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a,*
Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical and Pharmaceutical Engineering,
Wuhan Institute of Technology, Wuhan 430073, PR China
b
School of Physical Science, Wuhan Institute of Technology, Wuhan 430073, PR China
c
School of Mechanical and Aerospace Engineering, Nanyang Technological University, Singapore 639798, Singapore
Received 17 January 2006; accepted 14 September 2006
Available online 28 November 2006
Abstract
Adsorption of hydrogen sulphide (H2S) onto activated carbons derived from oil palm shell, an abundant solid waste from palm oil
processing mills, by thermal or chemical activation method was investigated in this paper. Dynamic adsorption in a xed bed conguration showed that the palm-shell activated carbons prepared by chemical activation (KOH or H2SO4 impregnation) performed better
than the palm-shell activated carbon by thermal activation and a coconut-shell-based commercial activated carbon. Static equilibrium
adsorption studies conrmed this experimental result. An intra-particle Knudsen diusion model based on a Freundlich isotherm was
developed for predicting the amount of H2S adsorbed. Desorption tests at the same temperature as adsorption (298 K) and at an elevated
temperature (473 K) were carried out to conrm the occurrence of chemisorption and oxidation of H2S on the activated carbon. Surface
chemistries of the palm-shell activated carbons were characterized by Fourier transform infrared spectroscopy and Boehm titration. It
was found that uptaking H2S onto the palm-shell activated carbons was due to dierent mechanisms, e.g. physisorption, chemisorption
and/or H2S oxidation, depending on the activation agent and activation method.
2006 Elsevier Ltd. All rights reserved.
1. Introduction
Hydrogen sulphide (H2S), a rotten-egg smell gas produced by anaerobic digestion in acid condition from
organic and inorganic compounds containing sulphur, presents dual problems of its toxicity and foul odour. H2S can
be detected by most people as low as 0.0047 ppm [1].
Although no signicant physical harm may be caused in
such a low concentration, the exposure to this nuisance
can lead to nausea, loss of appetite, and other negative
eects. From the point of view of engineering design of a
purication system, the odour threshold of H2S is
0008-6223/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2006.09.016
331
Nomenclature
C
Dk
F
L
LMTZ
m
Ms
M1
r
R
Greek letters
e
total porosity of the adsorbent (%)
s
time elapsed (s)
2. Experimental
2.1. Adsorbent preparation
Palm shells from a palm-oil mill in Selangor, Malaysia were dried,
crushed and sieved to a particle size fraction of 1.02.0 mm. 10 g of this
processed starting material was impregnated with 200 ml of H2SO4
(40%) or KOH (30%) at room temperature (298 K) for 24 hours and then
dried at 383 K overnight. The mixture was activated in a stainless-steel
reactor (550 mm length and 38 mm i.d.) under a stream of nitrogen (N2)
gas owing at 150 cm3/min. The reactor was heated in a vertical tube furnace (818 P, Lenton) from room temperature to a pre-set temperature
(973 K) for 2 h. After cooling to room temperature, the resulting products
were taken out and leached with distilled water. In another comparative
study, the preparation of activated carbons by thermal activation with carbon dioxide (CO2) gas (100 cm3/min) at 1173 K for 2 h was carried out. A
coconut-shell-based commercial activated carbon by steam (H2O) activa-
s0.05
s0.95
Subscripts
e
eective value of corresponding diusivity
i
serial number
0
initial state
tion (CAC, Damao Chemicals and Chemical Apparatus, Tanjin) was also
used for testing. The physical properties of the palm-shell and coconutshell activated carbons are given in Table 1.
2.2. Characterizations
Proximate analysis and ultimate analysis were carried out by a thermogravimetric analyzer (TGA-50, Shimadzu) and an elemental analyzer
(CHN-932, LECO) respectively. Textural characteristics of samples were
determined by N2 adsorption at 77 K with an accelerated surface area
and porosimeter (ASAP-2000, Micromeritics). The specic surface area
was calculated from the isotherms by the Brunauer-Emmett-Teller
(BET) equation [10]. The DubininRadushkevich (DR) equation was used
to calculate the micropore volume from the N2 adsorption data [11].
