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Study of the reaction of high-temperature H 2S decomposition on

metal oxides ( γ-Al 2O 3, α-Fe 2O 3,V 2O 5)

Article  in  International Journal of Hydrogen Energy · January 2002

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 International Journal of Hydrogen Energy 27 (2002) 387–394
www.elsevier.com/locate/ijhydene

Study of the reaction of high-temperature H2S decomposition

on metal oxides (
-Al2O3; -Fe2O3; V2O5)
T.V. Reshetenko, S.R. Khairulin, Z.R. Ismagilov ∗ , V.V. Kuznetsov
Boreskov Institute of Catalysis, Pr. Akad. Lavrentieva Avenue 5, Novosibirsk 630090, Russia

Abstract
Experimental study of the reaction of heterogeneous decomposition of the hydrogen sul5de on bulk oxides
-Al2 O3 , -Fe2 O3
◦
and V2 O5 in the interval of temperatures 500–900 C have been performed. Reaction orders by H2 S for
-Al2 O3 and V2 O5 are
2.0, and for -Fe2 O3 — 2.6; e;ective activation energies are respectively 72, 94 and 103 kJ=mol. Using the ESDR and XRD
methods, it is shown that in the course of hydrogen sul5de decomposition reaction, the reduction of transition metal oxide
catalysts (-Fe2 O3 and V2 O5 ) and also the formation of sul5des under the in@uence of reaction media proceed. Interaction of
hydrogen sul5de with aluminum oxide at low temperatures leads to formation of adsorbed species of H2 S as fragments HS−
◦
and S2− , which upon heating 100 –700 C transfer into di;erent species of sulfur: c-S8 , c-S12 , S4 . In separate experiments it
was demonstrated that the higher the temperature of H2 S interaction with Al2 O3 , the larger number of adsorbed sulfur species
are observed in the spectra. Molecular hydrogen sul5de interacts with the Al2 O3 surface with formation compounds of sulfur
with oxygen, which later transform into the 5nal reaction product — elemental sulfur. ? 2002 International Association for
Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Hydrogen; Hydrogen sul5de; Decomposition; Metal oxide catalysts

1. Introduction
To date the evident advantages of hydrogen production by
direct decomposition of H2 S are well known. This process
has signi5cant practical importance for the production not
only of elementary sulfur but also hydrogen on the industrial
scale. The decomposition of H2 S can be accelerated by using
highly active heterogeneous catalysts. The thermodynamics
of the thermal decomposition of H2 S is not favorable at low
◦
temperatures. For example, at temperatures below 550 C the
equilibrium concentration of H2 is less than 1%, and even
◦
at 900 C it is only 13%.
The use of membrane reactors can shift the equilibrium in
the direction of higher hydrogen sul5de conversion due to
the selective permeability of the reaction product hydrogen.
Di;erent types of membrane reactors are studied [1– 4]. For
the purpose of separation of hydrogen from products of the
thermal decomposition process of H2 S, zirconia (90 mol%)-
silica (10 mol%) composite membrane coated on porous ce-
ramic tubing were used [3]. A microporous Vycor-type glass
tubing membrane of a mean pore diameter of 45 A K and alu-
mina tubing membrane of a mean pore diameter of 1020 A K
were investigated and when these membranes were applied
to the direct decomposition of H2 S, the yield of H2 increased
by about two fold in comparison with the equilibrium data
calculated for the process without hydrogen removal [4].
The sul5des [5 –12] and oxides [11–14] of transition
metals are used as the solid catalysts for heterogeneous
high-temperature decomposition of hydrogen sul5de.

