international journal of hydrogen energy xxx (xxxx) xxx

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Conversion of ethane to ethylene and hydrogen by

utilizing carbon dioxide: Screening catalysts

Samira Zafarnak a, Ali Bakhtyari a, Hamed Taghvaei a,**,

Mohammad Reza Rahimpour a,*, Adolfo Iulianelli b
a
Department of Chemical Engineering, Shiraz University, Shiraz, 71345, Iran
b
Institute on Membrane Technology of the Italian National Research Council (CNR-ITM), via P. Bucci 17/C, Rende
(CS), 87036, Italy

highlights graphical abstract

Experimental investigation of the

conversion of C2H6 to C2H4 and H2.

The utilization of CO2 as a mild
oxidation agent.

Investigation of a wide range of
commercial alumina-supported
catalysts.

C2H6 and CO2 conversion into
C2H4 and H2 is a promising energy-
efficient process.

article info abstract

Article history: Owing to the necessity of carbon dioxide conversion and exploring new routes for ethylene
Received 24 April 2020 and hydrogen production, carbon-dioxide-assisted dehydrogenation over alumina-
Received in revised form supported catalysts is evaluated in the present contribution. In this regard, the experi-
17 September 2020 mental results of a wide range of catalysts at 700  C and the GHSV of 3600 Lreactants/
Accepted 19 September 2020 kgcatalyst.hr are presented and compared. The utilized catalysts showed activity toward the
Available online xxx conversion of ethane. However, a few of them showed good selectivity for the production
of either ethylene or hydrogen. The catalysts made up of the oxides of cobalt and mo-
Keywords: lybdenum showed very good conversion, selectivity, and yield for ethylene production.
Hydrogen Investigating the effect of time on steam on the catalyst performance indicated that these
Olefin catalysts would be suitable choices in the course of ethylene production. 58% conversion of
Oxidative dehydrogenation ethane and 21.9% ethylene yield are the achievements of utilizing the molybdenum-cobalt
Carbon dioxide oxide catalyst. By utilizing rhenium-platinum nickel-potassium catalysts, 100% ethane
Catalysis conversion in tandem with more than 260.0% hydrogen yield was also obtained.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author.
E-mail addresses: h.taghvaei@shirazu.ac.ir (H. Taghvaei), rahimpor@shirazu.ac.ir (M.R. Rahimpour).
https://doi.org/10.1016/j.ijhydene.2020.09.150
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
The push to replace current methods of olefin production and
reducing carbon emission is motivated by plenty of factors
including rising costs of raw material and operation. More-
over, hydrogen is a precious commodity in both industrial
sections and green energy delivery [1e8]. Hence, the devel-
opment of new strategies leading to the simultaneous pro-
duction of olefins and hydrogen in tandem with carbon
dioxide conversion is currently state of the art. Accordingly,
the carbon-dioxide-assisted conversion of ethane to ethylene
and hydrogen is of great industrial and environmental
interests.
Light olefins are of the main feedstock of the petrochemical
industry, among which ethylene is a key building block of
various processes. Due to its extensive application and high-
value derivatives such as polyethylene, polyvinyl chloride,
ethylene oxide, ethylene glycol, ethylbenzene, and styrene
[9e11], ethylene production is of great interest. Convention-
ally, ethylene is produced by steam cracking of hydrocarbons
such as naphtha, propane, and ethane [12,13]. Owing to the
several disadvantages such as high energy consumption,
thermodynamic limitation, rapid coke formation, low resi-
dence time, and decreased product yields, the oxidative
dehydrogenation (ODH) has been recently proposed as a
promising alternative [11,14e21]. Lower energy consumption
and the eradication of equilibrium restrictions are the benefits
of irreversible and exothermic ODH reactions [18e20,22,23].
Owing to its large energy density, hydrogen is currently
considered as an alternative for green energy delivery [4]. The
innate advantages of hydrogen as a green energy carrier
include carbon-free ignition, direct ignition in the conven-
tional internal combustion systems, blending with alcoholic
energy carriers, and enormous effective octane number [4].
Hydrogen is also a useful chemical to the refinery and petro-
chemical processes including hydrotreating, Fischer-Tropsch
synthesis, gas to liquid (GTL) process, acetylene removal,
ammonia synthesis, alcohols synthesis, dimethyl ether syn-
thesis, and bio-oil upgrading [4,24e26]. Although hydrogen is
commercially produced form the fossil hydrocarbon com-
pounds such as natural gas [27], it would be generated as a
