Stable High-Pressure Methane Dry Reforming Under Excess of CO2

Article abstract of DOI:10.1002/cctc.202001049

Dry reforming of methane (DRM), the conversion of carbon dioxide and methane into syngas, offers great promise for the recycling of CO₂. However, fast catalyst deactivation, especially at the industrially required high pressure, still hampers this process. Here we present a comprehensive study of DRM operation at high pressure (7–28 bars). Our results demonstrate that, under equimolar CH₄ : CO₂ mixtures, coke formation is unavoidable at high pressures for all catalysts under study. However, under substoichiometric CH₄ : CO₂ ratios (1 : 3), a stable high pressure operation can be achieved for most catalysts with no sign of deactivation for at least 60 hours at 14 bars, 800 °C and 7500 h^?1. In addition to the enhanced stability, under these conditions, the amount of CO₂ abated per mol of CH₄ fed increases by a 50 %.

Full text of DOI:10.1002/cctc.202001049

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Stable High-Pressure Methane Dry Reforming Under Excess of
CO2
Authors: Jorge Gascon, Adrian Ramirez, Kunho Lee, Aadesh Harale,
Lieven Gevers, Selvedin Telalovic, and Bandar Al Solami
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.202001049
Link to VoR: https://doi.org/10.1002/cctc.202001049
01/2020

10.1002/cctc.202001049
ChemCatChem
FULL PAPER
Stable High-Pressure Methane Dry Reforming Under Excess of
CO2
Adrian Ramirez[a], Kunho Lee[b], Aadesh Harale[b], Lieven Gevers[a], Selvedin Telalovic[a], Bandar Al
Solami[b] and Jorge Gascon[a]*
[a]
Dr. A. Ramirez, Dr. Lieven Gevers, Dr Selvedin Telalovic, Prof. Jorge Gascon
KAUST Catalysis Center (KCC), Advanced Catalytic Materials
King Abdullah University of Science and Technology
Thuwal 23955, Saudi Arabia
E-mail: jorge.gascon@kaust.edu.sa
[b]
Dr. K. Lee, Dr. A. Harale, Dr. B. Al Solami
Carbon Management Research Division, Research & Development Center
Saudi Aramco
Dhahran 31311, Saudi Arabia.
Supporting information for this article is given via a link at the end of the document.
Abstract: Dry reforming of methane (DRM), the conversion of carbon
dioxide and methane into syngas, offers great promise for the
recycling of CO2. However, fast catalyst deactivation, especially at the
industrially required high pressure, still hampers this process. Here
we present a comprehensive study of DRM operation at high pressure
(7–28 bars). Our results demonstrate that, under equimolar CH4:CO2
mixtures, coke formation is unavoidable at high pressures for all
catalysts under study. However, under substoichiometric CH4:CO2
ratios (1:3), a stable high pressure operation can be achieved for most
catalysts with no sign of deactivation for at least 60 hours at 14 bars,
800ºC and 7500 h-1. In addition to the enhanced stability, under these
conditions, the amount of CO2 abated per mol of CH4 fed increases
by a 50%.
been identified as the most promising non-noble system[19-21]
.
Nevertheless, coke formation was still a major issue until recently
Yavuz and coworkers[22] by following a novel approach, the so
called “Nanocatalyst On Single Crystal Edges” (NOSCE)
technique, developed a Ni-Mo catalyst that prevented the
formation of coke. The resulting material was shown to be stable
for at least 850 hours at atmospheric pressure, the greatest value
reached so far[23]
.
Besides these remarkable advances one last requirement that
could finally lead to industrial application is still needed: stability
of operation at high pressures. By operating DRM at high
pressure production capacity increases and, more importantly, no
intermediate syngas compression, one of the most expensive unit
operations in industry, is needed[24]. To illustrate these costs
constrains we performed Aspen Plus simulations of the
compression process of a Syngas stream from 1 to 50 bars (see
Figures S1 and S2). The equipment cost for compressing 100
ton/h of syngas, the size of a medium scale FTS plant[25], is
estimated in more than 36 million USD with an operation cost of
2240 USD per hour, with the precompression from 1 to 10 bars
representing more than 85% of the total capital investment and
60% of the operational costs. Surprisingly, in spite of the obvious
advantage of high-pressure operation, this is a topic that has
hardly been explored experimentally due to the operational
restrains[26], as inferred from the fact that almost no publications
touch upon this point.
