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Proceedings
of the
Combustion
Institute
Proceedings of the Combustion Institute 34 (2013) 625632
www.elsevier.com/locate/proci

Experimental and kinetic modelling study

of H2S oxidation
Chenlai (Ryan) Zhou, Karina Sendt, Brian S. Haynes
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia

Available online 21 June 2012

Abstract

Oxidation of H2S in an atmospheric pressure ow reactor at temperatures from 950 to 1150 K has been
studied under fuel-lean conditions (1.9 < [O2]0/[H2S]0 < 10). The reaction is strongly catalysed by silica sur-
face but this eect is suppressed with application of a B2O3 coating to the silica. A feature of the reaction is
the high selectivity (40%) to H2 formation, even in the presence of a large excess of oxygen.
A comprehensive chemical kinetic model for H2S oxidation has been developed. The model includes
detailed chemistry for disulfur interactions based on recent experimental and theoretical work. The model
shows extraordinary sensitivity to the rates of a signicant number of reactions that determine the radical
concentrations during the oxidation process. Minor variations (<factor 3) in the rate coecients of two of
the SH self-reaction channels allows accurate description of H2S consumption proles: on the one hand, the
reaction 2SH
H2S + S (followed by S + O2
SO + O and SO + O2
SO2 + O) is strongly branch-
ing whereas on the other, 2SH
HSSH (followed by HSSH + SH
H2S + HSS and HSS + SH

H2S + S2) is a powerful chain termination sequence, especially when the oxygen excess is reduced.
Disulfur interactions are extremely important in the ignition and propagation of H2S oxidation even
under fuel lean conditions.
2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Keywords: Hydrogen sulde; Chemical kinetic modelling; Disulfur species; Oxidation mechanism

1. Introduction While there are extensive kinetic studies of the

Hydrogen sulde (H2S) is commonly present in
some natural gases and is produced as a side prod-
uct in oil renery operations and fossil fuel gasi-
cation processes, often being further processed via
combustion in a Claus furnace. Sulfur chemistry
in these high-temperature processes is complex
and poorly understood, leading to uncertainties
in process design emissions control.
Corresponding author. Fax: +61 2 9351 3471.
E-mail address: brian.haynes@sydney.edu.au (B.S.
Haynes).
impact of doped sulfur species on the combustion
radical pool (see [1] and references therein), the
oxidation of H2S itself remains poorly understood.
Gargurevich [2] recently summarised the kinetics of
reactions thought to be important in very fuel-rich
Claus furnace combustion. Cerru et al. [3] recently
proposed a detailed sulfur mechanism validated
against the limited available literature data but
noted that the role of SH radical remains uncertain,
in particular SH self-reaction involving HSS and
HSSH species, which are especially important in
stoichiometric and fuel-rich conditions.
We [4] have recently combined experimental
and high-level theoretical studies of the H2/S2

