Olefins from Natural Gas by Oxychlorination

Article abstract of DOI:10.1002/anie.201706624

Ethylene and propylene are the key building blocks of the chemical industry, but current processes are unable to close the growing gap between demand and manufacture. Reported herein is an exceptional europium oxychloride (EuOCl) catalyst for the selective (≥95 %) production of light olefins from ethane and propane by oxychlorination chemistry, thus achieving yields of ethylene (90 %) and propylene (40 %) unparalleled by any existing olefin production technology. Moreover, EuOCl is able to process mixtures of methane, ethane, and propane to produce the olefins, thereby reducing separation costs of the alkanes in natural gas. Finally, the EuOCl catalyst was supported on suitable carriers and evaluated in extrudate form, and preserves performance for >150 h under realistic process conditions.

Full text of DOI:10.1002/anie.201706624

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Accepted Article
Title: Olefins from Natural Gas via Oxychlorination Catalysis
Authors: Guido Zichittella, Nicolas Aellen, Vladimir Paunović, Amol P
Amrute, and Javier Pérez-Ramírez
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201706624
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Olefins from Natural Gas via Oxychlorination Catalysis
Guido Zichittella, Nicolas Aellen, Vladimir Paunović, Amol P. Amrute, and Javier Pérez-Ramírez*
Abstract: Ethylene and propylene are the key building blocks of the
chemical industry, but current processes are unable to close the
growing gap between demand and manufacture. Herein, we report
an exceptional europium oxychloride (EuOCl) catalyst for the
selective (≥95%) production of light olefins from ethane and propane
via oxychlorination chemistry, achieving yields of ethylene (90%) and
propylene (40%) unparalleled by any existing olefin production
technology. The outstanding performance was rationalized by its
bifunctional character, integrating the alkane oxychlorination into
alkyl chloride and its dehydrochlorination into the olefin, thus
recycling the halogen source. Moreover, EuOCl is able to process
mixtures of methane, ethane, and propane to produce the olefins,
Figure 1. Closed-loop chlorine-mediated process for the one-step conversion
thereby reducing separation costs of the alkanes in natural gas.
Finally, the EuOCl catalyst was scaled up in technical form, which
preserves the outstanding performance for >150 h under realistic
process conditions.
of abundant light alkanes to valuable ethylene and propylene, which are the
main building blocks of the chemical industry. An optimal catalytic material for
this process should integrate the ability to functionalize the alkane into the
corresponding alkyl chloride and to dehydrochlorinate the latter to yield an
olefin, enabling the full recycle of the halogen source.
Vast conventional and unconventional natural gas reserves are
rich in ethane and propane, offering a great potential as
feedstock to produce ethylene and propylene, the platform
molecules for the manufacture of virtually all polymers,
pharmaceuticals, and chemicals.[1] Currently, these olefins are
produced via steam-cracking, fluid-catalytic cracking, and/or
catalytic dehydrogenation, which are highly capital- and energy-
intensive and are unable to close the growing gap between their
demand and manufacture.[1b,2] Thus, the replacement of these
highly endothermic technologies with one-step, exothermic
processes would result in enormous economic benefits.[2c,3] In
this direction, the oxidative dehydrogenation of ethane and
propane,[2a,4a] the partial oxidation of ethane,[4b,c] and the
oxidative coupling of methane[4d] have been extensively studied
for decades as a way to attain olefins, but so far they have failed
to reach commercial reality due to the lack of suitable catalysts
that can achieve economically attractive yields of ethylene and
propylene (<75% and 30%, respectively). The catalytic alkane
oxychlorination route, comprising the reaction of an alkane with
hydrogen chloride (HCl) and oxygen, is appealing as it enables
to selectively functionalize the alkane under moderate
conditions.[1a,5] However, so far this route has mainly targeted
the production of vinyl chloride monomer or alkyl chloride, where
ethylene or propylene was observed as a by-product with low
yields of 50% or 20%, respectively.[1a,6] The selective production
integrate the oxychlorination of the alkane to the alkyl chloride,
followed by its dehydrochlorination to yield the olefin (Figure 1).