The main issue to overcome when operating DRM at high
pressure is again coke formation, highly thermodynamically
favored under these conditions[27-29]. Figure 1 and Table 1 show
computed thermodynamic product distributions at different
pressures. In addition to the well-known positive effect of
temperature on reducing coke formation, the negative effect of
pressure can be clearly observed. We can also observe that
elemental carbon and water are the two main products at low
temperatures where coking prevails and only above 400 ºC
syngas is formed. These results are well in line with previous
works.[14, 30]
Introduction
Carbon dioxide (CO2) capture and utilization (CCU) technologies
are a conditio sine qua non for our society to be able to deal with
CO2 emission[1-3]
.
The multiple economic and technical
challenges associated have sparked scientific research
worldwide[4-6]. Among the different technological solutions, dry
reforming of methane (DRM), the reaction between CO2 and CH4
to form syngas (a mixture of CO and H2) has gained a great deal
of attention. Indeed, large amounts of CO2 could be valorized[7-9]
to form syngas, a very versatile building block for the synthesis of
chemicals and fuels via Fischer Tropsch (FTS) chemistry[10-11]. In
addition, the use of methane as co-reactant makes this
technology much more attractive than alternative valorization
[12-13]
routes that rely in i.e. H2
.
However, despite being a promising process, the lack of a coke
resistant and stable catalyst has hampered industrial application
of dry reforming. A great deal of effort has been devoted to better
understand the reasons behind severe coking. Nowadays it is well
accepted that support defects, particle size, particle aggregation
and active phase composition are the main parameters governing
catalyst deactivation[14-18]. Additionally, Nickel/Molybdenum has
1
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10.1002/cctc.202001049
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Figure 1. Thermodynamic simulations for the Dry Reforming reaction at different temperatures and pressures for a 1:1 CH4:CO2 mixture.
Table1. Equilibrium conversions for the Dry Reforming reaction at different
800ºC), pressure (7, 14 and 28 bars), water co-feeding (10% vol.)
temperatures and pressures for a 1:1 CH4:CO2 mixture.
and CO2 concentration in the feed. The six industrial catalyst
employed in the study were provided by Saudi Aramco and from
now on will be labeled as Cat1, Cat2, Cat3, Cat4, Cat5 and Cat6.
Pure magnesium oxide also was tested in all runs to ensure the
absence of activity of the blank. Due to confidential agreements
only basic characterization was performed. XRD analysis
confirms the presence of Ni, Mo or Rh oxides supported on either
Alumina, MgO or GDC (see Figure S3). Surface analysis also
demonstrates that the samples display a large variety of surface
area, ranging from 190 to 17 m2/g. Altogether, this heterogeneity
of the catalyst composition, in addition to the multiple conditions
tested, ensures the validity of the screening.
Conversion (%)
CH4
CO2
700 ºC
CH4
CO2
750 ºC
CH4
CO2
800 ºC
Pressure (bar)
7
76.8
70.5
64.9
53.5
50.7
49.1
81.1
74.6
68.3
61.6
56.4
52.8
88.9
78.7
71.9
71.1
64.6
58.9
14
28
Hence, in this work, by studying six different industrial catalysts
under a wide range of operating conditions, we demonstrate that,
under standard feed composition (CH4: CO2 = 1:1), high pressure
operation leads to a strongly thermodynamic controlled reaction
with very high rates of coke formation independently of the
catalyst used. In contrast, with the use of substoichiometric
CH4:CO2 reactant ratios (1:3), stable high pressure operation can
be achieved for most catalysts. The results are rationalized as
direct consequence of the Bouduard reaction that, in this
particular condition of high pressure and substoichiometric feed,
overcomes the increased carbon yield.
Table2. Screening conditions tested in the DRM reaction.
Test
1
CH4:CO2
1:1
P (bar)
7
T (ºC)
700
700
700
750
750
750
800
800
800
GHSV (h-1)
Water co-feed
1500
no
no
no
no
no
no
no
no
no
2
1:1
14
28
7
1500
3
1:1
1500
4
1:1
1500
5
1:1
14
28
7
1500
Results and Discussion
6
1:1
1500
7
1:1
1500
The design of the experiments (DOE) for the high-throughput
screening can be found in Table 2, with a total of 15 tests
performed in our high-throughput platforms for each one of the 6
catalysts. We studied the effect of temperature (700, 750 and
8
1:1
14
28
1500
9
1:1
1500
2
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10.1002/cctc.202001049
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only the CH4 conversion depends on the catalyst composition.
