ISSN 1810-2328, Journal of Engineering Thermophysics, 2017, Vol. 26, No. 3, pp. 314–324.


c Pleiades Publishing, Ltd., 2017.

Oxidation of Hydrogen Sulfide and Corrosion of Stainless Steel

in Gas Mixtures Containing H2 S, O2, H2 O, and CO2
A. A. Vostrikov1, 2* , O. N. Fedyaeva1 , A. V. Shishkin1, 2 , and M. Ya. Sokol1
1
Kutateladze Institute of Thermophysics, Siberian Branch, Russian Academy of Sciences,
pr. Akad. Lavrent’eva 1, Novosibirsk, 630090 Russia
2
Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
Received March 16, 2017

Abstract—The composition of volatile and solid products of oxidation of hydrogen sulfide and
stainless steel in gas mixtures containing H2 S, O2 , H2 O, and CO2 has been determined using
mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown
that holding an H2 S–O2 mixture at 301 K results in prevailing formation of elemental sulfur and
iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of
gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water
triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O2 medium is
accompanied by formation of SO2 and heat release at T > 508 K. After heating of the H2 S–CO2
mixture to 615 K, H2 and COS were found in the volatile reactants; no noticeable corrosion of the
reactor wall has been detected. It has been established that addition of O2 to the H2 S–CO2 mixture
and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed
processes are discussed.

DOI: 10.1134/S181023281703002X

INTRODUCTION
The study of the behavior of structural materials in hydrogen sulfide media is stimulated by the need
to desulfurize natural gas and petroleum feedstock [1, 2], corrosion of equipment in the geothermal
power industry [3, 4], and the possibility of using natural H2 S sources for hydrogen production [5, 6].
Our interest in studying these processes is primarily due to the fact that H2 S is the main product of
conversion of sulfur-containing fuels (oil shale [7], brown coal [8, 9], bitumen [10, 11], heavy oil [12],
and sewage sludge [13]) in supercritical water (T > 647 K, P > 22.1 MPa). The prospects for the use
of supercritical water (SCW) in the development of clean fuel energy production are associated with the
need to solve the problems of converting the S-containing components of fuels into hydrogen sulfide and
subsequent liberation of elemental sulfur in the condensed state [1] or in the form of zinc sulfides [11, 12,
14].
Corrosion of various types of steel has been studied in the systems H2 S–H2 O [15–18], H2 S–H2 O–
NaCl [19, 20], H2 S–CO2 [21–23], and CO2 –H2 O–O2 –H2 S [24]. Ning et al. [16] have shown that at
298 K mackinawite (tetragonal FeS) is the only product of sulfidation of low-carbon steel in saturated
aqueous solution of hydrogen sulfide, whereas at 333 K the products include greigite (cubic Fe3 S4 ) and
pyrite (cubic FeS2 ), along with mackinawite. Analysis by Bai et al. [17] of the products of corrosion
of steel X52 in saturated H2 S vapor and saturated aqueous solution of H2 S at 323 K revealed that in
both cases the process started at grain boundaries, and mackinawite and cubic FeS were, respectively,
the primary and secondary products of the iron sulfidation. From data on the corrosion of X52 and X80
steels in the system H2 S–H2 O–NaCl at 298–423 K [19, 20] it follows that increase in the concentration
of sulfide ions leads to growth in the rate of corrosion with prevailing formation of mackinawite. Ming
et al. [23] investigated the corrosion of steel FV520V in the mixture H2 S–CO2 (339–405 K) and found
the process rate to vary in the interval (1.9–5.7)·10−7 mm/s and tend to increase with growing H2 S
*
E-mail: vostrikov@itp.nsc.ru

