sulfur tolerance

a b s t r a c t
The use of activated carbon derived from sargassum (SAC), normally disposed as waste, has been examined as potential catalyst for selective catalytic reduction of NO with NH3 (NH3-SCR) in the temperature
range of 50250 C. The inuence of important process variables, such as preparation methods, phosphoric acid impregnation ratios and surface nitrogen functional groups, were investigated. The impacts of
water (H2O) and sulfur dioxide (SO2) on the SCR activity of the C/SAC-2/U-6 catalyst were also discussed.
An array of analytical techniques, including BrunauerEmmettTeller method (BET), Elemental Analysis
(EA), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were
also employed to study the structural properties, elemental content, and distribution of
nitrogen-containing groups of the catalyst prepared. Experimental results suggested that the urea modied C/SAC-2/U-6 sample exhibited higher NOx conversion, better N2 selectivity and broader operation
temperature window than all the SAC samples and the commercial activated carbon sample.
Moreover, it has good water and sulfur tolerance, making the sargassum derived catalyst as a promising
NH3-SCR catalyst for NOx emission from red power plant.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Nitrogen oxides (NOx) pose negative inuences on tropospheric
chemistry, leading to summer photochemical smog, acid deposition, and formation of nitrate aerosol [1]. Hence, the removal of
NOx from stack gases is one of the most important environmental
issues. Currently, NH3-SCR is a leading technology for the treatment of NOx. The commercial catalyst (V2O5/WO3/TiO2) exhibits
high catalytic activity in the temperature range of 300500 C,

Corresponding author. Tel.: +86 (0) 57187952513.

E-mail address: sujing-li@zju.edu.cn (S. Li).
http://dx.doi.org/10.1016/j.fuel.2015.07.045
0016-2361/ 2015 Elsevier Ltd. All rights reserved.

which is not suitable for the process with downstream dust

removal equipment and desulfurization devices (100150 C) [2].
Also, ue gases have a high concentration of particles and other
contaminants which are deleterious for the catalyst monoliths in
this temperature window [2]. Therefore, there is an urgent need
for the development of highly active SCR catalysts working at
low temperatures (<250 C). In this case, the use of activated carbon (AC) as catalyst for NH3-SCR has been recognized as one of
the advanced technologies for the clean-up of stack gas from coal
re power plant [3,4]. However, the main disadvantage of AC for
NO reduction is the low catalytic activity. Thus, nitrogen
-modied AC has been attracted much interest as metal-free catalyst due to their exceptional electronic property and high de-NOx

36

W. Li et al. / Fuel 160 (2015) 3542

efciency. In previous studies [57], it has been found that the

presence of nitrogen atoms in the carbon matrix was shown to
enhance the catalytic activity of carbon materials in oxidation
reactions and to increase the ability to adsorb acidic gases.
Nitrogen groups can be formed by carbonization of nitrogencontaining precursors or by reaction of the carbon material with
a suitable nitrogen compound, such as urea.
So far, signicant researches have been devoted to the production of activated carbon from biomass due to its environmental
friendliness and abundance. Its application on air pollution has
been a popular choice due to its unique and versatile characteristics that adsorb gas/liquid into internal pore surface and own high
degree of surface reactivity [8]. Yet recently, more attentions have
been paid on marine plants, as algae is an advantageous biomass
source over land-based plants, including lower price and higher
yields without requiring arable land, avoiding competition for fertilizers with food crops [9].
Sargassum, which is a common macroalgae in the southeastern
coast of china and is normally disposed as waste, has not been
reported as a SCR catalyst yet. This work aims to investigating
the potential of urea modied activated carbon derived from sargassum as a novel low temperature SCR catalyst. This study further
examines the inuence of important process variables, including
preparation methods, phosphoric acid impregnation ratio, surface
nitrogen functional groups. And the impact of H2O and SO2 and
the reactive mechanism of the C/SAC-2/U-6 catalyst were also discussed. This novel utilization of sargassum shows an effective
approach of combining waste disposal, biomass energy recovery
and air pollution control (NOx) in one process.
2. Material and methods
A Chinese sargassum was used as raw material. After receiving,
it was thoroughly washed to remove impurities and then dried at
110 C for 24 h. After drying, the sargassum samples were
grounded and sieved to get a uniform mesh size of 4060.
Elemental analysis and proximate analysis of the sargassum presented in Table 1 revealed that sargassum has high carbon content
and low ash content, indicating that sargassum is suitable for the
preparation of AC with high yield. Besides, sargassum has relatively higher nitrogen content compared with those activated carbon precursors reported previously, such as wheat-straw [10], rice
straw [11], and marine posidonia oceanica [12] with nitrogen content of 0.44%, 0.65%, and 1.52%, respectively. Since nitrogen functional groups are active species of AC-based catalyst in the SCR
reactions at low temperatures [2,13], it is expected that there is a
relatively high concentration of nitrogen functional groups on the
surface of the SAC samples as prepared.
The commercial activated carbon (CAC) made from wood was
purchased from Sinopharm Chemical Reagent limited corporation.
The CAC also has been sieved to get a uniform mesh size of 4060.