major byproduct of the carbon-dioxide-assisted conversion of
ethane. Accordingly, the simultaneous production of ethylene
and hydrogen from ethane by employing a carbon-dioxide-
assisted strategy is currently state of the art.
Choosing a suitable and efficient oxidant is of paramount
importance. In fact, the uncontrolled oxidation of ethane may
lead to large hydrogen production with zero ethylene pro-
duction yield [6,8,28]. Among various oxidants, oxygen
[29e35], nitrous oxide [29,31,36], and carbon dioxide [31,37,38]
have found an application for the conversion of ethane due to
abundance and low toxicity. However, the utilization of car-
bon dioxide is currently state of the art due to its mild
oxidizing properties and the prevention of its further emission
[11,14,17,38e43]. Chemical conversion of carbon dioxide as
the most abundant greenhouse gas, higher product yield,
lower energy consumption, and avoiding over-oxidation are
the possible intrinsic benefits of carbon dioxide utilization
[9,44e47]. Interestingly, a valuable byproduct of the carbon-
Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
dioxide-assisted conversion of ethane to ethylene is
hydrogen, which is not produced in the oxygen-assisted pro-
cess. Moreover, carbon dioxide is a byproduct of oxygen-
assisted ethane conversion, which impose extra charges for
its further separation, capture, and storage [48]. Carbon di-
oxide has been utilized for the oxidative dehydrogenation of
n-butane [49] and ethylbenzene [23,50]. Little has been done to
investigate the carbon dioxide assisted dehydrogenation of
ethane by utilizing the commercial catalysts. On the other
hand, despite numerous environmental and practical advan-
tages, this process is not yet commercialized.
Among the whole investigated catalysts for this system,
metallic oxides and multi-metal catalysts have demonstrated
suitable activity [51]. The results of previous studies indicate
that the transition metals show very good performance in this
system [21,52e58]. Catalyst supports such as alumina [59e63],
silica [62e64], magnesia [65], titania [66], and zeolites [67,68]
enhance metal dispersion over the catalyst surface and thus
result in better performance [35,63].
Liu et al. [47] investigated the chromium-based meso-
porous materials for the ODH of ethane in the presence of
carbon dioxide. They observed 58.0e68.1% ethane conversion
and 53.4e55.6% yield of ethylene. Baidya et al. [69] synthesized
calcium-doped thorium oxide catalysts and evaluated them in
the carbon-dioxide-assisted ODH of ethane. Cheng et al. [70]
studied the activity and stability of ZSM-5-supported chro-
mium catalysts. The utilized catalysts depicted high activity
and stability at 500e650  C. The ethane conversion and
ethylene yield were found to be about 65% and 49%, respec-
tively. Talati et al. [46] synthesized chromium/zirconia and
chromium/titania nanocatalysts. They observed that the cat-
alysts, which were prepared by the co-precipitation method,
offered higher ethane conversion and ethylene yield in com-
parison with the ones prepared by the impregnation method.
In the recent studies of Rahmani and colleagues [9,71], chro-
mium catalysts promoted by cerium were synthesized and
utilized for the ODH of ethane in the presence of carbon di-
oxide. It was concluded that cerium could significantly pro-
mote the performance of catalysts due to achieving better
textural properties, less agglomeration, uniform dispersion,
and more reducibility. Furthermore, a combination of H-ZSM-
5 and zirconia supports improved the performance of the
chromium catalyst. In a more recent study, Koirala et al. [39]
investigated the effect of cobalt loading on silica support in
the carbon-dioxide-assisted ODH of ethane. They observed
that the loading of cobalt has remarkable effects on the
structural and catalytic characteristics of catalyst particles.
They observed the highest stability of catalyst at 0.75 wt%
cobalt loading.
Although various catalysts have been investigated, the lack
of commercially-developed catalysts is still felt. Prompted by
this need, the current study is devoted to investigating this
suggestion. For attaining such a goal, a variety of
commercially-developed catalysts is experimentally investi-
gated. Very suitable for this purpose are the alumina-
supported catalysts. As far as the authors know, this is the
first study focusing on the application of the commercial
catalysts in hydrogen production through the carbon-dioxide-
assisted conversion of ethane to ethylene. To do so, the effects
of catalyst type and reaction time on the conversions of the
 international journal of hydrogen energy xxx (xxxx) xxx 3