314
 OXIDATION OF HYDROGEN SULFIDE AND CORROSION OF STAINLESS STEEL 315

concentration; the yield of the basic corrosion products (Fe2 O3 , Fe3 O4 , FeS2 , and FeS) also depends
on the H2 S concentration. Sun et al. [24] investigated the effect of adding O2 and H2 S on the corrosion
of steel X65 in supercritical CO2 at 323 K and showed that the corrosion products contained FeCO3 , S8 ,
FeS, FeOOH, and Fe2 O3 . On the basis of the fact that the corrosion rate in the mixture CO2 –H2 O–
O2 –H2 S is much higher than that in the mixtures CO2 –H2 O–O2 and CO2 –H2 O–H2 S, the authors
in [24] suggested that the H2 S and O2 had a synergistic effect on the corrosion. It was also shown in
[24] that formation of elemental sulfur accelerated corrosion, but the mechanisms were not described.
In this work we investigated the oxidation of hydrogen sulfide and corrosion of stainless steel, from
which the reactor is made, in gas mixtures containing H2 S, O2 , H2 O, and CO2 , which are the main
components of the reaction mixture for fuel conversion in SCW. Since the technological processes
include heating and cooling of the reaction mixture, the experiments were performed at temperature
varying from 301 to 673 K. We have shown earlier [25] that when the pyrite conversion products (the
main S-containing mineral component of fuels) in SCW are discharged from the reactor (923 K) in the
collector (298 K), the formation of elemental sulfur during the reaction

SO2 + 2H2 S = 3S(s) + 2H2 O, ΔH ◦r,298 = −145 kJ/mol,

causes blockage of the transport main. Here and below, the enthalpy ΔHr,298 ◦ is determined from
reference data [26] and corresponds to normal conditions; the superscript (s) indicates the solid state
of substance.

EXPERIMENT PROCEDURE
Figure 1 presents the scheme of the experimental setup [27], the main element of which is a tubular
reactor with an internal diameter of 30 mm and a volume of 65.0 cm3 . Reactor 1 is made of stainless steel
12H18N10T (analogue of AISI 321), whose composition is given in Table 1. The reactor was placed in
thermostat 5, whose temperature was regulated by a thermoprogrammer coupled to the thermocouple
Tout on the outer wall of the reactor. The temperature of the reactants was measured by the thermocouple
Tin introduced into the center of the reaction volume through the end of the reactor. The pressure of the
reactants PR was measured by membrane strain gage 2, connected to the reactor by means of a capillary.
The temperature and pressure were recorded digitally. The reagents were fed to the previously evacuated
reactor via needle valve 8 by a capillary welded into the central part of the reactor sidewall. The reactor
volume inside the thermostat is 64.1 cm3 , and the cold (parasitic) volumes outside the thermostat are
0.9 cm3 .
Four experiments were carried out, in correspondence with the following composition of the volatile
reagents: H2 S–O2 –H2 O, H2 S–O2 , H2 S–CO2 , and H2 S–CO2 –O2 . In Experiment 1, 0.9 cm3 of
water was charged into the reactor using a syringe through rubber membrane 7, mounted on the union
of the reagent supply valve (Fig. 1). When the reactor had been heated up to 393 K and held at this
temperature for 90 minutes, the water condensed in cold (parasitic) volumes, which prevented H2 S and
O2 entering them. The reactor was then cooled to 301 K, after which it was charged first with H2 S up to a
pressure of 1.72 MPa and then with O2 up to a pressure of 4.81 MPa. The amount of water in the reaction
volume was 0.061 mol, which corresponded to the saturated water vapor density (ρst = 0.953 mmol/dm3
[28]) at the cold-volume temperature (293 K). At the 270th minute of the experiment, the volatile
reactants taken from the reactor were subjected to mass spectrometric analysis. The total time of the
stay of the reactants in the reactor at 301 K was 1265 minutes. When the reactor was opened, on its wall
there was found a crust of solid products.

Table 1. Chemical composition of stainless steel 12H18N10T

Component Si Cu Mn Ni Ti P Cr S Fe
Composition (wt.%) ≤ 0.8 ≤ 0.30 ≤ 2.0 9.0–11.0 0.6–0.8 ≤ 0.035 17.0–19.0 ≤ 0.020 Mc∗
∗
Mc—main component.

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316 VOSTRIKOV et al.

Fig. 1. Scheme of experimental setup: 1—reactor; 2—membrane strain gage; 3—thermocouple inside reactor;
4—resistive heater; 5—thermostat; 6—controlling thermocouple on reactor wall; 7—rubber membrane; 8—control
valve; 9—prechamber; 10—mass spectrometric diagnostic unit; 11—manometer; 12—shut-off valve; 13—forevacuum
pump.

