Online citations, reference lists, and bibliographies.
← Back to Search

Towards A Continuous Formic Acid Synthesis: A Two-step Carbon Dioxide Hydrogenation In Flow

H. Reymond, Juan J. Helena Reymond, A. Urakawa, P. R. Rohr
Published 2018 · Materials Science

Save to my Library
Download PDF
Analyze on Scholarcy
Share
The need for long term, large-scale storage solutions to match surplus renewable energy with demand drives technological innovation towards a low-carbon economy. As a high hydrogen density energy carrier, formic acid streamlines functional storage of unscheduled intermittent power supply. However, the unfavourable thermodynamics of its direct synthesis from CO2 and H2 call for alternative processes to achieve substantial space time yields. This preliminary study investigates the feasibility of continuously producing formic acid in a two-step process by exploiting methyl formate as a thermodynamically stable intermediate. In order to prove the concept, the qualitative efficiency of several three-reactor configurations is evaluated and discussed with respect to the efficiency of a single reactor methanol synthesis over a commercial Cu catalyst. Although concrete solutions are not available yet and identification of formic acid remains arduous, the proposed reactive pathway exceeds the thermodynamic limits of the direct synthesis path over heterogeneous catalysts, and opens up avenues for advances in clean energy production.
This paper references
10.1016/S0166-9834(00)81884-9
Dehydrogenation of methanol to methyl formate over copper-based catalysts
M. Ai (1984)
10.1002/cssc.201403251
Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.
J. Su (2015)
10.1021/JA0706302
Carbon dioxide fixation into chemicals (methyl formate) at high yields by surface coupling over a Pd/Cu/ZnO nanocatalyst.
K. M. K. Yu (2007)
10.1002/cssc.201000447
Chemical technologies for exploiting and recycling carbon dioxide into the value chain.
M. Peters (2011)
10.1021/JA0167856
Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes: the accelerating effect of certain alcohols and amines.
P. Munshi (2002)
10.1021/ACS.IECR.6B04820
Reaction Process of Resin-Catalyzed Methyl Formate Hydrolysis in Biphasic Continuous Flow
H. Reymond (2017)
10.1002/CEAT.201200038
Potential Analysis of Smart Flow Processing and Micro Process Technology for Fastening Process Development: Use of Chemistry and Process Design as Intensification Fields
V. Hessel (2012)
10.1016/J.CES.2012.10.013
Methanol synthesis beyond chemical equilibrium
J. G. V. Bennekom (2013)
10.1002/cssc.201601361
Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol.
H. Reymond (2017)
10.1016/S1387-1811(99)00219-X
Silica xerogels containing bidentate phosphine ruthenium complexes: textural properties and catalytic behaviour in the synthesis of N,N-dimethylformamide from carbon dioxide
L. Schmid (2000)
10.1039/C3EE41151F
Life-cycle assessment of carbon dioxide capture and utilization: avoiding the pitfalls
N. V. D. Assen (2013)
10.1007/978-1-4615-0773-4
Environmental challenges and greenhouse gas control for fossil fuel utilization in the 21st century
M. Maroto-Valer (2002)
10.1002/CEAT.200900474
Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry
V. Hessel (2009)
10.1016/J.APCATA.2003.12.058
DME synthesis from synthesis gas on the admixed catalysts of Cu/ZnO/Al2O3 and ZSM-5
J. Kim (2004)
10.1038/NPJCOMPUMATS.2016.31
Autonomy in materials research: a case study in carbon nanotube growth
P. Nikolaev (2016)
10.1007/S10562-008-9601-7
The Deactivation Modes of Cu/ZnO/Al2O3 and HZSM-5 Physical Mixture in the One-Step DME Synthesis
F. R. Barbosa (2008)
10.1039/A608150I
Highly active ruthenium complexes with bidentate phosphine ligandsfor the solvent-free catalytic synthesis of N,N-dimethylformamideand methyl formate
O. Kröcher (1997)
10.1002/cctc.201402119