1540-7489/$ - see front matter 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.proci.2012.05.083
626 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
system (including H2, S2, HSSH, H2SS, 2SH, and
H + HSS) over a wide range of temperatures and
pressures. This study revealed complexity in the
kinetics that had not been included in any previ-
ous attempts to model H2S oxidation for exam-
ple, in the self-reaction of SH, formation of HSSH
HSO +
occurs in parallel with H2S + S production, with
H2S + SO ( R36)
reaction to HSS + H also becoming important at
higher temperatures (>1000 K).
The objective of this paper is to develop a
chemical kinetic model for fuel-lean H2S oxida-
tion that incorporates detailed characterisation
of the H2/S2 system along with additional new
results for other reactions not included in earlier
models. In support of the model development,
we have also obtained new data for oxidation of
H2S in a ow reactor in the critical temperature
regime around 1000 K.
2. Chemical kinetic model
The thermochemical data for the 41 species con-
sidered in H2S oxidation mechanism were mainly
adopted from literature, including Leeds Univer-
sity (H2S, SO2, SO, S, HSOH, HSO2, HOSO,
HOSO2 and SO3) [5], Burcats Thermodynamic
Data (H2O, H2, H2O2, HO2, S2, S3, S4, S5, S6, S7,
S8, O3, H, OH, O and O2) [6] and our own earlier
work (HSSH, HSS, S2O, H2S2O2, H2O. . .SO2,
H2S3O and HSSSOH) [7,8]. Recent updates were
used for the heats of formation of SH [9], HSO,
HOS [10] and HSOO [11]. For the remaining spe-
cies (HSSO2, singlet SO (SO*), SSO2, HSSO and
OSSO) we evaluated thermochemical data at the
G3 level [12,13] using statistical methods. Detailed
parameters in the 7-term polynomial form are tab-
ulated in the Supplementary data.
The mechanism (see Supplementary data) con-
sists of 277 reversible gas-phase elementary reac-
tions, including the well established H2 oxidation
mechanism [14], SO and SO2 oxidation chemistry
[1,15], reactions of SO3 with H, O, and OH radi-
cals [16] and the H/S subset [8] with updated
kinetic parameters [4]. Rate constants for reac-
tions in the H/S/O system (R42R44, R58 and
R78R83) are adopted from high-level theoretical
calculations [17].
With respect to SH oxidation channels, the
reaction SH + O2 was long considered to form
HSO + O (R39) as the favoured products. How-
ever, our recent theoretical work [11] revealed that
HSO + O formation is more than two orders of
magnitude slower than previous estimates [18]
allowing the reaction via a four-membered cyclic
transition state producing SO + OH (R40) to be
competitive at temperatures >1000 K. Very
recently, Garrido et al. [19] concluded that the
route leading to H + SO2 (R41) via three-centre
ring structure HSO2 intermediate is actually the
preferred channel for the reaction.
Theoretical calculations were also performed
for SH reactions with HO2, H2O2 and HSO spe-
cies and reported in elsewhere [12]. While substan-
tial barriers are present for the reaction SH +
H2O2 forming H2S + HO2 (R31) or HSOH + OH
(R32), it was found that SH + HO2
OH (R48) and SH + HSO
are fast and barrierless.
The chemistry of HSO interactions with H, O,
and OH (R85, R86, R88, R92 and R94) are
adopted from Rasmussen et al. [1]. Regarding
the reaction HSO + O2, our theoretical study
[12] revealed the formation of SO2 + OH (R72)
via the O2-insertion intermediate (HOOSO) to
be several orders of magnitude faster than their
[1] assumed channel to HSO2 + O (R74) at tem-
peratures below 800 K; at higher temperatures,
H abstraction to form SO + HO2 (R70) becomes
dominant.
The mechanism of SO2-catalysed radical
recombination primarily via HSO2 and HOSO
intermediates has been well studied, producing
reliable kinetic parameters for relevant channels
[1,20].
Except for the direct reactions H2S + SO2 and
H2S + S2O [7], the rate coecients and products
of the majority of sulfursulfur interactions are
simply assumed. These include dummy processes
that allow Sn (n = 38) species to form in partial
equilibrium with S2 (R259R264) in order to esti-
mate the potential for these species to act as a sul-
fur sink.
Chemical kinetic modelling of reaction condi-
tions was carried out using CHEMKIN [21]. Plug
ow was assumed for ow reactors and the PRE-
MIX [21] ame code was employed for modelling
ame conditions reported in the literature.
3. Experimental
The experimental set-up comprises a silica ow
reactor (ID = 7 mm) housed vertically in a tem-
perature-controlled furnace (Fig. 1). The reactant
streams (1.0% H2S in N2 and O2 in N2) are fed
and preheated by owing downwards through
