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Oxidative Dehydrogenation of Ethane to Ethylene over Potassium

Tungstate Catalysts
Duanxing Li, Zenghao Wei, and Kazuhiro Takanabe*
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ABSTRACT: This study elucidated the mechanism of catalytic oxidative

dehydrogenation (ODH) of ethane over K2WO4/SiO2 by using microkinetic analysis
and simulation with gas-phase chemistry. The K2WO4/SiO2 catalyst prepared with
amorphous silica as starting material and cristobalite produced during 900 °C
calcination exhibited better performance than catalysts prepared with crystallized
Downloaded via 49.231.135.83 on April 3, 2024 at 09:29:20 (UTC).

silica (cristobalite). The kinetic analysis suggested that both C2H6 and O2 show
positive dependences and the reaction proceeds by C−H activation via surface O
species (O*, likely peroxide species)-mediated H-abstraction at low conversion. Upon
addition of H2O in the reactant stream, the conversion rate drastically improved.
Kinetic orders with respective to O2 and H2O pressure are consistent with OH radical
formation through the reaction of O* species with H2O, which would then activate
the C−H of C2H6 molecules in the gas phase. The experimentally observed C2H6 conversion rate involved contributions from both
O*-mediated (dry) and OH radical-mediated (wet) parallel pathways. By assuming that the main kinetic consequence of cofed H2O
was generating OH radicals, kinetic simulation illustrated the promotional effect of cofed H2O on C2H6 activation while not affecting
the product distribution, which matched well with experimentally observed trends.

■ INTRODUCTION
Ethylene is a typical compound of short-chain olefins that plays
a critical role in modern society. It serves as a building block of
the global chemical industry including the manufacture of
plastics.1 Ethylene is currently produced via the cracking of
naphtha, which is a refinery product of crude oil.1,2 However,
alternative production routes are desired, because the current
cracking process is energy-intensive and reliant on crude oil. In
recent decades, natural gas has received growing interest due to
its large reserves and established exploitation technologies.3 As
the second abundant component of natural gas, ethane is an
attractive feedstock for ethylene production.2
Versus nonoxidative dehydrogenation (reaction 1), the
oxidative dehydrogenation of ethane (reaction 2) is advanta-
geous because it is thermodynamically favored, which requires
cofed O2 and forms H2O as a byproduct. The ODH reaction is
exothermic, which supplies the heat required for the reaction
by itself, lowering the energy consumption.4−6 Furthermore,
the oxidative atmosphere inhibits coke formation, which
challenges the catalyst lifetime in the nonoxidative dehydro-
genation process.7,8 The disadvantage of the ODH route is
however the overoxidation of C2H6 and C2H4, which forms
undesired COx products and decreases the C2H4 selectivity,
thus hampering the industrial application of the ODH
process.9,10 High selectivity is limited in that the alkene
product is more reactive than the corresponding alkane
reactant, which originates from the preferred adsorption of
alkene on the surface due to existence of π electrons.11
© 2024 The Authors. Published by
American Chemical Society
5646
C2H 6 C2H4 + H 2 H ° = 136 kJ mol 1 (1)
1
C2H6 + 0.5O2 C2H4 + H 2O H° = 105 kJ mol
(2)
For decades, supported transition metal oxides (e.g., V2O5
and MoO3) have been deemed promising catalysts for ethane
ODH due to their favorable redox properties.12 Hexagonal
boron nitride, a recent addition to this field, is gaining interest
as a selective and stable catalyst in the ODH of light
alkanes.13−15 The rate-determining step of ODH of C2H6 is
considered to be the first C−H bond activation.11 Although
the nature of the active site is still under debate and differs on
different catalyst systems, it is generally accepted that surface
oxygen-containing species act as the H-abstractor.16,17 A
distinctive reaction mechanism has been proposed for the
ODH of C2H6 and OCM over the Na2WO4/SiO2 catalyst,
where gas-phase OH radicals play a crucial role in activating
the C−H bond.18−22 In this complex homogeneous−
heterogeneous reaction network involving both gas-phase
radical reactions and surface-catalyzed reactions, the surface
likely promotes oxidative activation of H2O in addition to CH4
Received: December 21, 2023
Revised: February 21, 2024
Accepted: March 3, 2024
Published: March 22, 2024
https://doi.org/10.1021/acs.iecr.3c04549
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Industrial & Engineering Chemistry Research
and C2H6, which in turn forms OH radicals into the gas phase
as experimentally evident, according to reaction 3.19,20 The
water-induced promotional effect (activity and selectivity
enhancement) was proposed to be associated with OH
radical-mediated hydrocarbon activation.18−22
1 catalyzed radical reaction. The proposed reaction pathway with
2H 2O + O2 4OH · H° = 650 kJ mol (3)
Nevertheless, there are other proposals regarding this
promotional water effect, one being that water changes the
distribution of various surface active oxygen species.23−26
Wachs and co-workers stated that two kinds of active oxygen
species existed on the surface, namely, dissolved molecular O2
species and lattice atomic O species, by utilizing the temporal
analysis of products (TAP) technique.27,28 The atomic O
species contributed to CO formation, and molecular O2 was
associated with CO2 formation.27,28 Sinev et al. explained the
promotional water effect on C2 selectivity as water suppressing
the formation of surface molecular oxygen species. 23
Kondratenko and co-workers suggested that water induced
the transformation of molecularly adsorbed oxygen species
(O 2,s ) into their atomic counterparts (O s ). 24−26 O 2,s
participated in CH4 combustion to CO2, and Os was rather
responsible for C2 and CO formation. A higher C2 selectivity
was achieved because the water-induced lower O2,s concen-
tration inhibited the formation of undesired CO2.24−26 Such
hypothesis was consistent with the less pronounced water
promotional effect in the N2O-OCM system, which might be
caused by the low ability of N2O to generate O2,s species that is
responsible for the promotional water effect.25 However, the
experimentally observed kinetic behavior of decreased CO2
selectivity upon water addition24−26 does not contradict the
mechanism of OH radical-mediated hydrocarbon activation,
since the CO to CO2 conversion was inhibited in the gas phase
radical chemistry.
