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Article history:
Received 25 May 2013
Received in revised form 21 November 2013
Accepted 29 December 2013
Available online 3 January 2014
Keywords:
Biogas
Hydrogen sulde
Desulfurization
Breakthrough
Adsorption
Sewage sludge
a b s t r a c t
Biogas is a renewable source for power production, but the H2S present must be removed because it is
very corrosive and may damage the combustion engines. The adsorption using activated carbon is one
of the most used desulfurization methods. The operational life of the activated carbon could be extended
if the H2S concentration was reduced prior entering the activated carbon bed by using other cheaper
adsorbent. Sewage sludge is a possible inexpensive precursor to obtain adsorbents, and thus it would
be valorized. An experimental study was performed using three types of sludge from three Spanish locations, which were activated to increase their adsorption capacity. Two thermal treatments were tested
using nitrogen (pyrolysis) and air (calcination), as well as three heating temperatures. The adsorption
dynamics of the prepared adsorbents were investigated in a xed-bed column, determining the breakthrough curves and adsorption capacity of adsorbents. Besides, both their surface properties and their
chemical properties were analyzed to get more insight about the adsorbent behavior. In addition, the
effect of the oxygen content, relative humidity and the chemical impregnation, using different procedures, were also studied. As a relevant result, the adsorbent obtained by calcination at 700 C of one of
the three kinds of sludge showed a capacity twice of that of a commercial activated carbon without
impregnation, although somewhat lower than that of a commercial activated carbon impregnated with
a NaOH solution. The results showed that the use of this kind of precursors is very attractive to achieve
adsorbents with a relative high adsorption capacity valuable to apply them in an economically feasible
pretreatment.
2014 Elsevier B.V. All rights reserved.
1. Introduction
The organic matter that is present in a landll collecting municipal solid waste is degraded in an anaerobic process, which generates a gas mixture called biogas or landll gas. Biogas is obtainable
in a relatively economical way from anaerobic digestion [1]. The
main constituents of biogas are methane and carbon dioxide, but
it also contains nitrogen and oxygen, due to air incursion into the
gas collection system; oxygen concentration is continuously monitored and held low for safety reasons. Due to the high caloric value of methane and its high concentration, biogas is currently
considered a renewable energy source.
When biogas is used as a fuel for electricity generation, several
trace compounds may damage the combustion engines, requiring
expensive repairs and causing service interruptions. Among all of
the specic contaminants to biogas utilization, hydrogen sulde
(H2S) is the most relevant one, because it is highly corrosive during
the combustion process. Because hydrogen sulde concentration is
of up to 10002000 ppm, H2S removal is necessary to avoid
Corresponding author. Tel.: +34 95 448 72 68/60.
E-mail address: frajagutor@etsi.us.es (F.J. Gutirrez Ortiz).
1383-5866/$ - see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.12.025
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F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Table 1
Immediate and elemental analyses of activated carbons and sewage sludge.
Parameter (dry basis) wt%
Sludge LL
Sludge LF
Sludge LG
Carbon
Hydrogen
Nitrogen
Oxygen
Sulfur
Ash
88.12
0.76
0.79
1.37
0.35
Balance
73.32
0.81
0.48
8.10
0.30
Balance
38.49
5.42
6.54
19.42
1.32
Balance
39.12
5.48
5.86
19.77
1.26
Balance
36.90
5.07
4.72
16.38
1.54
Balance
(8.25)
(2.48)
(85.09)
(4.18)
(14.67)
(11.84)
(59.81)
(13.69)
(27.11)
(57.42)
(9.57)
(5.90)
(26.79)
(58.56)
(8.63)
(6.02)
(32.96)
(54.62)
(5.53)
(6.89)
2. Experimental section
2.1. Materials
Two commercial activated carbons, labeled as CAT and CAA,
were used as references to compare the results using the precursor-sludge. CAT is a fresh activated carbon, without impregnation,
while CAA is activated carbon impregnated with a NaOH solution.