2.1.1. Chemical activation

The activating agent used was an aqueous solution of H3PO4
(40 wt%). The activated carbon was prepared, using a mixture of
Table 1
Proximate analysis and ultimate analysis of raw sargassum (wt%. dry basis).

Sargassum

2.1.2. Physical activation

The air-dried sargassum samples were heated in the presence of
nitrogen and a heating rate of 10 C min1 was set. Once the activation temperature reached at 500 C, nitrogen ow was switched
to CO2. The physical activation was held for 1 h before cooled to
room temperature. The sample prepared was labeled as P/SAC,
where P represents physical activation. The resulting activated carbon was washed and sieved as followed the procedure described in
Section 2.1.1.
2.1.3. Co-activation
The air-dried sargassum samples were rstly chemicalactivated as described in 2.1.1, and then followed by physical
activation using CO2 for each sample as shown in Section 2.2.
Afterwards, the resulting activated carbon was washed and sieved
as followed the procedure described in Section 2.1.1. The samples
produced from Co-activation were labeled as Co/SAC-x, where Co
refers to physicalchemical activation, and x represents different
mass ratio of H3PO4/sargassum.
2.2. Urea modication of the catalysts
CAC and C/SAC-2 and Co/SAC-2 were chosen to be impregnated
using an aqueous solution of urea. The different mass ratios of
urea/SAC samples were employed, ranging from 3:1, 6:1, 9:1 and
12:1. The slurry was mixed via sonication for 2 h and then held
at ambient temperature for 12 h. Afterwards, the impregnated
samples were heated under a stream of nitrogen up to 500 C for
1 h before cooled to room temperature. The samples were then
washed and sieved as followed the procedure described in
Section 2.1.1. N-doped commercial activated carbon sample was
labeled as CAC/U-y and N-doped SAC samples were labeled as
P/SAC-2/U-y or Co/SAC-2/U-y, where U represents urea, and y
donates the different mass ratios of urea/AC samples.
2.3. Catalytic activity test

2.1. Catalyst preparation

Sample

H3PO4 and the air-dried sargassum with a mass ratio ranging from
0.5:1, 1:1, 1.5:1, 2:1 and 2.5:1. The precursor (liquid/solid slurry)
was mixed via sonication for 2 h and was then kept at room temperature for 12 h. Activation of the precursor was heated up to
500 C with a heating rate of 10 C min1 for 1 h in a tubular quartz
reactor under a stream of nitrogen (400 mL min1). Then, the
sample was cooled down to room temperature under nitrogen.
The samples obtained were labeled as C/SAC-x, where C represents
chemical activation, and x represents the mass ratio of
H3PO4/sargassum.
All the chemicals used were of analytical grade and commercially available. The resulting activated carbon was washed with
HCl solution, followed by hot water and distilled water until the
wash water reached a pH of 67 to remove residual organic and
mineral matters. The nal AC samples were dried and sieved to
obtain a particle size range of 4060 mesh.