In our quest for a novel multifunctional catalytic active
phase, we have investigated the gas-phase oxychlorination of
ethane and propane under variable conditions over different
catalytic families, including: cerium oxide (CeO2), vanadyl
pyrophosphate ((VO)2P2O7), titanium oxide (TiO2), iron
phosphate (FePO4), and europium oxychloride (EuOCl). The
oxide and phosphate systems were selected based on their
good activity in methane oxyhalogenation,[5b,7a] while the choice
of EuOCl was based on the recent studies revealing its
promising performance for ethylene oxychlorination to vinyl
chloride monomer,[7b] and of europium oxybromide for methane
oxybromination to methyl bromide and HBr oxidation to Br2.[7c]
The catalysts were compared by evaluating the product
distribution obtained in the oxychlorination of ethane and
propane at ca. 20% and 15% alkane conversion, respectively
(Figure 2a,b; Supporting Information, Figure S1), obtained by
adjusting the reaction temperature. Based on this criterion, the
catalysts can be classified into three different groups. The first
category is represented by CeO2, which led to the lowest yields
of olefin due to the formation of chlorinated hydrocarbons and
combustion products in EOC and particularly POC. The second
class, represented by (VO)2P2O7 and TiO2, achieved high yields
of ethylene (with 80% and 90% selectivity in EOC, respectively),
however, caused pronounced formation of combustion products
in POC. Finally, FePO4 and EuOCl enabled to reach over 95%
selectivity to alkene in both EOC and POC. EuOCl displayed the
highest yields of ethylene and propylene at unaltered selectivity
(vide infra Figure 3c; Supporting Information, Figure S4), thus
emerging as an outstanding catalyst for olefin production via
oxychlorination chemistry. X-ray diffraction (XRD) and N2
sorption analyses of all materials before and after the catalytic
tests showed no alterations of the crystallographic structure, but
evidenced a small decrease in the total surface area (Supporting
Information, Figure S2). We have assessed the stability of this
promising active phase, and demonstrated its robustness in
of ethylene and propylene in
a single step from the
corresponding alkane would be highly appealing. This requires
the design of a multifunctional catalytic material that can
[*]
G. Zichittella, N. Aellen, V. Paunović, Dr. A. P. Amrute,
Prof. J. Pérez-Ramírez
Institute for Chemical and Bioengineering
Department of Chemistry and Applied Biosciences, ETH Zurich
Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland
E-mail: jpr@chem.ethz.ch
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201706624
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preserving the outstanding performance for over 100 h on
stream in both EOC and POC (Supporting Information,
Figure S3). The XRD analysis of the samples collected after the
run indicated no alternation of the bulk structure (Supporting
Information, Figure S3) while a slight increase in the crystallinity
of the sample was evidenced from high resolution transmission
electron microscopy (HRTEM) and by a small drop in the total
surface area (Supporting Information, Figure S3). We sampled
the materials after 5 h on stream in both EOC and POC and
confirmed that the surface area (8 m2 g−1 in both cases)
stabilizes after few hours on stream. Thermodynamic
calculations show that the transformation of EuOCl to EuCl3 is
highly disfavored in the operating conditions of the
oxychlorination reaction (Supporting Information, Figure S3),
which might be due to its structural arrangement, alternating
halide and oxide layers, as shown in Figure 1. Finally, we have
conducted elemental analysis on the used catalyst and
confirmed the absence of coke deposits (Supporting Information,
Table S4).
range of temperatures (623-847 K), and feed concentration of
alkanes (1.5-6 vol.%), O2 (3-6 vol.%), and HCl (1-15 vol.%)
(Figure 2c,d), highlighting the robustness of EuOCl in both
reactions. The formation of alkenes might in principle come from
the oxidative dehydrogenation of the alkane over the catalyst.