Our previous work used near-ambient pressure X-ray
photoelectron spectroscopy (NAP-XPS) and showed the
presence of sodium peroxide21 and potassium (su)peroxide
species29 over supported Na2WO4 and K2WO4 catalysts in the
presence of O2 at above 560 °C, respectively. These
(su)peroxide species were proposed to react with H2O to
form OH radicals via H2O2 decomposition, which happens at
quasi-equilibrated steps in a low conversion regime at low
pressures. The benefits of the OH radical-mediated pathway in
improving the CH4 conversion rate and C2 selectivity during
OCM have been shown experimentally and theoreti-
cally.19,20,22 One of the proposed reasons for the improved
C2H4 selectivity was that surface combustion of C2H4, which
has a relatively high adsorption probability to the catalyst
surface due to π electrons, can be suppressed if the OH radical
reacts with C2H4 in the gas phase.20 This reasoning may be
applicable to the highly selective ODH of C2H6 using
Na2WO4/SiO2.18
Regarding OCM, our recent work demonstrated that the
selectivity versus conversion relationship for the Na2WO4/
SiO2 and K2WO4/SiO2 catalysts was similar, indicating that a
united reaction mechanism may prevail on both catalysts.29
However, the ODH of C2H6 over the K2WO4/SiO2 catalyst is
not yet explored in detail. Here, we report our experimental
study toward the ODH of C2H6 using the K2WO4/SiO2
catalyst. Compared to the case of the OCM, the weaker C−
H bond in C2H6 than in CH4 leads to lower reaction
temperatures, potentially changing the reaction network. It was
found that the crystallinity of starting silica and calcination
5647
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temperature affected the resulting K2WO4/SiO2 performance
in the ODH reaction. In addition, the impact of the presence
of H2O on catalyst performance was carefully investigated
experimentally. Microkinetic analysis was carried out to pin
down the detailed mechanism of this unique alkali metal-
H2O is integrated into the gas-phase radical chemistry to
confirm the effects of the H2O-involving pathway on the rates
and selectivity.
■ MATERIALS AND METHODS
Catalyst Preparation and Performance Evaluation.
The 5 wt % K2WO4/SiO2 catalyst was synthesized via the
impregnation method. Initially, 50 mg of K2WO4 (Alfa Aesar)
was dissolved in 2 mL of deionized water. The obtained
solution was added to 950 mg of SiO2 (Sigma-Aldrich, Silica
Gel grade 648) under constant stirring. The mixture was dried
at 130 °C for 5 h in static air. The dried samples were calcined
at 750 and 900 °C, respectively, for 8 h in flowing air (ramp
rate 2 °C min−1) and cooled naturally. The catalysts thus
obtained were designated as K2WO4/SiO2(A)−750 and
K2WO4/SiO2(A)−900, respectively, with A indicating that
the starting SiO2 was amorphous. Cristobalite (crystallized
SiO2) was prepared by calcining the received amorphous SiO2
at 1100 °C for 8 h (ramp rate 2 °C min−1). K2WO4 was
impregnated on cristobalite support following the same
manner as described above and calcined at 750 and 900 °C,
respectively, for 8 h in flowing air (ramp rate of 2 °C min−1)
and cooled naturally. The catalysts thus obtained were
designated as K2WO4/SiO2(C)−750 and K2WO4/SiO2(C)−
900, respectively, with C indicating that the starting SiO2 was
cristobalite. All catalysts were sieved to aggregates with a size
of 0.25−0.50 mm before use.
The C2H6 ODH reaction was carried out in a U-shaped
quartz reactor with an inner diameter of 4 mm. The catalyst
(0.8 g) was loaded in the reactor with quartz wool before and
after the catalyst bed. Various reaction temperatures were
achieved by an electric furnace with a K-type thermocouple
touching the outer surface of the reactor closest to the catalyst
bed. C2H6 (>99.995%), O2 (20.0%, diluted with Ar), and Ar
(>99.9999%) were mixed as reactant gas, and their
composition was adjusted by changing the flow rates of each
gas with calibrated mass flow controllers (Brooks SLA 5800).
A saturator with a temperature-controlled water jacket (5−20
°C) was used to supply H2O to the reactant feed.