1.1. Metal sul(des

∗ Corresponding author. Tel.: +7-3832-341219;
fax: +7-3832-397352. In search for the e;ective hydrogen sul5de decomposi-
E-mail address: zri@catalysis.nsk.su (Z.R. Ismagilov). tion catalysts, Kotera [5,6] and Fukuda [7] studied catalytic

0360-3199/02/$ 20.00 ? 2002 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 3 6 0 - 3 1 9 9 ( 0 1 ) 0 0 1 4 3 - 4
388 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394
activity of the following compounds: FeS, CoS, NiS, MoS2 ,
◦ ◦
WS2 , at temperature 500–800 C and pressure variation in
interval 0:08–0:13 atm. It was shown, that FeS, CoS, NiS in-
teract with hydrogen sul5de at high temperatures according
to the following reactions:
FeS + H2 S → FeS2 + H2 ;
NiS + H2 S → NiS2 + H2 ;
CoS + H2 S → CoS2 + H2 :
Disul5des formed in this reaction FeS2 , NiS2 and CoS2
exhibit rather low catalytic activity in H2 S decomposition. It
was determined, that Ea = 112:6 kJ=mol in the H2 S decom-
position reaction, where the MoS2 powder has been used as
a catalyst. The catalytic activity of MoS2 is higher, than of
WS2 [7].
Chivers and Lau [8–10] compared the catalytic activity of
some metal sul5de powders related to the hydrogen sul5de
decomposition in the quartz reactor. Results of H2 S catalytic
decomposition in the temperature interval 400–800 C are
◦
published in [9]. For the series Cr 2 S3 , MoS2 , WS2 it was re-
vealed, that MoS2 is the most active catalyst at T ¿ 600 C,
◦
but Cr 2 S3 and WS2 demonstrate greater yield of hydrogen
◦
at T ¡ 600 C, than MoS2 . It has been shown, that these sul-
5des do not change their phase composition under the in@u-
ence of reaction media. For disul5des FeS2 , CoS2 , NiS2 , the
thermal decomposition of MeS2 to non-stoichiometric sul-
5de (Fe7 S8 ; CoS1:13 -CoS1:2 ; NiS1:2 ) is observed at the tem-
◦
peratures ≈ 550 C. Monosul5des FeS, CoS, NiS exhibit
greater yield of hydrogen at the initial stages of reaction.
Further on, as authors suggest, sul5dation of the catalysts
is going on under the in@uence of reaction media, with for-
mation of the non-stoichiometric sul5des, which are not the
active catalysts for hydrogen sul5de decomposition. Taking
into account data for copper sul5des CuS, Cu2 S; Cu9 S5 , the
full list of studied sul5des can be placed in the following
◦
activity series at T = 800 C:
MoS2 ¿ Fe7 S8 ¿ = WS2 ¿ Cr 2 S3 ¿ NiS1:2
= Cu9 S5 ¿ CoS1:13−1:2 :
Chivers et al. and Chivers and Lau [9,10] suggest that
hydrogen sul5de decomposition can be represented in the
form of a two-stage process:
Mx Sy + zH2 S → Mx Sy+z + zH2 ; (1)
0
Mx Sy+z → Mx Sy + zS ; (2)
0 ules, as a potential adsorbent for hydrogen sul5de. The stud-
H 2 S → H2 + S :
The “lowest” metal sul5de Mx Sy interacts with hydrogen
sul5de, forming the “highest” sul5de Mx Sy+z and hydrogen
(1). The “lowest” sul5de appears as a result of regeneration
