Chemical Engineering Journal 287 (2016) 47–53

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Chemical Engineering Journal

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Adsorption of hydrogen sulfide (H2S) on zeolite (Z): Retention

mechanism
Léa Sigot, Gaëlle Ducom ⇑, Patrick Germain
Université de Lyon, INSA-Lyon, LGCIE-DEEP, EA4126, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Physicochemical characterization of Z
was performed before and after H2S
adsorption.

Water is present in Z pores and pH
promotes H2S dissociation in HS.

After H2S adsorption, the adsorbate
degraded between 300 and 630 °C in
inert atmosphere.

After H2S adsorption, the adsorbate
could oxidize around 355 °C in air
atmosphere.

An adsorption–dissociation–
oxidation mechanism led to the
formation of elemental sulfur.

a r t i c l e i n f o a b s t r a c t

Article history: Zeolites are efficient adsorbents for the removal of hydrogen sulfide (H2S) – a trace compound commonly
Received 30 August 2015 found in biogas. The assessment of zeolite regeneration potential is an important point to consider before
Received in revised form 2 November 2015 using them in adsorption processes for biogas treatment. In this study, it was first shown that after
Accepted 3 November 2015
adsorption of H2S, by heating a 13X zeolite at 350 °C, the desorbed quantities of sulfur compounds were
Available online 10 November 2015
very low. Afterwards, the objective was to understand H2S removal mechanism. Complementary physic-
ochemical characterizations of the studied zeolite before and after H2S adsorption were performed: speci-
Keywords:
fic surface area, porosity, pH, infrared spectroscopy, thermogravimetry and differential scanning
Zeolite
Hydrogen sulfide
calorimetry. The speciation of sulfur in the studied zeolite after H2S adsorption was investigated and a
Biogas retention mechanism was proposed. It was demonstrated that H2S was converted in elemental sulfur
Physicochemical characterization in the zeolite. This mechanism involves H2S adsorption at the zeolite surface, dissolution and dissociation
Adsorption–dissociation–oxidation of H2S in pore water, and oxidation to form elemental sulfur that can polymerize. The major formation of
mechanism elemental sulfur limits the thermal regeneration of the studied zeolite and other regeneration methods
should be considered.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction sulfide (H2S). Biogas desulfurization is commonly achieved by

Biogas is a promising source of energy. However, its use in
energy conversion devices is hampered by the presence of trace
compounds such as sulfur compounds and particularly hydrogen
⇑ Corresponding author.
E-mail address: gaelle.ducom@insa-lyon.fr (G. Ducom).
physical, chemical or biological treatments. Nevertheless, adsorp-
tion is required when a thorough removal of H2S is necessary, for
instance for fueling a fuel cell [1–6]. In a previous study [7], three
adsorbents were compared at lab-scale for the removal of H2S in a
synthetic gas: an activated carbon, a silica gel and a zeolite (Z). Z
proved to be the most efficient adsorbent for H2S removal, with
an adsorption capacity higher than 180 mgH2S/gZ.