The outlet gas composition was analyzed via online gas
chromatography (Shimadzu, GC-2014). C1−C4 hydrocarbons
were separated by a GS-GasPro column (inner diameter of
0.32 mm, length of 60 m) and detected by a flame ionization
detector. O2, CO, and CO2 were separated by a ShinCarbon
ST column (inner diameter 3 mm, length 2 m) and analyzed
by a thermal conductivity detector. The C2H6 conversion,
product selectivity, and yield were calculated according to eqs
4, 5, and 6, respectively. To minimize the effects of product
pressures in our kinetic analysis, the C2H6 conversion was
adjusted to be <5% by varying space velocity. Zero conversion
rate was obtained by extrapolation under each gas
composition.
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C2H6 conversion (%)
total moles of carbon in products
=
total moles of carbon in products and remaining C2H6
× 100
total moles of carbon in specific product
selectivity (%) =
total moles of carbon in all products
× 100
yield (%) = C2H6 conversion (%) × selectivity (%) ÷ 100
Catalyst Characterization. X-ray diffraction (XRD)
patterns were collected with a Rigaku Rint 2000 using Cu
Kα radiation. N2 adsorption−desorption measurement was
carried out at liquid nitrogen temperature with catalysts
pretreated at 300 °C for 30 min in vacuum (Micromeritrics,
3Flex). The specific surface area was calculated based on the
Brunauer−Emmett−Teller (BET) model.
Simulation Protocols. The simulations performed inves-
tigated the effect of cofed H2O on the reactivity of a gas
mixture of C2H6/O2 by assuming the main consequence of the
cofed H2O to be the generation of gas-phase OH radicals. The
simulations were performed in Chemkin [Ansys Chemkin-Pro
v. 17.2, 2018.] with the isothermal PFR module. The applied
gas-phase chemical kinetic model is KAUST-Aramco PAH
Mech 1-GS (KAM1-GS), which contains 574 species and 3379
reactions. The details of the KAM1-GS model and validation
can be found in the literature.30,31
Surface reactions were not included in the simulation.
Rather, reaction 3 was involved in the kinetic model to
represent the quasi-equilibrated nature of catalytic OH radical
generation. The forward reaction constant (kf) was varied to
adjust the extent of OH radical contribution to the entire
reaction network, as demonstrated in our previous work.22,32
Simulations were typically conducted with a total pressure of
101 kPa, various residence times, temperatures, and inlet
C2H6/O2 molar ratios. The C2H6 conversion, product
selectivity, and yield were calculated according to eqs 4, 5,
and 6, respectively.
■ RESULTS AND DISCUSSION
K2WO4/SiO2 catalysts were prepared with two kinds of
starting SiO2, which were amorphous SiO2 (denoted as
SiO2(A)) and cristobalite (crystallized SiO2, denoted as
SiO2(C)). For each type of starting SiO2, two calcination
temperatures (750 and 900 °C) were applied. The obtained
catalysts were hereafter designated as K2WO4/SiO2(A)−900,
K2WO4/SiO2(A)−750, K2WO4/SiO2(C)−900, and K2WO4/
SiO2(C)−750. Amorphous SiO2 without K2WO4 loading was
calcined under 900 and 1100 °C and designated as SiO2(A)−
900 and SiO2(A)−1100, respectively.
The XRD patterns of various K2WO4/SiO2 and calcined
SiO2 samples are shown in Figure 1. SiO2(A)−1100 exhibited
characteristic reflections at 2θ of 22.0, 28.5, 31.5, and 36.2°,
being consistent with the tetragonal SiO2 crystal phase
(cristobalite).33 The reflection at 2θ of 21.5° is assigned to a
tiny amount of tridymite phase of SiO2.34 On the contrary,
SiO2(A)−900 showed a broadened diffraction peak around
22.0°, suggesting its amorphous nature. Such results are
consistent with the previous report that amorphous silica
started to sinter and crystallize at temperatures >1100 °C.35
pubs.acs.org/IECR Article
(4)
(5)
(6)
Figure 1. XRD patterns of catalysts prepared starting from amorphous
SiO2 (K2WO4/SiO2(A)−900 and K2WO4/SiO 2(A)−750) and
starting from cristobalite (K2WO4/SiO2(C)−900 and K2WO4/
SiO2(C)−750). XRD patterns of amorphous SiO2 after calcination
(SiO2(A)−900 and SiO2(A)−750). The values 900 and 750 indicate
calcination temperatures of 900 and 750 °C, respectively.
The BET surface area of amorphous silica (276 m2 g−1)
decreased remarkably to 1 m2 g−1 due to sintering after
calcination at 1100 °C (SiO2(A)−1100, Table S1). The XRD
patterns of K2WO4/SiO2(C)−900 and K2WO4/SiO2(C)−750
indicated further increased SiO2 crystallinity compared to the
support SiO2(A)−1100, due to the calcination process in
catalyst synthesis. The BET surface area is 1 m2 g−1 for both
K2WO4/SiO2(C)−900 and K2WO4/SiO2(C)−750 catalysts.