Thus, to demonstrate the pivotal role HCl in the feed in alkane
activation and olefin generation, a test was performed in the
absence of HCl. Both the alkane conversions and alkene
selectivities were drastically dropped (Figure 2c,d). Interestingly,
by switching from 0 vol.% to 1 vol.% of HCl, the alkane
conversion and particularly olefin selectivity were boosted in
both alkane oxychlorination reactions. Further optimization of the
alkane inlet concentrations enabled the attainment of the highest
single-pass yields of ethylene and propylene (90% and 40%,
respectively) among any alkane-to-olefins upgrading route
(Figure 2c,d).
Olefin production from alkane via oxychlorination chemistry
stem from the integration of alkane oxychlorination to produce
alkyl chloride and subsequent dehydrochlorination of the latter to
to yield the corresponding alkene on the catalyst surface (vide
supra Figure 1). Nonetheless, these chloro-derivatives were not
Further evaluation of EuOCl under variable conditions
showed the preservation of high selectivity (>90%) in a wide
Figure 2. Catalytic performance expressed as single-pass yield of products (Y(j)) in the oxychlorination of a) ethane (EOC) and b) propane (POC) at ca. 20% and
15% alkane conversion, respectively, and alkene selectivity versus alkane conversion over EuOCl in c) EOC and d) POC at variable conditions. EuOCl represents
a superior catalyst for both reactions, leading to the highest yield of olefins (dashed lines in a) and b)). Conditions: Alkane:HCl:O2:Ar:He = 6:6:3:4.5:80.5.
GHSV = 2550-6950 h−1 (details in Supporting Information, Table S3). EuOCl was further studied in c) EOC and d) POC at variable temperature (black) and feed
concentration of HCl (green), O2 (red), and alkane (blue) (details of symbols in Supporting Information, Table S2). GHSV = 6370 h−1. The dashed gray lines
indicate the olefin yield, whereas the colored areas denote the alkane conversion and olefin selectivity achievable in the oxychlorination of light alkanes and their
mixtures over EuOCl (EOC, POC, MEPOC; green; vide infra Supporting Information, Figure S5), oxidative dehydrogenation of ethane and propane (ODH;
gray),[2a,4a] partial oxidation of ethane (POE; blue),[4b,c] oxidative coupling of methane (OCM; red),[4d] catalytic dehydrogenation of propane (CDP; light blue),[1b] fluid
catalytic cracking (FCC; orange)[8a] and steam cracking (SC; yellow)[8b] of ethane and naphtha. All results are expressed on a molar basis.
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10.1002/anie.201706624
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Figure 2a,b). However, if the reducibility is too low, the olefin
yield will be low as seen for FePO4. EuOCl appeared to have the
optimal oxidizing potential, as it achieves the highest yields of
olefins in both EOC and POC (Figure 3b; Supporting
Information, Figure S4). Thus, the outstanding performance of
EuOCl can be rationalized by its balanced redox properties,
enabling it to selectively functionalize the alkane and suppress
undesired reactions, and its unpaired ability to readily
dehydrochlorinate the produced alkyl chloride, allowing it to
selectively yield olefins and to recycle the halogen source
(Supporting Information, Figure S5.
Due to the increasing scarceness of oil reserves, the world
is currently undergoing an unprecedented revolution in raw
hydrocarbons feedstock supply, with vast natural gas being the
leading flag.[9] Consequently, we explored the potential of EuOCl
in the oxychlorination of mixtures of methane, ethane, and
propane (MEPOC) (Supporting Information, Figure S5) to show
the level of flexibility of this catalytic technology with respect to
the feed composition. In this reaction, the onset temperature for
propylene formation was lower than the one for ethylene, in line
with the higher activity observed in POC than EOC. At 773 K,
20% and 27% yield of ethylene and propylene were achieved at
>95% selectivity (Supporting Information, Figure S5). Methane
conversion and COx formation were negligible (<5%). Moreover,
we have investigated the effect of increased feed concentration
of HCl and varying reactants ratio on the catalytic performance
(Supporting Information, Figure S5), which show that the yields
of ethylene and propylene could be improved to 30% and 40%,
respectively, at >95% selectivity. In this respect, the olefins
mixture could then potentially be upgraded by known
technologies to gasoline blends over zeolite- or supported metal-
based systems.[10] These results show an attractive feature of
the EuOCl catalyst preserving the high alkene selectivity in the
alkane mixture, which gives an extra-potential for natural gas
upgrading due to its low sensitivity to feed purity.