of the “highest” (2), leading to the formation of elementary
sulfur.
Bishara and Salman in [11] studied hydrogen sul5de de-
composition reaction in the presence of supported catalysts:
(NiS; MoS2 )=
-Al2 O3 ; (CoS; MoS2 )=
-Al2 O3 and
-Al2 O3 in
the 5xed bed reactor at temperatures 600–800 C. It was
found for all samples studied, that the hydrogen yield reaches
◦
13% at T = 800 C and residence time 0:3 s. The conver-
sion exceeds thermodynamically calculated value [15], but
authors explain this phenomenon by quenching of reaction
mixture at the exit of reactor. Decomposition of H2 S is de-
scribed by the equation with second order by hydrogen sul-
5de for all samples, while the activation energies consti-
tute 69:3 kJ=mol for (NiS; MoS2 )=
-Al2 O3 , 59:2 kJ=mol for
(CoS; MoS2 )=
-Al2 O3 .
1.2. Metal oxides
In several works [11–13] the studies of high-temperature
hydrogen sul5de decomposition in the presence of
-Al2 O3
◦
in the temperature interval 500–800 C have been conducted.
Bishara [11] established that Ea = 76 kJ=mol and reaction
order by hydrogen sul5de is equal 2.0. It was shown in the
[12] that Ea = 31:38 kJ=mol while reaction has the 5rst order
by hydrogen sul5de.
Al-Shamma [12] had studied V2 O5 =
-Al2 O3 in the reac-
tion of H2 S decomposition in the interval of temperatures
◦
500–600 C and proposed, that H2 S is consumed in a result
of two processes:
• Reaction of H2 S interaction with vanadium oxide, which
can be written as
5H2 S + V2 O5 → V2 S3 + 5H2 O + 2S0 :
The formation of V2 S3 was registered by X-ray di;raction
analysis.
• As the surface of V2 O5 transforms into V2 S3 , the latter
plays the role of a catalyst in the reaction of hydrogen
sul5de decomposition and V2 S3 as an active center takes
part in the reaction:
V2 S3 + 5H2 S → VS4 + 5H2 ;
2VS4 → V2 S3 + 5S0 ;
H 2 S → H2 + S0 :
It was shown also, that 5% V2 O5 =
-Al2 O3 exhibits higher
catalytic activity, than specially prepared 5% V2 S3 =
-Al2 O3 .
For supported vanadia catalyst these authors proposed 5rst
order of reaction by hydrogen sul5de concentration and cal-
culated the activation energy as Ea = 33:98 kJ=mol.
Yumura and Furimsky [14] have studied manganese nod-
◦
ies have been conducted at T = 600–800 C. In the initial
period of exposition of sample to H2 S, the concentration
of hydrogen sul5de in the o;-gas is low and the hydrogen
almost absent. H2 S is removed from the reaction mixture
because of the chemical interaction with adsorbent. As the
sorbent undergoes sul5dation, the decomposition of H2 S,
detected by the increase of hydrogen concentration in the re-
action products, begins to play an important role. It is worth
 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394
Table 1
Characteristics of the metal oxides
Catalysts SBET (m2 =g) Phase composition Particle size (mm)