Both of them were milled and sieved between 1.41 and 2.83 mm,
as the rest of the materials tested. Likewise, three types of air-dried
sewage-sludge were crushed to pass between 1.41 and 2.83 mm
sieve. They are referred to as LG, LL, and LF, respectively, based
on their Spanish provenance. Table 1 shows the elemental and
immediate analyses of the two activated carbons and the three
types of sewage-sludge, as received, i.e., before undergoing any
treatment.
Experiments were carried out by a certied mixture of CH4
(60 vol.%), H2S (2000 ppmv) and CO2 (balance).
2.2. Methods
Precursors were treated in order to improve their adsorption
capacity by thermal and chemical procedures. Then, they were
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F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
(1) Dry N2 bottle, (2) Pressure reducer, (3) Air feed, (4) Gas rotameters, (5) Tubular furnace, (6) Copper
spiral, (7) Ball valve, (8) Safety valve, (9) Bubblers, (10) Cooling water feed, (11) Drain
Fig. 1. Facility scheme for thermally treating the precursors in a controlled atmosphere.
ID Fan
To the Atmosphere
Rotameter
FI-2
Adsorption
tower
E-1
E-3
S.A1
Conditioning
system
Al-3
H2S Analyzer
U-tube
I-1
Pressure reducer
V-1
FI-1
Rotameter
E-2
Condensate
container
Biogas bottle
Composition
CH4 (60 vol%)
H2S (2000 ppm)
CO2 (balance)
Fig. 2. Scheme of the laboratory plant for performing the adsorption tests.
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Z ts
x
Q MW
c0 t s
ctdt
M
w VM
0
where Q is the total inlet ow rate (m3/s), w is the weight of sludgebased material introduced into the column (g), MW is the molecular
weight of H2S (34 g/mol), VM is the molar volume (22.4 L/mol), c0 is
the inlet gas H2S concentration (ppmv), c(t) is the gas outlet concentration (ppmv), and ts is the bed saturation/exhaustion time (s). The
test was stopped at the breakthrough concentration of 200 ppm;
thus, ts is the time corresponding to this concentration.
Experimental tests were validated by performing, at least, three
replicates, verifying thus the reproducibility and the feasibility of
the tests.
2.2.3. Preparation of impregnated precursors
With the aim of improving the activated carbons performance,
these may be impregnated with caustic materials such as NaOH
or KOH. Unlike activated carbons, sewage-sludge (either thermally
treated or not treated) cannot be immersed in stirred caustic solutions because they disaggregate and partially dissolve. Then,
impregnation procedures were performed by other two ways: (1)
milling the NaOH or KOH lentils and mixing with the sludge-based
material, and (2) atomizing a concentrated aqueous solution of
NaOH or KOH on the precursor. In this latter case, due to the addition of water, the precursors were partially dissolved forming an
unwieldy paste that led to a poor result after calcination. The
agents were added using an agent-to-precursor mass ratio ranged
from 0.10 to 0.40.
2.2.4. Characterization of sludge
Surface properties and chemical properties of the precursors
were determined to get more insight about the adsorbent behavior.
The surface properties of adsorbents that affect the adsorption
capacity are mainly surface area, pore volume, and pore size distribution [8].
The BET surface area as well as the micropores and mesopores
areas and volumes were obtained by means of the Micromeritics
ASAP 2420 System, which based on physisorption determination
that uses nitrogen as adsorptive. The IUPAC nomenclature was followed: micropores correspond to pore size lower than 2 nm and
mesopores ranges from 2 to 50 nm. The BET surface area and the
micropores volume were computed using the Harkins and Jura
Thickness equation, and the mesopores and macropores volume
were calculated using the t-method by BarrerJoynerHalenda. Before each test, samples were degasied at 150 C for ten hours.
Regarding the chemical analyses, direct analyses of major elements (C, H, N, S, and O) of the dry sludge and thermally treated
precursors (both before and after carrying out the H2S adsorption
test) were performed using LECO Instruments (CHNS-932). Trace
metals were determined by means of inductively coupled plasma
atomic (optical) emission spectroscopy (Horiba Jobin Yvon Ultima
2 High resolution ICPOES spectrometer).
In order to obtain structural information on an atomic scale of
both crystalline and non-crystalline (amorphous) materials, X-ray
Diffraction (XRD) analyses were carried out by a Bruker D8 Advance A25, equipped with an X-ray tube of 40 kV and 30 mA,
D2h of 370, step scanning with a step size of 0.015 (2h) and a
scan step time of 0.1 s.