As for catalysts prepared starting from amorphous silica,
K2WO4/SiO2(A)−900 exhibited the highest SiO2 crystallinity,
although the calcination temperature was lower than the
crystallization temperature of silica. Such low-temperature
phase transition should be caused by the presence of K2WO4,
since calcining silica alone at 900 °C did not induce the phase
transition of silica. A previous study of the Na2WO4/SiO2
system suggested that it was Na species rather than W species
that enhanced the crystallization of silica at low temper-
atures.34 In the current study, it is reasonable to assume that
the K species played a similar role in enhancing crystallization,
because it belongs to the same group as Na and has similar
chemical properties. In K2WO4/SiO2(A)−750, silica showed
low crystallinity due to low calcination temperature. The BET
surface area is 17 m2 g−1, suggesting that silica was not fully
sintered. The diffraction peaks of the K2WO4 phase were not
observed in any K2WO4/SiO2 catalysts, due to the low loading
amount (5 wt %) and high dispersion of K2WO4 particles.
The catalytic C2H6 ODH performances of K2WO4/
SiO2(A)−900, K2WO4/SiO2(A)−750, K2WO4/SiO2(C)−
900, and K2WO4/SiO2(C)−750 catalysts were evaluated
(Figure 2). The C2H4 selectivity was similar for K2WO4/
SiO2(C)−900, K2WO4/SiO2(C)−750, and K2WO4/SiO2(A)−
900, reaching about 88% at C2H6 conversion 3−7%. K2WO4/
SiO2(A)−750 was relatively unselective, generating more
undesired products, such as COx and CH4. This is likely due
to the presence of an unselective amorphous SiO2 surface in
the K2WO4/SiO2(A)−750 catalyst, as suggested by the low
SiO2 crystallinity from XRD and surface area results (Figure 1
and Table S1). The C2H6 ODH performance over amorphous
SiO2 (Figure S1) showed that such a surface catalyzed
unselective C2H6 conversion with high COx selectivity reacting
50%. In the case of K2WO4/SiO2(C)−900, K2WO4/SiO2(C)−
750, and K2WO4/SiO2(A)−900, the SiO2 supports were fully
sintered with a surface area less than 1 m2 g−1. The catalytic
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Figure 2. (a) C2H6 conversion rate and (b) product selectivity of K2WO4/SiO2(A)−900, K2WO4/SiO2(A)−750, K2WO4/SiO2(C)−900, and
K2WO4/SiO2(C)−750 catalysts. Conditions: 0.8 g, 650 °C, C2H6 20 kPa, O2 7.7 kPa, total 101 kPa, Ar balance.

Figure 3. C2H6 initial conversion rate as a function of (a) C2H6 and (b) O2 partial pressures with the K2WO4/SiO2(A)−900 catalyst. Conditions:
0.8 g, 650 °C, C2H6 10−50 kPa, O2 3.3−9.9 kPa, total 101 kPa, Ar balance. Terms α and β are exponent dependents of the simplified rate equation,
r = k[C2H6]α[O2]β.

nature of these three catalysts mainly originated from K2WO4,
leading to similar and high C2H4 selectivity. In the case of
K2WO4/SiO2(A)−750, the low calcination temperature
limited the crystallization and sintering of SiO2. The remaining
amorphous SiO2 in the synthesized sample resulted in the
relatively low C2H4 selectivity.
In terms of activity, the K2WO4/SiO2(A)−900 and K2WO4/
SiO2(A)−750 catalysts exhibited a similar C2H6 conversion
rate, which is higher than that of K2WO4/SiO2(C)−900 and
K2WO4/SiO2(C)−750. A similar trend was observed in
methane oxidative coupling reaction with the Na2WO4/SiO2
catalyst, in which catalysts synthesized starting with amorphous
silica were more active than catalysts synthesized with
cristobalite.36 In the current study, the higher activation rate
might be caused by a better dispersion of K2WO4 on the SiO2
support in the catalysts synthesized starting from amorphous
SiO2. Loading K2WO4 to cristobalite (small surface area)
might lead to less dispersed K2WO4 in K2WO4/SiO2(C)−900
and K2WO4/SiO2(C)−750.
Because K2WO4/SiO2(A)−900 demonstrated both a better
C2H6 activity and a higher C2H4 selectivity, a microkinetic
analysis was specifically performed to investigate the C2H6
oxidative activation on this catalyst. The effects of inlet C2H6
and O2 pressure on C2H6 initial conversion rate were
investigated by varying the C2H6 pressure in 10−50 kPa and
the O2 pressure in 3.3−9.9 kPa ranges (total pressure balanced
5649
to 101 kPa with Ar). The initial C2H6 conversion rate was
plotted as a function of C2H6 and O2 partial pressure, shown
respectively in Figure 3a and b. The power function rate model
was used to fit the experimental data. Figure 3a indicates that
the C2H6 initial conversion rate increased with C2H6 pressure
but the dependence became weaker at higher C2H6 pressure
regions, which suggests that competitive adsorption started to
play a role: Higher C2H6 coverage on the catalyst surface
suppressed the overall rate. Figure 3b shows that the C2H6
initial conversion rate increased as the O2 pressure increased.
The rate dependence on the O2 pressure became weaker with
increasing O2 pressure, which was also a result of the
competitive adsorption between the O2 and C2H6 on the
catalyst surface.