-Al2 O3 220
-Al2 O3 1.5 –2.0
-Fe2 O3 19
-Fe2 O3 1.0 –2.0
V2 O 5 4.7 V 2 O5 1.0 –2.0
to note, that substantial amount of Fe2 O3 is presented in
studied samples of nodules. The iron oxide, as it is known,
is easily sul5dized to iron sul5de which exhibits catalytic
activity in the reaction of hydrogen sul5de decomposition.
In this work, we have measured kinetic parameters of
high-temperature catalytic decomposition of hydrogen sul-
5de on the
-Al2 O3 , V2 O5 , -Fe2 O3 . The structure of surface
intermediaters upon H2 S adsorption and molecular struc-
ture of formed sulfur compounds on the surface of catalysts
have studied by Fourier Transform Infrared Spectroscopy
(FTIR) and Electron Spectroscopy with Di;use Re@ectance
(ESDR) methods.
2. Experimental
2.1. Catalysts
The bulk oxides
-Al2 O3 , -Fe2 O3 , V2 O5 have been used
in experiments. The spherical granules of
-Al2 O3 are ob-
tained by the method of hydrocarbon–ammonia moulding of
the peptized aluminium hydroxide and their calcination at
◦ hydrogen (%), H2 the mole of hydrogen formed, and 0H2 S
550–600 C. The Fe2 O3 and V2 O5 were prepared by decom-
position FeC2 O4 · 2H2 O and (VO)SO4 · 3H2 O, respectively.
Characteristics of the oxides are listed in Table 1.
2.2. Equipment and materials
Catalytic activity of the metal oxides was measured in
a @ow set-up with vibrating quartz reactor. Initial reaction
mixture (3 vol% H2 S in Ar) has been fed into the reac-
tor with @ow rate 30 ml=min. The catalyst load −0:3–0:9 g.
Analysis of the gas mixtures was conducted using gas chro-
matograph “Tsvet-500” equipped with TCD, I = 130 mA
and stainless steel column (L = 3 m; ID = 3 mm) with sor-
bent “HayeSep B”. Flow rate of the carrier gas (Ar) is
◦
30 ml=min. Operation temperature of the column is 150 C.
The catalytic reactor heating furnace has been placed
in such a way, that only the catalyst loaded short zone
was heated, with the aim to provide conditions for con-
ducting of goal reaction in a “non-equilibrium” conditions.
The reaction has been studied in the range of temperatures
◦
500–900 C.
Spectroscopic studies were carried out on Fourier trans-
form IR-spectrometer “Bomem MB102” and “Specord
M40” with di;use re@ectance attachment. Adsorption of
the hydrogen sul5de has been studied in a high-temperature
spectroscopic cell.
389
X-ray powder di;raction measurements were carried out
on a “Siemens URD-63” di;ractometer using Cu K radi-
ation and graphite crystal monochromator. The lattice pa-
rameters were measured from XRD spectra using silicon as
internal standard.
2.3. Experimental procedure
A sample of metal oxide catalysts (m = 0:3–0:9 g) was
transferred into the quartz reactor. The reactor was placed
in an electric furnace which had an operating range of
◦ ◦
300–1000 C. The furnace was 5rst heated to 500 C and
then a stream of H2 S gas was introduced into the system.
The exit gas samples were analyzed every 15 min until
consistent results were obtained. When the temperature of
◦
the furnace was increased stepwise by 100 , the system
was allowed to remain at steady state 20–30 min before GC
analysis of the exit gas composition was performed. Second
gas sample was analyzed after a further 10 min at the same
temperature. After the experiments at highest temperature,
◦
e.g. 900 C, the catalyst was cooled to room temperature
and analyzed by XRD method.
The conversion of hydrogen sul5de was calculated on the
base of hydrogen formed in accordance with equation:
H2
xH2 = 100%;
0H2 S
where XH2 is the H2 S conversion found from formation of
the initial mole of hydrogen sul5de.
The reaction rate is calculated in accordance with follow-
ing equation:
uUcH2
w= molH2 =(m2 s);
mSBET
where u is the @ow rate (cm3 =s), UcH2 the concentration of
hydrogen produced (mol=cm3 ), m the catalyst loading (g),
and SBET the speci5c surface area of catalyst (m2 =g).
For ESDR studies the catalyst powder was placed into
spectroscopic cell, and then vacuumed at room temperature
for 1 h. After vacuuming the sample was exposed to H2 S at
100 Torr and room temperature for 30 min. The ESDR spec-
trum was registered and temperature was increased stepwise
◦
for 100 . After holding for 30 min at temperature of the ex-
periment the sample was cooled to room temperature and
ESDR spectra were registered.
The FTIR spectroscopic experimental procedure was as
following. The catalyst samples were pressed into the pel-
lets of 10–20 mg=cm2 thickness, a catalyst pellet was placed
◦
into the spectroscopic cell and treated in vacuum at 450 C
for 3 h. Adsorption of H2 S was studied at di;erent tem-
◦
peratures (20–600 C) and di;erent combination of heating,
cooling and evacuating, but spectra were recorded at room
temperature after each step.
390 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394