Proximate analysis (wt%)

Ultimate analysis
(wt%)

Water

Ash

Volatiles

Fixed
carbon

6.7

6.6

54.7

32

40.3

5.4

2.5

51.8

Catalytic activity tests were carried out in a xed-bed quartz

tube reactor under atmospheric pressure. The reactor conguration is shown in Fig. A1 (in supporting materials). The quartz reactor with an i.d of 6 mm was placed inside a temperature-controlled
furnace. 150 mg catalyst was placed between plugs of glass wool in
the reactor and a K-type thermocouple was inserted in the center
of the catalyst bed to measure the reaction temperature. Prior to
catalytic tests, the catalysts were heated up to 500 C for 30 min
under N2 to purify the sample surface. The reactor was then cooled
to 30 C and N2 was switched to reaction gas mixture. The simulated gas stream consisted of 500 ppm NO, 500 ppm NH3, 5 v/v%
O2, 50300 ppm SO2 (if added), 5% or 10% H2O (if added), and N2

37

W. Li et al. / Fuel 160 (2015) 3542

CNOx in  CNOx out

 100%
C NOx in

CNOx CNO CNO2 2CN2 O

in

CNH3

2  CN2 O
in  CNO out  CNO2

 100%

80

60

60

40

40

20

20

50

100

out

 CNH3

250

(a)

2


150
200
o
Temperature ( C)

N2 selectivity (%)

80

100

100

80

80

60

60

40

40

20

20

out

2.4. Sample characterization

The elemental analysis (EA) was carried out using a
ThermoFinningan Flash EA 1112 Series elemental analyzer. All
the measurements were repeated in triplicate and the value
reported was the mean value.
The specic surface areas were calculated using BrunauerEm
mettTeller method (BET) equation and total pore volume and
micropore surface area were calculated using the t-plot method.
X-ray photoelectron spectroscopy (XPS) was conducted using a
Thermo ESCALAB 250 electron spectrometer equipped with an Al
Ka X-ray source (hm = 1486.6 eV). The XPS spectra were calibrated
by taking the graphitic peak as 284.6 eV. Peak analysis was performed using Casa-XPS Version 2.1.9 software with all spectra
Shirley-background subtracted prior to tting. The peaks were
deconvoluted using a sum of Lorentzian/Gussian functions.
The main functional groups on the carbon surface were determined by using Fourier transform infrared spectroscopy (FTIR).
The spectra were obtained over the range of 4004000 cm1 and
30 scans were taken at a resolution of 16 cm1.
3. Results and discussions
3.1. SCR catalytic activity
3.1.1. Effect of precursor preparation methods on NH3-SCR activity of
the catalysts
The effect of different preparation methods on the catalytic
activity of the SAC samples was shown in Fig. 1(a). As seen in
Fig. 1(a), NOx conversion of the P/SAC sample was the lowest, while
that of the Co/SAC-2 was the highest, achieving a maximum NOx
conversion of 82.05% at 125 C. In addition, the NOx conversion
of the C/SAC-2 was only slightly lower than that of the Co/SAC-2.
All the SAC samples showed a similar curve shape at the temperature range of 50250 C. An approximately conversion efciency of 45% was achieved at 50 C. It then showed a decreasing
tendency, reaching a minimum at around 100 C. A rapid increase
of NOx conversion was observed at the temperature range of 100
125 C, reaching its maximum of around 80%. Afterwards, a slight
decrease was found with the temperature increasing from 125 C
to 250 C. In all cases, N2 selectivity was ranged between
90%-100%. This showed a similar trend with previous publications
[14,15]. A minimum NO conversion for activated carbons at 100 C

50

100

150

200

250

N2 selectivity (%)

N2 selectivity

1
CNOx

100

NOx conversion (%)

NOx conversion

100

NOx conversion (%)

was used as a balance gas. Water vapor was generated by passing

N2 through a heated bottle containing deionized water The GHSV
for catalytic tests was 15,000 h1. For every experiment, new fresh
samples were used, and the SCR activity of the catalysts was determined at 50250 C under steady-state conditions.
The outlet concentration of reactants and products was determined by a Nicolet iS50 FTIR spectrometer coupled with a heated
FTIR gas cell (Pike Technologies, optical path length = 2.4 m).
Spectra were acquired at 0.5 cm1 resolution and co-addition of
32 scans. The NOx conversion and N2 selectivity were obtained
by the following Eqs. (1)(3):

Temperature ( C)

(b)
Fig. 1. (a) Effect of preparation methods on NOx conversion (solid) and N2
selectivity (open) of the SAC samples. (j) Physical activation; (d) chemical
activation; (N) Co-activation. (b) Effect of impregnation ratios on NOx conversion
(solid) and N2 selectivity (open) of the Co/SAC-x sample. (j) 0.5:1; (d) 1:1; (N)
1.5:1; (.) 2:1; (H) 2.5:1.