http://dx.doi.org/10.1016/j.cej.2015.11.010
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
48 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53
From an industrial point of view, the regenerability of the cho-
sen adsorbent is a relevant issue in order to reduce the operating
costs. Moreover, it is a key concern for waste minimization as
adsorbents are generally disposed of after use. But incomplete
regeneration was reported after H2S adsorption on activated car-
bons and an iron-based adsorbent [3,4,8,9]. So, in this paper, Z
regenerability after H2S adsorption is investigated. The objective
is to identify the speciation of sulfur in Z and the associated H2S
removal mechanism.
The removal mechanisms of H2S have already been studied in
activated carbons (impregnated or unimpregnated). In the pres-
ence of oxygen, several authors revealed an oxidative mechanism
for H2S removal by activated carbons, leading to the formation of
elemental sulfur and water. As a function of pH and temperature,
H2S can also be oxidized to sulfur oxides or sulfuric acid [9–17].
But the retention mechanism of H2S in zeolites has not been widely
studied. Some authors suggested the formation of elemental sulfur
[10,18], but Micoli et al. proposed an acid-base reaction [5].
In this study, thermal desorption of H2S was first studied. Then,
to understand H2S removal mechanism, complementary physico-
chemical characterizations of Z solid matrix before and after H2S
adsorption were performed in order to compare the different
results and converge to a conclusion. A similar methodology was
used previously to understand the interactions between
octamethylcyclotetrasiloxane and a silica gel [19].
2. Material and methods
2.1. Materials: Z and H2S
Zeolites are crystalline and porous aluminosilicates made up of
a regular 3D framework resulting from the arrangement of SiO4
and AlO4 tetrahedrons [20,21]. A 13X zeolite (1.6–2.5 mm beads
SiliporiteÒ G5 from CECA) used previously in adsorption lab-tests
showed a very good H2S removal efficiency. These dynamic adsorp-
tion tests were described elsewhere [7]. They were performed with
a synthetic polluted gas containing 80 ppmv H2S. The diluent gas
was dry N2 containing 1% O2 due to incomplete air separation
in the N2 generator. N2 was used instead of methane (CH4) and car-
bon dioxide (CO2) which are the main components of biogas.
In this study, the zeolite was characterized before and after H2S
adsorption. In the following, the notation ‘‘Z” refers to zeolite
before adsorption (fresh Z) and the notation ‘‘Z+H2S” refers to zeo-
lite after H2S adsorption (spent Z).
For practical reasons, the characterizations were performed on
several polluted samples with different H2S uptakes. The average
quantity of H2S adsorbed by each sample (Z+H2S_1 to Z+H2S_3) is
given in Table 1 in mgH2S/gZ and in mgS/gZ+H2S (if expressed as total
adsorbed sulfur relatively to the mass of adsorbent after adsorption).
These quantities were determined by gas chromatography (GC)
analyses of the gas entering and leaving the adsorption column.
2.2. Thermodesorption
To assess the thermal regeneration potential of the zeolite, des-
orption tests in inert (He) and oxidant (air) flow were conducted at
Table 1
Average H2S quantity adsorbed in the different Z+H2S samples.
Sample H2S adsorbed quantity
(mgH2S/gZ) mgS/gZ+H2S
Z+H2S_1 133 110
Z+H2S_2 195 153
Z+H2S_3 252 189
350 °C for 30 min after H2S adsorption (Z+H2S) with samples of
600–910 mg (flow rate: 27–30 mL min1). The desorbed gas was
collected in a sampling bag. Sulfur compounds were immediately
quantified by micro GC coupled with mass spectrometry
(lGC-MS).
2.3. Elemental analysis
A sample of ground Z (<80 lm) was analyzed by ICP-OES
(inductively coupled plasma – optical emission spectrometry) after
alkaline fusion and acidic dissolution to determine its elemental
content. Major elements were quantified: silicon (Si), aluminum
(Al), iron (Fe), manganese (Mn), magnesium (Mg), calcium (Ca),
sodium (Na), potassium (K), titanium (Ti) and phosphorus (P).
2.4. Total sulfur content
The total sulfur content was measured for Z and Z+H2S ground
samples (<80 lm) using a carbon-sulfur analyzer. The measure-
ment principle is based on the total combustion of the sample in
oxygen flow in an induction furnace, followed by infrared analysis
of the formed SO2.
2.5. pH of the adsorbent leachate
The pH of Z and Z+H2S leachates was determined according to
the EN 12457-2 standard for leaching tests of granular waste mate-
rial [22]. A liquid to solid ratio of 10 L/kg was used. A volume of
200 mL of demineralized water was added to a sample of 20 g of
adsorbent and the mixture was stirred for 24 h to reach equilib-
rium. The suspension was then filtered (<0.45 lm) under vacuum
and the pH of the filtrate was measured.
2.6. Total soluble sulfur and sulfate ions in leachate
The total soluble sulfur content of the leachates obtained
according to the procedure described in Section 2.5 was measured
by ICP-OES following the NF EN ISO 11885 [23]. The total sulfur in
solution includes all soluble sulfur ions such as sulfates, thiosul-
fates and some sulfides, for the most common [24]. The spectral
band at 181.978 nm was used for the quantification. Measure-
ments were performed for Z and Z+H2S leachates.
These leachates were also analyzed by ion chromatography.
Sulfates (SO2
4 ) were quantified according to the NF EN ISO
10304-2 [25].
2.7. Specific surface area and porosity
Surface area, micropore volume and pore size measurements
were performed by nitrogen adsorption (at 77 K) in an ASAP
2010 (Micromeritics) instrument. Samples were first outgassed
under vacuum at 300 °C. Specific surface area and porosity were
determined before and after H2S adsorption (Z and Z+H2S). The
micro- and mesopore size distribution was determined by the den-
sity functional theory (DFT).
2.8. Fourier transform infrared spectroscopy (FTIR)
Z and Z+H2S ground samples (<1 mm) were analyzed by FTIR in
attenuated total reflectance (ATR) mode. FTIR analyses enable the
characterization of the chemical bonds present in the material
thanks to the measurement of their typical vibration frequency.
Absorbance spectra were acquired between 500 and 4000 cm1
with a resolution of 4 cm1. OMNIC software (Nicolet instrument)
was used for data acquisition and post-treatment. A qualitative and
comparative approach was favored.
 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53 49