332
Table 1
Physical properties of the coconut shell and palm shell activated carbons
Sample
Nitrogen adsorption
Porosity (%)
BET surface area (m2/g)
Micropore volume (cm3/g)
Proximate analysis (wt.%)
Volatile matter
Fixed carbon
Ash
Ultimate analysis (wt.%)
Carbon
Hydrogen
Nitrogen
Oxygen (by dierence)
58.4
1062
0.26
67.4
1183
0.35
56.3
1148
0.25
59.5
1014
0.28
6.4
86.1
7.5
4.5
91.9
3.6
10.6
83.0
6.4
14.2
82.0
3.8
87.1
1.0
1.1
10.8
87.5
0.9
2.0
9.6
84.1
0.8
0.6
14.5
83.3
0.4
0.2
16.1
the runs were carried out at the laboratory temperature of 298 K and an
ambient pressure of 1.0 bar. The time-dependent concentration at the
exit of the column was continually monitored by a ame photometric
detector (FPD, Fisher-Rosemount). The column was operated until saturation, that is, when the outlet concentration became equal to that of the
inlet.
Static adsorption of H2S was also carried out in the TGA. H2S
(1000 ppm, balanced by He) was introduced into the analyzer chamber,
where a platinum pan with about 20 mg of adsorbent was suspended.
At room temperature of 298 K, the subsequent sample weight gain due
to the amount of gas adsorbed onto the adsorbent was recorded. After
adsorption, desorption tests using He gas ushing through the analyzer
chamber at the same temperature of adsorption and a higher temperature
of 473 K were carried out to verify the occurrence of chemisorption and/or
oxidation of H2S.
1.0
0.8
LMTZ
Ls0:95 s0:05
s0:95 s0:05 =2
0.6
0.4
0.2
0.0
200
240
280
320
360
400
Time (min)
Fig. 1. Breakthrough curves for activated carbons prepared from coconut
shell by steam activation and palm shell by dierent activation methods.
1. The activated carbon particles are perfect spheres; diusion taking place along the radial direction (r) on the
adsorption sites that are uniformly distributed within
the particles.
2. External mass convective ux is negligible in comparison to transport by Knudsen diusion. Therefore, the
external adsorbate concentration can be considered to
be uniform (C0).
3. The adsorbent is isothermal (temperature constant) during the adsorption process.
4. Adsorption at the pore mouth follows a Freundlich
equilibrium isotherm.
5. The porosity e and the tortuosity factor n of the particle
are regarded as constant during the adsorption process.
6. No chemical reactions occur at the adsorbent surface.
333
Table 2
Breakthrough-curve characteristic parameters for the coconut shell and palm shell activated carbons
Activated carbon
Exhaustion time
s0.95(min)
Adsorption capacity
(mg/g)
245.6
270.7
316.1
359.4
5.0
5.6
46
53
291.5
304.3
323.8
334.0
2.1
1.9
68
76
at s 0
3a
120
80
Model prediction
Coconut shell: H2O activation
40
10
20
30
40
50
60
Time (min)
3b
3c
C 1m 2
os 1 eFm
or
160
200
eDke
C 1m can be regarded as a concentraThe coecient 1e
Fm
tion-dependent diusion coecient, which links the degree
of asymmetry in the rates of adsorption to the Freundlich
isotherm constant m.
The mass of the adsorbate that has entered the particle,
Ms, can be found by integrating the adsorbate adsorbed
over the entire adsorbent particle, i.e.
Z R
M s 3M 1
r2 C m r; sdr
6
0
334
200
10
20
30
40
50
60
Time (min)
Fig. 3. Experimental results and model predictions of amount H2S
adsorbed on palm shell activated carbons prepared by chemical activation.