has been ascribed to the difference in the controlling mechanisms

for the low and high temperature regimes [14,16]. It is reported
that carbon mainly acts as a concentrating medium for reactant
species (NO2 and NH3) at low temperature [2]. Hence, the initial
decrease in NO conversion during the temperature range of 50
100 C is due to a decreased adsorption degree of the reactant species on the catalyst surface as temperature increases. As the temperature continues increasing, chemisorption of the reactant
species takes over physical adsorption and the SAC samples act
as true catalysts in the SCR reaction [2]. With temperature increasing, the chemisorption of the reactant becomes a limited process,
resulting in a decrease of NOx conversion efciency at higher
temperature.
3.1.2. Effect of impregnation ratios on the NH3-SCR activity of the
catalysts
The effect of different impregnation ratios between phosphoric
acid and dry precursor on the catalytic activity of the Co/SAC samples was shown in Fig. 1(b). NOx conversion of the Co/SAC samples
increased with the impregnation ratio increasing from 0.5:1 to 2:1.
NOx conversion dramatically decreased when the impregnation
further increased to 2.5:1. N2 selectivity was maintained above
90% for all the samples at all temperatures. Hence, the impregnation ratio of 2:1 is the optimum value to prepare the SAC samples
by Co-activation. In addition, comparison of de-NOx performance

3.1.4. Effect of H2O and SO2 on NH3-SCR activity of the C/SAC-2/U-6

catalyst
Fig. 3(a) showed the impact of water on the SCR activity of the
C/SAC-2/U-6 catalyst at 150 C. Since water content in the ue
gases is around 218% [17], 5% and 10% H2O were added in the
feeding gas mixture, respectively, In the absence of H2O, the steady
state NO conversion over the C/SAC-2/U-6 catalyst was around
87%, and an abrupt decrease to about 76% after introducing 5%
H2O. This result showed that H2O had an inhibitory effect on the
SCR activity to C/SAC-2/U-6 catalyst, and the inhibition of water
might be due to the competition adsorption between H2O and
reactants (NH3 and/or NO). Previous reports [35,18] also found
that the addition of H2O inhibited the SCR reaction on various
other catalysts at low temperatures. The NO conversion did not
further decrease, and was still maintained at around 77% with
the increasing H2O content from 5% to 10%. However, NO conversion was restored completely to the previous level when H2O
was removed from the feed gas. This proves that the inhibitory
effect of H2O is reversible on the C/SAC-2/U-6 catalyst. In addition,

100

80

80

60

60

40

40

20

20

NOx conversion (%)

50

100

150

200

250

Temperature ( C)

(a)
100

80

80

60

60

40

40

20

20

50

100

150

200

250

N2 selectivity (%)

100

Temperature ( C)

(b)

100

100

80

80

60

60

40

40

20

20

50

100

150

200

250

N2 selectivity (%)

3.1.3. Effect of N contents on the NH3-SCR activity of the catalysts

In order to investigate the effect of nitrogen doping on the catalytic activity of different SAC samples, Co/SAC-2 and C/SAC-2 were
impregnated with an aqueous solution of urea in the same ratio of
1:6. Fig. 2(a) showed the catalytic activity of these two N-doped
SAC samples. It was observed that both of them presented a similar
curve plot at the temperature range of 50250 C and the
C/SAC-2/U-6 sample showed a better de-NOx performance. It
achieved a maximum NOx conversion of 87% at 150 C. As the temperature increases, it showed a slightly decreasing tendency and
the NOx conversion was still maintained above 75%. Also, N2 selectivity was maintained at above 95%. The Co/SAC-2/U-6 sample
achieved a maximum NOx conversion of 85%, while, it showed a
more dramatic drop of NOx conversion to 60% at the temperature
range of 150250 C. This indicated that the C/SAC-2/U-6 sample
showed a better SCR performance compared with the
Co/SAC-2/U-6.
Thus, different impregnations ratios between urea solution and
the C/SAC-2 sample were applied to examine the promotional
effect of nitrogen content on the NOx conversion efciency. As seen
in Fig. 2(b), all the N-doped SAC samples presented higher catalytic
activity versus the C/SAC-2 sample, and the C/SAC-2/U-6 presented
the highest catalytic performance among these samples. The
C/SAC-2/U-12 showed a highest NOx conversion of 85% at 150 C,
followed by a decrease to 60% at 250 C. The C/SAC-2/U-3 showed
a similar catalytic activity with the C/SAC-2/U-9 at all temperatures, reaching a maximum of 87% at 150 C and decreasing to
70% at 250 C. Hence, the optimum impregnation ratio between
urea and C/SAC-2 is 6:1 in this work, and the results also indicate
the modication with urea impregnation treatment could lead to
an increase of SCR activity and N2 selectivity.
Fig. 2(c) shows the NOx conversion on CAC/U-6 and
C/SAC-2/U-6 during the SCR test and Table 2 demonstrates the
low temperature de-NOx conversion of various catalysts from previous studies. It was observed that the CAC/U-6 showed a lower
NOx conversion. It achieved a maximum NOx conversion of 75%
at 150 C and then decreased to 55% at 250 C. This indicates a
higher catalytic performance of the N-doped SAC samples than that
of the N-doped CAC and other AC-based catalysts in previous studies. Hence, the C/SAC-2/U-6 catalyst has a great potential to be
used as SCR catalyst.

