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Title: Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques

Abstract

Developing fundamental insight for reactions between gas phase H2S and solid phase CuO has the potential to lead to improved materials and processes for natural gas purification. However, this insight requires detailed knowledge of the atomistic characteristics of the solid and how these characteristics influence the reaction mechanism and kinetics. Herein, we use fixed bed reactors, X-ray absorption spectroscopy, and transmission X-ray microscopy to simultaneously probe the fundamental kinetics of the reaction of CuO with H2S to form CuS, and thereby probe spatial-temporal chemical and structural changes of copper during this reaction. H2S removal reaction kinetics show similar trends in fixed bed reactors as in 10-20 µm sized particles. However, reaction fronts proceed through the entire diameter of particles heterogeneously, indicating the presence of pore diffusion resistance even at very small length scales. In addition, CuO sorbent samples with similar characteristics exhibit 3 times different sulfidation conversion with reaction rate constants that differ by a factor of 1.5. Furthermore, these differences in reaction kinetics and conversion indicate the critical impact of possible atomic scale differences and the formation of different copper sulfide products.

Authors:
 [1];  [2]; ORCiD logo [3];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Univ. of California, Los Angeles, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1484837
Alternate Identifier(s):
OSTI ID: 1458581
Grant/Contract Number:  
11535015; U1632110; 56978-DNI5; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Reaction Chemistry & Engineering
Additional Journal Information:
Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2058-9883
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hoffman, Adam S., Azzam, Sara, Zhang, Kai, Xu, Yahong, Liu, Yijin, Bare, Simon R., and Simonetti, Dante A. Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques. United States: N. p., 2018. Web. doi:10.1039/c8re00020d.
Hoffman, Adam S., Azzam, Sara, Zhang, Kai, Xu, Yahong, Liu, Yijin, Bare, Simon R., & Simonetti, Dante A. Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques. United States. doi:10.1039/c8re00020d.
Hoffman, Adam S., Azzam, Sara, Zhang, Kai, Xu, Yahong, Liu, Yijin, Bare, Simon R., and Simonetti, Dante A. Thu . "Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques". United States. doi:10.1039/c8re00020d. https://www.osti.gov/servlets/purl/1484837.
@article{osti_1484837,
title = {Direct observation of the kinetics of gas–solid reactions using in situ kinetic and spectroscopic techniques},
author = {Hoffman, Adam S. and Azzam, Sara and Zhang, Kai and Xu, Yahong and Liu, Yijin and Bare, Simon R. and Simonetti, Dante A.},
abstractNote = {Developing fundamental insight for reactions between gas phase H2S and solid phase CuO has the potential to lead to improved materials and processes for natural gas purification. However, this insight requires detailed knowledge of the atomistic characteristics of the solid and how these characteristics influence the reaction mechanism and kinetics. Herein, we use fixed bed reactors, X-ray absorption spectroscopy, and transmission X-ray microscopy to simultaneously probe the fundamental kinetics of the reaction of CuO with H2S to form CuS, and thereby probe spatial-temporal chemical and structural changes of copper during this reaction. H2S removal reaction kinetics show similar trends in fixed bed reactors as in 10-20 µm sized particles. However, reaction fronts proceed through the entire diameter of particles heterogeneously, indicating the presence of pore diffusion resistance even at very small length scales. In addition, CuO sorbent samples with similar characteristics exhibit 3 times different sulfidation conversion with reaction rate constants that differ by a factor of 1.5. Furthermore, these differences in reaction kinetics and conversion indicate the critical impact of possible atomic scale differences and the formation of different copper sulfide products.},
doi = {10.1039/c8re00020d},
journal = {Reaction Chemistry & Engineering},
number = 5,
volume = 3,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: a) Schematic of experimental setup for sulfidation of CuO samples at the XAS and TXM beam lines. b) XAS cell schematic used for the room temperature sulfidation of CuO. c) TXM cell schematic featuring 0.5 mm quartz capillary used for the room temperature sulfidation of CuO.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.