This latter fact is especially important and suggests that CO2
conversion, unlike the CH4 one, is strongly equilibrium limited for
all catalysts at high pressure. When increasing the pressure to 14
and 28 bar (Tests 2 and 3, Figures S5 and S6 respectively) we
observed that: i) deactivation rates increased rapidly with
pressure, with no sample being able to sustain syngas production
at 28 bars; ii) both CH4 and CO2 conversions are reduced upon
pressure increase, in line with the data in Table1; iii) at 14 bar the
reactions are not kinetically controlled anymore, with all catalysts
reaching equilibrium conversion. We also need to point out that,
after circa 10 hours on the reaction stream, some catalysts (Cat1,
Cat2, Cat6) show slight higher CH4 conversions than the
equilibrium (see Table 1), suggesting that methane
decomposition plays a key role here. This is also corroborated by
the high H2/CO ratios (above 1) of the mentioned catalysts.
10
11
12
13
14
15
1:1
1:1
1:3
1:3
1:3
1:3
14
14
14
14
14
14
750
800
750
800
800
800
1500
1500
1500
1500
1500
7500
yes
yes
no
no
yes
yes
The results of the first test performed at 700 ºC and 7 bar are
depicted in Figure 2. We can observe that: i) Cat3 and MgO (as
expected) are not active at this low temperature condition; ii) only
Cat4 is able to produce syngas without deactivation in the time
frames studied, with a carbon balance close to 100%; iii) the rest
of catalyst deactivate in a few hours and; iv) all catalysts gave
similar CO2 conversion (close to the equilibrium, see Table 1) and
Figure 2. Catalytic performance of all samples at 700 ºC and 7 bar (Test1). Reaction conditions: 700ºC, 7 bars, CH4:CO2 1:1, 1500h-1.
Next, we studied the effect of temperature (700, 750 and 800 ºC)
at the 3 pressure ranges (7, 14 and 28 bars). The results can be
found in Figures S7 to S12 (Test4 to 9 of Table 2). From these
results we can observe that: i) expectedly, magnesium oxide is
inert in all tests, ii) Cat3, that was inactive at 700 ºC, now is active
at both 750 ºC and 800 ºC; iii) no catalyst is able to produce
syngas in sustained way at any condition, deactivating after few
hours on the stream, iv) this deactivation is specially pronounced
at severe conditions, like 28 bars and 800ºC, with erratic
performance of the samples, v) increasing the temperature leads
to an increase of both CH4 and CO2 conversion (in line with the
data of Table1), vi) increasing the pressure decreases the CH4
and CO2 conversion (again in line with the data of Table1), vii) at
750 ºC and 7 and 14 bars all catalyst reach (again) the equilibrium
CO2 conversion.
In order to better observe these temperature and pressure
combined effects we gathered all the results of Cat4 and plotted
them in Figure 3. In line with our previous observations, it is clear
3
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that: i) temperature increases CH4 and CO2 conversion with
pressure having the opposite effect, ii) only at mild reaction
conditions (700 ºC, 7 or 14 bars) a stable syngas production is
achieved in contrast with the thermodynamically suggested
reduced coke formation at high temperatures (see Figure 1) and
iii) high pressure and temperature strongly increase the coke
formation, as derived from the low carbon balance.
To support this last statement, we performed thermogravimetric
analyses of the spent catalysts after 20 hours on stream. The
results are summarized in Table S2. These results confirm the
high degree of coking under severe operation conditions. Under
mild conditions, Cat4 seems to be the most coke resistant sample,
in line with the better performance displayed in Figure 2.
Figure 3. Effect of the reaction temperature (700, 750 and 800 ºC) and pressure (7, 14 and 28 bars) on the catalytic performance of Cat4 sample, CH4:CO2 1:1,
1500h-1.