annuli that surround the central reaction tube,
mixing at its base and exiting at the top. The
H2S concentration entering the reactor was in
the range 100520 ppm in order to eliminate reac-
tion heat release eects.
The countercurrent nature of the feed and
reaction streams ensured very precise temperature
regulation (<1 K) of these streams, as conrmed
by separate measurements and heat transfer mod-
elling. However, in passing through the insulation
surrounding the furnace box, the reaction gases
cooled only slowly, at about 1000 K s 1 this
eect was measured accurately and accounted
for in the kinetic modelling of the experimental
reaction conditions.
 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
Probe
Sampling
Pump
Thermocouple
Sampling
Fuel Oxidiser
Preheating
annulus
Reaction
tube
Mixing
zone
Furnace
Fig. 1. Schematic diagram of the experimental setup for
H2S oxidation.
A total reactant ow rate of 420 cm3 min 1
(294 K, 1 bar) is controlled by mass ow control-
lers to achieve residence times around 0.2 s in the
isothermal hot zone and 0.3 s in the cooling zone,
depending on actual reaction temperatures The
reactor pressure was maintained at 1.05 bar. In
some experiments in which reaction was com-
pleted inside the isothermal region, species were
withdrawn rapidly (<5 ms) from specic points
along the centreline of the central reaction tube
using a silica vacuum probe (3 mm OD  1 mm
ID with 30 lm orice at the tip).
The concentrations of H2S, H2 and SO2 were
measured by micro-GC (MTI 200) with a preci-
sion of 2%. Certied cylinder standards were used
for direct calibration for H2S and H2, while SO2
was calibrated using product gases from the com-
plete oxidation of a known inlet concentration of
H2S.
Since silica surface was found to promote the
oxidation of H2S [12], and since boric acid coating
was found in early studies of H2 and hydrocarbon
oxidation [2225] to be inert to the decomposition
of peroxy species, we investigated the use of this
coating here in our analogous H2/S2/H2S system.
Following [22], the reactor wall was rst coated
with boric acid that yielded a transparent impervi-
ous coating of B2O3 on baking at 773 K. A com-
parison of experimental proles (for 310 ppm
H2S oxidation with 600 ppm O2) measured in
the B2O3-coated reactor and in an uncoated silica
is presented in Fig. 2 it is apparent that the sys-
tem is much less reactive in the coated reactor,
with >200 K increase in the 50% conversion tem-
627
350
300 B 2O3-Coating
H2S concentration (ppm)
250 Bare Silica
200
150
100
50
0
500 600 700 800 900 1000 1100 1200
Temperature (K)
Fig. 2. Comparison of H2S oxidation in the uncoated
silica reactor with oxidation in the same reactor coated
with B2O3. Inlet composition 325 ppm H2S, 600 ppm O2.
perature. While it cannot be demonstrated that
B2O3 itself neither promotes nor inhibits the reac-
tion signicantly, the apparent activation energy
and overall reactivity of the system is less obvi-
ously catalytic in nature in the coated reactor.
All experimental proles reported here are there-
fore from measurements conducted in the B2O3-
coated reactor.
4. Experimental results
Figure 3 shows experimental results from the
ow reactor for three conditions, as a function
of reactor temperature. The data in Fig. 3a are
for low [H2S]0 (=100 ppm) and large oxygen
excess [O2]0/[H2S]0 = 10; those in Fig. 3b and c
are for increasing values of [H2S]0 (=325 and
520 ppm, respectively) and slight oxygen excess
([O2]0/[H2S]0  1.9). Based on the temperature at
which 50% conversion of the H2S is achieved,
the very lean condition (a) is most reactive;
increasing [H2S]0 at constant [O2]0 (c) raises the
conversion temperature by 40 K; relative to (c),
decreasing [H2S]0 at constant [O2]0/[H2S]0 raises
the reaction temperature by a further 35 K. In
all cases, there is substantial formation of H2, typ-
ically 35% selectivity at the lowest temperature
at which H2S conversion is substantially complete.
Qualitatively similar results, not reported here,
have been obtained over a wide range of condi-
tions [12].
The only sulfur components detected in the
product gases were H2S and SO2. As shown in
Fig. 4 the results for the low ratio of [O2]0/
[H2S]0 show a signicant decit (low SO2 yield).
This decit peaks at the temperature at which
the H2S conversion is 50%, but decreases to
the noise level at higher temperatures. According
to the simulations discussed in more detail below,
it is sulfur, mostly in the form of S2 with lesser
quantities of S4 and S8, that accounts for the def-
628 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632

