ELECTROCHEMICAL REACTOR
20220010438 · 2022-01-13
Assignee
Inventors
Cpc classification
C25B9/40
CHEMISTRY; METALLURGY
C25B9/63
CHEMISTRY; METALLURGY
C25B15/08
CHEMISTRY; METALLURGY
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C25B9/40
CHEMISTRY; METALLURGY
C25B15/08
CHEMISTRY; METALLURGY
Abstract
An electrochemical reactor comprising an electrolyte compartment wherein at least one of the side walls of the electrolyte compartment is an electrode and an opposite side wall comprises a separator element. Further there is a plurality of electrically conductive granules forming a working electrode for a electrochemical main reaction in the electrolyte compartment and enclosed in the electrolyte compartment. The granules comprise a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element. The electrochemical reactor comprises a spacer element for maintaining the granules at least at a distance d from the separator element on the electrolyte-facing side of the separator element. The spacer element is electrically conductive and comprises a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element and is larger than the first activation overpotential.
Claims
1. A method for carrying out an electrochemical main reaction in an electrochemical reactor (10), said electrochemical reactor (10) comprising at least one electrolyte compartment (4) for receiving an aqueous electrolyte, wherein at least one of the side walls of said electrolyte compartment (4) is an electrode or a feeder electrode (1) and an opposite side wall comprises or consist of a separator element (2), a plurality of electrically conductive granules forming a working electrode (6) for the electrochemical main reaction in the electrolyte compartment (4) and enclosed in the electrolyte compartment (4), said granules comprising or consisting of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element (2), wherein the electrochemical reactor (10) further comprises a spacer element (5) for maintaining the conductive granules at least at a distance d from the separator element (2) on at least the electrolyte-facing side of the separator element (2), wherein the spacer element (5) is electrically conductive and wherein the spacer element (2) comprises or consists of a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element (2) and wherein the second activation overpotential is larger than the first activation overpotential.
2. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) of claim 1, wherein the second material exhibiting a second activation overpotential is non-metallic or the first material exhibiting a first activation overpotential is carbon.
3. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) of claim 1, wherein the second activation overpotential is larger than the first activation overpotential by at least 100 mV.
4. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the spacer element (5) is in the form of a woven or non-woven textile, a knit textile, or combinations thereof.
5. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the spacer element (5) is in the form of a foam.
6. The method for carrying out an electrochemical main reaction in an electrochemical reactor according to claim 1, wherein the second material of the spacer element (5) exhibits elasticity.
7. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the electrochemical side reaction is either one of the half reactions of electrolysis of water.
8. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the electrochemical main reaction is the reduction of indigo to leuco-indigo.
9. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the separator element (2) is a membrane.
10. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, further comprising a connecting frame (8) connecting the side wall comprising or consisting of a separator element (2) and side wall forming an electrode or feeder electrode (1) such as to form the electrolyte compartment (4), wherein the connecting frame (8) is made from a polymer.
11. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the plurality of electrically conductive granules forming a working electrode (6) for the electrochemical main reaction in the electrolyte compartment (4) form a dragged bed and/or the electrochemical reactor (10) is configured for periodically carrying out an inversion of the flow of electrolyte in the electrolyte compartment (4).
12. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, wherein the spacer element (5) has a thickness of from 1 mm to 10 mm, and/or in the electrolyte compartment (4) the opposed side walls are spaced by 1 to 10 cm.
13. An electrochemical reactor (10) for carrying out an electrochemical main reaction, said electrochemical reactor (10) comprising at least one electrolyte compartment (4) for receiving an aqueous electrolyte, wherein at least one of the side walls of said electrolyte compartment is an electrode or a feeder electrode (1) and an opposite side wall comprises or consist of a separator element (2), a plurality of electrically conductive granules forming a working electrode (6) for the electrochemical main reaction in the electrolyte compartment (4) and enclosed in the electrolyte compartment (4), said granules comprising or consisting of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element (2), characterized in that the electrochemical reactor (10) further comprises a spacer element (5) for maintaining the conductive granules at least at a distance d from the separator element (2) on at least the electrolyte-facing side of the separator element (2), wherein the spacer element (5) is electrically conductive and wherein the spacer element (5) comprises or consists of a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element (2) and wherein the second activation overpotential is larger than the first activation overpotential, and the electrochemical side reaction is either one of the half reactions of electrolysis of water.