Following, we studied the effects of water co-feeding as steam
reforming is well-known for reducing the coke formation and
enhancing the H2/CO ratio[31]. The results can be found in Figures
S13 and S14 (Tests10 and 11 respectively). We can observe that
none of the conditions improve the stability of the catalysts despite
the presence of water. Nevertheless, in line with previous
reports[32-33], the H2/CO ratio was slightly enhanced. Next, looking
for more oxidizing conditions, we varied feed composition by
changing the CH4:CO2 ratios and increasing the CO2 up to a 1:3
ratio. The results can be found in Figure S15 (750ºC, Test12) and
Figure S16 (800ºC, Test 13). Extraordinarily, now all samples are
able to sustainably produce syngas at both 750ºC-800ºC and 14
bars with no sign of deactivation. Moreover, all catalyst showed
the same level of CH4 conversion (~95%), CO2 conversion
(~50%), and H2/CO ratio (~0.5) with a carbon balance close to
100%. This striking effect, already theoretically proposed by
Chein and coworkers[34], can only be explained as a result of the
Boudouard reaction[35-36] that, in these conditions, becomes the
dominant step, allowing us to overcome the increased carbon
yield at high pressures. To further unravel this effect we increased
the reaction time to 60 hours and added extra water to the feed,
trying to increase the low H2/CO ratio (see Figure S17, Test 14).
We can observe that all catalyst stay stable during the longer 60h
study and, as intended, the addition of H2O (10% vol. in the feed)
slightly enhanced the H2/CO ratio (0.6 vs 0.5).
Computed thermodynamic product distributions confirmed the
reduced carbon formation in comparison with the 1:1
stoichiometric ratio (see Figure S18). However, this Boudouard-
driven coke removal is (obviously) accompanied by CO formation
that reduces the H2/CO ratio, as we observed in our tests.
4
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Additionally, this low H2/CO ratio also indicates an important
contribution of the reverse water-gas shift reaction (RWGS:
CO2+H2→CO+H2O), especially when considering the excess of
CO2. Nevertheless, from a global CO2 removal point of view,
working with 1:3 CH4:CO2 ratio is advantageous as 1.5 mols of
CO2 per mol of CH4 can be abated (for a 50% CO2 and 100% CH4
maximum theoretical conversion) in comparison with the ratio of
1 with the common 1:1 CH4:CO2 ratio (for a 100% CO2 and 100%
CH4 maximum theoretical conversion). Last but not least, all
catalyst seemed to be able to reach equilibrium no matter the
actual catalyst composition, suggesting that, at high pressure and
low space times, the DRM is under thermodynamic regime with
kinetics having little to none control.
five times to 7500 h-1 GHSV while keeping the H2O addition (see
Figure4, Test 15). We can observe that now we are finally outside
thermodynamic control with catalyst composition playing a
determining role, showing Cat6 the highest CO2 conversion, Cat1
the highest H2/CO ratio (~0.7) and Cat3 the lowest H2/CO ratio
(~0.3) respectively. This effect of Cat3 can be linked to carbon
formation via CO2 direct reduction with hydrogen. Such
observation is consistent with the low CH4 conversion observed
for this catalyst in Figure 4. Nevertheless, still no deactivation was
observed for any of the samples despite the higher space time.
Hence, in addition to working with substoichiometric CH4:CO2
reactant ratios, high space times are also desired to escape the
strong thermodynamic control at high pressure operation.
To escape from this thermodynamic control and looking for an
accelerated deactivation test we further increased the space time
Figure 4. Catalytic performance of all samples at 800 ºC and 14 bars with additional CO2 feeding (Test15). Reaction conditions: 800ºC, 14 bars, CH4:CO2 1:3, 10%
vol. H2O, 7500h-1.
in a strongly thermodynamic controlled system at low space times.
Hence, more than developing complex catalytic systems, the
Conclusion
feeding of additional CO2 seems to be the easiest approach to
obtain a stable syngas production at high pressures. Moreover,
this extra CO2 also increases the mols of CO2 abated per mol of
CH4 fed by 50%. However, we also need to point out that this
additional CO2 feeding is accompanied by a decrease in the
H2/CO ratio to ~0.6 and, therefore, to obtain a viable high pressure
DRM process, poor hydrogen syngas applications need to be
In summary, our results demonstrate the enormous challenges of
stable DRM performance at high pressure, as coke formation
prevails no matter the catalyst employed. Only at mild conditions
(low temperature and pressure) catalyst composition seems to be
relevant. However, if additional CO2 is added to the feed, a stable
performance can be achieved in almost all catalytic systems
thanks to the Boudouard reaction that domains the coke removal
5
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X-Ray diffraction (XRD): XRD analysis was performed on BRUKER D8
ADVANCE instrument from 5 to 90 2 theta degrees and an increment of
0.01 degrees.
studied in parallel. We hope that these results encourage
researchers to study the industrial relevant high pressure
applications of DRM with the ultimate goal of a carbon neutral
economy.