100 14
SO2 (a) (b)
H2S 12
80

Sulfur Mass Deficit (%)

10
60
(c)
8

40
6
H2
20 4

0 2

300 0
H2S SO2 (b)
Concentration (ppm)

950 1000 1050 1100 1150

250 Temperature (K)
200
Fig. 4. Comparison between experimental data (sym-
150 bols) and modelling predictions using adjusted mecha-
nism (lines) for mass decit of sulfur calculated as 1 -
100 H2
50

0 350 1200

500 (c) 300

SO2 H2S SO2
H2S
Concentration (ppm)

1000
400 250

Temperature (K)
200 T
300
800
150 H2
200
100
H2 600
100
50

0
0 400
950 1000 1050 1100 1150 0 5 10 15 20 25 30
Temperature (K) Distance (cm)

Fig. 3. Comparison between experimental data (sym-
bols) and modelling predictions (lines) for H2S oxidation
in the B2O3 coated reactor. Dashed lines show the base-
case predictions for H2S; solid lines show predictions
using the adjusted mechanism (dependent on actual
experiments, see text). Inlet compositions: (a) [H2S] =
100 ppm, [O2] = 1000 ppm, (b) [H2S] = 325 ppm, [O2] =
600 ppm; (c) [H2S] = 520 ppm, [O2] = 1000 ppm.
Fig. 5. Comparison between experimental data (solid
symbols, probe sampling; open symbols, sampled at
reactor exit) and modelling predictions (base model
broken lines; adjusted model solid lines) for oxidation in
B2O3 lined reactor at 1120 K. Reactor inlet conditions
[H2S] = 310 ppm, [O2] = 600 ppm. Thick dashed line
shows the temperature prole through the reactor and
cooling section.

