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Title: Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

Abstract

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO 2 (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni 10CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH 4 and CO 2 decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H 2-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce 2O 3, CeO 2 and CeAlO 3 coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1406620
Resource Type:
Journal Article
Resource Relation:
Journal Name: International Journal of Hydrogen Energy; Journal Volume: 42; Journal Issue: 29
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Natural gas; Syngas; Dry reforming of methane; Nickel catalyst; Cerium oxide

Citation Formats

Han, Jun, Zhan, Yiqiu, Street, Jason, To, Filip, and Yu, Fei. Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts. United States: N. p., 2017. Web. doi:10.1016/j.ijhydene.2017.04.131.
Han, Jun, Zhan, Yiqiu, Street, Jason, To, Filip, & Yu, Fei. Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts. United States. doi:10.1016/j.ijhydene.2017.04.131.
Han, Jun, Zhan, Yiqiu, Street, Jason, To, Filip, and Yu, Fei. Sat . "Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts". United States. doi:10.1016/j.ijhydene.2017.04.131.
@article{osti_1406620,
title = {Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts},
author = {Han, Jun and Zhan, Yiqiu and Street, Jason and To, Filip and Yu, Fei},
abstractNote = {A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO2 (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni10CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH4 and CO2 decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni10CeAl catalyst was performed using BET, H2-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce2O3, CeO2 and CeAlO3 coexisted in the Ni10CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.},
doi = {10.1016/j.ijhydene.2017.04.131},
journal = {International Journal of Hydrogen Energy},
number = 29,
volume = 42,
place = {United States},
year = {Sat Jul 01 00:00:00 EDT 2017},
month = {Sat Jul 01 00:00:00 EDT 2017}
}
  • Carbon dioxide reforming of methane into syngas over Ni/{gamma}-Al{sub 2}O{sub 3} catalysts was systematically studied. Effects of reaction parameters on catalytic activity and carbon deposition over Ni/{gamma}-Al{sub 2}O{sub 3} catalysts were investigated. It is found that reduced NiAl{sub 2}O{sub 4}, metal nickel, and active species of carbon deposited were the active sites for this reaction. Carbon deposition on Ni/{gamma}-Al{sub 2}O{sub 3} varied depending on the nickel loading and reaction temperature and is the major cause of catalyst deactivation. Higher nickel loading produced more coke on the catalysts, resulting in rapid deactivation and plugging of the reactor. At 5 wt %more » Ni/{gamma}-Al{sub 2}O{sub 3} catalyst exhibited high activity and much lesser magnitude of deactivation in 140 h. Characterization of carbon deposits on the catalyst surface revealed that there are two kinds of carbon species (oxidized and -C-C-) formed during the reaction and they showed different reactivities toward hydrogenation and oxidation. Kinetic studies showed that the activation energy for CO production in this reaction amounted to 80 kJ/mol and the rate of CO production could be described by a Langmuir-Hinshelwood model.« less
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  • Steady-state tracing techniques, using isotopically labeled molecules, were applied to study mechanistic aspects of the carbon and oxygen reaction pathways to form CO over Ni/La{sub 2}O{sub 3} and Ni/Al{sub 2}O{sub 3} catalysts. Over the Ni/La{sub 2}O{sub 3} catalyst, it was found that under steady-state reaction conditions, the quantity of reversibly adsorbed CH{sub 4} and the active carbon-containing intermediate species in the carbon pathway to form CO originating from CH{sub 4} is higher than the respective quantities derived from the CO{sub 2} molecule. Over the Ni/Al{sub 2}O{sub 3} catalyst, much smaller quantities of reversibly adsorbed CH{sub 4} and active carbon-containing species,more » originated from the CH{sub 4} molecule, which lead to CO formation were detected. It was also determined that a large quantity of oxygen atoms, originating from the La{sub 2}O{sub 3} support of the Ni/La{sub 2}O{sub 3} catalyst, participate in the reaction scheme. It is concluded that La{sub 2}O{sub 2}CO{sub 3}, which form by the interaction of La{sub 2}O{sub 3} and CO{sub 2}, may decompose to produce CO or provide oxygen species which react with carbon accumulated on Ni crystallites due to CH{sub 2} cracking to produce CO. The latter process is very fast over the Ni/La{sub 2}O{sub 3} catalyst, as compared to carbon accumulation, and this imparts this catalyst its special stability characteristics.« less