35 -5.0
0
30 Fe2 O3 900 C
Al 2 O3
25 V 2 O5
equilibrium
20 -5.5 0
800 C
XH , %

15 nFe2O3=2.6
2

10
5 -6.0 0
700 C
0
500 600 700 800 900
T,0 C -6.5 900 C
0

-1
Fig. 1. Conversion of hydrogen sul5de vs. temperature (calculated

lgW, mole⋅m ⋅s
from hydrogen formation). The sample weight for all catalysts was

-2
equal m = 0:6 g and @ow rate u = 30 ml=min. nV205 =2.0
-7.0 800 C
0

3. Results and discussion

3.1. Study of the kinetics of high-temperature -7.5 0

700 C
hydrogen sul(de decomposition reaction

Experimental data on dependence of H2 S conversion on

temperature are presented in Fig. 1. As can be seen from -8.0
the Fig. 1, a noticeable decomposition of hydrogen sul5de
◦
begins at the temperature ¿ 600 C. The conversion of hy- 0
◦ 900 C
drogen sul5de at 900 C exceeds thermodynamically calcu-
lated value [15] because of quenching of reaction mixture -8.5 800 C
0

at the exit of reactor. The catalytic reactor heating furnace nAI203 =2.0
has been placed in such a way, that only the catalyst loaded 700 C
0

short zone was heated, the conditions for realization of goal

reaction were “non-equilibrium”. The similar phenomenon -9.0
was observed by Bishara et al. [11]. -3.2 -3.0 -2.8
Upon the increase of residence time, hydrogen yield is -1
becoming lower for all the samples. Apparently, this is the lgCH2S, mole⋅l
result of reverse reaction Fe2O3 V2O5 AI2O3
H2 S ↔ H2 + 1=nSn
Fig. 2. Dependence of lgWH2 -lgcH2 S for investigated catalysts.
playing a signi5cant role [11,16] in approaching the reaction
mixture to equilibrium.
The reaction order has been calculated from experimental
-5.0
data in coordinates lgwH2 -lgcH2 S (Fig. 2).
-5.5
Characteristics of metal oxides before and after the reac- Fe 2O 3
tion of hydrogen sul5de decomposition are listed in Table 2. -6.0
-1

The reaction rate (Figs. 2 and 3) was calculated using the -6.5
lgW, mole⋅m ⋅s
-2

value of speci5c surface area of spent catalysts (Table 2) -7.0 V2O 5

due to observed change in phase composition and speci5c -7.5
surface area of samples under reaction conditions. -8.0
Kinetic characteristics of reaction on the studied metal -8.5 Al 2O3
oxides are presented in Table 3. -9.0
Kinetic parameters for
-Al2 O3 : nH2 S = 2:0, Ea; e; : = 72 kJ=
mol, are in agreement with literature data [11]. The reaction 0.85 0.90 0.95 1.00 1.05
-3 -1
order by hydrogen sul5de for the V2 O5 catalyst is equal to 1/ T⋅ 10 , K
2.0, and the activation energy constitutes 94 kJ=mol. In the
case of -Fe2 O3 — nH2 S = 2:6, Ea; e; : = 103 kJ=mol. Fig. 3. Arrhenius plot for investigated catalysts.
 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394 391

Table 2
Characteristics of the metal oxides before and after reaction (12 h) of the high-temperature H2 S decomposition

Fresh catalysts Spent catalysts

Catalyst color Sspec:; (m2 =g) Phase composition color Sspec:; (m2 =g) Phase composition

-Al2 O3 white 220
-Al2 O3 yellow 115 40%-
-Al2 O3 ,
grey 60%--Al2 O3
V2 O5 yellow red 4.7 V 2 O5 black 3.9 V 3 S4 , V 2 O 3 ,
VOSO4
-Fe2 O3 red black 19 -Fe2 O3 black brown 0.14 Fe1−x S