in the quench zone, leading to the reduction of

icit. Indeed, prolonged reaction under these condi-
tions gave rise to an observable yellow sulfur
deposit on the wall at the reactor outlet. This phe-
nomenon precluded study of lower (stoichiometric
and fuel-rich) [O2]0/[H2S]0 ratios in the ow
reactor.
Figure 5 shows results obtained as a function
of position in the ow reactor. The conditions in
the experiment are close to those in Fig. 3(b) at
1120 K ([H2S]0 = 310 ppm, ([O2]0 = 600 ppm).
The lled symbols represent the results obtained
using the probe; the open symbols (at 28 cm from
the reactor inlet) were obtained directly at the
reactor outlet. The onset of reaction is detected
at 6 cm with complete consumption of H2S
being achieved at 9 cm. The peak H2 selectivity
(41%) coincides with the removal of the last
traces of H2S. The oxidation of H2 occurs early
H2 selectivity to 21% at the reactor outlet.
5. Modelling and discussion
5.1. Mechanistic overview
As shown by the dotted lines in Figs. 3 and 5,
the base case model qualitatively predicts the
overall trends of H2S consumption reaction; the
solid lines in Figs. 35 show the predictions after
minor adjustments to key rate constants, as dis-
cussed below. Before proceeding to these adjust-
ments, we rst describe the mechanism of
reaction as revealed by reaction path analysis, as
summarised in Fig. 6 for propagating conditions
(50% H2S consumption) solid lines show the
most important pathways in the presence of a
 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
large excess of oxygen ([O2]0/[H2S]0 = 10, Fig. 3a)
while the other lines show the additional pathways
that become increasingly competitive as [O2]0/
[H2S]0 is reduced, rst to 4 (dashed lines) and
then to 1.9 (as in Fig. 3b and c; dotted lines in
Fig. 6).
Under all conditions, H2S is largely consumed
by H (R2), OH (R27R28), and O (R29), forming
the SH radical. Consumption of SH occurs both
via its self-reaction forming S radical ( R3 and
R4) and via reaction with O forming SO and
H (R44). At high [O2]0/[H2S]0, S is predominantly
converted to SO (R59) which is further oxidised to
SO2. (R116), these processes being strongly
branching through their production of O radical.
The H + O2 recombination reaction (R221) plays
an important role in opposing chain branching.
With decreasing [O2]0/[H2S]0, the concentration
of S increases and S2 emerges as an important
intermediate through reaction of S with SH (R6);
H2S + S ( R4 and R3) has a sen-
the concentration of S2 rises because its consump-
tion occurs principally via its reaction (R174) with
O which is now less available. Reaction rates of
channels directly involving O2 (R59, R116 and
R221) also become less eective in competing with
other channels, particularly those that consume
SO + O (R59) and
the radicals S, SO and H (e.g. SH + S
S2 + H SO + O2
SO2 + O (R116). The sensitivity to
(R6), SO + SO
SO2 + S ( R133) and
SH + HO2 ( R25) arises from the
SH + H
S + H2 ( R5)). There is now signi-
cant formation of SO2 (10%) and H2 (15%)
via these secondary channels.
Approaching the stoichiometric condition
(Figs. 3b, 3c and 5), availability of O is further
reduced and the proportion of SH consumption
via reaction with O (R44) declines relative to reac-
tions with HSS and HSSH (R11 and R20, respec-
tively). These chain-terminating reactions together
HO2 + M (R221); nor about
produce more S2 which accumulates to signicant
levels (Fig. 4). The H + O2 recombination now
plays only a minor part in determining the state
of the radical pool.
+H -H2
R2
H2S
+O
R29
-OH
SH
+H +SH -H2S
-H2 -R3, -R4 +O
R44
-H
-R5
+O2 -O
S SO
R59
+O2 +SO
R116
-O -S
SO2
Fig. 6. Schematic mechanism for fuel lean H2S oxidation showing main consumption pathways. As the initial [O2]/[H2S]
is decreased, the additional pathways shown as dashed and dotted lines become competitive.
629
In considering the mechanism of ignition, it is
the direct reaction of H2S with O2 ( R25) that
creates the rst radical centres, as rst postulated
by Merryman and Levy [26]. Rapid branching
only occurs once SH has accumulated suciently
for its self-reaction to generate S ( R3, R4) for
the oxidation of S and then SO to occur at a sig-
nicant rate.
5.2. H2S consumption
Figure 7 shows the logarithmic sensitivity coef-
cients for [H2S] at the reactor exit for most sen-
sitive reactions under the conditions in Fig. 3a