100

NOx conversion (%)

between the Co/SAC-2 catalyst and the CAC is displayed in Fig. A2

(supporting materials). Without any modication, the SAC samples
showed a signicantly higher NOx conversion compared with that
of the CAC.

N2 selectivity (%)

W. Li et al. / Fuel 160 (2015) 3542

NOx conversion (%)

38

Temperature ( C)

(c)
Fig. 2. (a) Effect of nitrogen doping on NOx conversion (solid) and N2 selectivity
(open) of the SAC samples (j) P/SAC -2/U-6; (d) Co/SAC -2/U-6. (b) Effect of doped
nitrogen contents on NOx conversion (solid) and N2 selectivity (open) of the C/SAC2 samples. (j) Without; (d) 3:1; (N) 6:1; (.)9:1; (H)12:1. (c) Comparison of NOx
conversion (solid) and N2 selectivity (open) of CAC/U-6 and C/SAC-2/U-6. (j) CAC/
U-6; (d) Co/SAC-2/U-6.

N2 selectivity was maintained at above 95% for the whole experiments. This indicates that the C/SAC-2/U-6 catalyst has a good
water tolerance and high N2 selectivity.
The impact of SO2 on the SCR activity of the C/SAC-2/U-6 catalyst at 150 C was investigated as shown in Fig. 3(b). NO conversion
over C/SAC-2/U-6 catalyst exhibited almost no decrease after introducing 50 ppm and 100 ppm SO2. When switching off SO2, the NO

39

W. Li et al. / Fuel 160 (2015) 3542

Table 2
De-NOx performance of activated carbon based SCR catalysts at 150 C.
SCR catalyst

Catalyst preparation

Flue gas composition

GHSV (h1)

NOx conversion (%)

Reference

C/SAC-2/U-6

SAC modied with urea

15,000

87

Present study

C90/U/350/Air

Commercial AC modied with urea

8000

80

[17]

ACM-5-900

AC modied with melamine

5000

42

[18]

Co-ACS1.5-Mn/Ce

Cotton stalk based AC modied with Mn/Ce

20,000

25

[19]

FE-400/ONA

PAN-based ACF modied with NH3

3000

47

[5]

SCA750

Coal based AC with H2O activation

500 ppm NO,

500 ppmNH3,
5% O2, N2
800 ppm NO
800 ppm NH3
3% O2, He
500 ppm NO
500 ppm NH3
3% O2, N2
600 ppm NO
500 ppm NH3
5% O2, N2
700 ppm NO
800 ppm NH3
3% O2, N2
1000 ppm NO
1500 ppm NH3
3.5% O2, Ar

2571

40

[20]

the coexistence of 5% H2O and 50 ppm SO2 in a few minutes and it

was then increased to about 80% after 200 min. It was observed
that there was a thin layer (about 3 mm in height) of white crystal
formed on the C/SAC-2/U-6 catalyst after the reaction with the
coexistence of H2O and SO2, while nothing was observed on the
surface of the C/SAC-2/U-6 catalyst after the reaction with the
presence of H2O or SO2. As a result, the coexistence of H2O and
SO2 would result in the formation and deposition of
ammonium-sulfate salts, such as NH4HSO4 and (NH4)2S2O7 on
the catalyst surface, blocking the active sites on the catalyst and
deactivating the catalysts [1922]. The rate of the deactivation is
controlled by the formation and consumption rates of the
ammonium-sulfate salts.