ethane and carbon dioxide, as well as the selectivities and
yields of the desired products, i.e. ethylene and hydrogen, are
studied, experimentally. The results of this study might pave a
reliable path to the commercialization of carbon-dioxide-
assisted conversion of ethane as a multipurpose process for
ethylene and hydrogen generation.
Experimental
Materials
The characteristics of the utilized catalysts, including their
compositions, suppliers, shapes, and sizes are well presented
in Table 1. Ethane (99.9%), carbon dioxide (99.99%), and argon
(99.999%) were also utilized. As mentioned previously, the
main focus of the present contribution is on the evaluation of
commercially-developed catalysts for the simultaneous
ethylene and hydrogen production. The items with similar
ingredients (such as NiMo/Al2O3 catalysts) are distinguished
by the assigned numbers (i.e. NiMo/Al2O3 (1)-(3)).
Characterizations
The active phases, as well as the textural properties, of the
catalyst samples, were determined by X-ray diffraction (XRD)
and N2 adsorption/desorption measurements. To do so, a
Bruker (D8 Advance) X-ray diffractometer (2q ¼ 15e80 ,
Dq ¼ 0.05 ) and monochromatized Cu-Ka radiation (40 kV,
40 mA) were utilized. Furthermore, N2 isotherms (196  C, p/
p0 ¼ 0.001e0.999) data were measured by a Micromeritics
static apparatus (ASAP-2020). The measurements procedure
included samples were degassing (1 h, vacuum) at 300  C. The
textural properties including surface area, pore-volume, pore
size distribution, and mean pore diameter were then deter-
mined by employing Brunauer-Emmett-Teller (BET) and
Barret-Joyner-Halenda (BJH) methods. The thermogravi-
metric analysis (TGA) measurements (DuPont 501) were
employed to collect the weight loss, as well as the carbon
deposition, of the utilized samples. The TGA measurements
were implemented up to 1000  C (20  C/min) under a nitrogen
stream.
Catalytic activity measurements of ethane conversion to
ethylene and hydrogen
The catalytic activity measurements were implemented in a
quartz-made tubular continuous reactor. The length, inner
diameter, and thickness of the tube are 70 cm, 9 mm, and
2 mm, respectively. The reactor is equipped with an electric
furnace to provide a uniform high-temperature condition. The
catalyst particles are located in the middle section of the
reactor over a porous plate. The reactor was packed with
500 mg of catalyst particles. The height of the catalyst bed
depended on the catalyst shape and size. The reaction con-
ditions were 700  C, 5 mL/min ethane flow rate, and 25 mL/
min carbon dioxide flow rate resulting in a 3600 Lreactant/
kgcatalyst.hr gas hourly space velocity (GHSV). The total gas
flow rate was 50 mL/min balanced with argon. The experi-
ments were conducted at the atmospheric condition. Before
each experiment, the catalyst particles were activated at the
reaction temperature by 20 mL/min of argon for 30 min. From
a practical point of view, this step provides a uniform high-
temperature condition inside the catalyst bed. Such a condi-
tion would then result in the elimination of the adsorbed
species on the catalyst surface (such as water vapor and at-
mosphere gases) and also a uniform temperature distribution
inside the catalyst particles. As mentioned in Table 1, the
catalysts are utilized in their pellet forms. Hence, their
thickness might cause temperature gradients in the case of
short heating periods. The reaction temperature was
controlled by a thermocouple located on the top of the catalyst
bed. The output gas stream was analyzed by utilizing an on-
line gas chromatography (GC112A) with argon as the carrier
gas and a TCD (4 mm stainless steel packed column: Porapak
Q, 2 m in length). The quantified gaseous products were
ethane, ethylene, methane, hydrogen, carbon dioxide, and
carbon monoxide. All the catalytic activity tests were imple-
mented for 1 h reaction and the results of 5, 30, and 60 min
time on stream (TOS) are presented. The schematic diagram of
the apparatus is presented in Fig. 1.
The conversions (i.e. Xi), selectivity (Sj), and yield (Yj) were
calculated as follows:

Table 1 e The characteristics of studied catalysts.

Commercial Name Supplier Composition Shape Sizea Abbreviation
CR 8 CR 3S SRP Axens Al2O3 Sphere 3.0e4.0 Al2O3
DC 130 KHT Criterion Co(3.4%)-Mo (13.6%)/Al2O3 Cylinder 1.1  5.0 CoMo/Al2O3 (1)
RG-682 Axens Re (0.3%)-Pt (0.4%)/Al2O3 Cylinder 1.2  5.0 RePt/Al2O3
TL424 NHT Criterion Ni(3%)-Mo (13.0%)/Al2O3 Cylinder 1.5  5.0 NiMo/Al2O3 (1)
ICI-25-3 Johnson Matthey Ni(18%)-K (1.8%)/Al2O3 Cylinder 1.2  5.0 NiK/Al2O3
834 HC Iron guard Criterion Ni(1e5%)-Mo (3e7%)/Al2O3 -b e NiMo/Al2O3 (2)
HC-102 Criterion Ni(30e34%)-W (22e26%)/Al2O3eSiO2 Cylinder 1.5  5.0 NiW/Al2O3eSiO2
R 134 UOP Pt (0.29%)-Cl (1.00e1.20%)/Al2O3 Sphere 1.7 Pt/Al2O3
HDS 9A Cyanamid Ni(3.1%)-Mo (18.3%)/Al2O3 Cylinder 1.5  5.0 NiMo/Al2O3 (3)
HDS 16A Cyanamid Co(4.4%)-Mo (7.5%)/Al2O3 Cylinder 1.5  5.0 CoMo/Al2O3 (2)
G-58 C Süd-Chemie Pd (0.03%)-Ag (0.18%)/Al2O3 Sphere 2.3e2.8 PdAg/Al2O3
a
Diameter (mm) or diameter  length (mm  mm)
b
crushed and sieved (Mesh No. 12).