2.9. Thermogravimetry and differential scanning calorimetry (TG-DSC) Sulfite

Tetrathionate SO32-
S4O62-
Using a Labsys 1600 Setaram thermal analyzer, thermogravime- Elemental Sulfur
try (TG) and differential scanning calorimetry (DSC) were per- Sulfide sulfur Thiosulfate dioxide Sulfate
S2- S0 S2O32- SO2 SO42- Sulfur oxidaon
formed in replicates on Z and Z+H2S samples in either nitrogen
-II 0 +II +IV +VI degree
or air atmosphere. This apparatus, equipped with a thermobalance,
+V/2
recorded, as a function of temperature, both the weight sample
evolution (TG) and the heat flow variation between the sample Fig. 1. Main oxidation states of sulfur.
and a reference material (DSC). Samples of approximately 20 mg
were introduced in an alumina crucible and heated from 25 °C to
850 °C at a rate of 10 °C/min. Table 3
Z elemental analysis.

3. Results Composition (% weight)

Si Al Fe Mn Mg Ca Na K Ti P
3.1. Thermodesorption 21.32 13.62 0.72 0.01 0.76 0.46 10.14 0.26 0.08 0.03

Thermodesorption was performed at 350 °C in helium and air

after H2S adsorption. Results of the desorbed sulfur compound
analysis are given in Table 2.
In helium, the desorbed quantities of sulfur compounds were
significantly lower than the quantity of H2S adsorbed in the sample
(Z+H2S_3). Less than 6% of the adsorbed sulfur was desorbed.
Among the quantified sulfur species, H2S was actually measured
in the desorption gas, but SO2 was also analyzed, which seems to
indicate that H2S has been partly oxidized during the adsorption.
In air, about 19% of the adsorbed sulfur was desorbed and the
main analyzed specie was SO2. The amount of desorbed SO2 was
multiplied by 4 compared to desorption in He flow. This could be
due to the presence of some little desorbable sulfur compounds
that would be partially oxidized during the desorption process at
high temperature and oxidizing conditions.
Thus, poor thermal desorption was achieved by heating Z+H2S
at 350 °C in helium or air flow, demonstrating that H2S is not phys-
ically adsorbed. Consequently, the thermal regeneration of Z+H2S
seems limited. As a result, one objective of this study was to iden-
tify the chemical nature (sulfur speciation) of the adsorbate in Z
+H2S and to understand H2S removal mechanism.
Sulfur chemistry is complex. This element can be found in sev-
eral oxidation states, the most commons being summed-up in
Fig. 1. In Z+H2S, sulfur can a priori be speciated into hydrogen sul-
fide – the compound initially removed from the gas – or, in case of
chemisorption, as other sulfide or hydrosulfide compounds, ele-
mental sulfur, thiosulfates, tetrathionates, sulfur dioxide or other
sulfur oxides, sulfites or sulfates.
In the next sections, complementary physicochemical charac-
terizations of Z and Z+H2S are reported. By gathering all the results,
a removal mechanism could be proposed and is described in the
Discussion part (Section 4).
3.2. Elemental analysis
The studied zeolite is composed – in weight – of about 21% sil-
icon, 14% aluminum, 10% sodium and oxygen (Table 3). The molar
Si/Al ratio calculated from this analysis is 1.4, which is typical of
zeolites X (within the range 1–1.5) [21]. This Z is a Faujasite NaX.
The Si/Al ratio is lower than 8–10, indicating that Z is hydrophilic
[21]. The presence of metals (aluminum and sodium) can catalyze
chemical reactions. The catalytic potential of traces of iron (0.7% in
weight), magnesium (0.8% in weight) and calcium (0.5% in weight)
cannot be excluded either. Nguyen-Thanh and Bandosz [26]
showed that the impregnation of an activated carbon with iron
salts (1.3% Fe) double its H2S adsorption capacity.
3.3. Total sulfur content
The total sulfur content in Z was below the quantification limit
(<0.01% in weight). After H2S adsorption, the sample Z+H2S_1 con-
tained 12.6% sulfur in weight, that is to say an adsorbed quantity of
about 126 mgS/gZ+H2S. This result is consistent with the data pre-
sented in Table 1 (110 mgS/gZ+H2S) from GC analyses. This good
cross checking of the two mass balances suggests the formation
of strongly bonded species during the adsorption process because
no sulfur compound desorption occurred during the grinding pre-
vious to the total sulfur analysis (see Section 2.4).
3.4. pH of the adsorbent leachate
The pH of Z leachate was 10.0. After H2S adsorption, the lea-
chate became significantly more acidic: leachate pH was equal to
7.3, 7.2 and 6.6 for samples Z+H2S_1, Z+H2S_2 and Z+H2S_3
respectively.
In the presence of water, H2S is a weak diacid with two equilib-
rium constants [17]: pKa1 = 7.2 and pKa2 = 13.9 (Eqs. (1) and (2)).
H2 SðaqÞ þ H2 OðlÞ ¡ HSðaqÞ þ H3 OþðaqÞ pKa1 ¼ 7:2 ð1Þ
HSðaqÞ þ H2 OðlÞ ¡ S2 þ
ðaqÞ þ H3 OðaqÞ pKa2 ¼ 13:9 ð2Þ
Subscripts (aq) and (l) respectively stand for aqueous and
liquid.
Considering the pH value of Z leachate, H2S is a priori mainly
dissociated into HS (at least at the beginning of the adsorption
test). The occurrence of H2S (physical adsorption) is possible at

