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

Title: Condensed-phase low temperature heterogeneous hydrogenation of CO 2 to methanol

Abstract

A low-temperature CH 3OH synthesis was achieved at 120–170 °C using tertiary amine and alcohol in the presence of a Cu/ZnO/Al 2O 3catalyst by CO 2hydrogenation.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Energy Processes and Materials Division; Pacific Northwest National Laboratory; Richland; USA
  2. Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; Richland; USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1492552
Report Number(s):
PNNL-SA-133245
Journal ID: ISSN 2044-4753; CSTAGD
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 19; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Kothandaraman, Jotheeswari, Dagle, Robert A., Dagle, Vanessa Labarbier, Davidson, Stephen D., Walter, Eric D., Burton, Sarah D., Hoyt, David W., and Heldebrant, David J. Condensed-phase low temperature heterogeneous hydrogenation of CO 2 to methanol. United States: N. p., 2018. Web. doi:10.1039/C8CY00997J.
Kothandaraman, Jotheeswari, Dagle, Robert A., Dagle, Vanessa Labarbier, Davidson, Stephen D., Walter, Eric D., Burton, Sarah D., Hoyt, David W., & Heldebrant, David J. Condensed-phase low temperature heterogeneous hydrogenation of CO 2 to methanol. United States. doi:10.1039/C8CY00997J.
Kothandaraman, Jotheeswari, Dagle, Robert A., Dagle, Vanessa Labarbier, Davidson, Stephen D., Walter, Eric D., Burton, Sarah D., Hoyt, David W., and Heldebrant, David J. Mon . "Condensed-phase low temperature heterogeneous hydrogenation of CO 2 to methanol". United States. doi:10.1039/C8CY00997J.
@article{osti_1492552,
title = {Condensed-phase low temperature heterogeneous hydrogenation of CO 2 to methanol},
author = {Kothandaraman, Jotheeswari and Dagle, Robert A. and Dagle, Vanessa Labarbier and Davidson, Stephen D. and Walter, Eric D. and Burton, Sarah D. and Hoyt, David W. and Heldebrant, David J.},
abstractNote = {A low-temperature CH3OH synthesis was achieved at 120–170 °C using tertiary amine and alcohol in the presence of a Cu/ZnO/Al2O3catalyst by CO2hydrogenation.},
doi = {10.1039/C8CY00997J},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 19,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

Methanol synthesis from CO2 and H2 in multi-tubular fixed-bed reactor and multi-tubular reactor filled with monoliths
journal, November 2014

  • Arab, Sofiane; Commenge, Jean-Marc; Portha, Jean-François
  • Chemical Engineering Research and Design, Vol. 92, Issue 11
  • DOI: 10.1016/j.cherd.2014.03.009

Ruthenium complex catalysed hydrogenation of carbon dioxide to carbon monoxide, methanol and methane
journal, January 1993

  • Tominaga, Ken-ichi; Sasaki, Yoshiyuki; Kawai, Motomitsu
  • Journal of the Chemical Society, Chemical Communications, Issue 7
  • DOI: 10.1039/c39930000629

Conversion of CO 2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst
journal, January 2016

  • Kothandaraman, Jotheeswari; Goeppert, Alain; Czaun, Miklos
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b12354

Opportunities and prospects in the chemical recycling of carbon dioxide to fuels
journal, November 2009


Deactivation of Cu/ZnO/Al 2 O 3 Methanol Synthesis Catalyst by Sintering
journal, October 1999

  • Sun, James T.; Metcalfe, Ian S.; Sahibzada, Mortaza
  • Industrial & Engineering Chemistry Research, Vol. 38, Issue 10
  • DOI: 10.1021/ie990078s

Chemical Technologies for Exploiting and Recycling Carbon Dioxide into the Value Chain
journal, August 2011

  • Peters, Martina; Köhler, Burkhard; Kuckshinrichs, Wilhelm
  • ChemSusChem, Vol. 4, Issue 9
  • DOI: 10.1002/cssc.201000447

Catalytic reduction of CO 2 by H 2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
journal, January 2016

  • Porosoff, Marc D.; Yan, Binhang; Chen, Jingguang G.
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02657A

Cascade Catalysis for the Homogeneous Hydrogenation of CO 2 to Methanol
journal, November 2011

  • Huff, Chelsea A.; Sanford, Melanie S.
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja208760j

Hydrogenation of carbon dioxide to methanol using a homogeneous ruthenium–Triphos catalyst: from mechanistic investigations to multiphase catalysis
journal, January 2015

  • Wesselbaum, Sebastian; Moha, Verena; Meuresch, Markus
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC02087A

Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium-Phosphine Catalyst
journal, June 2012

  • Wesselbaum, Sebastian; vom Stein, Thorsten; Klankermayer, Jürgen
  • Angewandte Chemie International Edition, Vol. 51, Issue 30
  • DOI: 10.1002/anie.201202320

Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO 2 to Methanol
journal, January 2015

  • Rezayee, Nomaan M.; Huff, Chelsea A.; Sanford, Melanie S.
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja511329m

