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

Title: Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4

Abstract

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resultedmore » in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H2 production. Conversion and selectivity to CH4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1252849
Report Number(s):
PNNL-SA-111967
Journal ID: ISSN 0920-5861; 49140; 48163; BM0102060
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Catalysis Today
Additional Journal Information:
Journal Volume: 269; Journal Issue: C; Journal ID: ISSN 0920-5861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
biomass; steam reforming; aqueous phase; oxygenates; rhodium; nickel; cobalt; Environmental Molecular Sciences Laboratory

Citation Formats

Xing, Rong, Dagle, Vanessa Lebarbier, Flake, Matthew, Kovarik, Libor, Albrecht, Karl O., Deshmane, Chinmay, and Dagle, Robert A. Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4. United States: N. p., 2016. Web. doi:10.1016/j.cattod.2015.11.046.
Xing, Rong, Dagle, Vanessa Lebarbier, Flake, Matthew, Kovarik, Libor, Albrecht, Karl O., Deshmane, Chinmay, & Dagle, Robert A. Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4. United States. https://doi.org/10.1016/j.cattod.2015.11.046
Xing, Rong, Dagle, Vanessa Lebarbier, Flake, Matthew, Kovarik, Libor, Albrecht, Karl O., Deshmane, Chinmay, and Dagle, Robert A. 2016. "Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4". United States. https://doi.org/10.1016/j.cattod.2015.11.046.
@article{osti_1252849,
title = {Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4},
author = {Xing, Rong and Dagle, Vanessa Lebarbier and Flake, Matthew and Kovarik, Libor and Albrecht, Karl O. and Deshmane, Chinmay and Dagle, Robert A.},
abstractNote = {In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H2 production. Conversion and selectivity to CH4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.},
doi = {10.1016/j.cattod.2015.11.046},
url = {https://www.osti.gov/biblio/1252849}, journal = {Catalysis Today},
issn = {0920-5861},
number = C,
volume = 269,
place = {United States},
year = {2016},
month = {7}
}

Works referenced in this record:

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006


Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions
journal, January 2010


Developments in direct thermochemical liquefaction of biomass: 1983-1990
journal, May 1991


Production of hydrogen, alkanes and polyols by aqueous phase processing of wood-derived pyrolysis oils
journal, January 2009


Historical Developments in Hydroprocessing Bio-oils
journal, May 2007


Steam reforming of acetic acid for hydrogen production over bifunctional Ni–Co catalysts
journal, May 2013


Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts
journal, October 2005


Nature of the active sites in Ni/MgAl2O4-based catalysts designed for steam reforming of ethanol
journal, September 2013


Acetic Acid Reforming over Rh Supported on La 2 O 3 /CeO 2 –ZrO 2 : Catalytic Performance and Reaction Pathway Analysis
journal, July 2013


Production of hydrogen via steam reforming of biofuels on Ni/CeO2–Al2O3 catalysts promoted by noble metals
journal, June 2009


Production of Hydrogen from Biomass by Catalytic Steam Reforming of Fast Pyrolysis Oils
journal, January 1998


Hydrogen by Catalytic Steam Reforming of Liquid Byproducts from Biomass Thermoconversion Processes
journal, August 2002


Hydrogen Production via Steam Reforming of the Aqueous Phase of Bio-Oil in a Fixed Bed Reactor
journal, September 2006


Production of a hydrogen-rich gas from fast pyrolysis bio-oils: Comparison between homogeneous and catalytic steam reforming routes
journal, January 2014


Low-temperature conversion of phenol into CO, CO2 and H2 by steam reforming over La-containing supported Rh catalysts
journal, May 2012


Catalytic steam reforming of acetic acid for hydrogen production
journal, October 2007


Production of hydrogen for fuel cells by steam reforming of ethanol over supported noble metal catalysts
journal, July 2003


Hydrogen production via steam reforming of bio-oil components over calcium aluminate supported nickel and noble metal catalysts
journal, December 2008


Influence of the carrier on steam reforming of acetic acid over Ru-based catalysts
journal, July 2008


Investigation of steam reforming of acetic acid to hydrogen over Ni–Co metal catalyst
journal, January 2007


Hydrogen production from steam reforming of acetic acid over Cu–Zn supported calcium aluminate
journal, November 2012


Steam Reforming of Bio-Oil for Hydrogen Production: Effect of Ni-Co Bimetallic Catalysts
journal, November 2011


Catalytic steam reforming of bio-oil aqueous fraction for hydrogen production over Ni–Mo supported on modified sepiolite catalysts
journal, April 2013


Steam reforming of ethanol at medium pressure over Ru/Al2O3: effect of temperature and catalyst deactivation
journal, January 2012


Catalysts for the control of coking during steam reforming
journal, February 1999


Hydrogen production by steam reforming of acetic acid over Ni-based catalysts
journal, April 2011


The phenol steam reforming reaction over MgO-based supported Rh catalysts
journal, December 2004


Steam reforming of the aqueous fraction of bio-oil over structured Ru/MgO/Al2O3 catalysts
journal, September 2007


The steam reforming of phenol reaction over supported-Rh catalysts
journal, September 2004


Steam reforming of phenol over Ni-based catalysts – A comparative study
journal, August 2011


Methane dry reforming with CO2: A study on surface carbon species
journal, March 2010


Comparative Investigation of Benzene Steam Reforming over Spinel Supported Rh and Ir Catalysts
journal, April 2013


Biomass to Hydrogen via Fast Pyrolysis and Catalytic Steam Reforming of the Pyrolysis Oil or Its Fractions
journal, May 1997


Efficient Production of Hydrogen over Supported Cobalt Catalysts from Ethanol Steam Reforming
journal, July 2002


Novel Fe–Ni nanoparticle catalyst for the production of CO- and CO2-free H2 and carbon nanotubes by dehydrogenation of methane
journal, December 2008


Nonoxidative Activation of Methane
journal, January 2003


Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility
journal, January 2009


Progresses in the Preparation of Coke Resistant Ni-based Catalyst for Steam and CO2 Reforming of Methane
journal, February 2011


Works referencing / citing this record:

Methane and Ethane Steam Reforming over MgAl2O4-Supported Rh and Ir Catalysts: Catalytic Implications for Natural Gas Reforming Application
journal, September 2019


ZrMn Oxides for Aqueous-Phase Ketonization of Acetic Acid: Effect of Crystal and Porosity
journal, March 2018