Table 2
Sulfur compound quantities thermodesorbed from Z+H2S_3 at 350 °C in helium and air – comparison with the quantity of H2S adsorbed in the sample.

Compound Adsorbed quantity Thermodesorbed quantity

In helium In air
mgS/gZ+H2S mgcompound/gZ+H2S mgS/gZ+H2S mgcompound/gZ+H2S mgS/gZ+H2S
SO2 0 16.9 8.4 67.9 34.0
H2S 189 2.2 2.1 1.5 1.4
Sum 189 10.5 35.4
50 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53

the end of the dynamic adsorption test, when the pH significantly Table 4
acidifies. The formation of sulfide ions (S2) is unlikely and their Specific surface area and porosity of Z before and after H2S adsorption.

reaction with Z metal cations (e.g. Na+, Ca2+ or Fe2+ – cf. Table 3) Sample Specific surface Micropore Main pore
to produce metal sulfides is not realistic. area (m2/g) volume (cm3/g) diameter (Å)
The presence of water in Z pores – necessary for the dissociation Z 700 0.26 9.5
– is proved in Sections 3.7 and 3.8. The local pH in the porous net- Z+H2S_3 440 0.17 8.8
work has a significant effect on the speciation of the final products.
It seems to control the retention mechanism involved in the pores:
a pH variation can induce a diversity of products [15–17]. Note 0.35
that, in the presence of water, biogas is an acidic gas because it
is composed of an important part of CO2. Consequently, the varia- 0.3 Z

Differenal pore volume (cm3.g -1.Å-1)

tion of pH conditions in Z bed might be faster in biogas than in N2.
Z+H2S_3
0.25

3.5. Total soluble sulfur and sulfate ions in leachate 0.2

The main objective of this analysis was to evaluate the solubil- 0.15
ity of the sulfur specie(s) formed in Z+H2S.
Measurements revealed a quantity of total sulfur in solution of 0.1
about 0.07 mgS/gZ for Z sample and 15.1 mgS/gZ+H2S for Z+H2S_2
sample. The content of total soluble sulfur is naturally higher after 0.05