100
90
80

percentage (%)

70

0% H 2O

60

0% H 2O
5% H 2O

50

0% H 2O

0% H 2O

5% H 2O

10% H 2O

40
30
20

NOx conversion
N2 selectivity

10
0

100

200

300

400

500

600

700

800

Time (min)

(a)
100
90
80

0 ppm

percentage (%)

70

SO2

60

50 ppm 100 ppm 0 ppm 300 ppm

SO2

SO2

SO2

SO2

50

50 ppm SO2

40

+5%H 2O

30
20
NOx conversion
N2 selectivity

10
0

200

400

600

800

Time (min)

(b)
Fig. 3. (a) Impact of H2O on the SCR activity of the C/SAC-2/U-6 catalyst at 150 C.
Reaction conditions: 500 ppm NO + 500 ppm NH3 + 5% or 10% H2O (if added) + 5%
O2 + N2 balance, GHSV = 15,000 h1. (j) NOx conversion; (d) N2 selectivity. (b)
Impact of SO2 on the SCR activity of the C/SAC-2/U-6 catalyst at 150 C. Reaction
conditions: 500 ppm NO + 500 ppm NH3 + 0300 ppm SO2 (if added) + 5% H2O (if
added) + 5% O2 + N2 balance. (j) NOx conversion; (d) N2 selectivity.

conversion was still remained at 88%, There was only about 2%

decrease when adding 300 ppm SO2 into the reaction mixture,
indicating that the C/SAC-2/U-6 catalyst has a good SO2 tolerance.
However, the NO conversion displayed a decreasing tendency with

3.1.5. Reaction mechanism of the C/SAC-2/U-6 catalyst

In the SCR reaction, it is generally agreed that NH3 rstly forms
an adsorbed species on the catalysts surface [23]. Two types of
mechanisms have been proposed. EleyRideal (ER) mechanism proposed that the gaseous NO reacts with the adsorbed NH3 specie on
the catalyst surface. LangmuirHinshelwood (LH) mechanism proposed that the adsorbed NO specie and the adsorbed NH3 specie
react with each other on the catalyst surface [24]. In previous
researches, if the SCR reaction over the C/SAC-2/U-6 catalyst
mainly followed the ER mechanism, the ratio of NO conversion
would not decrease if doubling the GHSV; if it mainly followed
the LH mechanism, the ratio of NOx conversion would be halved
after GHSV was doubled [23,25]. In this study, the NOx conversion
obviously decreased. However, the ratio of NO conversion did not
halve, as shown in Fig. 2. Hence, it is assumed that both the ER
mechanism and the LH mechanism contributed to the SCR reaction
over the C/SAC-2/U-6 catalyst.
The transient response experiments were also employed to
study the role of the C/SAC-2/U-6 catalyst in the NH3-SCR reaction.
Fig. 4(b) showed the transient response experiment where NH3
was removed and subsequently added to the reaction mixture for
the C/SAC-2/U-6 catalyst. At the rst steady state, low NO and
NH3 concentration was observed. After the removal of NH3, the
outlet concentration of NO was remained at a low level for several
minutes because the adsorbed NH3 on the catalyst surface could
still react with NO. With the consumption of the adsorbed NH3
on the surface of the C/SAC-2/U-6 catalyst, the outlet concentration
of the NO started increasing and reached to a new steady-state of
about 400 ppm. When reintroducing NH3 into the feed gas, the outlet concentration of NO was dropped quickly to about 20 ppm,
equivalent to the initial outlet concentration of NO. At the same
time, the outlet concentration of the NH3 was very low for about

40

W. Li et al. / Fuel 160 (2015) 3542

3.2. Catalyst characterization

100

3.2.1. BET-analysis
The BET data of the AC prepared in this work were provided in
Table 3. It was observed that the increasing impregnation ratio of
urea/precursor resulted in a considerable decrease of surface area
and total pore volume. This might be resulted from the clogging
of pores and/or their inlets by the impregnated urea [26]. This also
might be due to the presence of numerous functional groups on the
activated carbon surface, partially blocking the access of N2 molecules to the micropores. In addition, both CAC and CAC/U-y have a
much higher surface area and lower pore diameter than the SAC
samples. However, in spite of their lower surface area, all the
SAC/U-y samples showed higher activity toward NO reduction.
This agrees with previous ndings that the catalytic activity is
more dependent on surface chemistry than surface area [2].