Experiment 2 included two stages. At the first stage, hereinafter referred to as Experiment 2(1), H2 S
was charged into the reactor at 298 K up to a pressure of 1.91 MPa. Next O2 was fed to the reactor up to
a pressure of 3.26 MPa, and the reactor was heated, first with the rate q + = 2.0 K/min up to 423 K and
then with the rate q + = 1.0 K/min up to 661 K. Then the reactor was cooled (q − = 6.0 K/min) to the
room temperature, and a mass spectrometric analysis was done. At the second stage of Experiment 2,
hereinafter referred to as Experiment 2(2), the reactor was evacuated, filled with O2 up to a pressure of
1.84 MPa and heated (q + = 2.0 K/min) up to 663 K. After cooling (q − = 6.6 K/min) of the reactor to
the room temperature, a mass spectrometric analysis of the composition of the volatile reactants was
done.
In Experiment 3, at a temperature of 299 K, the reactor was charged first with H2 S up to a pressure
of 1.68 MPa and then with CO2 up to a pressure of 3.32 MPa. After heating (q + = 2.0 K/min) of the
reactor, a mass spectrometric analysis was performed at 423 K during 30 min. Then, the heating of the
reactor was continued up to 615 K (q + = 1.5 K/min). After cooling (q − = 9.5 K/min) of the reactor to
473 K, a mass spectrometric analysis was carried out.
In Experiment 4, at a temperature of 323 K the reactor was sequentially charged with H2 S, CO2 , and
O2 up to pressures of 2.1, 4.2, and 9.0 MPa, respectively. Hydrogen sulfide was fed to the reactor from
the cylinder heated to 323 K, which made it possible to create in it the pressure of saturated H2 S vapor
necessary for filling the reactor [28]. Next the reactor was heated (q + = 1.0 K/min) up to 673 K and then
cooled to the room temperature. After opening of the reactor, yellow lamellar crystals were found on its
wall.
The quantity of reagents [X]0 charged into the reactor in each of the experiments, the rate q + and the
time of heating the reactor t to the final temperature T , as well as the volatile reactants composition, are
given in Table 2. The amount of each of the reagents [X]0 is calculated from the values of their partial
pressure and reactor volume using reference P–v–T data [28]. The composition of the volatile reactants
was determined using a quadrupole mass spectrometer MS-7303 according to the procedure in [8].
The surface images of the solid products were made using an optical Microscope LOMO MICMED-
5. The phase composition of the solid products was determined using a powder x-ray diffractometer
Bruker D8 Advance (vertical goniometer, θ/2θ-geometry, λ(Cu–Kα) = 0.15418 nm), equipped with
a linear semiconductor detector Lynx-Eye with a nickel filter (the PDF database was used for phase
identification [29]). The morphology and elemental composition of the solid products were determined
using a scanning electron microscope (SEM) Hitachi S-3400N, equipped with an EDX spectrometer.

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 OXIDATION OF HYDROGEN SULFIDE AND CORROSION OF STAINLESS STEEL 317

Table 2. Experimental conditions and composition of volatile reactants

Test [H2 S]0 [O2 ]0 [CO2 ]0 q+ t T Composition of reactants (mol. %)

mmol mmol mmol K/min min K H2 S O2 H2 O H2 SO2 CO2 COS CS2
1 50.2 78.8 – – 270 301 25.2 71.7 2.7 0.3 Trace – – –
2(1) 68.0 42.7 – 2.0 / 62.5 / 298–423 / Trace Trace 9.3 0 90.6 – – –
1.0 238 423–661
2(2) – 48.2 – 2.0 185 293–663 0.4 1.9 6.1 1.0 90.5 – – –
∗
3 47.8 – 52.2 1.0 124 299–423 47.8 – 0 0 0 52.2 0 0
1.5 128 423–615 45.0 – 6.2 1.0 Trace 45.5 2.2 Trace
4 59.0 118.0 55.4 1.0 350 323–673 – – – – – – – –
∗
Temperatures at which the mass spectra were obtained are given in the experimental part.