Nitrogen adsorption: Nitrogen physisorption measurements were
performed on an ASAP2420 MICROMERITICS instrument. Prior to
obtaining the isotherm the samples were dried under vacuum with a ramp
rate of 10 ºCmin-1 up to 90 ºC for 60 min followed by a final heat treatment
at 300 Cº for 720 min. After weighing the dried samples they were
additionally degassed under vacuum at 90 ºC for 120 min at the analysis
ports of the instrument prior to acquirement of isotherm by stepwise dosing
of N2 at 77 K. As last the correct free space values were obtained by
performing additionally 1 point measurement using N2 and exposing the
sample to Helium.
Experimental Section
Chemicals: Magnesium Oxide (MgO, Sigma Aldrich) was used as received.
Catalyst preparation: Catalyst samples with different compositions, based
on Ni, Mo or Rh oxides supported on either Alumina, MgO or GDC
(Gadolinium doped Ceria)were provided by Saudi Aramco. All samples
were sieved between 150 and 250 µm before used.
Process simulations and thermodynamic calculations: Process simulations
were carried out with steady-state simulation models developed in Aspen
Plus V8.8 software. Economic analysis was carried out with the Economics
Solver extension of Aspen Plus. The selected property method was
Redlich-Kwong-Soave. The Wegstein method was used for flowsheet
convergence with a mass balance closure of the system better than 0.0001.
The total flow is 100 tons/hour of Syngas (CO:H2 1:1) with a target
pressure of 50 bars. The feed stream was compressed by 4 four isentropic
compressors (C1 to C4 in FigureS1) with intercooling heat exchangers
(HX1 to HX3 in Figure S1) to cool down the pressurized streams.
Thermodynamic equilibrium was calculated by using HSC 5.1 chemistry
software with a method of Gibbs free energy minimization. Same feed
compositions of reactants as the experimental conditions were used and
calculated with varying pressures and temperatures. In order to investigate
carbon formation, solid carbon was considered to be one of the products
as well as gaseous H2, CO, and H2O. Thermodynamic equilibrium results
were used as reference data to compare the experimental results.
Catalytic tests: Catalytic tests were executed in a 16 channel Flowrence®
from Avantium. 125 µL of catalyst sample was typically used. The reactors
are 300 mm long quartz tubes inserted in a furnace. The outside and inside
diameters of the tubes are 3 and 2 mm, respectively. One reactor was
always used without catalyst as a blank. The reactor design allows the use
of quartz reactors at high pressures (see Figure S3). The 46 ml/min of
mixed feed had a composition CH4:CO2:N2 = 1:1:1. In addition, 4 ml/min of
He were mixed with the feed as internal standard. We aimed to have 1500
h-1 GHSV per channel. One of the 16th channels was always used without
catalyst as blank. Prior to feeding the reaction mixture all samples were
pretreated in-situ with a pure H2 atmosphere for 4 hours at 800°C. The
tubes were then pressurized using a membrane pressure controller.
GC is an Agilent 7890B with two sample loops. After flushing the loops for
24 min, the content is injected. One sample loop goes to TCD channel with
2 Haysep pre-column and MS5A, where He, H2, CH4 and CO are
separated. Gases that have longer retention times than CO2 on the
Haysep column (Column 4 Haysep Q 0.5 m G3591-80023) are back-
flushed. Further separation of permanent gases is done on another
Haysep column (Column 5 Haysep Q 6 Ft G3591-80013) to separate CO2
before going to MS5A. Another sample loop goes to an Innowax pre-
column (5m, 0.20mm OD, 0.4 µm film), first 0.5 min of the method the
gases coming from pre-column are sent to Gaspro column (Gaspro 30M,
0.32 mm OD) followed by FID. After 0.5 min, valve is switched and gases
are sent to Innowax column (45 m, 0.2 mm OD, 0.4 µm) followed by FID.
Gaspro column separates C1-C8, paraffins and olefins. Innowax separates
larger hydrocarbons (>C9) and aromatics BTX and C9+ aromatics. No C2+
products were detected in any of the performed tests. Conversions (X, %)
and carbon balance are defined as follows:
Acknowledgements
Funding for this work was provided by Saudi Aramco and King
Abdullah University of Science and Technology (KAUST).