NOx conversion (%)

80

60

40
-1

GHSV = 15000 h
-1
GHSV = 30000 h

20

50

100

150
200
o
Temperature ( C)

250

(a)

3.2.2. EA analysis
C/H/O/N elemental analysis of the resulting activated carbons
produced from the sargassum was given in Table 4. The elemental
content of a typical CAC was found to be 87.16 wt% for C, 1.45 wt%
for H, and 0.23 wt% for N. In comparison, the SAC samples were
rich in nitrogen contents that are derived from its precursor. In
addition, it was observed that the nitrogen content of

500
Remove NH 3

add NH 3

Concentration (ppm)

400
NO

300

C/SAC-2/U-6

200

50

100

150

200

250

300

350

400

450

500

Transmittance (%)

1175.6

P/SAC

100

1587.0

3405.9

NH3

550

Time (min)

(b)

Fig. 4. (a) Inuence of GHSV on NOx conversion over the C/SAC-2/U-6 catalyst. (j)
15,000 h-1; (d) 30,000 h1. (b) Transient response experiment where NH3 were
removed and subsequently added to the reaction mixture for the C/SAC-2/U-6
catalyst at 150 C. Reaction conditions: 500 ppm NO + 0 or 500 ppm NH3 + 5%
O2 + N2 balance. (j) NO; (N) NH3.

1569.2

3405.9

1428.9
1142.9

C/SAC-2
1580.7
3405.1

1171.4

Co/SAC-2

1792.8
1580.4

2916.4

1172.7

3405.9

4000

3000

2000

1000
-1

Wave number (cm )

200 min. This indicated that the C/SAC-2/U-6 catalyst was mainly
used as a SCR catalyst, and that NH3 was the dominant reducing
agent.

Fig. 5. FTIR spectra of SAC samples prepared via different techniques and the C/
SAC-2/U-6 sample.

Table 3
BET data for the catalysts prepared in this study.
Sample

Surface area, A/(m2/g)

Total pore volume, v/(cm3/g)

Average pore size, d/(nm)

C/SAC-2
C/SAC-2/U-3
C/SAC-2/U-9
C/SAC-2/U-12
CAC
CAC/U-6

604.0
565.4
346.1
174.1
1337.0
925.7

0.9
0.9
0.6
0.5
0.8
0.5

6.3
6.6
7.1
10.3
2.3
2.2

Table 4
Elemental analysis for the catalysts under study.
Sample

C (%) EA

N (%) EA

H (%) EA

O (%) EA

C1s XPS

O1s XPS

N1s XPS

P2p XPS

Si2p XPS

C/SAC-2
C/SAC-2/U-3
C/SAC-2/U-6
C/SAC-2/U-12
CAC

79.0
65.3
67.3
63.1
87.2

2.4
8.6
15
20.2
0.2

2.4
1.6
1.6
1.5
1.5

16.2
24.4
16.2
15.2
11.2

74.3
81.7
80.8
58.6
89.1

18.7
8.0
9.9
8.1
8.4

10.3
9.3
33.3
2.5

3.5

3.6

41

W. Li et al. / Fuel 160 (2015) 3542

Table 5
Distribution of nitrogen groups of catalysts prepared determined from deconvolution of XPS N 1s spectra.
Catalysts Name

C/SAC-2
C/SAC-2/U-6
Co/SAC-2/U-6

Functional group distribution (%)

N-6 (398.5 ev)

N-5 (400.2 ev)

NAQ (401.9 ev)

NAX (402.4 ev)

ANO2 (405.3 ev)

NCHON (%)

14.4
59.6
53.1

41.2
22.8
26.7

16.1

0.6

5.1
11.2
9.7

23.2
6.4
9.8

2.4
15
5.3

C/SAC-2/U-y samples is proportional to the amount of urea added,

indicating the good distribution and incorporation of urea into the
activated carbon matrix. Moreover, all the C/SAC-2/U-y samples
have massive nitrogen content of above 8%. This explained the
higher catalytic activity, higher selectivity and wider operation
temperature window of all the C/SAC-2/U-y samples during SCR.