RESULTS AND ITS DISCUSSION

Transformations in the system H2 S–O2 –H2 O. Figure 2 shows the time dependence of the
reactant pressure PR (t) in the reactor obtained in Experiment 1 (curve 1). As can be seen, after the
fill-up of the reactor with hydrogen sulfide and oxygen, the pressure PR began going down because of
the formation of elemental sulfur and water during the reaction

◦
H2 S + 0.5O2 = H2 O + 0.5S2 , ΔHr,298 = −157 kJ/mol, (1)

and their condensation on the reactor wall. In reaction (1), the molar ratio [O2 ]/[H2 S] = 0.5, whereas the
reactor charge ratio was [O2 ]0 /[H2 S]0 = 1.57 (Table 2). This means that the oxidation of H2 S occurred
in excess of oxygen. The pressure created by this excess in complete oxidation of H2 S, calculated from
reference data [28], was expected to be 2.13 MPa, while in reality PR = 2.39 MPa (Fig. 2, curve 1), i.e.,
part of the hydrogen sulfide did not oxidize during the experiment (t = 1265 min). From the measured
pressure PR it was found that the degree of conversion of H2 S at the end of the experiment was 91% of
the initial amount [H2 S]0 .
The rate of the process under the conditions of Experiment 1 qualitatively characterizes the time
dependence dPR /dt (Fig. 2, curve 2). The presence of the maximum on curve 2 at t = 84 min is caused
by the self-acceleration of reaction (1) at the initial stage of oxidation. From the measurements of the
pressure PR (t) and the thermal effect of reaction (1) it follows that about 26% of hydrogen sulfide
oxidized in 84 minutes, which corresponds to an amount of released heat of 2.1 kJ and an average
heat liberation power of 0.4 W. It is obvious that the heat release could not lead to self-acceleration
of reaction (1) at the initial stage of Experiment 1. We believe that the self-acceleration of reaction (1)
was caused by the catalytic effect of sulfur particles (S2 molecules and Sn clusters) arising in the gas
phase. The time for reaction (1) to reach the maximum rate is determined by the time for attaining a
steady-state concentration of sulfur particles in the reaction volume with simultaneous decrease in the
amount of the reagents.
According to mass spectrometric analysis carried out at t = 270 min, in addition to H2 S, O2 , and
H2 O, the volatile reactants contained H2 and trace amounts of SO2 (Table 2). The presence of trace
amounts of SO2 results from the oxygen oxidation of the sulfur (see below). The presence of H2 is due
to the sulfidation of the iron, the initial stage of which is the formation of mackinawite [17]:

◦
Fe + H2 S = FeS + H2 , ΔHr,298 = −80 kJ/mol. (2)

After the completion of Experiment 1, dark crust with bright yellow inclusions on the outer surface
was found on the walls of the reactor. Figure 3 presents a photograph of the surface of this crust.
According to x-ray diffraction analysis (Fig. 4) of the crust ground in an agate mortar, those bright yellow

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318 VOSTRIKOV et al.

Fig. 2. Variation in reactant pressure PR in reactor 1 and in derivative dPR /dt 2 vs time in Experiment 1 at T = 301 K.
Time t = 0 corresponds to completion of oxygen supply to reactor.

Fig. 3. Image of outer surface of sulfur-sulfide crust in Experiment 1, obtained using LOMO MICMED-5 optical
microscope (×100); arrows point at elemental sulfur.

inclusions on the surface of the crust are elemental sulfur (S8 –α-S, rhombic crystal lattice). In addition
to elemental sulfur, there were found FeS (mackinawite) and Fe3 S4 (greigite), as well as trace amounts
of FeS2 (pyrite), α-Fe2 O3 (orthorhombic), α-Fe1.8 O2.4 (OH)0.6 (rhombohedral), Ni6 S7 (godlevskite),
Cr2 S3 (hexagonal), and CrOOH (grimaldiit). Obviously, this composition of the products is a result
of corrosion, which, according to [19–24], is of an electrochemical nature. Note that no appreciable
corrosion of the reactor wall was observed in the research on zinc sulfidation in supercritical H2 S and
a H2 S–H2 O mixture [14] and on pyrite conversion in SCW [25], that is, in the absence of O2 . This is
consistent with the conclusion of the authors in [24] on the synergistic effect of H2 S and O2 on corrosion.
Figures 5a and 5b present electron microscope images of the outer and inner surfaces of the sulfur-
sulfide crust. It can be seen that the crust is highly porous (the average pore size ≈ 4μm). In addition to