H2S adsorption. However, the quantity of total soluble sulfur mea-

0
sured in Z+H2S_2 leachate is only 10% of the quantity adsorbed, 5 7 9 11 13 15
with one fifth as SO2 4 (Fig. 2). Sulfur compounds present in Z Pore diameter (Å)
+H2S are rather insoluble: used leaching conditions conducted only
Fig. 3. Pore size distribution of Z and Z+H2S_3.
to a partial leaching. A replicate realized with Z+H2S_1 sample gave
similar results.
Insoluble sulfur species include H2S, other sulfides, tetrathion-
ates or elemental sulfur. However, the first two propositions are Furthermore, this adsorbate is well bonded to the adsorbent since
not in accordance with pH considerations (§ 3.4). it was not removed during the outgassing under vacuum at 300 °C
before the analysis (Section 2.7). In the case of activated carbon,
Adib et al. [15] consider that a desorption at 120 °C under vacuum
3.6. Specific surface area and porosity
(105 Torr) totally removes physically adsorbed compounds such
as H2S. They also point out that elemental sulfur (if produced)
The specific surface area of Z was 700 m2/g (Table 4), which is in
should be deposited on pore walls and/or block some pore
the range of literature data [20]. Its micropore volume was
entrances. Our observations are similar and indicate the possible
0.26 cm3/g. The measured pore size distribution was very narrow
formation of elemental sulfur in Z+H2S, reducing the micropore
– which is typical of zeolites – with a peak centered at 9.5 Å
volume and the pore diameter.
(Fig. 3). Theoretically, the pore diameter is 7.4 Å for 13X zeolites
resulting from the assembly of tetrahedra (SiO4 and AlO4) in cages
[21]. The kinetic diameter of H2S is 3.6 Å [27]. The diameter of Z 3.7. FTIR
pores is larger than the size of H2S molecules; consequently, H2S
can enter the pores. In the case of H2S adsorption in activated car- Z and Z+H2S_3 FTIR spectra are presented in Fig. 4. The global
bon, conclusions from the literature converge toward a major shape of Z spectrum is quite similar to the spectra presented by
activity in the pores of small diameters (<10 Å) [14,15,17,26]. Thus, Montanari et al. [28] for a 13X zeolite and by Zhdanov et al. [29]
Z porous structure seems appropriate. for several types of synthetic faujasites with different Si/Al ratios.
The specific surface area and the micropore volume measured The bands visible between 400 and 1400 cm1 (Fig. 4) are char-
after H2S adsorption were divided by 1.5 (Table 4). A part of the acteristic of bond vibrations between Si, O and Al [29,30]. It is a sig-
porous network was no longer accessible. The peak of porosity nature of Z skeleton.
was less intense and slightly shifted toward smaller diameters
(Fig. 3). This is due to the deposit of the adsorbate in Z+H2S pores.
0.7 Z+H2S_3 Z 445
957-959
180 0.6
0.04 2700-3700
160 S adsorbed 1654
Quanty of sulfur compound

Sulfate 0.5 0.03

140
Other soluble sulfur species 0.02
Absorbance

120 0.4
+ = total S in soluon
(mgs/gZ+H2S)

100 0.01
0.3 561
80 0.00
672
3400 2400 1400 742
60 0.2
40
0.1 2700-3700
20 1654

0 0.0
Solid matrix Leachate 3900 3400 2900 2400 1900 1400 900 400
Wavenumber (cm-1)
Fig. 2. Comparison of the sulfur quantity adsorbed in Z+H2S_2 sample with the
quantity of total soluble sulfur (including SO2
4 ) measured in the leachate. Fig. 4. FTIR spectra of Z and Z+H2S_3.
 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53 51

The comparison of Z and Z+H2S spectra shows very few differ- Temperature (°C) Exothermic
ences. In particular, no S-H stretching vibration characteristic of 0 100 200 300 400 500 600
H2S is observed between 2500 and 2625 cm1 on Z+H2S spectrum
0 3,500
3,000
(Fig. 4) [18,31]. This vibration is not visible either because its inten- -5
m1_Z+H2S 2,500
sity is too low in comparison to the signal baseline (weak stretch)

DSC : Heat flux (mW/g)

-10

TG : Weight loss (%)

or because there is no (or few) S–H bonds, which means that sulfur 2,000
is not mainly speciated as H2S. Note that if elemental sulfur was -15 1,500
formed as suggested in Section 3.6, it could not be highlighted -20 m2_Z+H2S 1,000
because it does not have a recognizable signature in FTIR. 500
The large band at 2700–3700 cm1 and the peak centered at
-25
0
1654 cm1 (Fig. 4) are representative of OH bond vibrations -30
-500
(stretching and bending respectively). These bonds can be associ-
-35 -1,00
ated with water signature. After H2S adsorption, these vibrations 0.0
are more intense, which suggests the formation of water. A chem-

dTG : (%/min)
ical reaction producing water can be supposed. -0.5

-1.0

3.8. TG-DSC -1.5

Samples of Z and Z+H2S were analyzed in replicates by TG-DSC -2.0

in nitrogen and air. Profiles are presented in Figs. 5 and 6. Fig. 6. TG-DSC profiles and dTG for Z+H2S_3 in air.