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
4 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 1 e The schematic diagram of the experimental apparatus for catalytic activity measurement.
Fin  Fout
Xi ¼ i in i i ¼ Ethane or carbon dioxide (1)
Fi
Fout
j
Sj ¼ j ¼ Ethylene or hydrogen (2)
Ethane  FEthane
out
Fin
Yj ¼ XEthane  Sj j ¼ Ethylene or hydrogen (3)
where F is the flow rate of components.
Results and discussions
Characterizations
To confirm the active phases and crystals of the catalyst, XRD
patterns are depicted in Fig. S1 of the Supplemental Material.
In almost all cases, the sharp peaks are observed confirming
the crystallinity of the samples. Weak peaks in some cases are
due to the low concentration of crystals as well as non-
uniform powder particles. The utilized samples are the com-
mercial ones in their extruded form. Hence, crushing and
making powders might result in the formation of non-uniform
particles and noises in the XRD spectra. The XRD spectra of
PdAg/Al2O3, NiK/Al2O3, and NiMo/Al2O3 exhibit sharp peak at
2q z 25 . As reported by Haider et al. [72], this is a character-
istic of a-Al2O3. Hence, the supports of these catalysts have a
degree of a-content. Other samples do not exhibit such a peak.
Moreover, Pt/Al2O3 and RePt/Al2O3 samples are characterized
by broad peaks at 2q z 30e35 , 45 , and 65e70 , which are, on
the one hand, the typical fingerprints of d,q-Al2O3 phases. The
observations of Haider et al. [72] prove such a statement.
Hence, the XRD results reveal that the alumina phases of the
utilized commercial catalysts are different. More discussions
on the XRD spectra of CoMo/Al2O3 [73e78], NiMo/Al2O3
[78e83], nickel [84e91], platinum [92e95], and palladium
[96e99] catalysts could be found in the literature.
Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
The results of nitrogen adsorption/desorption isotherms
and pore size distributions are depicted in Supplemental
Material (Figs S2 and S3, respectively). The surface areas, pore
volumes, and mean pore diameters are summarized in Table
2. The catalysts demonstrate type IV isotherm, which is the
indication of porous material with a capillary condensation in
the mesopores [91,100]. All the samples demonstrate revers-
ible hysteresis loops. Types H1 (formerly named Type A) are
observed in the majority of samples. However, some samples
(NiMo/Al2O3 (2) and NiW/Al2O3eSiO2) tend to form type H2
(formerly named Type E) hysteresis. The pore size distribu-
tions of Fig. S3 are well uniform.
Catalytic activity measurements of ethane conversion to
ethylene and hydrogen
The results of catalytic activity measurements are presented
and compared in this section. The average carbon balance
deviation in the whole measurements was 3.15%. A typical
carbon balance for NiMo/Al2O3 (1) catalyst is presented in
Table 3.
The conversions of ethane and carbon dioxide are
compared in Fig. 2. As depicted in this figure, the catalyst RG
682, which is made up of rhenium and platinum, and catalyst
ICI-25-3, which is made up of nickel and potassium, offer a
higher activity for the conversion of ethane and carbon diox-
ide. However, the ethylene selectivities and yields that are
depicted in Fig. 3 reveal that these catalysts are not suitable for
ethylene production. On the one hand, although all the
introduced ethane is converted by utilizing these catalysts,
they catalysis the reactions toward the production of
hydrogen with zero ethylene production. Accordingly, these
catalysts are suitable for massive hydrogen production from
ethane. Catalysts that are composed of molybdenum and the
promoters such as nickel and cobalt offer a high activity for
the conversion of ethane and carbon dioxide. Furthermore,
these catalysts exhibit high selectivity of ethylene. These
catalysts also produce considerable quantities of hydrogen.
 international journal of hydrogen energy xxx (xxxx) xxx 5

Table 2 e The textural properties of the studied catalysts.