3.2.3. IR analysis
The FTIR spectra of SAC samples prepared by different activation methods were given in Fig. 5. The broad band appeared at
3400 cm1 in all spectra was assigned to the OAH stretching vibration of the hydroxyl functional groups or NAH bond. The band
locating at 1800 cm1 in the spectrum of the C/SAC-2 can be
ascribed to the vibration of C@O bond in carboxylic acids, ketones,
aldehydes, lactones, or esters. The peak at around 1600 cm1 in all
spectra is resulted from C@O stretching vibration of carbonyl
groups, or carboncarbon double bonds. The adsorption at around
12001000 cm1 indicates the existence of CAO single bond in carboxylic acids, alcohols, phenols and esters. The peaks at 950
650 cm1 are ascribed to NAH bonding vibration peak outside surface. The new band at 2920 cm1 for the Co/SAC-2 was attributed
to the CAH stretching vibration. A small peak in the spectrum of
the P/SAC was observed at 1428.9 cm1, which was assigned to
CAH group in various C@CAH structures. It was shown that the
spectrum of the Co/SAC-2 has more peaks than those of the
C/SAC-2 and the P/SAC, indicating the existence of more surface
functionalities. From the spectrum of C/SAC-2/U-6, it has similar
peaks as the SAC samples. In addition, the small peak appeared
at 12501340 cm1 is caused by the stretching vibration of CAN
bond [27], indicating the existence of N in the carbon framework
of the C/SAC-2/U-6.

4. Conclusions
All the SAC/U-y samples presented higher catalytic activity than
the virgin SAC samples. NOx conversion was maintained above 75%
and achieved a maximum of 87% at 150 C for the
C/SAC-2/U-6.While the CAC/U-6 sample achieved a maximum
NOx conversion of 75% at 150 C and then decreased to 55% at
250 C. As shown in the XPS analysis, the SAC/U-y with higher
N-6 and N-5 species shows higher NOx conversion, suggesting
the presence of nitrogen groups enhances the oxidation of NO to
NO2. The extra electrons can be transferred to adsorbing species
to form reactive surface intermediates. Additionally, the negative
impact of water is reversible on the SCR activity of the
C/SAC-2/U-6 catalyst and SO2 does not have any obvious effects.
However, the co-existence of H2O and SO2 has a slightly negative
impact on its NOx removal efciency. Also, it is assumed that both
the LH mechanism and the ER mechanism contributed to the SCR
reaction over the C/SAC-2/U-6 catalyst. The transient response
experiment also indicates that NH3 was the main reducing reactant
and the C/SAC-2/U-6 catalyst was mainly used as catalyst for the
SCR reaction, In conclusion, the C/SAC-2/U-6 catalyst prepared
from sargassum had a higher NOx conversion, better N2 selectivity
and it has an excellent water-tolerance and sulfur-tolerance.
Hence, it could be used as a potential alternative SCR catalyst for
the low-temperature SCR catalyst.
Acknowledgments
The work was supported by the Natural Science Fund of
Zhejiang Province, China (LQ14B060006), and the National
Natural Science Foundation of China (21276233 and 21306166).
Appendix A. Supplementary material

3.2.4. XPS-analysis
Signicant amounts of nitrogen were introduced on the surface
of the carbon materials after the treatment with urea. To fully
understand the chemical composition differences between virgin
SAC and NSAC, XPS analysis was carried out on the SAC materials.
For the SAC/U-y samples, the peak appeared at the binding energy
of around 399.5 B.E was assigned to the element of nitrogen, as
shown in Fig. A3 (supporting materials). High-resolution N 1s spectra were obtained in the range of 396408 eV [28]. The deconvolution results (as seen in Table 5) showed that nitrogen atoms were
incorporated into the carbons, mostly in the form of pyridine nitrogen (N-6) and pyrrolic nitrogen (N-5), which were located at the
edges of graphene structures. N-5 increases with formation of
NH groups at the edges of the graphene layers [29]. Pyridine nitrogen is corresponding to basicity of the catalyst surface.
C/SAC-2/U-6, which has the largest N-6 content, is the most basic
sample[30]. The percentage of NAQ and ANO2 shows a signicant
decrease, which is probably related to the transformation of these
groups to N-6 and N-5[24]. Also, N-species are mainly pyridine and
pyrrole in SAC/U-y samples, as shown in the XPS analysis. The presence of nitrogen groups enhances the oxidation of NO to NO2 [30].
These correspond with the higher NOx conversions of SAC/U-y
samples.

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.fuel.2015.07.045.
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