3.8.1. In nitrogen
TG curve of Z shows a weight loss (Dm1_Z) associated with a
broad endothermic peak between 100 °C and 440 °C (Fig. 5). This
observation can be related to the vaporization of bonded water
contained in Z pores. Yang [20] stated that a temperature of
350 °C is needed to desorb water from zeolites. The same observa-
tion is noticed for Z+H2S_3 sample but at lower temperatures,
between 100 and 300 °C (Dm1_Z+H2S). This shift toward lower tem-
peratures could be explained by the beginning of a second phe-
nomenon hiding the end of the first one. Another possibility is
that water may be ‘‘more accessible” after adsorption (lower tem-
perature required for the vaporization). The quantity of water after
H2S adsorption is higher than the one before adsorption (Fig. 5). As
suggested by FTIR analyses (§ 3.7), water formation during adsorp-
tion seems confirmed. The analysis of another sample (Z+H2S_2)
showed that the quantity of additional water seems related to
the H2S uptake in the sample. It is also possible that this increase
in weight loss is partly due to some molecular H2S or to SO2
desorbed from the Z+H2S sample, but H2S and SO2 quantities are
probably negligible, as shown in Section 3.1.
A second weight loss (Dm2_Z+H2S) associated with an endother-
mic peak between 300 and 630 °C is observed for Z+H2S sample in
nitrogen (Fig. 5). It is correlated to H2S adsorption in Z+H2S as it is
absent on Z sample. The presence of a unique weight loss indicates
that the system is relatively homogenous with the presence of a
single major compound [16]. Given the range of temperature, this
compound is difficult to desorb.
Temperature (°C)
0 100 200 300 400 500
0 1200
m1_Z
-5
m1_Z+H2S
TG : Weight loss (%)
This weight loss (Dm2_Z+H2S) can be attributed to the presence
of elemental sulfur [8,16]. As it is quite spread around the sulfur
boiling point (444.6 °C), it is possible that sulfur is present as sev-
eral chemical forms: radicals or different polymers [16]. During
adsorption tests, the accumulation of sulfur atoms may conduct
to the formation of more stable linear or cyclic sulfur molecules
such as S8. The desorption peak is then larger because different
kinds of elemental sulfur based compounds are present [17]. This
second weight loss cannot be assigned to H2S because if it was
physically adsorbed, it would have desorbed at temperatures lower
than 120 °C [8,16]. Likewise, the presence of SO2 would be charac-
terized by a weight loss centered at 250 °C. No such observation is
highlighted in Fig. 5; consequently, neither H2S nor SO2 seems sig-
nificantly retained in Z+H2S. The weight loss cannot either be
assigned to sulfides and sulfates which degrade at temperatures
higher than those studied here.
The weight loss (Dm2_Z+H2S) for Z+H2S_3 is 176–197 mg/gZ+H2S
(Fig. 5) depending on the replicate (5 replicates). The amount of
H2S adsorbed in this sample is about 189 mgS/gZ+H2S. Considering
the formation of elemental sulfur only, the mass balance is satis-
factory. H2S removal by Z seems actually based on adsorption–
oxidation mechanisms. Involved reactions do not form oxidation
products easy to desorb but elemental sulfur strongly bonded to Z.
Note that a small endothermic peak is visible around 115 °C
corresponding to the sulfur fusion point (113–119 °C).
3.8.2. In air
Z+H2S_3 sample was also analyzed in air (Fig. 6). Derivative
thermogravimetric curve (dTG) is also given in Fig. 6.
Exothermic
600 700 800 TG curve shape is similar to the one obtained in nitrogen with
two successive weight losses. The first weight loss (Dm1_Z+H2S)
assigned to bonded water is about 107–132 mgwater/gZ+H2S (2 repli-
TG_Z+H2S 900 cates) which is in the range of measurements performed in N2
(102–149 mgwater/gZ+H2S). The second weight loss (Dm2_Z+H2S) is
DSC : Heat flux (mW/g)