Commercial Name Catalyst BET Surface Area (m2/g) BJH Volume (cm3/g) Mean Pore Diameter (nm)
CR 8 CR 3S SRP Al2O3 4 0.013 12.3
DC 130 KHT CoMo/Al2O3 (1) 224 0.462 7.4
RG-682 RePt/Al2O3 208 0.631 8.7
TL424 NHT NiMo/Al2O3 (1) 145 0.391 7.9
ICI-25-3 NiK/Al2O3 13 0.073 17.9
834 HC Iron guard NiMo/Al2O3 (2) 250 0.381 5.4
HC-102 NiW/Al2O3eSiO2 243 0.407 5.9
R 134 Pt/Al2O3 150 0.784 15.1
HDS 9A NiMo/Al2O3 (3) 157 0.462 10.5
HDS 16A CoMo/Al2O3 (2) 137 0.368 7.9
G-58 C PdAg/Al2O3 34 0.168 16.5

Table 3 e Carbon balance and outlet gas composition for NiMo/Al2O3 (1) catalyst.
Species Input mole/min Input C mole/min Output mole/min Output C mole/min Output gas composition (vol%)
C2H6 0.000185072 0.000370144 0.000067435 0.000134869 4.26
CO2 0.001198357 0.001198357 0.001016296 0.001016296 65.20
C2H4 0 0 0.000036836 0.000073671 2.50
CH4 0 0 0.000045652 0.000045652 2.92
CO 0 0 0.000279588 0.000279588 17.90
Total 0.001383429 0.001568501 0.001445807 0.001550076 92.78a

Carbonin  Carbonout
Carbon balance deviation ¼  100 ¼ 1.7%
Carbonin

a
The remaining (7.22 vol%) includes H2.

100.0 100.0
100
Ethane Carbon Dioxide
90

80 76.2

70
Conversion [%]

62.4
60 58.0
52.4
50 47.8
39.2 38.5 40.0
40
30.2
30 27.4 25.5
22.1
20 15.7
10.3 12.4
10 5.5 7.3 7.3
3.1 1.3
0

Fig. 2 e Conversions of ethane and carbon dioxide over various catalysts.

Interestingly, catalyst G-58 C (PdAg/Al2O3), which is made up
of small quantities of silver and palladium, shows high
selectivity toward the production of ethylene. However, it
does not exhibit very high ethane and carbon dioxide con-
versions. The yields of ethylene and hydrogen can be
considered to provide a fair comparison of a catalyst perfor-
mance with that of other catalysts. Fig. 3 presents the yields of
ethylene and hydrogen obtained by utilizing various catalysts.
Accordingly, the utilization of molybdenum catalyst (CoMo/
Al2O3 (1) and CoMo/Al2O3 (2)) results in higher ethylene pro-
duction. However, the silver-palladium catalyst (PdAg/Al2O3)
could also provide a good ethylene production rate. Also,
worth paying special attention to is the results of single
alumina (i.e. CR8 CR3S SRP) catalyst. It shows activity toward

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
6 international journal of hydrogen energy xxx (xxxx) xxx

(a)

80 Selectivity Yield

70

58.6 59.5
Selectivity/Yield [%] 60
50.1
50

40 37.8
32.9
30.7
30
22.3 22.0 20.5 19.7
20 17.7 16.3 17.4
15.0
12.0 12.8
9.1
10 5.7
0.0 0.0 0.0 0.0
0

(b)
300
262.7 266.0
Selectivity Yield 261.1

250

200
Selectivity/Yield [%]

150
128.3
262.7 266.0
101.8
100 88.1
68.0
56.6 54.7 136.7
50.4
50 34.1
63.5 67.1
50.2
17.1 18.7 8.7 19.4 31.7
0

Fig. 3 e Ethylene (a) and hydrogen (b) selectivity and yield over various catalysts.

the desired products. However, the synergistic effect arises TL424 NHT (NiMo/Al2O3 (1)) and HDS 9A (NiMo/Al2O3 (1)) cat-
out of the acidity function of the alumina support and metallic alysts, which are composed of z3 wt% nickel, it is revealed
function of silver, cobalt, nickel, and molybdenum leads to that increasing molybdenum content leads to lower ethane
higher conversion, ethylene selectivity and yield, and conversion and higher carbon dioxide conversion. However,
hydrogen selectivity and yield. Hence, the obtained results increasing molybdenum content results in lower ethylene
demonstrate that the oxides of cobalt, nickel, and molybde- selectivity and yield and higher hydrogen production. This
num offer suitable performance for the conversion of ethane could be due to lower surface area owing to the presence of
in the presence of carbon dioxide and the simultaneous pro- more oxides on the surface. The catalysts made up of cobalt,
duction of ethylene and hydrogen. The presence of the oxides i.e. DC 130 KHT (CoMo/Al2O3 (1)) and HDS 16A (CoMo/Al2O3 (2))
of molybdenum promoted with cobalt and nickel on the offer very good yields of ethylene. Cobalt catalysts are difficult
alumina surface results in the higher ethylene yield. Among to reduce [14,39]. Hence, a non-redox mechanism for the
the molybdenum catalyst, NiMo/Al2O3 (3) catalyst shows high cleavage of the CeH bond in ethane molecule is incorporated
selectivity toward the production of hydrogen. If we compare to manage good yields of ethylene [14,39]. Generally, higher