Keywords: Dry Reforming • CO2 • CH4 • Hydrogen • Syngas •
Pressure
[1]
[2]
[3]
[4]
N. Mac Dowell, P. S. Fennell, N. Shah, G. C. Maitland, Nat
Clim Change 2017, 7, 243-249.
C. F. Shih, T. Zhang, J. H. Li, C. L. Bai, Joule 2018, 2, 1925-
1949.
R. Dittmeyer, M. Klumpp, P. Kant, G. Ozin, Nature
Communications 2019, 10, 1818.
A. Alvarez, A. Bansode, A. Urakawa, A. V. Bavykina, T. A.
Wezendonk, M. Makkee, J. Gascon, F. Kapteijn, Chem Rev
2017, 117, 9804-9838.
퐶푂2푖푛
퐶푂2표푢푡
⁄
−
⁄
퐻푒표푢푡
퐻푒푖푛
퐶표푛푣퐶푂2 (%) =
퐶표푛푣퐶퐻4 (%) =
× 100
퐶푂2푖푛
⁄
퐻푒푖푛
퐶퐻4푖푛
퐶퐻4표푢푡
⁄
−
⁄
퐻푒
퐻푒푖푛
표푢푡 × 100
퐶퐻4푖푛
⁄
퐻푒푖푛
퐶표푢푡
∑
⁄
퐻푒
표푢푡 × 100
퐶퐵푎푙푎푛푐푒(%) =
[5]
[6]
[7]
[8]
G. Centi, E. A. Quadrelli, S. Perathoner, Energ Environ Sci
2013, 6, 1711-1731.
A. Dokania, A. Ramirez, A. Bavykina, J. Gascon, Acs
Energy Lett 2019, 4, 167-176.
C. O. Hawk, P. L. Golden, H. H. Storch, A. C. Fieldner, Ind
Eng Chem 1932, 24, 23-27.
N. A. K. Aramouni, J. G. Touma, B. Abu Tarboush, J.
Zeaiter, M. N. Ahmad, Renew Sust Energ Rev 2018, 82,
2570-2585.
퐶푖푛
∑
⁄
퐻푒푖푛
where Ciin and Ciout, are the concentrations determined by GC analysis in
the blank and in the reactor outlet respectively.
Thermogravimetric analysis (TGA): TGA Analysis was performed with a
METTLER TOLEDO TGA/DSC 1 instrument. Approximately 10 mg of
sample was weighed inside an alumina crucible. In order to remove any
volatile species, samples were heated from RT to 200 ºC with an ramp of
10 Cmin-1 under a flow of N2 (50 mLmin-1) followed by an isothermal step
of 60 min. The temperature was again increased up to 800 ºC with a ramp
of 10 Cmin-1 in order to pyrolyze the coked samples. The sample was kept
at 800 ºC under a flow of N2 (50 mLmin-1) for 30 min before switching the
gas to Air (50 mlmin-1) in order to oxidized the coked sample.
[9]
J. M. Lavoie, Front Chem 2014, 2.
[10]
V. P. Santos, T. A. Wezendonk, J. J. D. Jaen, A. I. Dugulan,
M. A. Nasalevich, H. U. Islam, A. Chojecki, S. Sartipi, X.
Sun, A. A. Hakeem, A. C. J. Koeken, M. Ruitenbeek, T.
Davidian, G. R. Meima, G. Sankar, F. Kapteijn, M. Makkee,
J. Gascon, Nature Communications 2015, 6.
G. P. Van der Laan, A. A. C. M. Beenackers, Catal Rev
1999, 41, 255-318.
[11]
6
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001049
ChemCatChem
FULL PAPER
[12]
A. Gonzalez-Garay, M. S. Frei, A. Al-Qahtani, C. Mondelli,
G. Guillen-Gosalbez, J. Perez-Ramirez, Energ Environ Sci
2019, 12, 3425-3436.
[13]
[14]
[15]
G. Glenk, S. Reichelstein, Nat Energy 2019, 4, 216-222.
S. Arora, R. Prasad, Rsc Adv 2016, 6, 108668-108688.
O. Muraza, A. Galadima, Int J Energ Res 2015, 39, 1196-
1216.
