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Title: Understanding zeolite deactivation by sulfur poisoning during direct olefin upgrading

Abstract

The presence of sulfur contaminants in bitumen derived crude oils can lead to rapid catalyst deactivation and is a major problem faced by downstream refiners. Whilst expensive hydrotreating steps may remove much of the sulfur content, it is important to understand how catalyst deactivation by sulfur poisoning occurs and how it may be mitigated. Here we report a mechanistic study of sulfur poisoning over a zeolite catalyst promoted with silver and gallium Lewis acids. Olefin upgrading, an essential process in the refinement of heavy oils, is used as a model reaction. Access to the zeolite inner pores is blocked by bulky, weakly adsorbed sulfur species. Pore access and thus catalyst activity is restored by increasing the reaction temperature. We also show that a simple alkaline treatment greatly improves both the sulfur tolerance and performance of the catalyst. Furthermore, these findings may enhance the rational design of heterogenous catalysts for olefin upgrading.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. Univ. of Calgary, Calgary, AB (Canada)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Soochow Univ., Jiangsu (China)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1562863
Report Number(s):
NREL/JA-5100-74857
Journal ID: ISSN 2399-3669; MainId:12828;UUID:1867063b-77d5-e911-9c26-ac162d87dfe5;MainAdminID:1308
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Communications Chemistry
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2399-3669
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalytic mechanisms; heterogeneous catalysis; petrol

Citation Formats

Harrhy, Jonathan H., Wang, Aiguo, Jarvis, Jack S., He, Peng, Meng, Shijun, Yung, Matthew M., Liu, Lijia, and Song, Hua. Understanding zeolite deactivation by sulfur poisoning during direct olefin upgrading. United States: N. p., 2019. Web. https://doi.org/10.1038/s42004-019-0141-4.
Harrhy, Jonathan H., Wang, Aiguo, Jarvis, Jack S., He, Peng, Meng, Shijun, Yung, Matthew M., Liu, Lijia, & Song, Hua. Understanding zeolite deactivation by sulfur poisoning during direct olefin upgrading. United States. https://doi.org/10.1038/s42004-019-0141-4
Harrhy, Jonathan H., Wang, Aiguo, Jarvis, Jack S., He, Peng, Meng, Shijun, Yung, Matthew M., Liu, Lijia, and Song, Hua. Mon . "Understanding zeolite deactivation by sulfur poisoning during direct olefin upgrading". United States. https://doi.org/10.1038/s42004-019-0141-4. https://www.osti.gov/servlets/purl/1562863.
@article{osti_1562863,
title = {Understanding zeolite deactivation by sulfur poisoning during direct olefin upgrading},
author = {Harrhy, Jonathan H. and Wang, Aiguo and Jarvis, Jack S. and He, Peng and Meng, Shijun and Yung, Matthew M. and Liu, Lijia and Song, Hua},
abstractNote = {The presence of sulfur contaminants in bitumen derived crude oils can lead to rapid catalyst deactivation and is a major problem faced by downstream refiners. Whilst expensive hydrotreating steps may remove much of the sulfur content, it is important to understand how catalyst deactivation by sulfur poisoning occurs and how it may be mitigated. Here we report a mechanistic study of sulfur poisoning over a zeolite catalyst promoted with silver and gallium Lewis acids. Olefin upgrading, an essential process in the refinement of heavy oils, is used as a model reaction. Access to the zeolite inner pores is blocked by bulky, weakly adsorbed sulfur species. Pore access and thus catalyst activity is restored by increasing the reaction temperature. We also show that a simple alkaline treatment greatly improves both the sulfur tolerance and performance of the catalyst. Furthermore, these findings may enhance the rational design of heterogenous catalysts for olefin upgrading.},
doi = {10.1038/s42004-019-0141-4},
journal = {Communications Chemistry},
number = 1,
volume = 2,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 2 works
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Figures / Tables:

Fig. 1 Fig. 1: Olefin reduction over Ag-Ga/ZSM-5 at various temperatures and times. a Olefin reduction performance at varying temperatures using 1-decene as substrate. Black bars indicate olefin reduction and magenta squares indicate liquid yield. b Selectivity towards paraffins and aromatics in product oil using 1- decene as substrate. Magenta squares indicatemore » aromatics and black squares indicate paraffins. c Olefin reduction at varying temperatures using 1-decene as substrate in the presence of DBT and DES. Black bars indicate olefin reduction and magenta squares indicate liquid yield. d Selectivity towards paraffins and aromatics in product oil using 1-decene as substrate in the presence of DBT and DES. Magenta squares indicate aromatics and black squares indicate paraffins. e Olefin reduction performance of fresh, deactivated following reaction with DBT and DES and reused deactivated catalyst samples at reaction temperature of 330 °C. Black bars indicate olefin reduction and solid magenta line with magenta shaded squares indicates selectivity towards paraffins, dashed magenta line with magenta hollow squares indicates selectivity towards aromatics. All error bars represent ±4% calculated as standard deviation« less

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