Recent Advances in CO 2 Capture and Utilization
journal, November 2008

  • Yu, Kai Man Kerry; Curcic, Igor; Gabriel, Joseph
  • ChemSusChem, Vol. 1, Issue 11
  • DOI: 10.1002/cssc.200800169

Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts
journal, March 2017


Anhydrous tertiary alkanolamines as hybrid chemical and physical CO 2 capture reagents with pressure-swing regeneration
journal, January 2011

  • Rainbolt, James E.; Koech, Phillip K.; Yonker, Clement R.
  • Energy Environ. Sci., Vol. 4, Issue 2
  • DOI: 10.1039/C0EE00506A

Carbon dioxide-to-methanol single-pot conversion using a C-scorpionate iron( ii ) catalyst
journal, January 2017

  • Ribeiro, A. P. C.; Martins, L. M. D. R. S.; Pombeiro, A. J. L.
  • Green Chemistry, Vol. 19, Issue 20
  • DOI: 10.1039/C7GC01993A

CO2 absorption by aqueous NH3 solutions: speciation of ammonium carbamate, bicarbonate and carbonate by a 13C NMR study
journal, January 2006

  • Mani, Fabrizio; Peruzzini, Maurizio; Stoppioni, Piero
  • Green Chemistry, Vol. 8, Issue 11
  • DOI: 10.1039/b602051h

CO2 hydrogenation over metal/zirconia catalysts
journal, January 1999

  • Wambach, Jörg; Baiker, Alfons; Wokaun, Alexander
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 22
  • DOI: 10.1039/a904923a

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment
journal, December 2017


Water-Lean Solvents for Post-Combustion CO 2 Capture: Fundamentals, Uncertainties, Opportunities, and Outlook
journal, May 2017

  • Heldebrant, David J.; Koech, Phillip K.; Glezakou, Vassiliki-Alexandra
  • Chemical Reviews, Vol. 117, Issue 14
  • DOI: 10.1021/acs.chemrev.6b00768

Transformation of Carbon Dioxide
journal, June 2007

  • Sakakura, Toshiyasu; Choi, Jun-Chul; Yasuda, Hiroyuki
  • Chemical Reviews, Vol. 107, Issue 6
  • DOI: 10.1021/cr068357u

Anthropogenic Chemical Carbon Cycle for a Sustainable Future
journal, August 2011

  • Olah, George A.; Prakash, G. K. Surya; Goeppert, Alain
  • Journal of the American Chemical Society, Vol. 133, Issue 33
  • DOI: 10.1021/ja202642y

Homogeneous Hydrogenation of CO 2 to Methyl Formate Utilizing Switchable Ionic Liquids
journal, August 2014

  • Yadav, Mahendra; Linehan, John C.; Karkamkar, Abhijeet J.
  • Inorganic Chemistry, Vol. 53, Issue 18
  • DOI: 10.1021/ic501378w

Using carbon dioxide as a building block in organic synthesis
journal, January 2015

  • Liu, Qiang; Wu, Lipeng; Jackstell, Ralf
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6933

Chemical Recycling of Carbon Dioxide to Methanol and Dimethyl Ether: From Greenhouse Gas to Renewable, Environmentally Carbon Neutral Fuels and Synthetic Hydrocarbons
journal, January 2009

  • Olah, George A.; Goeppert, Alain; Prakash, G. K. Surya
  • The Journal of Organic Chemistry, Vol. 74, Issue 2, p. 487-498
  • DOI: 10.1021/jo801260f

Low-temperature methanol synthesis from carbon dioxide and hydrogen via formic ester
journal, April 1999


Methanol Synthesis
journal, May 1992


Quantification of Zinc Atoms in a Surface Alloy on Copper in an Industrial-Type Methanol Synthesis Catalyst
journal, April 2014

  • Kuld, Sebastian; Conradsen, Christian; Moses, Poul Georg
  • Angewandte Chemie International Edition, Vol. 53, Issue 23
  • DOI: 10.1002/anie.201311073

The promoting effect of alcohols in a new process of low-temperature synthesis of methanol from CO/CO2/H2
journal, January 2002


Pd/ZnO catalysts for direct CO2 hydrogenation to methanol
journal, November 2016


Alcohol promoted methanol synthesis enhanced by adsorption of water and dual catalysts
journal, March 2018


Low-Temperature CO 2 Hydrogenation to Liquid Products via a Heterogeneous Cascade Catalytic System
journal, February 2015

  • Chen, Yuan; Choi, Saemin; Thompson, Levi T.
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501656x

High yield production of formate by hydrogenating CO 2 derived ammonium carbamate/carbonate at room temperature
journal, January 2015


Manganese-Catalyzed Sequential Hydrogenation of CO 2 to Methanol via Formamide
journal, August 2017


Electron Spectroscopic Studies of CH 3 OH Chemisorption on Cu 2 O and ZnO Single-Crystal Surfaces:  Methoxide Bonding and Reactivity Related to Methanol Synthesis
journal, February 1998

  • Jones, Paul M.; May, Jennifer A.; Reitz, J. Brad
  • Journal of the American Chemical Society, Vol. 120, Issue 7
  • DOI: 10.1021/ja963990q

