skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts

Abstract

In this paper, the Pechini synthesis was used to prepare nickel aluminate catalysts with the compositions NiAl 4O 7, NiAl 2O 4, and Ni 2Al 2O 5. The samples have been characterized by N 2 physisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Characterization results indicate unique structural properties and excellent regeneration potential of nickel aluminates. Prepared samples were tested when unreduced and reduced prior to reaction for methane dry reforming and methane steam reforming reactivity. NiAl 2O 4 in the reduced and unreduced state as well as NiAl 4O 7 in the reduced state are active and stable for methane dry reforming due to the presence of 4-fold coordinated oxidized nickel. The limited amount of metallic nickel in these samples minimizes carbon deposition. Finally, on the other hand, the presence of metallic nickel is required for methane steam reforming. Ni 2Al 2O 5 in the reduced and unreduced states and NiAl 2O 4 in the reduced state are found to be active for methane steam reforming due to the presence of sufficiently small nickel nanoparticles that catalyze the reaction without accumulating carbonaceous deposits.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [5]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering. Renewable Bioproducts Inst.; The Dow Chemical Company, Freeport, TX (United States)
  2. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering
  3. Micromeritics Instrument Corporation, Norcross, GA (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Technology Division
  5. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical & Biomolecular Engineering. Renewable Bioproducts Inst.
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Technology Division; Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); The Dow Chemical Company (United States); Georgia Institute of Technology (United States)
OSTI Identifier:
1341645
Report Number(s):
BNL-113364-2016-JA
Journal ID: ISSN 2155-5435; TRN: US1701775
Grant/Contract Number:
AC02-06CH11357; AC02-98CH10886
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Spinel; Synthesis gas; X-ray absorption spectroscopy; Coordination number; Regeneration

Citation Formats

Rogers, Jessica L., Mangarella, Michael C., D’Amico, Andrew D., Gallagher, James R., Dutzer, Michael R., Stavitski, Eli, Miller, Jeffrey T., and Sievers, Carsten. Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01133.
Rogers, Jessica L., Mangarella, Michael C., D’Amico, Andrew D., Gallagher, James R., Dutzer, Michael R., Stavitski, Eli, Miller, Jeffrey T., & Sievers, Carsten. Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts. United States. doi:10.1021/acscatal.6b01133.
Rogers, Jessica L., Mangarella, Michael C., D’Amico, Andrew D., Gallagher, James R., Dutzer, Michael R., Stavitski, Eli, Miller, Jeffrey T., and Sievers, Carsten. 2016. "Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts". United States. doi:10.1021/acscatal.6b01133. https://www.osti.gov/servlets/purl/1341645.
@article{osti_1341645,
title = {Differences in the Nature of Active Sites for Methane Dry Reforming and Methane Steam Reforming over Nickel Aluminate Catalysts},
author = {Rogers, Jessica L. and Mangarella, Michael C. and D’Amico, Andrew D. and Gallagher, James R. and Dutzer, Michael R. and Stavitski, Eli and Miller, Jeffrey T. and Sievers, Carsten},
abstractNote = {In this paper, the Pechini synthesis was used to prepare nickel aluminate catalysts with the compositions NiAl4O7, NiAl2O4, and Ni2Al2O5. The samples have been characterized by N2 physisorption, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Characterization results indicate unique structural properties and excellent regeneration potential of nickel aluminates. Prepared samples were tested when unreduced and reduced prior to reaction for methane dry reforming and methane steam reforming reactivity. NiAl2O4 in the reduced and unreduced state as well as NiAl4O7 in the reduced state are active and stable for methane dry reforming due to the presence of 4-fold coordinated oxidized nickel. The limited amount of metallic nickel in these samples minimizes carbon deposition. Finally, on the other hand, the presence of metallic nickel is required for methane steam reforming. Ni2Al2O5 in the reduced and unreduced states and NiAl2O4 in the reduced state are found to be active for methane steam reforming due to the presence of sufficiently small nickel nanoparticles that catalyze the reaction without accumulating carbonaceous deposits.},
doi = {10.1021/acscatal.6b01133},
journal = {ACS Catalysis},
number = 9,
volume = 6,
place = {United States},
year = 2016,
month = 7
}

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

Citation Metrics:
Cited by: 5works
Citation information provided by
Web of Science