Table 3
5
Kinetic parameters of reaction on the studied metal oxides

Catalyst nH2 S Ea; e; :; (kJ=mol) 4

6

-Al2 O3 2.0 72
5
4
V2 O5 2.0 94 3

F(R)
-Fe2 O3 2.6 103 3

2 2

658

We observe transformation of oxides to sul5des accom-
panied by decrease in speci5c surface area. Let us consider
the mechanism of H2 S decomposition. We suppose that the
process of H2 S decomposition on transition metal oxide cat-
alysts proceeds in two steps. Transition metal sul5des are
formed on the 5rst step in accordance with the following
equation [12,14]:
Mx Oy + yH2 S → Mx Sy + yH2 O:
This explains the absence of H2 evolution along with ob-
served hydrogen sul5de absorption in the low-temperature
range. The increase in temperature probably speeds up
the process of oxide catalyst reduction and appearance of
non-stoichiometric sul5de.
The formed sul5de plays a role of active component of
the catalyst.
Further interaction of hydrogen sul5de with metal sul5de
leads to the formation of hydrogen and sulfur by two step
process [7,9,10] shown in the following equations:
Mx Sy + zH2 S → Mx Sy+z + zH2 ;
Mx Sy+z → Mx Sy + zS0 :
This process proceeds through the decomposition of hy-
drogen sul5de with formation of hydrogen and ‘higher’
sul5de, which decomposes to elemental sulfur and initial
sul5de Mx Sy .
3.2. Study of the heterogeneous hydrogen sul(de
decomposition reaction by ESDR and FTIR methods
ESDR spectra of H2 S adsorbed on Fe2 O3 are presented
◦
in Fig. 4. Upon adsorption of 100 Torr H2 S at T = 25 C,
the intensities of bands at 658 and 847 nm, characteristic
to d–d of Fe3+ in Fe2 O3 [17], are decreasing in compari-
son with spectra of fresh catalyst. Subsequent heating up to
847
Fe3+
1
1
200 300 400 500 600 700 800 900
nm
Fig. 4. ESDR spectra of Fe2 O3 after H2 S adsorption. (1) initial
◦ ◦
Fe2 O3 , (2) 100 Torr of H2 S at T = 25 C, (3) T = 200 C, (4)
◦ ◦
T = 500 C, (5) T = 700 C, (6) spent Fe2 O3 after catalytic test
run.
◦
700 C leads to their vanishing. It can be suggested, that iron
in the Fe2 O3 is being reduced to Fe2+ (whose characteris-
tic bands are located in the region of lower wavenumbers)
with simultaneous transformation of the oxide of Fe3+ to
sul5de of Fe2+ .
This result is also con5rmed by the X-ray di;raction anal-
ysis of the sample after experiments.
ESDR spectra of fresh and H2 S treated vanadium oxide
are presented in Fig. 5. After the adsorption of 10 Torr H2 S
at room temperature, a new band originates in the region of
690 nm, which is due to the formation of V4+ with d 1 con-
5guration [17,18]. Subsequent heating and increase in the
hydrogen sul5de presence (250 Torr) leads to the increase
in intensity of this band (Fig. 5). Electron spectra of a V2 O5
after kinetic experiments of H2 S decomposition also has a
band in the region 690 nm, characteristic of V4+ [17].
It must be noted that the information about sulfur species,
formed as a result of H2 S decomposition on vanadium
and iron catalyst, is hardly accessible because these oxides
have very intensive bands in the region of wavelengths
300 –540 nm, which are typical for bands of S2 , S3 , S4 ,
c-S8 , c-S12 [19,20].
Using ESDR technique we cannot observe the change
in valence state of alumina. But we observed the various
types of elemental sulfur formed during hydrogen sul5de
392 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394

0.5
5 HS-, S 2-
4

230
p.a.H2S
V 4+ 0.4 4

237
1
3
4 0.3 3
S4
F(R)