Harnessing renewable energy with CO 2 for the chemical value chain: challenges and opportunities for catalysis
journal, February 2016

  • Klankermayer, Jürgen; Leitner, Walter
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2061
  • DOI: 10.1098/rsta.2015.0315

Spontaneous Growth of ZnCO 3 Nanowires on ZnO Nanostructures in Normal Ambient Environment: Unstable ZnO Nanostructures
journal, January 2010

  • Pan, Zhengwei; Tao, Jing; Zhu, Yimei
  • Chemistry of Materials, Vol. 22, Issue 1
  • DOI: 10.1021/cm902734e

Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts
journal, January 2012

  • Lebarbier, Vanessa M.; Dagle, Robert A.; Kovarik, Libor
  • Catalysis Science & Technology, Vol. 2, Issue 10
  • DOI: 10.1039/c2cy20315d

A Diagonal Approach to Chemical Recycling of Carbon Dioxide: Organocatalytic Transformation for the Reductive Functionalization of CO2
journal, September 2011

  • Das Neves Gomes, Christophe; Jacquet, Olivier; Villiers, Claude
  • Angewandte Chemie International Edition, Vol. 51, Issue 1
  • DOI: 10.1002/anie.201105516

Homogeneous Hydrogenation of Carbon Dioxide to Methanol Catalyzed by Ruthenium Cluster Anions in the Presence of Halide Anions
journal, October 1995

  • Tominaga, Ken-ichi; Sasaki, Yoshiyuki; Watanabe, Taiki
  • Bulletin of the Chemical Society of Japan, Vol. 68, Issue 10
  • DOI: 10.1246/bcsj.68.2837

Homogeneous Hydrogenation of Carbon Dioxide
journal, March 1995

  • Jessop, Philip G.; Ikariya, Takao.; Noyori, Ryoji.
  • Chemical Reviews, Vol. 95, Issue 2
  • DOI: 10.1021/cr00034a001

In situ IR studies on the mechanism of methanol synthesis from CO/H2 and CO2/H2 over Cu-ZnO-Al2O3 catalyst
journal, June 2010

  • Wang, Xiaojuan; Zhang, Haipeng; Li, Wei
  • Korean Journal of Chemical Engineering, Vol. 27, Issue 4
  • DOI: 10.1007/s11814-010-0176-9

A New Method of Low-Temperature Methanol Synthesis
journal, January 2001

  • Tsubaki, Noritatsu; Ito, Motoaki; Fujimoto, Kaoru
  • Journal of Catalysis, Vol. 197, Issue 1
  • DOI: 10.1006/jcat.2000.3077

The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012


The steps of activating a prospective CO 2 hydrogenation catalyst with combined CO 2 capture and reduction
journal, January 2016

  • Lao, D. B.; Galan, B. R.; Linehan, J. C.
  • Green Chemistry, Vol. 18, Issue 18
  • DOI: 10.1039/C6GC01800A

A New Low-Temperature Synthesis Route of Methanol:  Catalytic Effect of the Alcoholic Solvent
journal, January 2002

  • Zeng, Jianqing; Fujimoto, Kaoru; Tsubaki, Noritatsu
  • Energy & Fuels, Vol. 16, Issue 1
  • DOI: 10.1021/ef0100395

Methanol from CO 2 by Organo-Cocatalysis: CO 2 Capture and Hydrogenation in One Process Step
journal, November 2014

  • Reller, Christian; Pöge, Matthias; Lißner, Andreas
  • Environmental Science & Technology, Vol. 48, Issue 24
  • DOI: 10.1021/es503914d

Methanol synthesis from CO2 and H2 over Pd/ZnO/Al2O3: Catalyst structure dependence of methanol selectivity
journal, March 2016


CO 2 capture by amines in aqueous media and its subsequent conversion to formate with reusable ruthenium and iron catalysts
journal, January 2016

  • Kothandaraman, Jotheeswari; Goeppert, Alain; Czaun, Miklos
  • Green Chemistry, Vol. 18, Issue 21
  • DOI: 10.1039/C6GC01165A

A Study of Methyl Formate Production from Carbon Dioxide Hydrogenation in Methanol over a Copper Zinc Oxide Catalyst
journal, November 2010


Ethyl formate hydrogenolysis over Mo2C-based catalysts: Towards low temperature CO and CO2 hydrogenation to methanol
journal, January 2016


On the Synergetic Catalytic Effect in Heterogeneous Nanocomposite Catalysts
journal, November 2012


Catalysis for CO2 conversion: a key technology for rapid introduction of renewable energy in the value chain of chemical industries
journal, January 2013

  • Centi, Gabriele; Quadrelli, Elsje Alessandra; Perathoner, Siglinda
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee00056g

Kinetics and Mechanism of Carbamate Formation from CO 2 (aq), Carbonate Species, and Monoethanolamine in Aqueous Solution
journal, April 2009

  • McCann, Nichola; Phan, Duong; Wang, Xiaoguang
  • The Journal of Physical Chemistry A, Vol. 113, Issue 17
  • DOI: 10.1021/jp810564z