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 OXIDATION OF HYDROGEN SULFIDE AND CORROSION OF STAINLESS STEEL 319

Fig. 4. Diffractogram of solid residue in Experiment 1. a—experiment and bar charts [29]; b—sulfur S8 (orthorhombic,
PDF Card 01-077-0145); c—greigite Fe3 S4 (cubical, PDF Card 04-008-7806); d—mackinawite FeS (tetragonal,
PDF Card 00-015-0037).

Fig. 5. SEM images of surface of sulfur-sulfide crust in Experiment 1. a—Outer surface; b—inner surface; A, B, C,
and D—areas under elemental analysis with EDX spectrometer (the results are given in Table 3).

Fe, Cr, Ni, and Si atoms, which occur in the original steel (Table 1), EDX elemental analysis of the crust
surface areas marked in Fig. 5 revealed high content of S and O atoms (Table 3). Comparison of the
content of chromium and nickel in the initial steel and in the sulfur-sulfide crust shows that the nickel
content in the crust is several times lower. Obviously, this is because chromium is more affine to oxygen
than nickel [30]. The higher content of S atoms in region A (Table 3, Fig. 5) is due to the presence of
elemental sulfur. The abnormally high oxygen content in regions A, B, C, and D is a consequence of the
formation of water during reaction (1) and its condensation in the pores of the crust. The contribution of
oxides and oxyhydroxides of metals to the oxygen content is insignificant because of their low content in
the sulfur-sulfide crust (Fig. 4). The results obtained make it possible to assert that the water arising in
reaction (1) is a trigger for corrosion of the reactor wall.

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320 VOSTRIKOV et al.

Table 3. Results of elemental analysis of the surface of the sulfur-sulfide crust in Experiment 1 (at. %)

Location O S Si Cr Fe Ni
Fig. 5a (area A) 46.25 33.22 0 1.84 18.69 0
Fig. 5a (area B) 72.99 6.44 0 2.34 18.23 0
Fig. 5b (area C) 68.42 12.10 0.52 7.19 10.13 1.64
Fig. 5b (area D) 78.00 6.87 0 7.56 7.57 0

Transformations in the system H2 S–O2 . In Experiment 2(1), the reagent ratio [O2 ]0 /[H2 S]0 =
0.63 exceeds the stoichiometric ratio for reaction (1). According to mass spectrometry analysis (Table 2),
heating of the reagents up to 661 K resulted in formation of SO2 and H2 O. Taking into account the
results of Experiment 1 and the almost complete absence of H2 S and O2 in the products (Table 2), it
can be assumed that the following sequence of reactions occurred in Experiment 2(1). First, elemental
sulfur and iron sulfide arose in reactions (1) and (2), respectively, and then, with the temperature growth,
the oxygen residue almost completely reacted with the sulfur and iron sulfide by the mechanism of the
following reactions:

◦
S2 + 2O2 = 2SO2 , ΔHr,298 = −722 kJ/mol, (3)
◦
2FeS + 3.5O2 = Fe2 O3 + 2SO2 , ΔHr,298 = −1216 kJ/mol. (4)
According to reference data [31], the autoignition temperature of sulfur TSI = 505 K, and that of
hydrogen sulfide in the reaction