Save / Share:
  • The partial oxidation of methane to ethane over a model Li/MgO catalyst has been studied using combined surface science techniques/elevated pressure kinetic measurements. The results indicate that [Li[sup +]O[sup [minus]]] centers are not likely directly involved in the methane activation step. Rather, addition of lithium promotes the production of F centers which are considered to be responsible for this key step in the methane coupling reaction.
  • The steam reforming of methane on iron or nickel, CH/sub 4/ + H/sub 2/O ..-->.. CO + 3H/sub 2/, can be regarded as a sequence of two reactions with adsorbed carbon as an intermediate species: CH/sub 4/ ..-->.. C(ads) + 2H/sub 2/, C(ads) + H/sub 2/O ..-->.. CO + H/sub 2/. As the first reaction is rate limiting, the following rate law can be applied to methane reforming catalysed by iron: v = k/sub 2//sup Fe/ a/sub 0//sup -n/ p/sub CH/sub 4///P/sub H/sub 2///sup 1/2/, 0.6 less than or equal to n less than or equal to 1.0. The oxygenmore » activity a/sub 0/ on the catalyst surface is virtually determined by the ratio P/sub H/sub 2/O//P/sub H/sub 2// in the gas atmosphere. The above rate equation was confirmed by measurements in a flow apparatus for the temperature range 700 to 900/sup 0/C. In agreement with the reaction model the steady-state carbon activity on the iron surface and the steady-state carbon concentration in the iron catalyst are very low. With nickel as catalyst the reaction rate is much higher and independent of the oxygen activity on the catalyst surface. The rate equation reads: v = k/sub 2//sup Ni/ P/sub CH/sub 4//. Different partial reaction steps of the methane decomposition are rate determining on iron and nickel.« less
  • Carbon dioxide reforming of methane to synthesis gas was studied by employing a Ni/La{sub 2}O{sub 3} catalyst as well as conventional nickel-based catalysts, i.e., Ni/{gamma}-Al{sub 2}O{sub 3}, Ni/CaO/{gamma}-Al{sub 2}O{sub 3}, and Ni/CaO. It is observed that, in constrast to conventional nickel-based catalysts, which exhibit continuous deactivation with time on stream, the rate of reaction over the Ni/La{sub 2}O{sub 3} catalyst increase during the initial 2-5 h and then tends to be essentially invariable with time on stream. X-ray photoelectron spectroscopy (XPS) studies show that the surface carbon on spent Ni/Al{sub 2}O{sub 3} catalyst is dominated by -C-C- species that eventuallymore » block the entire Ni surface, leading to total loss of activity. The surface carbon on the working Ni/La{sub 2}O{sub 3} catalyst is found to consist of -C-C- species and a large amount of oxidized carbon. Both XPS and secondary ion mass spectrometry results reveal that a large fraction of surface Ni on the working Ni/La{sub 2}O{sub 3} catalyst is not shielded by carbon deposition. FTIR studies reveal that the enhancement of the rate of reaction over the Ni/La{sub 2}O{sub 3} catalyst during the initial 2-5 h of reaction correlates well with increasing concentrations of La{sub 2}O{sub 2}CO{sub 3} and formate species on the support, suggesting that these species may participate in the surface chemistry to produce synthesis gas. 47 refs., 12 figs., 2 tabs.« less
  • The kinetics of elementary surface reactions involved in the reforming of methane to synthesis gas over supported nickel were studied using transient isotopic methods. To investigate methane adsorption and dehydrogenation, the reaction between CD{sub 4} and H{sub 2} was studied. To investigate water adsorption and dissociation, the reaction between H{sub 2}O and D{sub 2} was studied. To investigate the formation and cleavage of C-O bonds on the nickel surface, transient CO methanation experiments were performed. Rate constants of surface elementary reactions were extracted from the data by fitting the measured response curves to microkinetic models. An overall model that describesmore » the reactions of methane with steam and CO{sub 2} in microkinetic terms was constructed based on these rate constants and on previously published steam reforming and CO{sub 2} methanation data. The model suggests that there is no single rate-determining step in methane reforming with either steam or CO{sub 2}, and that under some conditions the availability of surface oxygen may play a key role in determining the rate. 63 refs., 10 figs., 3 tabs.« less
  • It has been observed that carbon-free steam reforming of methane can be obtained on a partly sulfur-passivated nickel catalyst under conditions which, without the presence of sulfur, would result in formation of whisker carbon. This effect has been studied by means of kinetic experiments and thermogravimetry. The kinetic data can be explained by simple blockage of the surface as reflected in the observed kinetic orders and activation energy. The studies of carbon formation confirm a threshold coverage of about 70% of full coverage below which the inhibition of carbon is not effective. Above this coverage, amorphous carbon structures may bemore » formed at a very high carbon potentials. The retarding effect of sulfur on carbon formation is a dynamic phenomenon. Sulfur inhibits the rate of carbon formation more than the rate of the reforming reactions. The effects are explained by assuming that a large ensemble is involved in the nucleation of carbon, whereas the reforming reaction can proceed on the small ensembles left a high sulfur coverages. 6 figures, 6 tables.« less