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 4 e Effect of time on stream on the conversion of

ethane over CoMo/Al2O3(1), RePt/Al2O3, NiMo/Al2O3(1), NiK/
Al2O3, CoMo/Al2O3(2) (a) and over NiMo/Al2O3(2), NiW/
Al2O3(3), Al2O3, Pt/Al2O3, PdAg/Al2O3 (b) catalysts.
ethylene production yield (22.0%) and hydrogen production
yield (266.0%) were obtained by utilizing HDS 16A (CoMo/Al2O3
(2)) and ICI-25-3 (NiK/Al2O3) catalysts, respectively.
To have an insight into the performance of catalysts with
time, the effect of time on stream on the conversions, selec-
tivities, and yields are presented in Figs. 4e9. Fig. 4 depicts
that slight decreases in the conversion of ethane with time are
observed. Catalyst sintering or even coke deposition might be
the reasons for such observation. However, different trends
are observed in the case of carbon dioxide conversion. The
conversions of carbon dioxide with time are presented in
Fig. 5. Some of the investigated catalysts such as TL424 NHT
(NiMo/Al2O3 (1)), which is made up of nickel and molybdenum,
and HC-102 (NiW/Al2O3eSiO2), which is made up of nickel and
tungsten, show increasing trends. The selectivities of ethylene
by utilizing various catalysts are depicted in Fig. 6. As per
figure, a considerable decrease in the selectivity of ethylene is
Fig. 5 e Effect of time on stream on the conversion of
carbon dioxide over CoMo/Al2O3(1), RePt/Al2O3, NiMo/
Al2O3(1), NiK/Al2O3, CoMo/Al2O3(2) (a) and over NiMo/
Al2O3(2), NiW/Al2O3, NiMo/Al2O3(3), Al2O3, Pt/Al2O3, PdAg/
Al2O3 (b) catalysts.
observed in the case of nickel-molybdenum and nickel-
tungsten catalysts. However, the other catalysts exhibit
increasing trends in the selectivities of ethylene. The yields of
ethylene are depicted in Fig. 7. Based on the obtained results,
the yield of ethylene production over the catalysts composed
of nickel-molybdenum (i.e. TL424 NHT), nickel-tungsten (i.e.
HC-102), and palladium-silver (i.e. PdAg/Al2O3) decreases with
the time. Furthermore, cobalt-molybdenum catalysts (i.e. HDS
16A and DC 130 KHT) have the highest ethylene production
rates and the highest stability toward the reaction condition.
Figs. 8 and 9 depict the results of hydrogen selectivity and
yield, respectively. In almost all cases, the selectivities of
hydrogen increase with TOS. This might be due to catalyst
decay and lower ethylene production. On the one hand, by
decreasing the activity of catalyst toward the catalytic con-
version of ethane, the thermal non-ethylene-selective routes

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 6 e Effect of time on stream on the selectivity of Fig. 7 e Effect of time on stream on the yield of ethylene
ethylene over CoMo/Al2O3(1), PdAg/Al2O3, NiMo/Al2O3(1), over CoMo/Al2O3(1), PdAg/Al2O3, NiMo/Al2O3(1), NiMo/
NiMo/Al2O3(2), CoMo/Al2O3(2) (a) and over NiW/Al2O3, Al2O3(2), CoMo/Al2O3(2) (a) and over NiW/Al2O3, NiMo/
NiMo/Al2O3(3), Al2O3, Pt/Al2O3 (b) catalysts. Al2O3(3), Al2O3, Pt/Al2O3 (b) catalysts.

