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Title: Silver-Promoted Dehydroaromatization of Ethylene over ZSM-5 Catalysts

Abstract

The shape selectivity of ZSM-5 (MFI type) catalysts is ideal for the production of C6–C8 aromatics. Developing high-performance zeolite catalysts with improved selectivity to aromatics, particularly from diversified (non-petroleum) feedstocks, has broad commercial appeal. Non-oxidative coupling (NOC) of ethylene was examined over Ag-ZSM-5 catalysts at 400 °C and shows that Ag+ sites promote dehydroaromatization with enhanced selectivity to toluene and xylenes. Metal exchange of H-ZSM-5 results in Ag zoning wherein Ag+ site density is higher on the exterior of ZSM-5 particles. Catalyst performance was characterized with varying Ag loading as well as the use of methane co-feed. Aromatic selectivity is about 60 % on Ag-ZSM-5 compared to 20 % on H-ZSM-5, which is qualitatively consistent with density functional theory (DFT) showing that ethylene forms strong complexes with Ag+ (Lewis acid) sites. DFT calculations also reveal that ethylene activation on H+ (Brønsted acid) sites is more energetically favorable, and likely constitutes the first mechanistic step in ethylene-to-liquids (ETL) reactions. Ag-ZSM-5 is thus identified as an effective catalyst for low-temperature ETL reactions that has the potential to outperform conventional metal-exchanged zeolites.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. University of Houston, Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543477
Alternate Identifier(s):
OSTI ID: 1401762
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; dehydroaromatization; ethylene upgrading; natural gas; silver; zeolites

Citation Formats

Hsieh, Ming‐Feng, Zhou, Yunwen, Thirumalai, Hari, Grabow, Lars C., and Rimer, Jeffrey D. Silver-Promoted Dehydroaromatization of Ethylene over ZSM-5 Catalysts. United States: N. p., 2017. Web. doi:10.1002/cctc.201700192.
Hsieh, Ming‐Feng, Zhou, Yunwen, Thirumalai, Hari, Grabow, Lars C., & Rimer, Jeffrey D. Silver-Promoted Dehydroaromatization of Ethylene over ZSM-5 Catalysts. United States. doi:10.1002/cctc.201700192.
Hsieh, Ming‐Feng, Zhou, Yunwen, Thirumalai, Hari, Grabow, Lars C., and Rimer, Jeffrey D. Thu . "Silver-Promoted Dehydroaromatization of Ethylene over ZSM-5 Catalysts". United States. doi:10.1002/cctc.201700192. https://www.osti.gov/servlets/purl/1543477.
@article{osti_1543477,
title = {Silver-Promoted Dehydroaromatization of Ethylene over ZSM-5 Catalysts},
author = {Hsieh, Ming‐Feng and Zhou, Yunwen and Thirumalai, Hari and Grabow, Lars C. and Rimer, Jeffrey D.},
abstractNote = {The shape selectivity of ZSM-5 (MFI type) catalysts is ideal for the production of C6–C8 aromatics. Developing high-performance zeolite catalysts with improved selectivity to aromatics, particularly from diversified (non-petroleum) feedstocks, has broad commercial appeal. Non-oxidative coupling (NOC) of ethylene was examined over Ag-ZSM-5 catalysts at 400 °C and shows that Ag+ sites promote dehydroaromatization with enhanced selectivity to toluene and xylenes. Metal exchange of H-ZSM-5 results in Ag zoning wherein Ag+ site density is higher on the exterior of ZSM-5 particles. Catalyst performance was characterized with varying Ag loading as well as the use of methane co-feed. Aromatic selectivity is about 60 % on Ag-ZSM-5 compared to 20 % on H-ZSM-5, which is qualitatively consistent with density functional theory (DFT) showing that ethylene forms strong complexes with Ag+ (Lewis acid) sites. DFT calculations also reveal that ethylene activation on H+ (Brønsted acid) sites is more energetically favorable, and likely constitutes the first mechanistic step in ethylene-to-liquids (ETL) reactions. Ag-ZSM-5 is thus identified as an effective catalyst for low-temperature ETL reactions that has the potential to outperform conventional metal-exchanged zeolites.},
doi = {10.1002/cctc.201700192},
journal = {ChemCatChem},
number = 9,
volume = 9,
place = {United States},
year = {2017},
month = {2}
}

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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: (A) Powder XRD patterns of (i) H-ZSM-5, (ii) as-prepared Ag25ZSM-5, and (iii) calcined Ag25-ZSM-5 are shown in black, red, and blue, respectively. (B) XPS spectra of (ii) as-prepared Ag25-ZSM-5 and (iii) calcined Ag25-ZSM-5 are shown in red and blue, respectively. Binding energies of 375.3 and 369.3 eV aremore » characteristic of Ag + species.« less

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