To demonstrate the practical potential of EuOCl-based
system for olefin production, we developed a technical catalyst
by dispersing europium (10 wt.%) onto millimeter-sized bodies of
silicon carbide (SiC), silicon oxide (SiO2), zirconium oxide (ZrO2),
and titanium oxide anatase (TiO2-a). Evaluation of these
systems in EOC and POC identified EuOCl/TiO2-a as the best
catalyst for ethylene production, enabling unaltered ethylene
selectivity and higher ethane conversion compared to bulk
EuOCl, and EuOCl/SiC as the best system for propylene
production, maintaining >90% propylene selectivity and reaching
40% propylene yield (Supporting Information, Figure S6). This
suggests that the carrier selection plays an important role in
controlling the performance of the EuOCl phase. We performed
XRD analysis of the best ethylene and propylene generators
before and after the catalytic tests (Figure 4a,b, Supporting
Information, Figure S7). No europium phases were identified
over EuOCl/TiO2-a, indicating its high dispersion. On the other
hand, reflections of Eu2O3 phase could be distinguished in the
equilibrated EuOCl/SiC sample, suggesting (i) lower europium
dispersion, and (ii) likely strong active phase-support electronic
interactions that inhibits the transformation of Eu2O3 into EuOCl
over SiC. Transmission electron microscopy (TEM) in high-angle
annular dark field mode (HAADF) and high resolution TEM
corroborated the high and low europium dispersion in the
Figure 3. a) Yields of ethylene versus temperature in C2H5Cl
dehydrochlorination (open symbols) and in EOC (solid symbols) over EuOCl
(orange) and FePO4 (blue). Conditions: GHSV = 3570-6370 h−1 (details in
Supporting
Information,
Table S3).
C2H5Cl
dehydrochlorination:
C2H5Cl:Ar:He = 1:4.5:94.5, EOC: C2H6:HCl:O2:Ar:He = 6:6:3:4.5:80.5. b)
Selectivity (solid symbols) and yield (open symbols) of ethylene in EOC
versus the oxidizing ability of the catalyst under typical oxychlorination
conditions (T10(HCl)). The latter is measured as the temperature to attain 10%
HCl conversion in the gas-phase HCl oxidation to Cl2 (Supporting Information,
Figure S4). Conditions: C2H6:HCl:O2:Ar:He = 6:6:3:4.5:80.5. GHSV = 2550-
6950 h−1 (details in Supporting Information, Table S3).
observed over EuOCl (vide supra Figure 2a,b; Supporting
Information, Figure S1), which might be explained by its fast
dehydrochlorination kinetic. To confirm this, we performed ethyl
chloride and propyl chloride dehydrochlorination experiments on
EuOCl and FePO4 and observed that ethylene and propylene
generation occurred at much lower temperature compared to
EOC and POC, particularly in the case of EuOCl (Figure 3a;
Supporting Information, Figure S4).
To rationalize the different performance of the catalysts in
EOC and POC, the gas-phase HCl oxidation to Cl2 was studied
(Supporting Information, Figure S4) and taken as a relative
measure of the oxidizing ability of the catalysts under typical
oxychlorination conditions. Thus, if the temperature at which ca.