became dominant. Hence, the cracking and reforming re-
actions leading to higher hydrogen production became
dominant.
Eqs (4)e(10) are presented to explain the mechanisms of
carbon-dioxide-assisted conversion of ethane to ethylene and
hydrogen on the alumina-supported metallic oxides. In the
absence of reactive oxygen sources (such as carbon dioxide),
thermodynamic restrictions limit the direct dehydrogenation
of ethane. Such restrictions result in very low conversion and
yield at low temperatures. The oxidative reaction path occurs
in tandem with the direct dehydrogenation in the presence of
reactive oxygen sources such as carbon dioxide [9,45,101]. In
the oxidative reaction path, the reduction of surface oxide
species occurs in the vicinity of ethane and hydrogen. Then,
the reoxidation of generated lattices in the vicinity of surface
oxygen that is supplied by carbon dioxide occurs. These
reduction/reoxidation cycles in the presence of oxygen
sources such as carbon dioxide results in the elimination of
the thermodynamic restrictions. Carbon dioxide plays a key
role in the reaction network of this system. Reverse water gas
shift reaction in the presence of the generated hydrogen,
carbon monoxide production in the presence of generated
coke, and the redox of catalyst active phases are the major
reactions carbon dioxide participates in Ref. [39,43,102].
Reverse water gas shift reaction could also help to shift the
equilibrium of direct dehydrogenation reaction. Carbon di-
oxide also participates in the reforming of ethane to carbon
monoxide and hydrogen and reverse Boudouard reaction to
convert the generated coke [14,39,43,102]. Hence, carbon di-
oxide could participate in two reaction paths, i.e. the non-
oxidative and oxidative paths. Hydrogen is generated in the
direct dehydrogenation and the reforming of ethane re-
actions, while consumed in the reverse water gas shit and
cracking of ethane reactions. According to the observations of

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
 international journal of hydrogen energy xxx (xxxx) xxx 9

Fig. 8 e Effect of time on stream on the selectivity of Fig. 9 e Effect of time on stream on the yield of hydrogen
hydrogen over CoMo/Al2O3(1), Pt/Al2O3, NiMo/Al2O3(2), over CoMo/Al2O3(1), Pt/Al2O3, NiMo/Al2O3(2), CoMo/
CoMo/Al2O3(2), Al2O3 (a) and over NiW/Al2O3,NiMo/Al2O3(3), Al2O3(2), Al2O3 (a) and over NiW/Al2O3, NiMo/Al2O3(3),
PdAg/Al2O3, NiMo/Al2O3(1) (b) catalysts. PdAg/Al2O3, NiMo/Al2O3(1) (b) catalysts.

Koirala et al. [14,39], cobalt catalysts do not tend to reduce in Reforming of ethane C2 H6 þ 2CO2 /4CO þ 3H2 (7)
the lower temperatures. In fact, the reduction of alumina-
supported catalysts is not possible in the temperature below Cracking of ethane C2 H6 þ H2 /2CH4 (8)
900  C. Hence, the oxidative reaction path is not suggested for Oxidative Path:
such catalysts. As a whole, two following reaction paths are
suggested based on the observations of the present study and Reduction of metallic oxide ðMOxÞ C2 H6 þ MOx /C2 H4 þ MOx1
the considerations of previous ones. þ H2 O
Non-oxidative Path: (9)

Direct Dehydrogenation C2 H6 / C2 H4 þ H2 (4)

Reoxidation metallic oxide ðMOx  1Þ MOx1 þ CO2 /CO þ MOx

Reverse water gas shift CO2 þ H2 /CO þ H2 O (5) (10)

A quantitative comparison of the obtained results of pre-

Reverse Boudouard reaction CO2 þ C/2CO (6) vious studies with the best results of the present contribution

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
10 international journal of hydrogen energy xxx (xxxx) xxx

Table 4 e Comparison of catalyst initial activity with the results of the literature.
Catalyst Operating Condition Initial Activity Ref.
Metal oxide Support T ( C) GHSV (L/kcat.hr) mcat (gr) Feed C2H6/CO2/Inerta XEthane YEthylene
Gallium e 650 9000 0.20 1/5 19.6 18.6 [105]
Vanadium e 650 9000 0.20 1/5 9.8 9.5 [105]
Chromium HZSM-5 650 20,000 0.30 1/9 z33.0 z29.0 [106]
Thorium e 725 7500 0.40 1/0.78/0.45 46.0 45.0 [69]
Chromium Alumina 650 3600 1.00 1/5/4 19.2 18.5 [63]
Chromium Zirconia 650 3600 1.00 1/5/4 57.3 34.6 [63]
Chromium Silica 650 3600 1.00 1/5/4 56.1 52.1 [63]
Chromium Zirconia-Alumina 650 3600 1.00 1/1/2 36.0 20.2 [107]
Chromium MSU-1 700 3600 0.20 1/3 68.1 55.6 [47]
Chromium SBA-15 700 3600 0.20 1/3 46.3 43.8 [41]
ChromiumeCerium SBA-15 700 3600 0.20 1/3 55.0 52.8 [41]
Chromium MCM-41 700 9000 0.50 1/5/4 40.9 30.8 [108]
Chromium Titania-Zirconia 700 9000 0.50 1/5/4 41.4 39.3 [109]
Chromium HZSM-5 700 6000 0.50 1/5/4 64.6 56.4 [9]
Cobalt Silica 700 6000 0.15 1/2.5 46.0 39.0 [39]
MolybdenumeCobalt Alumina 700 6000 0.50 1/5/4 58.0 21.9 Present
Study
a
N2, Ar, or He