F(R)
S3, S4

540
2 0.2 S 2-

455
c-S8 2 4
3

380
c-S12

330
300

520
1 0.1 2
2
3

690
1 2
0.0 1
0
200 300 400 500 600 700 800 900 220 240 260 300 400 500 600 700 800 900 1000
nm nm

Fig. 5. ESDR spectra of V2 O5 after H2 S adsorption. (1) ini- Fig. 7. ESDR spectra of sulfur formed upon adsorption of 100 Torr
◦ ◦ ◦
tial V2 O5 , (2) 10 Torr H2 S at T = 20 C, (3) 10 Torr H2 S at of H2 S at temperatures: (1) T = 100 C, (2) T = 300 C, (3)
◦ ◦ ◦ ◦
T = 200 C, (4) 250 Torr H2 S at T = 400 C, (5) spent V2 O5 after T = 500 C, (4) T = 700 C.
catalytic test run.
◦
2-
tion of 100 Torr H2 S at 100 C, bands appear in the regions
230 and 240 nm, which are assigned to formation of S2− ,
S p.a. H2S
240
230

0.8
1 HS− (230 nm) and physically adsorbed hydrogen sul5de
S -?
(240 nm). Bands in the regions 330 and 510 nm can be as-
◦
0.6
c-S8 , c-S6 c-S7 4 ? signed to formation of c-S8 and S4 . Adsorption at 300 C
leads to the appearance of bands: 237; 330, and 510 nm,
475

