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Title: Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

Abstract

The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observedmore » to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3];  [1]
  1. Univ. of Kentucky, Lexington, KY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Canadian Light Sources, Inc., Saskatoon, SK (Canada)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1340425
Report Number(s):
BNL-113340-2016-JA
Journal ID: ISSN 1011-372X
Grant/Contract Number:
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Catalysis Letters
Additional Journal Information:
Journal Volume: 146; Journal Issue: 10; Journal ID: ISSN 1011-372X
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; Fischer-Tropsch synthesis; iron; cobalt; hydrogen chloride; activity; selectivity; XANES

Citation Formats

Pendyala, Venkat Ramana Rao, Jacobs, Gary, Ma, Wenping, Sparks, Dennis E., Shafer, Wilson D., Khalid, Syed, Xiao, Qunfeng, Hu, Yongfeng, and Davis, Burtron H.. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co. United States: N. p., 2016. Web. doi:10.1007/s10562-016-1820-8.
Pendyala, Venkat Ramana Rao, Jacobs, Gary, Ma, Wenping, Sparks, Dennis E., Shafer, Wilson D., Khalid, Syed, Xiao, Qunfeng, Hu, Yongfeng, & Davis, Burtron H.. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co. United States. doi:10.1007/s10562-016-1820-8.
Pendyala, Venkat Ramana Rao, Jacobs, Gary, Ma, Wenping, Sparks, Dennis E., Shafer, Wilson D., Khalid, Syed, Xiao, Qunfeng, Hu, Yongfeng, and Davis, Burtron H.. Sat . "Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co". United States. doi:10.1007/s10562-016-1820-8. https://www.osti.gov/servlets/purl/1340425.
@article{osti_1340425,
title = {Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co},
author = {Pendyala, Venkat Ramana Rao and Jacobs, Gary and Ma, Wenping and Sparks, Dennis E. and Shafer, Wilson D. and Khalid, Syed and Xiao, Qunfeng and Hu, Yongfeng and Davis, Burtron H.},
abstractNote = {The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.},
doi = {10.1007/s10562-016-1820-8},
journal = {Catalysis Letters},
number = 10,
volume = 146,
place = {United States},
year = {Sat Jul 23 00:00:00 EDT 2016},
month = {Sat Jul 23 00:00:00 EDT 2016}
}

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