X-ray Photoelectron Spectroscopy (XPS) was used (Leybold
Heraeus LHS-10/20) to discriminate on the different oxidation
states.
Scanning Electronic Microscopy (SEM) observations were carried out with a Philips XL30 microscope with secondary and backscattered electron imaging, equipped with an integrated Energy
Dispersive X-ray Spectrometer to analyze the elements and their
contents.
203
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F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Table 2
Trace metal composition of precursors and adsorbents obtained.
Precursors
Si (mg/g)
Al (mg/g)
Fe (mg/g)
Ca (mg/g)
Mg (mg/g)
Na (mg/g)
K (mg/g)
P (mg/g)
S (mg/g)
Cu (mg/g)
Zn (mg/g)
LL
LG
LF
LG500A
LG500PA
LG700A
LG700PA
LG900A
LG900PA
LL500PA
LL700A
LL700PA
LL900PA
91.77
126.11
163.48
112.47
100.32
140.21
266.66
109.53
103.80
111.38
112.15
102.40
147.23
17.67
19.15
17.35
39.79
38.39
44.89
49.93
50.30
48.17
39.74
42.72
43.07
48.93
30.43
31.14
16.19
49.57
46.80
64.61
66.62
67.46
66.59
24.38
28.43
28.18
29.42
36.32
43.43
35.21
57.78
54.04
105.56
108.51
83.76
88.34
40.51
41.67
44.49
24.34
11.07
9.21
10.92
18.52
17.78
22.44
18.22
23.46
21.68
11.30
11.96
12.84
14.23
1.63
1.61
1.53
4.76
4.55
4.88
4.05
5.48
5.60
1.77
2.56
3.08
3.05
3.21
3.69
3.26
10.06
9.72
12.04
10.73
13.27
12.58
9.07
9.79
10.13
11.66
18.11
16.48
18.12
33.43
32.32
41.68
39.96
42.02
40.17
43.51
46.63
47.53
55.33
9.05
11.25
8.64
9.09
7.45
12.13
13.08
14.36
12.66
4.11
3.88
4.36
4.64
0.36
0.18
0.44
0.25
0.24
0.33
0.33
0.34
0.32
0.44
0.49
0.49
0.57
0.56
0.38
0.52
1.08
1.07
1.12
1.09
1.02
0.61
2.05
2.23
2.28
1.80
PA denotes a thermal treatment in which a pyrolysis is carried out from room temperature up to 500 C, and then a calcination takes place from 500 C until reaching the
nal temperature (500, 700 or 900 C).
A denotes that the calcination was performed entering air from room temperature up to the nal temperature.
Table 3
Weight loss of adsorbents after being thermally treated and adsorption capacity.
Precursor
Adsorption capacity
(mg H2S/g ads.) limit: 200 ppm
LF 500 PA
LF 700 PA
LF 900 PA
LL 500 PA
LL 700 PA
LL 900 PA
LF 500 A
LF 700 A
LF 900 A
LL 500 A
LL 700 A
LL 900 A
LG 500 PA
LG 700 PA
LG 900 PA
LG 500 A
LG 700 A
LG 900 A
53.79
58.46
62.16
52.59
57.40
61.95
53.21
58.29
61.88
52.73
57.49
61.31
51.80
56.78
61.60
51.00
56.85
61.05
2.23
2.12
4.37
3.42
4.71
3.80
1.41
2.19
3.68
3.37
4.93
3.72
5.15
8.63
2.89
3.65
6.64
2.67
Note 1: The precursor amount entered the electrical furnace was 100 g.
Note 2: The adsorption capacity of CAT and CAA was 4.42 and 12.75 mg/g, respectively.