and b, in each case at the predicted temperature
for 50% H2S consumption. It is immediately
apparent that the model predictions are extremely
sensitive to the rate parameters of a signicant
number of reactions. In particular, the reaction
SH + SH
sitivity coecient near 2 with both high (a) and
low (b) oxygen excess. From the discussion of
reaction pathways above, it is apparent that this
sensitivity arises from the fact that the formation
of S atoms in turn promotes the chain branching
reactions S + O2
H2S + O2
role of this reaction in determining the ignition
temperature. Among channels inhibiting H2S oxi-
dation, pathways involving SH (R6, R9, R10
and R44) have the greatest sensitivity, especially
under the low O2 excess condition.
The rates of some of the reactions appearing in
Fig. 7 are better known than others: for example,
there is relatively little uncertainty about the rate
of H + O2 + M
the rates of reactions S and SO with O2 (R59
and R116, respectively) which are well known
from combustion and atmospheric chemistry
studies. There are few experimental rate determi-
+OH -H2O
R27, R28 O2 in large excess
O2 in moderate excess
O2 in low excess
+S -H +SH +SH + M
R6 -R9 R10
-H
+SH +SH
+O -S -H2S -H2S
S2 HSS HSSH
R174 R11 R20
-R133
630 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
S + SH = S2 + H (R6)
SH + SH = HSS + H (-R9)
SH + SH + M = HSSH + M (-R10)
SH + O = SO + H (R44)
H2S + S + M = HSSH + M (R24)
H + O2 + M = HO2 + M (R221)
(R29) H2S + O = SH + OH
(R39) SH + O2 = HSO + O
(-R31) H2S + HO2 = H2O2 + SH
(R174) S2 + O = SO + S
(-R25) H2S + O2 = SH + HO2
(-R3) SH + SH = H2S + S
(R116) SO + O2 = SO2 + O
(R59) S + O2 = SO + O
(-R4) SH + SH = H2S + S
-2 -1 0 1
H2S Sensitivity
Fig. 7. Sensitivity coecients with respect to H2S
calculated using the base model at the temperature
corresponding to a predicted 50% consumption of H2S.
Grey bars: [H2S] = 100 ppm, [O2] = 1000 ppm, T =
1005 K; black bars: [H2S] = 325 ppm, [O2] = 600 ppm,
T = 1025 K. Reactions are written in the direction in
which they proceed.
nations for most of the other reactions, and the
model employs theoretical estimates. Overall,
there are too many reactions with signicant rate
uncertainty and high sensitivity coecients to
enable comprehensive model validation. There-
fore we have chosen to investigate how well the
model can simulate the detailed experimental
observations through changes in rate parameters
of limited set of reactions. For this purpose, we
consider the SH self-reactions forming (i)
H2S + S ( R3 and R4) which, together, have
the greatest sensitivity coecients in the mecha-
nism under all conditions; and (ii) HSSH (R10)
which has a more pronounced eect when the
availability of oxygen is reduced.
As expected, there is no pair of scaling factors
that enabled the model to reproduce the H2S con-
sumption proles under all the experimental con-
ditions. However, the very high sensitivity of the
system to the reactions chosen for adjustment
means that only modest adjustments were
required in all cases. The reactions R3/ R4
and R10 have opposite temperature dependence
so some ne-tuning of the conversion curves
(e.g. in Fig. 3) can be achieved by adjusting the
balance between these pathways. For the adjusted
simulation results (solid lines) in Figs. 3 and 4, the
scaling factor on R10 is always 3; on R3/ R4,
the factor is 1.5, 1.05 and 0.8 for curves (a), (b)
and (c), respectively. In Fig. 5, these factors are
1 and 2.8 for R10 and R3/ R4, respectively,
these values giving rise to more rapid ignition than
predicted by the base case parameters. Here it
HSS + M) and R19 (HSSH + H
should be noted that the overall consumption of
H2S is completed in the isothermal zone of the
furnace in Fig. 5, the reaction proceeds strongly
well into the cooling zone when the furnace is at
lower temperature due to the accumulation of
SO and S2 (at lower values of [O2]0/[H2S]0) which
continue to react even down to a few hundred
degrees. The dierent scaling factors for similar
reaction conditions (curves in Figs. 3b and 5)
are attributed to the fact that we are adjusting
only a minimal subset of the reactions and that
there are other highly sensitive reactions whose
impact would have to be considered in a full
model validation. Notwithstanding the variability
in the adjustment factors needed under dierent
conditions, their magnitude is always within the