4000
3400
2800
2200
659
754
1251
1204
1507
1502
1504
CO2 activation
2439
1723
50
1627
Model prediction
1613
100
H2SO4 activation
3415
150
1745
KOH activation
250
1600
1000
400
These surface functional groups account for the chemisorption of H2S gas.
The spectra of the activated carbon prepared by 40%
H2SO4 impregnation in Fig. 4 displayed the following
bands: 3415 cm1: HO stretching in hydroxyl groups;
1723 cm1: C@O stretching in carboxylic acids or isolated
carbonyl groups; 1627 cm1: C@O stretching in quinones
or carboxylic anhydrides; 1502 cm1: C@C stretching in
aromatic rings, and 1204 cm1: COC stretching in ethers
or ether bridges between rings.
The oxygen functional groups are likely to be phenols,
carboxylic acids (or carboxylic anhydrides if they are close
together) and carbonyl groups (either isolated or arranged
in quinone-like fashion), all of which are typical acidic functional groups [19]. The surface structure of the H2SO4impregnated palm-shell activated carbons is given below.
O O
O
O
O
C
H
HO
H
R
O
C
O
C
HO
O
O
O
O
Table 3
Desorption properties of the coconut shell and palm shell activated carbons
Activated carbon
Total amount
adsorbed (mg/g)
Percentage of
desorption at 298 K (%)
Percentage of
desorption at 473 K (%)
Percentage of
residue (%)
131
100
162
100
169
79
21
203
83
10
335
For the activated carbon prepared by CO2 thermal activation, the band at 2439 cm1 is attributed to CH stretching vibrations in aliphatic structures, in addition to phenols
and the aromatic rings. In this case, the surface structure of
the thermally activated carbon is given below:
H
H
HO
Hydrogen atoms in H2S could strongly interact with oxygen in form of hydroxyl (HO) and carbonyl (C@O)
groups due to the high electrostatic attraction. H2S can
therefore preferably adsorb onto active adsorption sites
provided by oxygen functional groups via hydrogen bonds
besides on pure carbon sites. Other researchers also conrmed the formation of hydrogen bonds during chemisorption [2022]. In addition, due to the oxygen functional
groups, H2S was easily oxidised as follows:
Cn Hx Oy3 H2 S ! Cn Hx Oy2 Selement H2 O
Table 4
Number of surface groups (meq/g) obtained from Boehm titration
Activated carbon
Carboxyl
Lactone
Phenol
Carbonyl
0.089
0.355
0.416
0.120
0.208
0.285
1.167
0.604
Fig. 5. XPS spectra of the activated carbon surfaces before and after H2S
adsorption processes.
4. Conclusions
From the adsorption of H2S onto the activated carbons
prepared from oil-palm shells with and without preimpregnation, the following conclusions can be drawn:
(1) Compared to the palm-shell activated carbon by thermal activation and coconut-shell activated carbon, the
activated carbons prepared by KOH and H2SO4 activation had better dynamic adsorption performances
due to longer breakthrough times, prolonged exhaustion times, and relatively short MTZs. Therefore, the
corresponding adsorption capacities were also larger.
(2) The Freundlich constants were obtained from experimental data under dierent adsorption temperatures
by curve tting. In this study, the Freundlich constants F of 1.19 103 and m of 0.84 were used. It
could be seen that the predicted result by diusion
model based on Freundlich isotherm agreed with
the experimental data very well.
(3) For both KOH and H2SO4 used as activation agent,
the diusion model based on Freundlich isotherm
always under-estimated the amount of H2S adsorbed.
The possible reason was that this model did not take
into account chemical reactions (e.g. chemisorption
or H2S oxidation), which are related to the samples
surface chemistry.
(4) The main surface functional groups present on the
KOH-impregnated adsorbent are presumed to be
alkaline groups of pyrones (cyclic ketone) and other
keto-derivatives of pyran. The oxygen functional
groups on the H2SO4-impregnated sample are likely
to be phenols, carboxylic acids (or carboxylic anhydrides if they are close together) and carbonyl groups
(either isolated or arranged in quinone-like fashion),
all of which are typical acidic functional groups.
336