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

Title: Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates

Abstract

The need for a sustainable energy supply in the face of depleting oil reserves has reignited the importance of Fischer Tropsch (FT) Synthesis technology. Presently, the FT process is practiced at the industrial scale to predominately produce synthetic diesel-type fuels and lubricants. More recently, the possibility of hydrogenating CO towards oxygenates, and not just hydrocarbons, has been explored. We have developed a series of CoCuMn and CoMnK catalysts prepared via the oxalate co-precipitation route that are capable of forming oxygenates with desirable selectivity. Upon H2-assisted thermal decomposition of the resultant mixed metal Co1Cu1Mn1 oxalates, catalysts naturally exhibited a cobalt core-copper shell configuration with Mn5O8 throughout the catalyst nanoparticle as determined via Atom Probe Tomography (APT). We suggest structural changes are induced by the CO and H2 reactants to form the catalytically active phase under real-time reaction conditions as demonstrated by corroborative density functional theory calculations and experimental evidence. APT studies also showed that a Co4Mn1K0.1 catalyst post reaction contained a cobalt carbide phase as determined from a Co/C ratio of 2/1. Manganese and potassium were found only in the outermost part of the particle. Both catalysts were found to contain the presence of a Mn5O8 oxidic phase before and postmore » reaction which we attribute to the high activity toward oxygenates of these two catalysts.« less

Authors:
 [1];  [2];  [2]; ORCiD logo [3];  [3];  [1];  [1]
  1. Washington State University
  2. WASHINGTON STATE UNIV
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1509861
Report Number(s):
PNNL-SA-129636
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 61; Journal Issue: 9-11
Country of Publication:
United States
Language:
English

Citation Formats

Voss, Jenny, Xiang, Yizhi, Collinge, Gregory B., Perea, Daniel E., Kovarik, Libor, McEwen, Jean-Sabin, and Kruse, Norbert. Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates. United States: N. p., 2018. Web. doi:10.1007/s11244-018-0938-x.
Voss, Jenny, Xiang, Yizhi, Collinge, Gregory B., Perea, Daniel E., Kovarik, Libor, McEwen, Jean-Sabin, & Kruse, Norbert. Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates. United States. doi:10.1007/s11244-018-0938-x.
Voss, Jenny, Xiang, Yizhi, Collinge, Gregory B., Perea, Daniel E., Kovarik, Libor, McEwen, Jean-Sabin, and Kruse, Norbert. Fri . "Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates". United States. doi:10.1007/s11244-018-0938-x.
@article{osti_1509861,
title = {Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates},
author = {Voss, Jenny and Xiang, Yizhi and Collinge, Gregory B. and Perea, Daniel E. and Kovarik, Libor and McEwen, Jean-Sabin and Kruse, Norbert},
abstractNote = {The need for a sustainable energy supply in the face of depleting oil reserves has reignited the importance of Fischer Tropsch (FT) Synthesis technology. Presently, the FT process is practiced at the industrial scale to predominately produce synthetic diesel-type fuels and lubricants. More recently, the possibility of hydrogenating CO towards oxygenates, and not just hydrocarbons, has been explored. We have developed a series of CoCuMn and CoMnK catalysts prepared via the oxalate co-precipitation route that are capable of forming oxygenates with desirable selectivity. Upon H2-assisted thermal decomposition of the resultant mixed metal Co1Cu1Mn1 oxalates, catalysts naturally exhibited a cobalt core-copper shell configuration with Mn5O8 throughout the catalyst nanoparticle as determined via Atom Probe Tomography (APT). We suggest structural changes are induced by the CO and H2 reactants to form the catalytically active phase under real-time reaction conditions as demonstrated by corroborative density functional theory calculations and experimental evidence. APT studies also showed that a Co4Mn1K0.1 catalyst post reaction contained a cobalt carbide phase as determined from a Co/C ratio of 2/1. Manganese and potassium were found only in the outermost part of the particle. Both catalysts were found to contain the presence of a Mn5O8 oxidic phase before and post reaction which we attribute to the high activity toward oxygenates of these two catalysts.},
doi = {10.1007/s11244-018-0938-x},
journal = {Topics in Catalysis},
number = 9-11,
volume = 61,
place = {United States},
year = {2018},
month = {6}
}

Works referenced in this record:

Diesel Production from Fischer−Tropsch: The Past, the Present, and New Concepts
journal, May 2009


Higher Alcohol Synthesis
journal, February 1991


A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics
journal, January 2012


Long-Chain Terminal Alcohols through Catalytic CO Hydrogenation
journal, May 2013

  • Xiang, Yizhi; Chitry, Véronique; Liddicoat, Peter
  • Journal of the American Chemical Society, Vol. 135, Issue 19
  • DOI: 10.1021/ja402512r

Status and prospects in higher alcohols synthesis from syngas
journal, January 2017

  • Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla
  • Chemical Society Reviews, Vol. 46, Issue 5
  • DOI: 10.1039/C6CS00324A

Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles
journal, May 2007

  • Pan, Xiulian; Fan, Zhongli; Chen, Wei
  • Nature Materials, Vol. 6, Issue 7
  • DOI: 10.1038/nmat1916

Deactivation study of CuCo catalyst for higher alcohol synthesis via syngas
journal, July 2016


Synthesis of higher alcohols from syngas over Fischer–Tropsch elements modified K/β-Mo2C catalysts
journal, April 2008


Effects of La 2 O 3 on the Mixed Higher Alcohols Synthesis from Syngas over Co Catalysts: A Combined Theoretical and Experimental Study
journal, August 2011

  • Lebarbier, Vanessa M.; Mei, Donghai; Kim, Do Heui
  • The Journal of Physical Chemistry C, Vol. 115, Issue 35
  • DOI: 10.1021/jp204003q

Higher Alcohols through CO Hydrogenation over CoCu Catalysts: Influence of Precursor Activation
journal, July 2014

  • Xiang, Yizhi; Barbosa, Roland; Kruse, Norbert
  • ACS Catalysis, Vol. 4, Issue 8
  • DOI: 10.1021/cs500696z

Synthesis of higher alcohols from syngas - recently patented catalysts and tentative ideas on the mechanism
journal, December 1987


Effect of ZrO2, Al2O3 and La2O3 on cobalt–copper catalysts for higher alcohols synthesis
journal, October 2015


Ternary Cobalt–Copper–Niobium Catalysts for the Selective CO Hydrogenation to Higher Alcohols
journal, March 2015


Density Functional Theory Study of Iron and Cobalt Carbides for Fischer−Tropsch Synthesis
journal, December 2009

  • Cheng, Jun; Hu, P.; Ellis, Peter
  • The Journal of Physical Chemistry C, Vol. 114, Issue 2
  • DOI: 10.1021/jp908482q

A Review of Recent Literature to Search for an Efficient Catalytic Process for the Conversion of Syngas to Ethanol
journal, March 2008

  • Subramani, Velu; Gangwal, Santosh K.
  • Energy & Fuels, Vol. 22, Issue 2
  • DOI: 10.1021/ef700411x

Investigation of the synthesis of oxygenates from carbon monoxide/hydrogen mixtures on supported rhodium catalysts
journal, September 1992


C1-C6 alcohols from synthesis gas on copper-cobalt catalysts
journal, November 1982


A DRIFTS study of CO adsorption and hydrogenation on Cu-based core–shell nanoparticles
journal, January 2012

  • Subramanian, Nachal D.; Kumar, Challa S. S. R.; Watanabe, Kazuo
  • Catalysis Science & Technology, Vol. 2, Issue 3
  • DOI: 10.1039/c2cy00413e

CO-induced inversion of the layer sequence of a model CoCu catalyst
journal, June 2016


Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins
journal, October 2016


In situ site-specific specimen preparation for atom probe tomography
journal, February 2007


Cobalt carbide nanoprisms for direct production of lower olefins from syngas
journal, October 2016


Selective Catalytic CO Hydrogenation to Short- and Long-Chain C2+ Alcohols
journal, July 2013


Cobalt–copper based catalysts for higher terminal alcohols synthesis via Fischer–Tropsch reaction
journal, November 2016


Mixed alcohol synthesis from carbon monoxide and dihydrogen over potassium-promoted molybdenum carbide catalysts
journal, August 1991


Mechanistic Aspects of the Formation of Hydrocarbons and Alcohols from CO Hydrogenation
journal, February 1993


Surface analysis of transition metal oxalates: Damage aspects
journal, May 2016

  • Chenakin, S. P.; Szukiewicz, R.; Barbosa, R.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 209
  • DOI: 10.1016/j.elspec.2016.04.001

Role of the Cu–Co alloy and cobalt carbide in higher alcohol synthesis
journal, September 2000

  • Volkova, G. G.; Yurieva, T. M.; Plyasova, L. M.
  • Journal of Molecular Catalysis A: Chemical, Vol. 158, Issue 1
  • DOI: 10.1016/S1381-1169(00)00110-2

CO chemisorption on two-dimensional cobalt clusters: A surface science approach to cluster chemistry
journal, July 1984


Short history and present trends of Fischer–Tropsch synthesis
journal, October 1999


A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas
journal, September 2009


Dealloying of Cobalt from CuCo Nanoparticles under Syngas Exposure
journal, March 2013

  • Carenco, Sophie; Tuxen, Anders; Chintapalli, Mahati
  • The Journal of Physical Chemistry C, Vol. 117, Issue 12
  • DOI: 10.1021/jp4000297

High Alcohols Synthesis via Fischer–Tropsch Reaction at Cobalt Metal/Carbide Interface
journal, May 2015