experimental/computational uncertainty for these
2
channels [4].
5.3. H2 selectivity
In general, while the adjusted model is able to
predict the H2S and SO2 proles, only qualitative
agreement is achieved for the extent of H2 forma-
tion which is overpredicted, especially at high tem-
peratures under conditions with low O2 excess
(Fig. 3).
The formation of H2 occurs predominantly in
the reactions of H with H2S (R2) and, at lower
oxygen concentrations, with SH ( R5); forma-
tion of H2O is almost entirely via H2S + OH
(R27/R28), with OH being formed from
H2S + O (R29). The high selectivity to H2 under
oxygen-rich conditions arises because most H is
itself generated by reaction of O with SH (R44)
as shown in Fig. 3a, the model captures the
competition between H2 and H2O formation
under these conditions. When the oxygen excess
is reduced and the reactions of S2 species become
more important, more reactions contribute to the
production of H but the experimental H2 selectiv-
ity declines slightly, an eect that is not captured
in the model - as with the overall consumption of
H2S, the system is sensitive to a large number of
reactions and there is no obvious adjustment that
can address this decit. As is evident in Fig. 5,
some of the discrepancy at higher temperatures
arises from a failure to predict H2 consumption
in the quench zone.
5.4. Comparisons with other published data
A number of sulfur channels (R34, R6, R9
10, R12R15) belonging to the H/S subset of
Sendt et al. [8] have been updated. We therefore
checked the revised model against the validation
targets used in that work. While the revised model
slightly underpredicts the overall reaction rates
under all conditions, the predictions were particu-
larly sensitive only the rates of R7 (S2 + H +
M
H2S + SH). Doubling of each of these rate con-
stants was sucient to obtain satisfactory ts to
the data, as shown in the Supplementary data.
 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
When applied to the low-pressure fuel-lean (/
HSSH (R10)
 0.5) and stoichiometric (/ = 1) H2S ame data
H2S + HSS (R20), HSS +
of Merryman and Levy [26,27], the base model
H2S + S2 ( R11) is a powerful chain ter-
captures the experimental proles of the all major
species except for H2 selectivity which is signi-
cantly overpredicted see Supplementary data.
It is noteworthy that the experimental data show
greater H2 selectivity in the lean ame.
Flame speeds estimated using the model are in
reasonable agreement with measurements of
Chamberlin and Clark [28], peak values being
58 cm s 1 versus 50 cm s 1, respectively.
6. Conclusions
Recent research into the fundamental kinetics
of sulfur reactions has highlighted the need for
inclusion of new and revised pathways in the
mechanism of H2S oxidation, particularly in rela-
tion to disulfur species such as S2, HSS, and
HSSH. We have developed a comprehensive
kinetic model that addresses this need.
We have shown that H2S oxidation is strongly
catalysed by silica surface but that this eect is
apparently negated by the application of a B2O3
coating. While it is not possible to prove conclu-
sively that this coating has no residual eect on
the course of the reaction, the characteristic tem-
perature for reaction rises by some hundreds of
degrees when the coating is applied, making it
much more likely that gas-phase reactions domi-
nate. We therefore report data for the atmo-
spheric pressure fuel-lean H2S oxidation (100
520 ppm H2S in 2001000 ppm O2; N2 ballast)
in a B2O3-coated reactor in the temperature range
9501150 K. Studies under stoichiometric and
fuel-rich conditions were precluded because of
the excessive build-up of elemental sulfur under
these conditions. The reaction shows up to 40%
selectivity to H2, even under the most fuel lean
conditions, [O2]0/[H2S]0 = 10.
Predictions of the base model are in qualita-
tively good agreement with the experiments, with
product proles shifted by no more than 50 K.
A striking feature of the mechanism is the large
number of reactions to whose rate parameters
the overall oxidation is very sensitive. These reac-
tions are those that are responsible for the forma-
tion and destruction of radicals in the system and
increasingly include reactions of disulfur species
as the ratio [O2]0/[H2S]0 is reduced.
With a large choice of highly sensitive reac-
tions, the model could be adjusted in many ways