TG_Z
-10 600
DSC_Z+H2S shifted toward lower temperatures (between 290 °C and 400 °C).
-15 DSC_Z 300 The weight loss in air (Dm2_Z+H2S = 99–111 mg/gZ+H2S) is signifi-
m2_Z+H2S
cantly lower than the one in N2 (176–197 mg/gZ+H2S), but this
-20 0 remains unexplained.
DSC profile in air is significantly different: an intense exothermic
-25 -300
peak (centered at 355 °C) is associated with the second weight loss.
This heat release is probably related to the oxidation (in the
-30 -600
calorimeter) of the elemental sulfur formed in Z+H2S. Adib et al.
Fig. 5. Comparison of TG-DSC profiles for Z and Z+H2S_3 in nitrogen. [15] observed a similar peak at 347 °C and drew the same
52 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53
conclusion. In air, elemental sulfur seems oxidized (in the calorime-
ter) before reaching its boiling point (444.6 °C). This hypothesis was
confirmed by the TG-DSC analysis of a sample of pure sulfur in air
that also showed an exothermic peak centered at 360 °C associated
with a total weight loss.
Considering that H2S is retained as elemental sulfur in Z+H2S,
the oxidation reaction is given by Eq. (3).
SðsÞ þ O2ðgÞ ! SO2ðgÞ
Subscripts (s) and (g) correspond respectively to solid and gas.
The associated standard enthalpy of reaction DHreaction is equal
to the SO2 standard enthalpy of formation, that is DHreaction =
296.8 kJ/mol at 25 °C [32]. As a first approximation, the influence
of the temperature is neglected. This enthalpy of reaction
corresponds to the oxidation of one mole of elemental sulfur i.e.
DHreaction = 9.3 kJ/gS of elemental sulfur.
The integration of the exothermic peak (Fig. 6) indicates a heat
release of 1.06 J/gZ+H2S, that is to say, by dividing by the associated
weight loss Dm2_Z+H2S, an experimental enthalpy of 9.5 kJ/glost.
The energy balance (comparison of DSC result with DHreaction) is
convincing: elemental sulfur is then identified as the major specie
formed in Z+H2S. The presence of the small endothermic peak asso-
ciated with sulfur fusion can be seen again on Fig. 6. Note that the
standard enthalpy of reaction associated with H2S oxidation
(Eq. (4)) is equal to 15.2 kJ/gH2S at 25 °C. This confirms that the
presence of molecular H2S is not likely in Z+H2S.
H2 SðgÞ þ 3=2O2ðgÞ ! SO2ðgÞ þ H2 OðgÞ
4. Discussion: H2S removal mechanism by Z
The global mechanism of H2S retention in the studied Z is a
combination of ‘‘adsorption–dissociation–oxidation”. Thanks to
the different characterizations performed, the following successive
steps are proposed to describe the mechanism:
a. H2S adsorption at Z surface: H2S(g) ? H2S(ads)
b. H2S dissolution in water contained in Z pores:
H2S(ads) ? H2S(aq)
c. H2S dissociation in the water film:
H2S(aq) + H2O(l) ? HS +
(aq) + H3O(aq)
d. Oxidation of HS with adsorbed oxygen:
HS 
(aq) + O(ads) ? S(ads) + OH(aq)
e. Formation of linear or cyclic sulfur polymers: xS(ads) ? Sx(ads)
Subscript (ads) corresponds to adsorbed compounds. O(ads) rep-
resents dissociatively adsorbed oxygen. S(ads) and Sx(ads) symbolize
elemental sulfur in simple or polymeric form.
The global reaction leads to the formation of elemental sulfur
and water as proposed in Eq. (5).
H2 S þ 0:5O2 ! S þ H2 O
The first step (a) underlines the importance of Z physical char-
acteristics (specific surface area, pore volume, pore size) and gas
dynamics in the adsorption capacity and probably the adsorption
kinetics.
The second step (b) highlights the role of water contained in Z
pores, as also found with other adsorbents [13,15,33]. The amount
of water must be sufficient but not too important to prevent pores
from filling with condensed water. The dissolution step is also
affected by the adsorbent morphology. Indeed, pores must be suf-
ficiently small to allow the formation of a water film even at low
humidity [15], but sufficiently large to contain the adsorbate and
oxygen molecules. The presence of bonded water in Z pores was
shown by TG-DSC. Water molecules association via hydrogen
bonds conducts to the formation of a water film in the pores.
The step (c) raises once again the importance of water, but also
the role of pH. Water is indispensable for H2S dissociation provided
pH allows it. A pH value included between the two H2S acidity con-
