The influence of cell design and electrolysis parameters on the electrosynthesis of carboxylic acids from carbon dioxide and 1,3 - butadiene
The influence of cell design and electrolysis parameters on the electrosynthesis of carboxylic acids from carbon dioxide and 1,3 - butadiene
The electrochemical reduction of carbon dioxide in acetonitrile in the presence of excess 1,3-butadiene is studied. The electrolysis products obtained consist mainly of a mixture of pentenoic, C5, acids (two isomers), hexenedioic, C6, acids (two isomers) and decadienedioic, C10, acids (three isomers). It is found that the total current yield and the ratio of the acids are strongly dependent on cell design and other experimental parameters. The electrolysis is investigated in several reactors, namely a dividend and an undivided batch cell and three undivided flow cells (a parallel plate cell, a swiss-roll and a fluidized bed used in monopolar and bipolar configurations). In all undivided cells the supporting electrolyte is a mixture of ditetraethylammonium oxalate and tetraethylammonium formate, which also provide the anode reactions by being oxidized to carbon dioxide and CO2 and protons, respectively. The current yield and product distribution of the unsaturated acids are investigated as a function of the electrolyte composition (salt and water contents), electrode material and form, electrolyte flow rate, electrode potential or current density and electrolysis duration. The total current yield of the three acids is higher in the flow cells. With the parallel plate configuration, using a reticulated carbon foam cathode, it can exceed 60% at high current densities (42mA.cm-2) when both electrolyte salts are present; the selectivity to the decadienedioic acids can be as high as 50%. Similar current yields can be obtained in a bipolar fluidized bed made of carbon spheres with the C10 acids initially formed with a selectivity of about 80%. The space time yield is also very high but as the electrolysis continues, the formation of the C10 acids decreases drastically and C5 acids become the major products. It is shown that the behaviour of the electrolysis depends on the electrode material and structure and on the supporting electrolyte but little on hydrodynamic parameters. It is therefore concluded that the process proceeds via species adsorbed at the electrode surface. (D72866/87)
University of Southampton
1986
Tietje-Girault, Jördis
(1986)
The influence of cell design and electrolysis parameters on the electrosynthesis of carboxylic acids from carbon dioxide and 1,3 - butadiene.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The electrochemical reduction of carbon dioxide in acetonitrile in the presence of excess 1,3-butadiene is studied. The electrolysis products obtained consist mainly of a mixture of pentenoic, C5, acids (two isomers), hexenedioic, C6, acids (two isomers) and decadienedioic, C10, acids (three isomers). It is found that the total current yield and the ratio of the acids are strongly dependent on cell design and other experimental parameters. The electrolysis is investigated in several reactors, namely a dividend and an undivided batch cell and three undivided flow cells (a parallel plate cell, a swiss-roll and a fluidized bed used in monopolar and bipolar configurations). In all undivided cells the supporting electrolyte is a mixture of ditetraethylammonium oxalate and tetraethylammonium formate, which also provide the anode reactions by being oxidized to carbon dioxide and CO2 and protons, respectively. The current yield and product distribution of the unsaturated acids are investigated as a function of the electrolyte composition (salt and water contents), electrode material and form, electrolyte flow rate, electrode potential or current density and electrolysis duration. The total current yield of the three acids is higher in the flow cells. With the parallel plate configuration, using a reticulated carbon foam cathode, it can exceed 60% at high current densities (42mA.cm-2) when both electrolyte salts are present; the selectivity to the decadienedioic acids can be as high as 50%. Similar current yields can be obtained in a bipolar fluidized bed made of carbon spheres with the C10 acids initially formed with a selectivity of about 80%. The space time yield is also very high but as the electrolysis continues, the formation of the C10 acids decreases drastically and C5 acids become the major products. It is shown that the behaviour of the electrolysis depends on the electrode material and structure and on the supporting electrolyte but little on hydrodynamic parameters. It is therefore concluded that the process proceeds via species adsorbed at the electrode surface. (D72866/87)
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Published date: 1986
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Local EPrints ID: 460872
URI: http://eprints.soton.ac.uk/id/eprint/460872
PURE UUID: 6871527d-5f65-4507-a306-87abc26c24a4
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Date deposited: 04 Jul 2022 18:31
Last modified: 04 Jul 2022 18:31
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Author:
Jördis Tietje-Girault
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