Domino catalysis for selective dehydrogenation of ethane with shifted thermodynamic equilibrium

doi:10.1016/j.joule.2023.03.004

Joule

Volume 7, Issue 4, 19 April 2023, Pages 753-764

https://doi.org/10.1016/j.joule.2023.03.004 Get rights and content

Highlights

•
The catalysts for dehydrogenation and hydrogen combustion were combined
•
The domino catalysis efficiently shifted the equilibrium for ethane dehydrogenation
•
The MnO_x@Na₂WO₄ oxide was crucial for achieving the selective hydrogenation combustion
•
High ethane conversion was realized with well-maintained ethylene selectivity

Context & scale

Ethylene is one of the most important platform molecules in the modern chemical industry and building units of polymers. Generally, ethylene is produced from naphtha cracking, which relies on petroleum feedstock. The catalytic dehydrogenation of ethane (EDH) has been regarded as a promising non-petroleum route to produce ethylene, because ethane has been abundantly produced from shale gas. However, the non-oxidative EDH is thermodynamically limited, resulting in insufficient ethane conversions. In this work, we overcome this limitation through a domino process by interleaving MnO_x@Na₂WO₄ oxide with the dehydrogenation catalyst (Co-zeolite) in multiple-bed manners. The ethane dehydrogenation and selective hydrogen consumption occurred alternately in this process, thus shifting the reaction equilibrium to give significantly improved ethane conversions where the high ethylene selectivity was maintained.

Summary

Catalytic dehydrogenation of ethane is a promising non-petroleum route to produce ethylene but it suffers from insufficient conversion at mild temperatures because of the thermodynamic equilibrium limitation, leading to the high cost of product separation. Here, we developed a reaction process by interleaving the cobaltosilicate zeolite catalyst (CoS-1) for non-oxidative dehydrogenation and sodium tungstate-modified manganese oxide promoter (MnO_x@Na₂WO₄) for selective hydrogen combustion in multiple beds as a domino mode in the reactor. The ethane dehydrogenation and hydrogen consumption occurred alternately on the spatially separated sites, which efficiently promoted ethane dehydrogenation by shifting the equilibrium to improve the ethane conversion with hindered excessive hydrocarbon combustion. As a result, the per-pass ethane conversion up to 43.2% and ethylene selectivity at 93.1% were achieved at 590°C with 0.8 bar of ethane feed. This domino process would provide an efficient strategy for boosting the thermodynamically limited reactions and improving the vitality of the catalytic dehydrogenation of ethane.

Graphical abstract

Introduction

Cascade reactions over multiple functional catalysts have been extensively explored for optimizing the conversions and selectivities in various processes.¹^,²^,³^,⁴^,⁵^,⁶^,⁷^,⁸ A typical one is the non-oxidative dehydrogenation of light alkanes, which are limited thermodynamically⁷^,⁸^,⁹^,¹⁰^,¹¹^,¹²^,¹³^,¹⁴^,¹⁵^,¹⁶^,¹⁷ and usually require high temperatures to realize the commercially desired one-pass yields. A more recent trend is removing the hydrogen product to shift the equilibrium via dehydrogenation and hydrogen combustion cascades over the rationally designed bifunctional catalysts in continuous reactions or chemical-looping modes.¹⁸^,¹⁹^,²⁰^,²¹^,²²^,²³^,²⁴^,²⁵^,²⁶^,²⁷ However, this methodology presents a great challenge in controlling the selective hydrogen combustion,⁷^,²²^,²⁸^,²⁹ which is that the alkanes and olefins are also combusted to undesired CO/CO₂ products that result in insufficient selectivity to olefins. To overcome this issue, general strategies were focused on engineering the catalyst surface by chemical modification to poison the active sites of overoxidation.²⁰^,²¹^,²² In some cases, the dehydrogenation activity was also reduced. As a result, the dehydrogenation requires a high reaction temperature for achieving desired per-pass conversion, such as 700°C–850°C for the ethane dehydrogenation (EDH).²⁰^,³⁰^,³¹

On the other hand, many biological systems provide solutions for this problem, where the intermediate molecules are repeatedly transferred and reacted between spatially separated active sites with different functions for consuming the specific products and/or intermediates, which benefits the high yield of target products.³² This motivated our exploration of reactions with spatially separated active sites for dehydrogenation and hydrogen combustion, respectively. Key to the successes is to employ sodium tungstate-modulated manganese oxide (MnO_x@Na₂WO₄, mixed phases of Mn₂O₃/MnO₂ and Na₂WO₄, Figures S1 and S2) as a promoter for selective hydrogen combustion but inactive for the oxidation of hydrocarbons. By physically interleaving a known dehydrogenation catalyst of cobaltosilicate zeolite (CoS-1, cobalt loading at 1.86 wt %, Figures S3–S5)³³^,³⁴ and this MnO_x@Na₂WO₄ promoter in a domino mode, the EDH and hydrogen combustion occur alternately on the spatially separated sites at the industrially desired temperature (e.g., 590°C), simultaneously achieving high ethane conversion by shifting the thermodynamic equilibrium and ethylene selectivity by hindering the overoxidation.