10% HCl conversion is attained in HCl oxidation, T10(HCl), is
high, the material possesses a low oxidizing character. This
temperature was found to correlate linearly with olefin selectivity
in EOC and POC (Figure 3b; Supporting Information,
Figure S4), suggesting that the systems with lower reducibility
are preferred to achieve a high olefin selectivity, as a likely
consequence of the suppressed combustion reactions as
evidenced in the case of EuOCl and FePO4 (vide supra
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EuOCl/TiO2-a
and
EuOCl/SiC
catalysts,
respectively
(Figure 4c,d, Supporting Information, Figure S8).
Further evidence on the importance of the carrier selection
comes from the alkane oxidation, and the alkyl chloride
dehydrochlorination (in the presence or absence of oxygen)
tests conducted over these catalysts (Supporting Information,
Figure S9 and 10). It was found that EuOCl/TiO2-a possesses
low tendency towards alkane combustion, and high activity in
the dehydrochlorination of C2H5Cl, making it a very effective
catalyst for ethylene production. On the other hand, it fails in
POC due to its high reactivity in combusting C3H7Cl. EuOCl/SiC,
instead, is more inert towards C3H7Cl oxidation. This together
with its low tendency to combust the alkane, and its good activity
in dehydrochlorination makes it a much better catalyst for POC.
To further demonstrate the practical relevance of the
presented catalytic technology, the best ethylene producer,
EuOCl/TiO2-a extrudates, was taken as representative, analyzed
in greater details and evaluated under more demanding
conditions. Microscopy measurements by scanning TEM in
HAADF mode with elemental mapping by energy-dispersive
X-ray (EDX) spectroscopy showed the regularity of the surface
as well as uniform distribution of europium along the extrudate
before and after the reaction (Supporting Information,
Figure S11). Mercury porosimetry showed the preservation of
the meso- and macroporosity of the extrudate (Supporting
Information, Figure S12). X-ray photoelectron spectroscopy of
the samples evidenced the presence of Eu2+ on the catalytic
surface, which slightly increases after being exposed to the
reaction environment (Supporting Information, Figure S12),
suggesting the Eu3+/Eu2+ to be the active redox couple, in line
with other studies on Eu-based catalysis.[7c]
To verify the robustness of shaped EuOCl/TiO2-a, we have
studied the effect of higher reactants partial pressure and total
pressure over this catalyst in EOC. A three-fold increase in the
concentration of reactants led to a more than three times higher
ethylene space time yield at ≥90% selectivity. Likewise, upon
increasing the total pressure from atmospheric until 1.75 bar, a
two-fold increment of STY(C2H4) was achieved at >90%
selectivity (Figure 4e). Carbon elemental analysis (Supporting
Information, Table S4) of the sample recovered after 5 h
exposure to three times higher reactant concentration
demonstrated the absence of coke. Moreover, we have tested
EuOCl/TiO2-a by using N2 as the carrier gas instead of He and
observed that the catalytic performance was preserved.
Although today mature technologies for HCl/H2O
separation are applied in industry,[11a,b] effective and tailored
methods would be required to separate water since it is a net
reaction product. In this view, we have studied the effect of
stoichiometric water addition to EOC feed over EuOCl/TiO2-a.
Ethylene selectivity of ≥90% was attained despite a small drop in
productivity, which could be partially restored by doubling all
reactants partial pressures (Figure 4e), demonstrating that an
operation with dry HCl is not critical to maintain the outstanding
performance. Finally, we have evaluated EuOCl/TiO2-a
Figure 4. X-ray diffractograms and total surface area of a) EuOCl/TiO2-a and
b) EuOCl/SiC prior to (fresh) and after EOC and POC. The insets magnify the
diffractograms in the region of 20°-40° 2q. Marked reflections according to the
JCPDS reference patterns: TiO2-anatase (triangle), SiC (star), Eu2O3
(diamond). c) Transmission electron microscopy (TEM) in high-angle annular
dark field mode (HAADF), and high resolution TEM of used EuOCl/TiO2-a,
and d) HAADF-TEM of used EuOCl/SiC. e) Ethylene space time yield
(STY(C2H4); solid bars) and ethylene selectivity (open bars) in EOC at
increasing reactants concentration (gray) and total pressure (orange), and in
the presence of water (blue). The numbers in the sample code denote the
molar feed ratio (C2H6:HCl:H2O:O2). f) Alkane conversion, product selectivity
and ethylene space time yield versus time-on-stream over EuOCl/TiO2-a
extrudates in the oxychlorination of ethane. Conditions: Wcat = 0.5 g,
GHSV = 8080 h−1, C2H6:HCl:H2O:O2:Ar:He = 12:12:12:6:4.5:65.5.