The effects of reactant concentrations on rate are indicative
of the Langmuir−Hinshelwood mechanism on the catalyst
surface, in which both C2H6 and O2 are adsorbed on the
surface (eqs 7 and 8) and the reaction between adsorbed
species determined the rate (eq 9). Two surface OH*
molecules coupled and completed the catalytic circle (eq
10). The C2H6 conversion rate was derived as eq 11 where the
apparent rate constant (kO*) contains the contribution from
the quasi-equilibrium adsorption of C2H6 and O2 molecules on
the surface (KO2 and KC2H6) and the activation of C2H6* by
surface O* via H-abstraction (kO*,C2H6). The functional form
of eq 11 accurately describes all experimentally measured C2H6
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Figure 4. Effect of H2O partial pressure on the C2H6 ODH performance with the K2WO4/SiO2(A)−900 catalyst. (a) C2H6 conversion rate and (b)
product distribution in C2H6 conversion <5% (C2H6 10 kPa, O2 7.7 kPa, H2O 0−2.0 kPa). (c) OH radical-induced C2H6 conversion rate as a
function of (PH2O)0.5(PO2)0.25 (C2H6 10 kPa, O2 3.3−7.7 kPa, H2O 0−2.0 kPa). (d) Parity plot for the measured C2H6 conversion rates and those
calculated from rate eq 18 (dry: C2H6 10−50 kPa and O2 3.3−9.9 kPa; wet: C2H6 10 kPa, O2 3.3−7.7 kPa, H2O 1.4−2.0 kPa). All experiments
were conducted with 0.8 g of catalyst, 650 °C, 101 kPa, Ar balanced.

ODH rates (as shown in the parity plot in Figure S2), the C 2 H 6 concentration (reactions 13 and 14, with
supporting the proposed C2H6 activation mechanism on the corresponding rate constants kb and kc). The initial product
K2WO4/SiO2 surface (elementary steps 7−10). distribution was determined by kb/kc (≈24 by considering the
KO
2
initial C2H4 selectivity to be 96%), which was not affected by
O2 + 2* HoooI 2O*, [O*] = K O1/2
2
[O2 ]1/2 [*] (7) C2H5 radical concentration. Upon H2O involvement into C2H6
activation kinetics, the rates of two parallel pathways forming
KC
2 6 H C2H4 and COx increased to the same extent with increasing
C2H6 + * HoooooI C2H6*, [C2H6*] = K C2H6[C2H6][*] (8) C2H5 radical concentration, resulting in no influence on
k O ,C2H6
product selectivity. Of note, during the OCM (CH 4
*
C2H6* + O* C2H5·+OH* + * (9) activation), improved conversion rate by the presence of
H2O leads to improved CH3 radical formation, resulting in
2OH* F H 2O + O* + * (10) higher selectivity to C2 compared to its oxidation to COx as the
coupling is the second order regarding CH 3 radical
r = k O*,C2H6[C2H6*][O*] concentration (rC2 ∼ [CH3·]2) while the overoxidation is the
first order (rCOx ∼ [CH3·]). Which component of such alkali-
= k O*[C2H6][O2 ]1/2 tungstate catalysts indeed contributed to the promotional H2O
/(1 + K O1/2[O2 ]1/2 + K C2H6[C2H6])2 effect and the exact function of Mn element has long been
2
under debate.20,24,25 In the current study, we did not
(k O* = k O*,C2H6K O1/2
2
K C 2 H 6) specifically investigate the function of each element in the
K2WO4/SiO2 catalyst, for example, by testing the catalytic
(11)
performance of KxOy/SiO2, WO3/SiO2, and so on. However,
Various amounts of H2O were specifically involved into the by combining with the previous study of C2H6 ODH reaction
inlet reactant stream to investigate the H2O effect on the C2H6 on the Na2WO4/SiO2 catalyst, we could conclude that the
ODH performance. Figure 4a,b shows that the C 2 H 6 addition of the Mn element is not essential to observe the
conversion rate was enhanced with 1.4−2.0 kPa of cofed promotional H2O effect on C2H6 activation with alkali
water. The cofed water did not affect the C2H4 initial tungstate catalysts.18
selectivity. At the initial stage of the reaction, C2H6 was
activated to form C2H5 radicals (reaction 12), which further ka
transformed to C2H4 or COx in parallel with the first order to C2H6 + O2 C2H5·+HO2 · (12)

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Industrial & Engineering Chemistry Research
C2H5·+ O2
kb
C2H4 + HO2 ·
kc
C2H5·+ (x + 1.25)O2 2COX + 2.5H 2O
As shown in Figure 4c, the incremental C2H6 conversion
rate upon H2O addition has a linear relationship with
(PH2O)0.5(PO2)0.25, which is consistent with the C2H6 activation
by the quasi-equilibrated OH radical from the H2O−O2
mixture (eqs 15 and 16). Such radical was experimentally
detected over Na2WO4/TiO2 in a H2O/O2 mixture at 900 °C,
where the alkali metal participated in catalyzing the formation
of OH radicals.21 The C2H6 conversion rate by gas-phase OH
radicals was derived as in eq 17. In eq 17, the apparent rate
constant (kOH·) involves the contribution from the quasi-
equilibrium formation of OH radical (KOH·) and OH radical-
mediated C2H6 activation (kOH·,C2H6).