[16]
[17]
[18]
[19]
[20]
[21]
[22]
P. Djinovic, I. G. O. Crnivec, B. Erjavec, A. Pintar, Appl
Catal B-Environ 2012, 125, 259-270.
J. M. Ginsburg, J. Pina, T. El Solh, H. I. de Lasa, Ind Eng
Chem Res 2005, 44, 4846-4854.
L. Guczi, G. Stefler, O. Geszti, I. Sajo, Z. Paszti, A. Tompos,
Z. Schay, Appl Catal a-Gen 2010, 375, 236-246.
L. Yao, M. E. Galvez, C. W. Hu, P. Da Costa, Int J Hydrogen
Energ 2017, 42, 23500-23507.
Z. W. Yao, J. Jiang, Y. Zhao, F. B. Luan, J. Zhu, Y. Shi, H.
F. Gao, H. Y. Wang, Rsc Adv 2016, 6, 19944-19951.
C. Shi, S. H. Zhang, X. S. Li, A. J. Zhang, M. Shi, Y. J. Zhu,
J. S. Qiu, C. T. Au, Catal Today 2014, 233, 46-52.
Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S.
Subramanian, A. Harale, M. Albuali, B. A. Fadhel, A. Jamal,
D. Moon, S. H. Choi, C. T. Yavuz, Science 2020, 367, 777-
+.
[23]
[24]
[25]
A. Ramirez, J. Gascon, Joule 2020, 4, 714-716.
S. S. Penner, Energy 2006, 31, 33-43.
H. Er-rbib, C. Bouallou, F. Werkoff, Energy Procedia 2012,
29, 156-165.
[26]
L. C. S. Kahle, T. Roussiere, L. Maier, K. H. Delgado, G.
Wasserschaff, S. A. Schunk, O. Deutschmann, Ind Eng
Chem Res 2013, 52, 14727-14727.
[27]
[28]
R. Y. Chein, Y. C. Chen, C. T. Yu, J. N. Chung, J Nat Gas
Sci Eng 2015, 26, 617-629.
L. A. Schulz, L. C. S. Kahle, K. H. Delgado, S. A. Schunk,
A. Jentys, O. Deutschmann, J. A. Lercher, Appl Catal a-
Gen 2015, 504, 599-607.
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
I. Khan, A. Ramirez, G. Shterk, L. Garzon-Tovar, J. Gascon,
Catalysts 2020, 10.
D. Pakhare, C. Shaw, D. Haynes, D. Shekhawat, J. Spivey,
Journal of CO2 Utilization 2013, 1, 37-42.
P. Gangadharan, K. C. Kanchi, H. H. Lou, Chem Eng Res
Des 2012, 90, 1956-1968.
W. J. Jang, D. W. Jeong, J. O. Shim, H. M. Kim, H. S. Roh,
I. H. Son, S. J. Lee, Appl Energ 2016, 173, 80-91.
K. Y. Koo, H. S. Roh, U. H. Jung, D. J. Seo, Y. S. Seo, W.
L. Yoon, Catal Today 2009, 146, 166-171.
R. Y. Chein, W. H. Hsu, C. T. Yu, Int J Hydrogen Energ
2017, 42, 14485-14500.
J. W. Snoeck, G. F. Froment, M. Fowles, Ind Eng Chem
Res 2002, 41, 4252-4265.
B. P. Jalan, Y. K. Rao, Carbon 1978, 16, 175-184.
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10.1002/cctc.202001049
ChemCatChem
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Towards High-Pressure Methane Dry Reforming. The conversion of both CO2 and CH4 greenhouse gases via dry methane reforming
(DRM) could provide an environmentally friendly route for the synthesis of valuable chemicals. However, to achieve the final industrial
application research at high pressure feeds is still required. In this work we have explored the DRM reaction at high pressure via a
comprehensive high-throughput screening on 6 different industrial catalysts. Our results demonstrate the enormous challenges of stable
DRM performance under these high pressure conditions. Nevertheless, we have also found that with the use of substoichiometric
CH4:CO2 reactant ratios (i.e. 1:3) stable high pressure operation can be achieved for most catalysts with no sign of deactivation.
Institute and/or researcher Twitter usernames: @jorgascon, @KCCkaust, @adv_cat_mat, @Saudi_Aramco, @Aramco
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This article is protected by copyright. All rights reserved.