◦
H2 S + 1.5O2 = H2 O + SO2 , ΔHr,298 = −518 kJ/mol, (5)
TSI = 533 K. In this experiment, during the heating of the reactor a jump in the internal thermocouple
temperature Tin was observed at 508 K (with a maximum at 530 K) and the temperature growth slowed
down at T > 568 K (Fig. 6, curve 1). The temperature jump is explained by the intensive oxidation of
sulfur, iron sulfide and hydrogen sulfide in reactions (3)–(5); the slowing of the temperature growth is
caused by the depletion of oxygen in the reactor, which agrees with the results of mass spectrometry
analysis (Table 2).
In Experiment 2(2), after the reactor was evacuated, re-filled with oxygen (Table 2), and heated to
663 K, a jump in the internal thermocouple temperature Tin was registered again (Fig. 6, curve 2). This
confirms our conclusion that formation of SO2 in reactions (3)–(5) caused the temperature jump in
Experiment 2(1) (Fig. 6, curve 1). In addition to SO2 , the volatiles in Experiment 2(2) contained H2 O,
H2 , and H2 S (Table 2). The presence of water is explained by its partial removal from the sulfur-sulfide
crust during the evacuation of the reactor after the completion of Experiment 2(1); the appearance of H2
and H2 S is due to the reaction

◦
1.5S2 + 2H2 O + O2 = H2 S + H2 + 2SO2 , ΔHr,298 = −323 kJ/mol. (6)
This reaction was chosen because the composition of the products in Experiment 2(2) differs from
that in Experiment 2(1) in the presence of H2 and H2 S (Table 2). It is apparent that reaction (6) occurred
at the end of Experiment 2 (2), otherwise hydrogen sulfide would have reacted completely with the
oxygen and partially with the hydrogen (TSI = 783 K [31]) by the mechanism of, respectively, reaction (6)
and the following reaction:

◦
H2 + 0.5O2 = H2 O, ΔHr,298 = −242 kJ/mol. (7)
Transformations in the system H2 S–CO2 . In Experiment 3, when the H2 S–CO2 mixture was
heated up to 423 K, a linear increase in the pressure of the reagents and in the temperature of the internal

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Fig. 6. Temperature difference ΔT = Tin − Tout vs. internal thermocouple temperature Tin at the first (1) and second
(2) stages of Experiment 2.

thermocouple was observed. From the mass spectrometry analysis data (Table 2) one can see that no
changes in the composition of the reaction mixture happened under these conditions. After heating of
the reactor up to 673 K, in the products there appeared H2 O, COS, H2 , and trace amounts of SO2 and
CS2 (Table 2). The presence of COS, apparently, is a result of the reaction

◦
H2 S + CO2 = COS + H2 O, ΔHr,298 = +30 kJ/mol. (8)
In reaction (8) the numbers of moles of the arising COS and H2 O are equal, and the real molar ratio
[COS]/[H2 O] = 0.35. Since all the water formed in reaction (8) in the reactor was in the form of vapor,
the resulting [COS]/[H2 O] ratio can be a consequence of both the thermal decomposition of COS at
T > 573 K and the following disproportionation reaction [32]:

◦
COS = CO + S(s) , ΔHr,298 = +32 kJ/mol, (9)
◦
2COS = CS2 + CO2 , ΔHr,298 = +8 kJ/mol. (10)
The presence of H2 in the products of Experiment 3 appears to be a result of the water gas-shift reaction
coupled with reaction (9):

◦
CO + H2 O = CO2 + H2 , ΔHr,298 = −41 kJ/mol. (11)
Unfortunately, it was impossible to register CO because of the high content of CO2 and the respective
high yield of CO+ ions in dissociative ionization of CO2 [33].
Transformations in the system H2 S–CO2 –O2 . In Experiment 4, the ratio [O2 ]0 /[H2 S]0 = 2 (Ta-
ble 2), i.e., it is four times larger than the stoichiometric ratio for reaction (1), and the amount of [CO2 ]0
is slightly less than the amount of [H2 S]0 . In this experiment, as in Experiment 1, strong corrosion of
the reactor wall was revealed. The corrosion products were yellow lamellar crystals. Figure 7 shows a
diffractogram of these crystals. It can be seen that iron sulfate Fe2 (SO4 )3 (mikasaite, rhombohedral)

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Fig. 7. Diffractogram of solid residue in Experiment 4. a—Experiment and bar charts [29]; b—mikasaite
Fe2 (SO4 )3 (rhombohedral, PDF Card 00-033-0679); c—2Fe(OH)SO4 (orthorhombic, PDF Card 00-021-0428);
d—Fe3 (SO4 )4 (H2 O)2 (monoclinic, PDF Card 04-009-5705]); e—goethite α-FeO(OH) (orthorhombic, PDF Card
00-003-0249).