Highly Efficient Reversible Hydrogenation of Carbon Dioxide to Formates Using a Ruthenium PNP‐Pincer Catalyst
Georgy A. Filonenko (2014)
10.1126/scirobotics.aat5559
ChemOS: Orchestrating autonomous experimentation
Loïc M. Roch (2018)
10.1007/S11144-009-0096-Z
Hydrogen storage and delivery: immobilization of a highly active homogeneous catalyst for the decomposition of formic acid to hydrogen and carbon dioxide
Weijia Gan (2009)
10.1002/cctc.201500123
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu‐Based Catalysts
Felix Studt (2015)
10.1021/acscentsci.7b00492
Optimizing Chemical Reactions with Deep Reinforcement Learning
Zhenpeng Zhou (2017)
10.1021/ACS.IECR.7B04866
Thermodynamic Analysis of Chemical and Phase Equilibria in CO2 Hydrogenation to Methanol, Dimethyl Ether, and Higher Alcohols
Kristian Stangeland (2018)
10.1002/cssc.201403173
Efficient production of hydrogen from formic acid using a covalent triazine framework supported molecular catalyst.
A. Bavykina (2015)
10.1002/cssc.201000327
Interconversion between formic acid and H(2)/CO(2) using rhodium and ruthenium catalysts for CO(2) fixation and H(2) storage.
Y. Himeda (2011)
10.1016/J.CEJ.2014.10.059
A novel condensation reactor for efficient CO2 to methanol conversion for storage of renewable electric energy
M. J. Bos (2015)
10.1016/J.SUPFLU.2013.03.027
CO2 hydrogenation to methanol at pressures up to 950bar
B. Tidona (2013)
10.1021/acs.chemrev.6b00816
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes
A. Alvarez (2017)
10.1038/nnano.2011.42
Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst.
K. Tedsree (2011)
10.1002/anie.201203185
Continuous-flow hydrogenation of carbon dioxide to pure formic acid using an integrated scCO2 process with immobilized catalyst and base.
Sebastian Wesselbaum (2012)
10.1016/J.CATCOM.2004.08.001
Silica immobilized ruthenium catalyst used for carbon dioxide hydrogenation to formic acid (I): the effect of functionalizing group and additive on the catalyst performance
Y. Zhang (2004)
10.1016/J.CEP.2013.01.001
High pressure plant for heterogeneous catalytic CO2 hydrogenation reactions in a continuous flow microreactor
B. Tidona (2013)
10.5860/choice.42-5612
Lange's Handbook of Chemistry
J. A. Dean (1978)
10.1016/J.FLUID.2013.06.006
Liquid–liquid equilibrium data for systems containing of formic acid, water, and primary normal alcohols at T =298.2K
H. Gilani (2013)
10.1002/cssc.201200957
Hydrogen production by dehydrogenation of formic acid on atomically dispersed gold on ceria.
N. Yi (2013)
10.1039/C2CY20604H
Impact of K and Ba promoters on CO2 hydrogenation over Cu/Al2O3 catalysts at high pressure
A. Bansode (2013)
10.1038/s41578-018-0005-z
Accelerating the discovery of materials for clean energy in the era of smart automation
D. Tabor (2018)
10.1021/EF901489K
Comparative Study of Methyl Butanoate and n-Heptane High Temperature Autoignition
B. Akih-Kumgeh (2010)
10.1016/J.JCAT.2012.10.028
Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water
Y. Yang (2013)
10.1002/ANIE.200704487
Hydrogenation of carbon dioxide is promoted by a task-specific ionic liquid.
Z. Zhang (2008)
10.1021/JA953097B
HOMOGENEOUS CATALYSIS IN SUPERCRITICAL FLUIDS : HYDROGENATION OF SUPERCRITICAL CARBON DIOXIDE TO FORMIC ACID, ALKYL FORMATES, AND FORMAMIDES
P. Jessop (1996)
10.1021/jacs.8b08505
Decisive Role of Perimeter Sites in Silica-Supported Ag Nanoparticles in Selective Hydrogenation of CO2 to Methyl Formate in the Presence of Methanol.
Juan José Corral-Pérez (2018)
10.1039/C4GC01818D
Highly efficient hydrogenation of carbon dioxide to methyl formate over supported gold catalysts
Congyi Wu (2015)
10.1016/J.APCBEE.2012.06.042
Overview on Direct Formic Acid Fuel Cells (DFAFCs) as an Energy Sources
Norraihanah Mohamed Aslam (2012)



This paper is referenced by
Semantic Scholar Logo Some data provided by SemanticScholar