KOH·
1/4 1/4
O2 + 2H 2O HooooI 4OH ·, [OH ·] = K OH ·[O2 ] [H 2O]1/2
kOH·,C2H 6
C2H6 + OH · C2H5·+H 2O
rOH· = k OH·,C2H6[C2H6][OH ·]
= k OH·[C2H6][O2 ]1/4 [H 2O]1/2 (k OH· = k OH·,C2H6K OH
1/4
·)
The observed C2H6 conversion rate in the water-cofed case
was the combined contribution from the surface O* (rO*) and
the gas-phase OH radical (rOH·)-mediated C2H6 activation, as
shown in eq 18. Figure 4d shows that the functional form of eq
18 accurately describes all of the experimentally measured
C2H6 conversion rates within a wide reactant pressure range,
supporting the proposed mechanism of C2H6 activation by
both surface O* and gas-phase OH radicals over the K2WO4/
SiO2 catalyst. Kondratenko and co-workers proposed the
water-induced transformation of surface diatomic O species
(O2*) to single O species (O*), as shown in eqs 19−21.24,25
The formed O* activated C2H6 molecules, contributing to the
enhanced rate. We do not rule out the possibility that such
transformations (eqs 19−21) exist in the ODH reaction.
However, to the best of our knowledge, we could not fit the
experimental kinetic data to this mechanism, where H2O-
induced rate enhancement should be first order to both the O2
and H2O partial pressures, as suggested by eq 21 (assuming
that the C2H6 activation by O* limited the rate). It is rather
more reasonable to fit the kinetic data with the OH radical-
mediated C2H6 activation mechanism (as demonstrated in
Figure 4c). Moreover, the consequence of H2O2 in the O2* to
O* transformation (eqs 20 and 21) should be explained, which
probably indeed decompose and form OH radicals at high
temperatures.36
r = r O* + rOH·
k O*[C2H6][O2 ]1/2
= 1/2
(1 + K O1/2
2 [O2 ] + K C2H6[C2H6])2
+ k OH·[C2H6][O2 ]1/4 [H 2O]1/2
(k O = k O*,C2H6K O1/2 1/4
K C2H6 , k OH· = k OH·,C2H6K OH ·)
* 2
O2 + * F O2*
pubs.acs.org/IECR Article
(13) O2* + H 2O F O* + H 2O2 (20)
O2 + * + H 2O F O* + H 2O2 (21)
(14)
The activation energy of the C2H6 ODH reaction with the
K2WO4/SiO2(A)-900 catalyst was investigated, as shown in
Figure 5. By applying the Arrhenius equation to the kinetic
(15)
(16)
Figure 5. Arrhenius plot of C2H6 ODH reaction via O*-mediated
(red plot) and H2O-involved (blue plot) C2H6 activation pathways.
Conditions: 0.8 g, 600−635 °C, C2H6 20 kPa, O2 3.3 kPa (closed
circle) and 5.5 kPa (open circle), H2O 0 or 1.6 kPa, total pressure101
kPa, Ar balance.
(17)
data, the apparent activation energy of the O* pathway (EO*)
was calculated to be 203 ± 13 kJ mol−1 and the apparent
activation energy of the H2O-involving pathway (EOH·) was
calculated to be 171 ± 7 kJ mol−1. In the H2O-involving
pathway, if the OH radical was the H-abstractor activating
C2H6 as being consistent with the rate dependence (Figure 4c,
eqs 15−17), then EOH· should be demonstrated as eq 22. In eq
22, EOH· involved contributions from both the enthalpy of OH
radical formation (ΔHOH·, reaction 15) and activation energy
of the OH radical activating C2H6 (EOH·,C2H6, reaction 16). By
considering ΔHOH· to be 650 kJ mol−1,37 and EOH·,C2H6 to be
3.6 kJ mol−1,38 EOH· is estimated to be 166 kJ mol−1 (eq 22),
which is close to the experimentally measured result (171 ± 7
kJ mol−1). The match between the experimentally measured
activation energy and the estimated value by assuming OH
radical-mediated C2H6 activation further supported the
proposed mechanism in which the gas-phase OH radical
served as the H-abstractor when there was cofed H2O.
1
EOH· = EOH·,C2H6 + HOH·
4 (22)
The C2H6 ODH performance over the K2WO4/SiO2(A)−
900 catalyst was investigated at elevated temperatures (700
and 750 °C) to achieve a higher attainable yield (Figure 6).
C2H4 selectivity decreased with higher C2H6 conversion,
resulting from the secondary reactions in which C 2H4
combusted to form COx. C2H4 selectivity was 80−95% at
C2H6 conversion of 20−70%. The maximum C2H4 yield of
58% was experimentally achieved at the C2H6 conversion of
75% at 750 °C.