extrudates in
a long-term test at higher reactants partial
pressure and by water co-feeding, which showed its ability to
retain the outstanding performance for over 150 h and its
mechanical, surface, and bulk physicochemical properties
(Figure 4f; Supporting Information, Figure S12).
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[1]
[2]
a) R. Lin, A. P. Amrute, J. Pérez-Ramírez, Chem. Rev. 2017, 117,
4182-4247; b) J. J. H. B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez,
B. M. Weckhuysen, Chem. Rev. 2014, 114, 10613-10653.
In conclusion, we have discovered EuOCl as a highly
promising catalytic technology for the selective one-step
conversion of ethane and propane into olefins via
oxychlorination chemistry, providing the highest single-pass
yields of ethylene and propylene (90% and 40%, respectively)
among any existing technology for olefin production. The
performance of EuOCl was rationalized by (i) its balanced redox
properties that allows to functionalize the alkane and to avoid
combustion, and by (ii) its unpaired ability to dehydrochlorinate
the formed alkyl chloride to olefin, enabling the recycling of the
halogen source. Moreover, EuOCl is also able to selectively
process mixtures of methane, ethane, and propane to produce
ethylene and propylene. Finally, we demonstrated the scalability
of the EuOCl-based catalyst in extrudate form using widely
available carriers. Titanium oxide anatase was identified as the
best support for ethylene production, which maintained the
outstanding performance for over 150 h on stream at both
increased reactants partial pressure and by co-feeding water.
These results show the practical relevance of the EuOCl-based
chemistry for natural gas upgrading, and drives future research
on several macroscopic engineering aspects, such as heat
management, products separation (i.e. H2O, HCl, COx), reactor
design etc., for further demonstration of the applicability of this
highly promising catalytic technology, although relevant
solutions can be extrapolated from applied technologies.[11]
a) F. Cavani, N. Ballarini, A. Cericola, Catal. Today 2007, 127, 113-131;
b) T. Ren, M. Patel, K. Blok, Energy 2006, 31, 425-451; c) F. J. Brazdil,
Top. Catal. 2006, 38, 289-294.
[3]
[4]
E. McFarland, Science 2012, 338, 340-342.
a) C. A. Gärtner, A. C. van Veen, J. A. Lercher, ChemCatChem 2013, 5,
3196-3217; b) D. A. Goetsch, L. D. Schmidt, Science 1996, 271,
1560-1562; c) A. S. Bodke, D. A. Olschki, L. D. Schmidt, E. Ranzi,
Science 1999, 285, 712-715; d) R. Horn, R. Schlögl, Catal. Lett. 2015,
145, 23-39.
[5]
[6]
a) V. Paunović, G. Zichittella, R. Verel, A. P. Amrute, J. Pérez-Ramírez,
Angew. Chem. Int. Ed. 2016, 55, 15619-15623; Angew. Chem. 2016,
128, 15848-15852; b) G. Zichittella, V. Paunović, A. P. Amrute, J.
Pérez-Ramírez, ACS Catal. 2017, 7, 1805-1817.
a) L. Xueju, L. Jie, Z. Guangdong, Z. Kaiji, L. Wenxing, C. Tiexin, Catal.