stants (pKa1 = 7.2 and pKa2 = 13.9) enables the formation of HS.
This is the case for the studied Z, which leachate pH is 10.0. Note
that after adsorption, the environment becomes more acidic: the
ð3Þ pH of the leachate (6.6–7.3) tends toward the inferior limit of
HS predominance zone. pH has a significant role in the final spe-
ciation of sulfur. pH is related to the adsorbent composition. The
presence of calcium and magnesium oxides can contribute to the
alkalinity of Z.
The step (d) underlines the role of adsorbed oxygen in the adsor-
bent. Nguyen-Thanh and Bandosz [26] stated that the lack of avail-
able oxygen can stop the oxidation well before all the pores are
filled with sulfur. In our study, the main source of oxygen is the
gas matrix used for the adsorption tests that is composed of approx-
imately 1% oxygen in volume (see Section 2.1). In addition, the pres-
ence of metals in Z is able to catalyze H2S oxidation reaction.
The final speciation of sulfur depends on all these conditions.
TG-DSC analyses confirmed that elemental sulfur is the main spe-
cie formed in Z. Note that sulfur itself is also a catalyst of H2S oxi-
dation [10] that is to say the more sulfur is adsorbed, the more H2S
oxidation is promoted.
Finally, elemental sulfur can arrange in more stable linear or
cyclic polymers (step (e)) [14,17]. In standard temperature and
ð4Þ pressure conditions, the most stable allotropic sulfur specie is
cyclo-octasulfur (S8 – practically insoluble in water).
The formation of a minor part of SO2 cannot be excluded but the
quantity of formed SO2 is negligible (see Section 3.1). Indeed, TG-
DSC results show that S mainly oxidizes in SO2 at temperature
higher than ambient temperature.
In the context of biogas purification, this mechanism may be
affected by the presence of other kinds of compounds (especially
CO2) and humidity. CO2 (about 40% v/v in biogas) could be partly
adsorbed and may affect the adsorption capacity of H2S. Indeed, zeo-
lites can be used for biogas upgrading (CO2 removal) [34,35]. A con-
sequence of this carbonation would be a rapid pH decrease and H2S
might be retained as molecular H2S (pKa1 = 7.2, see Section 3.4). Yet
some metals from Z structure might solubilize, which would
increase their reactivity with H2S. A deficit of O2 could negatively
affect the removal of H2S. As concerns humidity, some tests were
performed at laboratory with a humid N2 matrix and the adsorption
capacity of H2S was reduced because of Z affinity for water.
5. Conclusion
Characterizations of Z before and after H2S adsorption led to
several key observations:
– poor thermal desorption at 350 °C indicating there is no physi-
cal adsorption of H2S,
ð5Þ
– presence of water and pH promoting H2S dissociation in HS,
– adsorbate almost insoluble,
– adsorbate deposit in the pores reducing the specific surface
area, pore volume and pore diameter,
– formation of water during adsorption,
– no S–H bonds,
– degradation of the adsorbate between 300 and 630 °C in inert
atmosphere,
– oxidation of the adsorbate around 355 °C in air atmosphere.
The results of the different characterizations converged to pro-
pose a removal mechanism of H2S in Z based on adsorption–oxida-
tion and formation of elemental sulfur.
 L. Sigot et al. / Chemical Engineering Journal 287 (2016) 47–53
From an operational point of view, the formation of stable sulfur
polymers compromise the thermal regeneration of Z but the
understanding of this mechanism should facilitate the develop-
ment of efficient regeneration processes. For instance, zeolite
regeneration by high temperature desorption at 500–600 °C in
inert atmosphere (but this process is very energy consuming and
high temperature might damage Z crystalline pore structure) or
by desorption–oxidation in air at a temperature <400 °C could be
investigated. Desorption under reduced pressure to sublime the
formed elemental sulfur is another option. Chemical dissolution
with organic solvents is also possible but these solvents are not
environmentally friendly.
Acknowledgements
This study, part of the PILE-EAU-BIOGAZ project, was supported
by the French Agence Nationale de la Recherche (ANR), program H-
PAC 2010.
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