Vacuum-assisted carbon molecular sieve membrane reactor for non-oxidative ethane dehydrogenation

Bhowmick, Antara; Koybasi, H. Hasan; Ku, Ching-En; Chen, Genwei; Hwang, Sooyeon; Zhang, Chen; Vlachos, Dionisios G.; Liu, Dongxia

doi:10.1016/j.cej.2025.164563

Vacuum-assisted carbon molecular sieve membrane reactor for non-oxidative ethane dehydrogenation

Journal Article · Wed Jun 11 04:00:00 EDT 2025 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2025.164563· OSTI ID:2587392

Bhowmick, Antara ^[1]; Koybasi, H. Hasan ^[1]; Ku, Ching-En ^[2]; ^[1]; ^[3]; Zhang, Chen ^[2]; ^[1]; ^[1]

Univ. of Delaware, Newark, DE (United States)
Univ. of Maryland, College Park, MD (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Non-oxidative ethane dehydrogenation (EDH) is equilibrium-limited and endothermic. Selective hydrogen removal using a gas-permeable membrane within the EDH reaction zone can overcome the thermodynamic equilibrium, enabling higher ethane conversions. Employing vacuum as the permeation driving force, rather than a sweep gas, enhances the industrial viability of membrane reactors by eliminating additional post-reaction separation units. This study presents a membrane reactor that integrates H₂-permeable carbon molecular sieve (CMS) hollow fiber membranes embedded in a fixed bed of cobalt in a dealuminated beta zeolite (Co@DeAl-BEA) catalyst, utilizing a vacuum to remove hydrogen efficiently. The CMS membrane exhibits high hydrogen permeance and an excellent H₂/C₂H₆ separation factor. The membrane reactor significantly enhanced the ethane conversion under reaction conditions comparable to those reported in the literature. A Langmuir-Hinshelwood kinetic rate expression was developed and incorporated into a one-dimensional steady-state reactor model. The experimentally validated model indicates that increasing the number of hollow fibers improves ethane conversion, although ethane loss to the permeate limits the benefit. The contact area between the catalyst and the membrane limits the reactor performance more than the catalytic throughput. Furthermore, we find that the location of the catalyst packing relative to the hollow fiber membranes influences ethane loss and conversion. Higher reactor pressures and inlet ethane flow rates improve space-time yield at the expense of lower ethane conversion. Increasing reactor temperature or packing length promotes both performance metrics. The EDH membrane reactor demonstrated durability over 200 h of continuous operation, maintaining record-low deactivation rates and high ethylene selectivity. Protocols for catalyst regeneration were developed.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: SC0023357; SC0012704; EE0010313

OSTI ID:: 2587392

Report Number(s):: BNL--228515-2025-JAAM

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 518; ISSN 1385-8947

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

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32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
CMS membrane
Langmuir-Hinshelwood kinetic model
ethane dehydrogenation
membrane reactor
reactor model
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zeolite catalyst

Vacuum-assisted carbon molecular sieve membrane reactor for non-oxidative ethane dehydrogenation

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