525
412

which are caused by the presence of physically adsorbed

325
F(R)

0.4 2
3 4
0.2 4 3
5 mation of di;erent sulfur species on the surface of Al2 O3
0.0
240 270 300 400
nm
Fig. 6. ESDR spectra of sulfur formed upon adsorption of 100 Torr
of H2 S on alumina with subsequent increase in temperature: (1)
◦ ◦ ◦ ◦
T = 20 C, (2) T = 200 C, (3) T = 300 C, (4) T = 400 C, (5)
◦
T = 600 C.
decomposition. The ESDR spectra of sulfur, formed upon
hydrogen sul5de adsorption on Al2 O3 are presented in
Fig. 6.
Upon adsorption of 100 Torr H2 S at room temperature,
the bands: 230 and 240 nm appear. In [19,20] these bands
were assigned to the formation of surface species S2− , HS−
(230 nm) and physically adsorbed H2 S (240 nm). The in-
◦
crease in temperature from room temperature to 600 C leads
to the decreasing of intensity of these bands, while a num-
ber of new bands appear at 325; 412, and 475 nm, which can
be assigned to c-S8 and c-S6 , c-S7 , S4 , respectively [19,20],
and also the band in the region of 525 nm, which we could
not assign. Upon the increase in temperature, intensities of
bands 325; 412, and 475 nm grow up.
Fig. 7 demonstrates the results of H2 S adsorption on
◦ ◦
Al2 O3 at temperatures from 100 C to 700 C. After adsorp-
5
H2 S, c-S8 and S4. The characteristic bands of chemisorbed
◦
and physisorbed hydrogen sul5de disappear at 700 C, but
on the other hand, a number of bands caused by the for-
2 appear: 300; 330; 380; 455, and 540 nm, which are assigned
to c-S12 , c-S8 , S2−
1
2 , (S3 ; S4 ), and S4 , respectively.
600 800 Intensities of these bands had substantially increased at
◦
700 C compared with the results of previous experiment at
◦
500 C, it means that, upon the increase in hydrogen sul5de
adsorption temperature the fraction of S4 and c-S8 forms
grows up and a number of new sulfur species are formed.
So the ESDR investigations of interaction of hydrogen
sul5de with Fe2 O3 and V2 O5 show that the reduction of
Fe3+ –Fe2+ and V5+ –V4+ takes place. These results are in a
good agreement with X-ray analysis that indicates the for-
mation of Fe1−x S and V3 S4 during hydrogen sul5de decom-
position process.
We did not observe the formation of sul5des and sul-
fates at the interaction of hydrogen sul5de with alumina by
ESDR and X-ray analysis. However the formation of sul-
fates on alumina was reported early [21,22]. For the better
understanding of the nature of hydrogen sul5de interaction
with alumina we studied the adsorption of H2 S at elevated
temperatures by FTIR technique.
The results of FTIR spectroscopic studies of H2 S ad-
sorption on Al2 O3 are presented in Fig. 8. After hydrogen
sul5de adsorption at room temperature (2), the bands
characteristic of physically adsorbed hydrogen sul5de ap-
pear at 2560; 1333 cm−1 [21,22], and the band at 3770 cm−1
vanishes, probably as a result of hydroxyl interaction with
 T.V. Reshetenko et al. / International Journal of Hydrogen Energy 27 (2002) 387–394
(a)
3250
5
4
2560
Absorbance
1640
2 aluminum and vanadium oxides are equal 2.0, and for
1 2. The hydrogen sul5de decomposition reaction on -Fe2 O3
3730
3673
3770
4000 3500 26002400 1600
-1
Wavenumber, cm
Fig. 8. FTIR-spectra of H2 S adsorbed on Al2 O3 in the range of
hydroxyl group vibrations (A) and in the range of S–O stretching
vibrations (B): (1) after pretreatment 3 h under vacuum at 450 C;
◦
◦ ◦
(2) adsorption 80 Torr H2 S at 20 C; (3) after 1 h heating at 600 C;
◦ ◦
(4) evacuation at 20 C, 1 h; (5) evacuation at 100 C 1 h. In plot
(A) the curve (1) is the absorbance of the sample after pretreatment,
and curves 2–5 are spectra obtained by subtraction of the spectrum
after pretreatment.
H2 S and formation of the complexes:
◦ solutions. In: Internation Symposium, Grimstad, Horway,
Heating of the sample at 600 C during 1 h (3) leads to the
appearance of bands 1325; 1226 cm−1 , which characterize
formation of the compounds like:
Intensity of the band 2560 cm−1 is slightly decreased,
and the band 1640 cm−1 appeared, which can be assigned
to water formation on the surface of the sample. Apparently,
the formation of H2 O is resulting from the reaction [22,24]:
H2 S + [O] → H2 O + [S]:
Vacuuming (4) leads to the disappearance of physically ad-
sorbed hydrogen sul5de, which is evidenced by absence of
the band at 2560 cm−1 , but the oxygen-containing sulfur
compounds still remain and disappear only upon vacuuming
◦
at 100 C for 1 h (5), upon which the band at 3770 cm−1 is
restored.
Therefore, it can be suggested that a part of physi-
cally adsorbed H2 S interacts upon heating with the sur-
face via hydroxyl groups with the formation of water and
oxygen-containing compounds of sulfur. It must be noted,
that after the experiment a white pellet of aluminum ox-
ide acquired the black–violet color, which indicates the
formation of elementary sulfur Sn [21,24,25].
393
(b) 4. Conclusions
5
1. The kinetic parameters: reaction orders and activation
1226
1325
energies of catalytic hydrogen sul5de decomposition
4
3 are determined. Reaction orders by hydrogen sul5de for
2 the iron oxide — 2.6. E;ective activation energies are
72; 94; 103 kJ=mol, respectively.
1333
1
and V2 O5 catalysts leads to reduction of these oxides with
simultaneous formation of sul5des of Fe2+ and V4+ .
1400 1200
3. As a result of interaction of hydrogen sul5de with alu-
minum oxide at low temperatures, the adsorbed species
of H2 S are formed as HS− and S2− , which upon heating
transform into the various modi5cations of elementary
sulfur.
4. In accordance with the IR spectroscopic data hydrogen
sul5de adsorbed on Al2 O3 interacts with the oxide surface
with formation of the oxygen–sulfur compounds which
further on transform into the elementary sulfur.
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