The performance of the ODH with different inlet C2H6 and
O2 pressures fell into a single trend line, suggesting the
reaction order of the specific compound is similar among these
(18) three parallel and consecutive pathways. By assuming pseudo−
first−order in the reaction network shown in Figure 6 and rate
(19) constants to be k1, k2, and k3, the C2H4 selectivity (SC2H4)
5651 https://doi.org/10.1021/acs.iecr.3c04549
Ind. Eng. Chem. Res. 2024, 63, 5646−5654
Industrial & Engineering Chemistry Research
Figure 6. C2H4 selectivity and yield as a function of C2H6 conversion
with the K2WO4/SiO2(A)−900 catalyst. Conditions: 0.8 g, 700 °C
(green plot) and 750 °C (orange plot), C2H6 10 kPa (closed) and 20
kPa (open), O2 3.3−9.9 kPa, H2O 2.0 kPa, total pressure 101 kPa, Ar
balance.
versus C2H6 conversion (X) relationship was derived to be eq
23.
(1 X) (1 X )k 2 / k1/1 + k 3/ k1
SC2H4 =
( k2
k1
1
k3
k1 )X (23)
The rate constant ratios, k2/k1, k3/k1, and k2/k3, were
derived by fitting eq 23 to C2H4 selectivity−C2H6 conversion
data (Figure 6) experimentally measured at various temper-
atures and reactant gas compositions of the K2WO4/SiO2(A)−
900 catalyst. The calculated rate constant ratios are listed in
Table 1. In the simplified C2H6 ODH pathway, pathway 1
Table 1. Ratio of Rate Constants (k1, k2, and k3 of the
Simplified Reaction Pathway Demonstrated in Figure 6) at
700 and 750 °C with the K2WO4/SiO2(A)−900 Catalysta
k2/k1 k3/k1 k2/k3
700 °C 0.32 0.06 5.3
750 °C 0.29 0.04 7.3
800 °C (Na2WO4/SiO2) 0.28 0.02 14
a exhibited a combined contribution of both homogeneous gas-
Previously reported values of the Na2WO4/SiO2 catalyst at 800 °C
was listed for comparison. Data was adapted from 18, copyright 2016
The Authors AIChE Journal published by Wiley Periodicals, Inc., on
behalf of the American Institute of Chemical Engineers.
leads to C2H4 production while pathways 2 and 3 lead to
overoxidation of hydrocarbons forming COx. Values of k2/k3
were larger than unity, indicating that undesired COx was
mainly generated from the overoxidation of the C2H4 product
rather than reactant C2H6. It is likely attributed to easier
adsorption and activation of C2H4 molecules on the catalyst
surface due to the presence of π-electrons in a double bond.
The low value of k3/k1 suggested that C2H6 was selectively
transformed to C2H4 rather than overoxidation COx products,
consistent with the high C2H4 initial selectivity (ca. 96%,
extrapolated to zero conversion) in Figure 4b. The ratios of
rate constants on the Na2WO4/SiO2 catalyst were summarized
from a previous report.18 Basically, the low k3/k1 and high k2/
k3 values lead to similar conclusions that C2H6 was selectively
transformed to C2H4 and COx was mainly generated from the
overoxidation of C2H4. However, the Na2WO4/SiO2 catalyst
was relatively more selective as suggested by the initial C2H4
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pubs.acs.org/IECR Article
selectivity approaching 100%.18 Such a difference in the initial
selectivity should originate from the different C2H6 activation
properties of surface O species formed in Na- and K-tungstate
catalyst systems.
Ethane thermal dehydrogenation was reported to proceed at
high temperatures (>700 °C) via radical reactions.4,5,39 To
investigate the contribution of thermal reaction in the K2WO4/
SiO2 catalyst system, we performed a series of experiments
with K2WO4/SiO2, quartz sand, and empty reactor, respec-
tively, with the same space time around 0.4−1.2 s. As shown in
Figure S3a, homogeneous gas-phase radical reactions nearly
did not proceed in an empty reactor at 650 °C. C2H6
conversion increased drastically at >700 °C, suggesting that a
certain temperature (average kinetic energy of molecules) is
necessary to initialize the radical reaction. In the cases of
K 2 WO 4 /SiO 2 and quartz sand, there is a combined
contribution of both surface-catalyzed reactions and gas-
phase radical reactions.
At 650 °C (Figure S3b), K2WO4/SiO2 and quartz sand
showed higher conversion compared to an empty reactor,
which evidenced the contribution of the surface in activating
C2H6 directly or via OH radicals. As shown in Figure S4, the
surface was required for CO2 formation and, therefore, nearly
no CO2 was observed in the empty reactor where only gas-
phase radical reactions proceeded. The quartz surface was
unselective, and CO2 was the main byproduct. In contrast, the
K2WO4/SiO2 catalyst catalyzed C2H6 ODH reaction with ca.
90% of C2H4. CO2 was formed but to a lesser extent compared
to quartz. Such results suggest that the quartz sand was not
inert enough and the active sites and reaction pathways were
different between K2WO4/SiO2 and quartz surfaces. K2WO4
generated OH radicals and gas-phase radical reactions became
dominant, leading to higher C2H4 selectivity and less CO2
formation. In Figure S3c,d, at >700 °C, K2WO4/SiO2 and
quartz surfaces induced volume occupation and radical
quenching, resulting in lower conversions than empty reactors.
The higher conversion of K2WO4/SiO2 than quartz was
because K2WO4/SiO2 promoted gas-phase radical reactions,
which were remarkable in high-temperature regions.