Fig. 3. Breakthrough curves for the activated carbons used as reference framework.
treatment A for the precursor LG, while there are no signicant differences between both treatments for the precursor LL. Precursors
LF and LL have a similar behavior, although the former has lower
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
205
(a)
(b)
(c)
Fig. 4. Breakthrough curves for the precursors thermally treated at three temperatures in the absence of humidity and oxygen: precursor (a) LF, (b) LL, and (c) LG.
206
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Table 4
BET surface area and pore structure for some samples of the treated precursor LG.
LG 500 A
LG 500 PA
LG 700 A
LG 700 PA
LG 900 A
LG 900 PA
49.246
14.209
35.037
0.037
1.464E02
2.241E02
3.65
72.822
21.845
50.977
0.049
2.100E02
2.800E02
5.15
82.150
28.617
53.533
0.060
2.186E02
3.772E02
6.64
89.937
29.031
60.906
0.062
2.500E02
3.700E02
8.63
100.353
61.165
39.188
0.113
2.005E02
9.293E02
2.67
118.096
69.626
48.470
0.101
2.100E02
8.000E02
2.78
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F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Table 5
BET surface area and pore structure for some samples of the treated precursors LL and LF.
LL 700 PA
LL 900 PA
LF 900 PA
13.363
5.066
8.297
0.015
0.003
0.011
3.42
94.384
16.857
77.527
0.051
0.031
0.020
4.93
79.870
15.089
64.779
0.044
0.026
0.018
4.71
122.040
56.200
65.840
0.093
0.027
0.066
4.19
126.090
67.900
58.190
0.094
0.024
0.069
4.12
(b)
3000
(a)
2000
Counts
1000
300
600
Counts
LL 700 A
3000
LL 500 PA
10
20
30
40
50
10
60
20
30
40
50
60
3000
2000
1000
Counts
300
600
Counts
3000
10
20
30
40
50
60
10
20
Counts
30
40
50
60
(c)
300
600
10
20
30
40
50
60
Counts
300
600
10
20
30
40
50
60
and 900 C a crystalline phase of phosphate with calcium and aluminum was measured (Ca9Al(PO4)7).
Fig. 7 shows the SEM images at a magnication so as to get
micrographs with a scale of 2000, 500, 50 and 20 lm for precursors
coded as LG 700 PAG and LL 700 PAG after the adsorption of hydrogen sulde. The nal G denotes that the sample corresponds to a
spent adsorbent. The images magnied at 2000 lm depict a more
irregular shape of LG precursor particles, with many grooves, while
208
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
Fig. 7. SEM micrographs of the adsorbents for LG and LL at 700 C and treatment PA, once used for H2S adsorption.
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
209
Fig. 8. EDS analysis of the adsorbents for LG and LL at 700 C and treatment PA, once used for H2S adsorption.
LG 700PAG and LG 500 PAG, the rst peak was observed at a binding energy of 169.7 eV and 169.6 eV, respectively. This veries the
sulfate existence, which could be iron sulfate as iron was detected
in the general spectrum. The second peak occurs at a binding energy of 164.2 eV, which corresponds to elemental sulfur. This peak
was not obtained for the LG 500 PAG sample.
3.4. Possible reactions involved in the adsorption process
If iron oxide is present, the following reactions may take place
[16]:
Fe3+ complex ions would shift reaction (4) to the right side [17].
Furthermore, the phosphoric acid is a well-known chelating agent,
with a complexing action. Taking into account the relative high proportion of phosphorous in the tested samples, phosphoric acid may
be probably formed during the adsorption process.