to achieve a better quantitative t to the data.
We have shown how minor variations in the rates
of just two of the SH self-reaction channels allows
accurate description of H2S consumption proles.
On the one hand, the sequence 2SH
H2S + S Database with Updates from Active Thermochemical
( R3/ R4), S + O2
SO + O (R60), SO + Tables, available at http://gareld.chem.elte.hu/
O2
SO2 + O (R117) is strongly branching
631
whereas on the other, 2SH
HSSH + SH
SH
mination sequence, especially when the oxygen
excess is reduced. All the ow reactor data could
be modelled with changes to the rate constants
for R3/ R4 and R10 less than a factor of 3.
The factors required for this sub-optimal tting
are dierent for the dierent cases but the point
remains that the model does reproduce the exper-
imental results for H2S when changes within the
likely uncertainty bounds for the rate parameters
are made.
The selectivity of H2S oxidation to H2 in the
ow reactor and in ames is overpredicted by the
model. This selectivity is controlled by the relative
concentrations of radicals, especially H, OH, O
and S, and is therefore sensitive also to many the
relative rates of the many reactions that determine
these concentrations. The apparent discrepancy in
the prediction of H2 proles in H2S oxidation sug-
gests the need for further improvement in both the
experiments and the sulfur mechanism.
The importance of disulfur species in H2S oxi-
dation even under fuel lean conditions is clearly
demonstrated in this work.
Acknowledgements
The authors acknowledge the support of the
Australian Research Council for part of this
work. Chenlai (Ryan) Zhou thanks the School
of Chemical and Biomolecular Engineering of
the University of Sydney for the award of the
FH Loxton Postgraduate Scholarship.
Appendix A. Supplementary data
Supplementary data associated with this article
can be found, in the online version, at http://
dx.doi.org/10.1016/j.proci.2012.05.083.
References
[1] C.L. Rasmussen, P. Glarborg, P. Marshall, Proc.
Combust. Inst. 31 (2007) 339347.
[2] I.A. Gargurevich, Ind. Eng. Chem. Res. 44 (2005)
77067729.
[3] F.G. Cerru, A. Kronenburg, R.P. Lindstedt, Com-
bust. Flame 146 (2006) 437455.
[4] Y. Gao, C. Zhou, K. Sendt, B.S. Haynes, P.
Marshall, Proc. Combust. Inst. 33 (2011) 459465.
[5] Leeds University Sulphur Mechanism, version 5.2,
available at http://www.chem.leeds.ac.uk/Combus-
tion/sox.htm/.
[6] A. Burcat, B. Ruscic, Ideal Gas Thermochemical
Burcat/burcat.html/.
632 C. Zhou et al. / Proceedings of the Combustion Institute 34 (2013) 625632
[7] K. Sendt, B.S. Haynes, J. Phys. Chem. A 109 (2005)
81808186.
[8] K. Sendt, M. Jazbec, B.S. Haynes, Proc. Combust.
Inst. 29 (2003) 24392446.
[9] R.C. Shiell, X.K. Hu, Q.J. Hu, J.W. Hepburn, J.
Phys. Chem. A 104 (2000) 43394342.
[10] P.A. Denis, Chem. Phys. Lett. 402 (2005)
289293.
[11] C. Zhou, K. Sendt, B.S. Haynes, J. Phys. Chem. A
113 (2009) 29752981.
[12] C. Zhou, Kinetic Study of The Oxidation of Hydro-
gen Sulde, Ph.D. thesis, The University of Sydney,
2009.
[13] L.A. Curtiss, K. Raghavachari, P.C. Redfern, V.
Rassolov, J.A. Pople, J. Chem. Phys. 109 (1998)
77647776.
[14] J. Li, Z.W. Zhao, A. Kazakov, F.L. Dryer, Int. J.
Chem. Kinet. 36 (2004) 566575.
[15] N.L. Garland, Chem. Phys. Lett. 290 (1998) 385
390.
[16] L. Hindiyarti, P. Glarborg, P. Marshall, J. Phys.
Chem. A 111 (2007) 39843991.
[17] K. Sendt, B.S. Haynes, Proc. Combust. Inst. 31
(2007) 257265.
[18] A. Goumri, J.D.R. Rocha, D. Laakso, C.E. Smith,
P. Marshall, J. Phys. Chem. A 103 (1999) 11328
11335.
[19] J.D. Garrido, M.Y. Ballester, Y. Orozco-Gonzalez,
S. Canuto, J. Phys. Chem. A 115 (2011) 14531461.
[20] M.A. Blitz, K.J. Hughes, M.J. Pilling, S.H. Rob-
ertson, J. Phys. Chem. A 110 (2006) 29963009.
[21] R.J. Kee, F.M. Rupley, J.A. Miller, et al., CHEM-
KIN: Release 4.1.1, Reaction Design, San Diego,
CA, 2007.
[22] A. Egerton, D.R. Warren, Proc. R. Soc. London.
Ser. A 204 (1951) 465476.
[23] R.R. Baldwin, L. Mayor, Trans. Faraday Soc. 56
(1960) 103114.
[24] R.R. Baldwin, R.W. Walker, D.H. Langford,
Trans. Faraday Soc. 65 (1969) 792805.
[25] Z.H. Lodhl, R.W. Walker, J. Chem. Soc. Faraday
Trans. 87 (1991) 681689.
[26] E.L. Merryman, A. Levy, J. Air Pollut. Control
Assoc. 17 (1967) 800806.
[27] E.L. Merryman, A. Levy, J. Phys. Chem. 76 (1972)
19251931.
[28] D.S. Chamberlin, D.R. Clarke, Ind. Eng. Chem. 20
(1928) 10161018.