In summary, the C2H6 ODH reaction over K2WO4/SiO2
phase radical reactions and heterogeneous surface-catalyzed
reactions under 650−750 °C. The function of K2WO4 was to
generate OH radicals and initialize radical reactions, of which
the autoinitialization was difficult at 650 °C, resulting in higher
activity than pure gas phase and remarkably higher selectivity
than quartz sand. At 700−750 °C, the function of K2WO4 to
promote the gas-phase radical reaction was clearly demon-
strated by the higher activity and selectivity of K2WO4/SiO2
versus quartz sand.
Chemical kinetic simulations investigated the effect of cofed
H2O on the performance of C2H6 ODH reaction by assuming
the main kinetic consequence of cofed H2O to be generating
gas-phase OH radicals. The OH radical formation from the
O2−H2O mixture (reaction 3) was integrated into the gas-
phase reaction network, with arbitrarily adjusted formation rate
constants (kf) from zero to 1018 mol cm−3 s−1 atm−3. In Figure
S5a, conversion-residence time plots with kf set as zero and
1012 mol cm−3 s−1 atm−3 overlapped. Both C2H6 and O2
conversions proceeded faster as the kf increased stepwise from
1012 to 1014, 1016, and 1018 mol cm−3 s−1 atm−3, indicating that
C2H6 and O2 activation was enhanced upon H2O induced OH
radical involvement. Figure S5b suggests that product
https://doi.org/10.1021/acs.iecr.3c04549
Ind. Eng. Chem. Res. 2024, 63, 5646−5654
Industrial & Engineering Chemistry Research
distributions were not apparently influenced with enhanced
extent of OH radical involvement. This nicely fitted the
experimentally observed trends in Figure 4a,b.
The reactant and product profiles at 650 °C, with an inlet
C2H6/O2 ratio of 6 and a total pressure of 101 kPa, are shown
in Figure S6. The results showed that the conversions of C2H6
and O2 increased as the reaction proceeded. Various carbon-
containing species were formed, including C2+ species (C2H4,
C3H6, C3H8, and C4H10), CH4, and COx (CO and CH2O). H2
was also formed as a dehydrogenation product, whose
selectivity apparently increased after O2 depletion. At the
steady state, the C2+ selectivity was 79% at the C 2H6
conversion of 49%, reaching a C2+ yield of 62%. The
simulation results were compared to experimentally obtained
data (Figure S7). In the C2H6 conversion <5% region, the
simulation predicted C2+ selectivity around 5% higher and COx
selectivity around 5% lower than experimental results. The
deviation in CH 4 selectivity between simulation and
experimental results was negligible. This overestimated C2+
selectivity in the simulation originated from the lack of surface
pathways with higher rate constants to combust C 2+
products.40,41
■ CONCLUSIONS
For the ODH of C2H6, the K2WO4/SiO2 catalyst prepared
starting with amorphous silica and calcined at 900 °C exhibited
a faster C2H6 conversion rate and higher C2H4 selectivity. The
outstanding performance may result from the good dispersion
of K 2WO4 and sintered silica suppressing unselective
contribution of support. Under dry conditions (no H2O
present), C2H6 and O2 competitively adsorb on the surface and
the activation of C2H6* by O* limits the rate. The addition of
H2O in the reactant stream enhanced the C2H6 conversion rate
but did not affect product selectivity. Microkinetic analysis
suggested that the H2O-involving pathway might proceed with
the mechanism in which the OH radical equilibrated from the
H2O−O2 mixture and contributed to C2H6 activation.
Chemkin analysis demonstrated that both the C2H6 and O2
conversions were improved with more involvement of H2O-
induced OH radical formation into the gas-phase reaction
network. The product distribution of C2+, COx, and CH4 did
not change upon OH radical involvement, which is consistent
with the experimentally observed trend.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.3c04549.
Experimental ethane oxidative dehydrogenation results
(with K2WO4/SiO2 catalyst, quartz sand and in empty
reactor); Chemkin simulation resutls; specific surface
area (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Kazuhiro Takanabe − Department of Chemical System
Engineering, School of Engineering, The University of Tokyo,
Tokyo 113-8656, Japan; PRESTO, Japan Science and
Technology Agency (JST), Kawaguchi 332-0012 Saitama,
Japan; orcid.org/0000-0001-5374-9451;
Email: takanabe@chemsys.t.u-tokyo.ac.jp
5653
pubs.acs.org/IECR Article
Authors
Duanxing Li − Department of Chemical System Engineering,
School of Engineering, The University of Tokyo, Tokyo 113-
8656, Japan; orcid.org/0000-0002-6669-5912
Zenghao Wei − Department of Chemical System Engineering,
School of Engineering, The University of Tokyo, Tokyo 113-
8656, Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.3c04549
Author Contributions
D.L. and Z.W. contributed to data curation, investigation, and
analysis. K.T. contributed to data analysis, funding acquisition,
and project administration. The manuscript was written
through contributions of all authors. All authors have given
approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank the contribution of Dr. Bhavin Siritanar-
atkul at The University of Tokyo for fruitful discussion. This
work was partly supported by MHI Innovation Accelerator
LLC and by JSPS KAKENHI Grant Number 19KK0126.
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