is presented in Table 4 It is also worth mentioning that the

definitions of selectivity and yield are different in the reported
studies in Table 4. The authors collected and reported the
quantities presented in the original works with no further
change and adaptation. As presented, the other alumina-
supported catalyst does not show high activity and yields to-
ward the carbon dioxide-assisted conversion of ethane to
ethylene. However, there are silica, H-ZSM5, and MSU-1 sup-
ported catalysts with comparable conversions and ethylene
yields. Nonetheless, worth paying special attention to is that
the main advantage of utilized catalysts in the present
contribution is their well-developed commercialized status. In
fact, the results of the present contribution reveal that these
commercial catalysts could be utilized for the conversion of
ethane to ethylene in the presence of carbon dioxide on a
commercial scale. As a whole, HDS 16A which is an alumina-
supported catalyst composed of the oxides of cobalt and mo-
lybdenum is a superior catalyst for ethylene production. 58.0%
ethane conversion and 21.9% ethylene yield which are com- Fig. 10 e TGA patterns of the NiMo/Al2O3(1) and CoMo/
parable with the highest quantities of newly synthesized Al2O3(1) catalysts.
catalysts, as well as its stability in the reaction condition,
indicate the applicability of HDS 16A catalyst for the large-
scale applications. temperature rise above 100  C results in the elimination of
Coke formation, catalyst thermal degradation, and the the molecular water, i.e. strongly-bonded molecules to the
transformation of the active phase may occur during the alumina surface [104]. When temperature increases beyond
high-temperature reactions [103]. To determine the catalyst 250  C, gradual weight losses are observed. This would be due
deactivation, TGA analysis is employed. To do so, the TGA to the elimination of the deposited carbon from the catalyst
pattern of the utilized NiMo/Al2O3(1) and CoMo/Al2O3(1) surface. Up to 800  C, the CoMo/Al2O3(1) and NiMo/Al2O3(1)
samples were collected at 20e1000  C. These samples were samples undergo 7.9% and 9.0% weight losses, respectively.
selected because they had large decays in ethane conversion In the range of 800e1000  C, sharp weight losses are
with TOS (Fig. 4). The results are demonstrated in Fig. 10. In observed. This would be due to simultaneous carbon elimi-
the experimented range, 4 different regions are observed in nation, thermal degradation, and the transformation of the
the whole cases. The first region, i.e. initial sharp weight loss active phases. 5.5% and 4.5% weight losses are observed in
includes the dehydration of the samples. This region, on the this temperature range in the CoMo/Al2O3(1) and NiMo/
one hand, includes the removal of surface moisture, i.e. the Al2O3(1) samples, respectively. Total weight losses of the
elimination of physically-adsorbed water molecules (surface CoMo/Al2O3(1) and NiMo/Al2O3(1) samples in the 20e1000  C
hydroxyl groups) from the alumina surface [104]. A further are 13.2% and 14.1%, respectively.

Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150
 international journal of hydrogen energy xxx (xxxx) xxx
Conclusion
Commercial alumina-supported catalysts were characterized
and examined for the dehydrogenation of ethane in the
presence of carbon dioxide at 700  C. This is a novel route for
the simultaneous production of ethylene as a valuable build-
ing block and hydrogen as a valuable industrial commodity
and energy carrier. Almost all the utilized catalysts show ac-
tivity toward the conversion of ethane. However, few of them
show good activity and selectivity for the production of
ethylene. The catalysts made up of the oxides of cobalt and
molybdenum showed very good conversion, selectivity, and
yield for ethylene production, while the catalysts made up of
rhenium-platinum, nickel-potassium, and nickel-
molybdenum offered higher hydrogen production yields.
Furthermore, investigating the effect of time on steam on the
catalyst performance indicated that the catalysts made up of
the oxides of cobalt and molybdenum would be suitable
choices in the course of ethane conversion to ethylene. 58%
conversion of ethane in tandem with 21.9% ethylene yield are
the achievements of utilizing alumina-supported molybde-
num-cobalt oxide catalyst, while 100% ethane conversion in
tandem with more than 260.0% hydrogen yield is obtained by
utilizing alumina-supported rhenium-platinum nickel-
potassium catalysts. To prove the feasibility of the utiliza-
tion of these catalysts, lifetime tests under practical condi-
tions are necessary for the upcoming studies.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2020.09.150.
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Please cite this article as: Zafarnak S et al., Conversion of ethane to ethylene and hydrogen by utilizing carbon dioxide: Screening
catalysts, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.09.150