Lett. 2005, 100, 153-159; b) J. P. Henley, M. E. Jones, D. A. Hickman,
K. A. Marshall, D. J. Reed, W. D. Clarke, M. M. Olken, L. E. Walko
(Dow Global Technologies Inc.), US-B1 6933417, 2005; c) R. T. Carrol,
E. J. De Witt, C. Falls, L. E. Trapasso (B. F. Goodrich Company), US
3173962, 1965; d) A. Shalygin, E. Paukshtis, E. Kovalyov, B.
Bal’zhinimaev, Front. Chem. Sci. Eng. 2013, 7, 279-288; e) C. Li, G.
Zhou, L. Wang, S. Dong, J. Li, T. Cheng, Appl. Catal., A 2011, 400,
104-110; f) D. Shi, R. Hu, Q. Zhou, L. Yang, Chem. Eng. J. 2016, 288,
588-595; g) A. E. Schweizer, M. E. Jones, D. A. Hickman (Dow Global
Technologies Inc.), US-B2 6984763, 2006.
[7]
a) V. Paunović, G. Zichittella, M. Moser, A. P. Amrute, J. Pérez-
Ramírez, Nat. Chem. 2016, 8, 803-809; b) M. Scharfe, P. A Lira-Parada,
A. P. Amrute, S. Mitchell, J. Pérez-Ramírez, J. Catal. 2016, 344, 524-
534; c) V. Paunović, R. Lin, M. Scharfe, A. P. Amrute, S. Mitchell, R.
Hauert, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2017,
Experimental Section
doi:10.1002/anie.201704406;
doi:10.1002/ange.201704406.
Angew.
Chem.
2017,
Details on the catalyst preparation, characterization, and
evaluation are provided as Supporting Information.
[8]
[9]
a) N. Rahimi, R. Karimzadeh, Appl. Catal., A 2011, 398, 1-17; b) H.
Zimmermann, R. Walzl, Ullmann’s Encyclopedia of Industrial Chemistry,
Vol. 13, Wiley-VCH, Weinheim, 2012, pp. 465-529.
B. G. Hashiguchi, M. M. Konnick, S. M. Bischof, S. J. Gustafson, D.
Devarajan, N. Gunsalus, D. H. Ess, R. A. Periana, Science 2014, 343,
1232-1237.
Acknowledgements
This work was supported by ETH Research Grant ETH-04 16-1
and by the Swiss National Science Foundation (project no.
200021-156107). Dr. Sharon Mitchell and Dr. Roland Hauert are
kindly acknowledged for performing the microscopy and XPS
measurements, respectively.
[10] a) E. N. Givens, C. J. Plank, E. J. Rosinki (Mobil Oil Corporation), US-A
3960978, 1974; b) A. Giusti, S. Gusi, G. Bellussi, V. Fattore
(Eniricerche S. P. A.), US-A 4831201, 1989.
[11] a) J. A. Cowfer, M. B. Gorensek, Kirk-Othmer Encyclopedia of
Chemical Technology, Wiley-VCH, Weinheim, 2006; b) Sulzer-
ChemTech Separation Technology for the Hydrocarbon Processing
Industry, www.sulzer.com, accessed May 20th, 2017, 10:00 GMT;
c) Honeywll-UOP Technology for Purification of Olefin and Polymer
Process Streams, www.uop.com, accessed May 20th, 2017, 11:00 GMT.
Keywords: europium oxychloride • halogen chemistry •
heterogeneous catalysis • light olefins • natural gas upgrading
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Entry for the Table of Contents
COMMUNICATION
Gas to olefins: Ethylene and
propylene can be generated from
ethane, propane, or mixtures of
methane, ethane, and propane
over europium oxychloride via
oxychlorination chemistry at yields
surpassing any existing
Guido Zichittella, Nicolas Aellen,
Vladimir Paunović, Amol P. Amrute, and
Javier Pérez-Ramírez*
Page No. – Page No.
Olefins from Natural Gas via
Oxychlorination Catalysis
technology for alkene production.
Its performance can be preserved
in technical form, testifying the
practical relevance of this catalytic
technology for olefin production.
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