Section snippets

Domino catalysis in EDH

Data characterizing the performances in the EDH (partial pressure at 0.8 bar, helium as balance) are shown in Figure 1. Under the given reaction conditions, the ethane conversion at thermodynamic equilibrium was 15.5% (Figures 1A and S6). The sole CoS-1 catalyst efficiently catalyzed the reaction, exhibiting the ethane conversion at 15.4%, which is close to the thermodynamic equilibrium with a 98.7% selectivity to ethylene and a stoichiometric hydrogen product. When a MnO_x@Na₂WO₄ bed was packed

Selectivity in hydrogen and hydrocarbon combustion

The MnO_x@Na₂WO₄ is crucial in domino catalysis because of its superior selectivity for combusting hydrogen rather than ethylene. This similar trend was previously observed on Na₂WO₄-modified multiple oxides, which have worked in a wide range of temperatures for hydrogen combustion.²⁰^,²¹^,²³^,³⁹^,⁴⁰ However, how to combine such features in the EDH process to realize high ethane conversions at mild temperatures was still a great challenge, but here, it was achieved on the domino catalysts. The

Lead contact

Further information and requests for resources should be directed to and will be fulfilled by the lead contact.

Materials availability

This study did not generate new unique reagents.

Acknowledgments

This work was supported by the National Key Research and Development Program of China (2022YFA1503502) and the National Natural Science Foundation of China (22288101, 22241801, and U21B20101). We thank Fang Chen at Zhejiang University for kindly helping in SEM and TEM characterization and Dr. Xuefeng Chu at Jilin Jianzhu University for help in XPS characterization.

Author contributions

X.Q. carried out the catalyst preparation, characterization, and catalytic tests. H.W. and B.Y. performed the theoretical

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³: These authors contributed equally

⁴: Lead contact

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Joule

ArticleDomino catalysis for selective dehydrogenation of ethane with shifted thermodynamic equilibrium

Highlights

Context & scale

Summary

Graphical abstract

Introduction

Section snippets

Domino catalysis in EDH

Selectivity in hydrogen and hydrocarbon combustion

Lead contact

Materials availability

Acknowledgments

Author contributions

Joule

Joule

Appl. Catal. B

Fuel Process. Technol.

Catal. Commun.

J. Catal.

J. Catal.

J. Catal.

Chem. Eng. J.

Fuel

J. Catal.

Propane to olefins tandem catalysis: a selective route towards light olefins production

Chem. Soc. Rev.

Catalytic alkane metathesis by tandem alkane dehydrogenation-olefin metathesis

Science

Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization

Science

Recent advances in direct synthesis of value-added aromatic chemicals from syngas by cascade reactions over bifunctional catalysts

Adv. Mater.

Ternary platinum–cobalt–indium nanoalloy on ceria as a highly efficient catalyst for the oxidative dehydrogenation of propane using CO2

Nat. Catal.

Tandem In2O3-Pt/Al2O3 catalyst for coupling of propane dehydrogenation to selective H2 combustion

Science

Near 100% ethene selectivity achieved by tailoring dual active sites to isolate dehydrogenation and oxidation

Nat. Commun.

Subsurface catalysis-mediated selectivity of dehydrogenation reaction

Sci. Adv.

Propane dehydrogenation: catalyst development, new chemistry, and emerging technologies

Chem. Soc. Rev.

In situ formation of ZnOx species for efficient propane dehydrogenation

Nature

First-principles design of a single-atom–alloy propane dehydrogenation catalyst

Science

Article
Domino catalysis for selective dehydrogenation of ethane with shifted thermodynamic equilibrium

Ternary platinum–cobalt–indium nanoalloy on ceria as a highly efficient catalyst for the oxidative dehydrogenation of propane using CO₂

Tandem In₂O₃-Pt/Al₂O₃ catalyst for coupling of propane dehydrogenation to selective H₂ combustion

In situ formation of ZnO_x species for efficient propane dehydrogenation