is the main component. The content of iron hydroxyl sulfate 2Fe(OH)SO4 (orthorhombic), iron sulfate
dihydrate Fe3 (SO4 )4 (H2 O)2 (monoclinic), and iron oxyhydroxide α-FeOOH (goethite, orthorhombic)
in the sample is much less than the content of Fe2 (SO4 )3 . No elemental sulfur or iron sulfides were
detected in the products. This indicates complete oxidation of hydrogen sulfide, sulfur and sulfides to
sulfates, which was not observed in Experiments 1–3. It can be assumed that in Experiment 4 the
elemental sulfur that had formed in reaction (1) completely oxidized in reaction (3), and the iron sulfide
that had formed in reaction (2) reacted with oxygen and water in the presence of dissolved CO2 in the
following reactions [34, 35]:

Fe1−x S + (2 − 0.5x)O2 + xH2 O → (1−x)FeSO4 + xH2 SO4 , (12)

4Fe1−x S + 3(1−x)O2 + 6(1 − x)H2 SO4 → 2(1 − x)Fe2 (SO4 )3 + 4S + 6(1 − x)H2 O. (13)
According to [35], the iron sulfate that formed in reaction (12) oxidizes in the water-oxygen medium
during the reaction

2FeSO4 + H2 O + 0.5O2 = 2Fe(OH)SO4 , (14)

with formation of iron hydroxy sulfate, the hydrolysis of which, in turn, leads to formation of iron
oxyhydroxide and sulfuric acid:

2Fe(OH)SO4 + 2H2 O = 2FeO(OH) + 2H2 SO4 . (15)

Note that, in contrast to the results of Experiment 4, no iron sulfates have been found in corrosion
products in [24]. In our opinion, this is because the values of temperature and O2 concentration in this
paper are higher than in [24].
The results of this work show that in conversion of S-containing fuels using SCW, the main
problems associated with the presence of sulfur can arise in the cooling of the reactants during their

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outflowing from the reactor. In the regime of fuel complete combustion in the SCW/O2 fluid, i.e., at
high concentration of CO2 in the reactants [9, 10], decrease in the temperature and formation of liquid
water will inevitably lead to appearance of sulfates (Fig. 7). In the case of incomplete oxidation of fuel in
the SCW/O2 fluid, there can appear elemental sulfur (Fig. 3) and the transport mains will be blocked
[25]. Besides that, there can arise sulfides of metals (Fig. 4) that enter into the structural materials. The
danger is that the iron sulfides and elemental sulfur that settled in the transport mains can self-ignite at
T > 508 K during discharge of reaction mixture containing O2 (Fig. 6).

CONCLUSIONS
In this paper, oxidation of hydrogen sulfide and stainless steel 12H18N10T in gas mixtures initially
containing H2 S, O2 , H2 O, and CO2 was studied for the first time at a temperature of 301–673 K. It was
shown that holding the H2 S-O2 mixture at 301 K results in prevailing formation of elemental sulfur and
iron sulfides in the form of porous hygroscopic crust on the wall surface of the reactor. At the initial stage
of hydrogen sulfide oxidation, there is observed nonthermal self-acceleration of the reaction due to the
catalytic effect of sulfur particles arising in the gas phase. It has been found that the formation of water
during the oxidation of hydrogen sulfide is a corrosion trigger. From analysis of the composition of the
gaseous products and the time dependence of the temperature of the reagents it follows that oxidation
of elemental sulfur and iron sulfides in the O2 medium is accompanied by formation of SO2 and heat
release at T > 508 K. After heating of the H2 S–CO2 mixture up to 615 K, no noticeable corrosion of the
reactor wall was recorded. Addition of O2 to this mixture leads to formation of ferrous sulfates.

ACKNOWLEDGMENTS
The authors are grateful to E.A. Maksimovsky and D.A. Yatsenko for electron microscopy and x-ray
diffraction analysis of the samples.

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