Additionally, other metals such as copper and zinc can act as
catalyst in a second stage, once sulfate is formed, based on the following reactions:
Me2 H2 S 2SO2
4 ! MeSs 2HSO4
2Fe3 H2 S 2Fe2 S0 2H
210
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
40k
169.6
LG 500 PA
Intensity CPS
1350
35k
Mg(1s)
30k
1250
1200
C(AES)
Intensity CPS
1300
25k
Ca(AES)
SULFUR
SPECTRUM
1150
O(AES)
180
178
176
174
172
170
168
166
164
P(2s)
S(2p)
162
O(1s)
20k
Si(2s)
N(AES)
Mg(AES)
Fe(AES)
P(2p)
Al(2s)
N(1s)
15k
Si(2p)
Fe(2p)
Ca(2s)
Ca(2p)
Mg(2s)
Al(2p)
10k
C(1s)
5k
O(2s)
0k
200
400
600
800
1000
1200
1400
Kinetic Energy eV
Mg(1s)
60k
169.7
1300
SULFUR
SPECTRUM
1250
Intensity CPS
LG 700 PA
50k
164.2
1200
1150
1100
Intensity CPS
40k
1050
180
178
176
174
172
170
168
166
164
162
P(2s)
S(2p)
C(AES)
30k
Si(2s)
Ca(AES)
P(2p)
O(AES)
Fe(AES)
N(AES)
Mg(AES)
O(1s)
Al(2s)
Si(2p)
N(1s)
20k
C(1s)
Fe(2p)
Ca(2s)
Mg(2s)
Ca(2p)
Al(2p)
10k
O(2s)
0
200
400
600
800
1000
1200
1400
Kinetic Energy eV
Fig. 9. XPS analysis (general spectrum with embedded sulfur spectrum) of the precursor LG heated at 500 and 700 C, following the treatment PA.
clear improvement. Fig. 10 shows the breakthrough curves obtained using saturated biogas. Results obtained by pre-humidifying
the adsorbent bed were similar, so they are not shown. No clear effect of the experimental conditions was noticed and the adsorption
capacities measured using dry and saturated biogas were almost
the same. A slightly better performance of the precursor in dry conditions may suggest that water contributes to deactivation of surface-active centers in the H2S retention, counteracting a clearer
positive effect. Probably, it is because the inorganic phase of the
sewage-sludge contains alkaline earth oxides that are nonreactive
with water, as pointed out by other researchers [20]. In addition,
water in the gas mixture hinders the adsorption capacity because
it plugs the pore structure. In any case, this nding agrees with a
result encountered in a previous study [12]; some other researchers found a positive effect (the breakthrough time increases as the
humidity increases), although in studies carried out using a mixture of air and H2S instead of a simulated or real biogas [9]. Finally,
the water present in the biogas is adsorbed on the adsorbent particles, providing a liquid phase where CO2 may be dissolved, forming carbonates and contributing to the formation of sulfurous acid,
which deactivates the basic catalytic sites, resulting in a lower
capacity.
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
211
(a)
(b)
(c)
Fig. 10. Breakthrough curves for the precursors thermally treated at three temperatures in the absence of oxygen: precursor (a) LF, (b) LL, and (c) LG.
The use of air may have an important effect due to the oxygen
content, as next described.
3.6. Inuence of the oxygen presence
To test the effect of the oxygen on the H2S removal, oxygen was
added to the dry biogas stream before entering the xed bed. For
212
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
H2 S OH ! H2 O HS
10
F.J. Gutirrez Ortiz et al. / Separation and Purication Technology 123 (2014) 200213
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adsorbents obtained by pyrolysis of sewage sludge-derived fertilizer, Carbon
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[13] T.J. Bandosz, K. Block, Effect of pyrolysis temperature and time on catalytic
performance of sewage sludge/industrial sludge-based composite adsorbents,
Appl. Catal. B Environ. 67 (2006) 7785.
[14] O.C. Cariaso, P.L. Walker, Oxidation of hydrogen sulde over microporous
carbons, Carbon 13 (1975) 233239.
[15] A. Bagreev, T.J. Bandosz, On the mechanism of hydrogen sulphide adsorption/
oxidation on catalytic carbons, Ind. Eng. Chem. Res. 44 (2005) 530538.
[16] A. Kohl, R. Neilsen, Gas Purication, fth ed., Gulf Professional Publ., Houston,
1997.
[17] M.S. Horikawa, F. Rossi, M.L. Gimenes, C.M.M. Costa, M.G.C. Silva, Chemical
absorption of H2S for biogas purication, Braz. J. Chem. Eng. 21 (2004) 415
422.
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