14. The electrochemical reactor (10) for carrying out an electrochemical main reaction according to claim 13, wherein the electrochemical main reaction is the reduction of indigo to leuco-indigo.
15. A method of manufacturing an electrolyte compartment (4) of an electrochemical reactor (10) for carrying out an electrochemical reaction according to claim 13, said electrolyte compartment (4) being formed by a side wall comprising or consisting of a separator element (2), a side wall forming an electrode or a feeder electrode (1) and being the opposite side wall of the side wall comprising or consisting of a separator element (2), and a connecting frame (8) connecting the side wall comprising or consisting of a separator element (2) and side wall forming an electrode or feeder electrode (1), the method comprising the steps of: placing the side wall comprising or consisting of a separator element (2) in a horizontal plane, placing the connecting frame (8) onto the side wall comprising or consisting of a separator element (2) such as to form an interior space delimited by the side wall comprising or consisting of a separator element (2) and the connecting frame (8), filling the interior space such that it is filled essentially to the brim with a plurality of electrically conductive granules (6), placing the side wall forming an electrode or feeder electrode (1) onto the connecting frame (8), fastening the side wall comprising or consisting of a separator element (2), the side wall forming an electrode or feeder electrode (1) and the connecting frame (8) together, wherein on at least the inner space-facing side of the separator element (2), the separator element (2) is equipped with a spacer element (5) having a thickness d and/or wherein in the electrolyte compartment (4) the opposed side walls are spaced by 1 to 10 cm, wherein the plurality of electrically conductive granules (6) comprises or consist of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element (2) and wherein the spacer element (5) is electrically conductive and comprises or consists of an a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element (2), and wherein the second activation overpotential is larger than the first activation overpotential.
16. A method of manufacturing an electrolyte compartment of an electrochemical reactor for carrying out an electrochemical reaction according to claim 13, said electrolyte compartment being formed by a side wall comprising or consisting of a separator element, a side wall forming an electrode or a feeder electrode and being the opposite side wall of the side wall comprising or consisting of a separator element, and a connecting frame connecting the side wall comprising or consisting of a separator element and side wall forming an electrode or feeder electrode, the method comprising the steps of: placing the side wall comprising or consisting of a separator element (2) in a horizontal plane, placing the connecting frame (8) onto the side wall comprising or consisting of a separator element (2) such as to form an interior space delimited by the side wall comprising or consisting of a separator element (2) and the connecting frame (8), filling the interior space such that it is filled essentially to the brim with a plurality of electrically conductive granules (6), placing the side wall forming an electrode or feeder electrode (1) onto the connecting frame (8), fastening the side wall comprising or consisting of a separator element (2), the side wall forming an electrode or feeder electrode (1) and the connecting frame (8) together, wherein on at least the inner space-facing side of the separator element (2), the separator element (2) is equipped with a spacer element (5) having a thickness d of from 1 mm to 10 mm and/or wherein in the electrolyte compartment (4) the opposed side walls are spaced by 1 to 10 cm, wherein the plurality of electrically conductive granules (6) comprises or consist of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element (2) and wherein the spacer element (5) is electrically conductive and comprises or consists of an a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element (2), and wherein the second activation overpotential is larger than the first activation overpotential.
17. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) of claim 2, wherein the second material exhibiting a second activation overpotential is graphite and the first material exhibiting a first activation overpotential is anode-grade coke.
18. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 9, wherein the separator element (2) is a fluoropolymer membrane.
19. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 5, wherein the spacer element (5) is in the form of a foamed inert material.
20. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 5, wherein the spacer element (5) is in the form of an open-cell graphite foam.
21. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 7, wherein the electrochemical side reaction is the electrolytic generation of hydrogen gas from water.
22. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 10, further comprising a connecting frame (8) connecting the side wall comprising or consisting of a separator element (2) and side wall forming an electrode or feeder electrode (1) such as to form the electrolyte compartment (4), wherein the connecting frame (8) is made from a polyolefin.
23. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 1, further comprising a connecting frame (8) connecting the side wall comprising or consisting of a separator element (2) and side wall forming an electrode or feeder electrode (1) such as to form the electrolyte compartment (4), wherein the connecting frame (8) is made from an inorganic material.
24. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 23, further comprising a connecting frame (8) connecting the side wall comprising or consisting of a separator element (2) and side wall forming an electrode or feeder electrode (1) such as to form the electrolyte compartment (4), wherein the connecting frame (8) is made from a ceramic.
25. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 11, wherein the electrochemical reactor (10) is configured for periodically carrying out an inversion of the flow of electrolyte in the electrolyte compartment (4) every 2 to 30 minutes.
26. The method for carrying out an electrochemical main reaction in an electrochemical reactor (10) according to claim 12, wherein the spacer element (5) has a thickness of from 5 mm to 10 mm.
27. A method of manufacturing an electrolyte compartment of an electrochemical reactor for carrying out an electrochemical reaction according to claim 14, said electrolyte compartment being formed by a side wall comprising or consisting of a separator element, a side wall forming an electrode or a feeder electrode and being the opposite side wall of the side wall comprising or consisting of a separator element, and a connecting frame connecting the side wall comprising or consisting of a separator element and side wall forming an electrode or feeder electrode, the method comprising the steps of: placing the side wall comprising or consisting of a separator element (2) in a horizontal plane, placing the connecting frame (8) onto the side wall comprising or consisting of a separator element (2) such as to form an interior space delimited by the side wall comprising or consisting of a separator element (2) and the connecting frame (8), filling the interior space such that it is filled essentially to the brim with a plurality of electrically conductive granules (6), placing the side wall forming an electrode or feeder electrode (1) onto the connecting frame (8), fastening the side wall comprising or consisting of a separator element (2), the side wall forming an electrode or feeder electrode (1) and the connecting frame (8) together, wherein on at least the inner space-facing side of the separator element (2), the separator element (2) is equipped with a spacer element (5) having a thickness d of from 1 mm to 10 mm and/or wherein in the electrolyte compartment (4) the opposed side walls are spaced by 1 to 10 cm, wherein the plurality of electrically conductive granules (6) comprises or consist of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element (2) and wherein the spacer element (5) is electrically conductive and comprises or consists of an a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element (2), and wherein the second activation overpotential is larger than the first activation overpotential
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,
[0039]
[0040]
[0041]
DESCRIPTION OF PREFERRED EMBODIMENTS
[0042] It is an object of the present invention to provide an electrochemical reactor for carrying out an electrochemical main reaction, or a method for carrying out an electrochemical main reaction in said electrochemical reactor, comprising [0043] at least one electrolyte compartment for receiving an aqueous electrolyte, wherein at least one of the side walls of said electrolyte compartment is an electrode and an opposite side wall comprises or consist of a separator element, [0044] a plurality of electrically conductive granules forming a working electrode for the electrochemical main reaction in the electrolyte compartment and enclosed in the electrolyte compartment, said granules comprising or consisting of a first material exhibiting at least a first activation overpotential for an electrochemical side reaction within a distance d from the separator element,
characterized in that the electrochemical reactor further comprises [0045] a spacer element for maintaining the plurality of electrically conductive granules at least at a distance d from the separator element on at least the electrolyte-facing side of the separator element where the working electrode granules are comprised, wherein the spacer element is electrically conductive and wherein the spacer element comprises or consists of a second material exhibiting a second activation overpotential for the electrochemical side reaction within a distance d from the separator element and wherein the second activation overpotential is larger than the first activation overpotential.
[0046] In a preferred embodiment, the second activation overpotential is larger, i.e. more negative or more positive, than the first activation overpotential by at least 100 mV, preferably by at least 200 mV or 200 mV to 400 mV, more preferably by at least 250 mV or 200 mV to 350 mV.
[0047] The electrochemical reactor according to the present invention is not limited to a particular application such as the electrochemical reduction or oxidation of vat dyes. Nonetheless, the electrochemical reduction of vat dyes is an application where the benefits of using electrochemical reactors instead of aggressive chemical agents results in both environmental and economic benefits, especially when the electrochemical reactor can be run at higher efficiency as is the case in the electrochemical reactor of the present invention.
[0048] In a preferred embodiment, the spacer element may be formed from any suitable electrically conductive material such as metals, in particular noble metals or may be formed from a non-metallic material that is electrically conductive. In a more preferred embodiment, the spacer element is formed from a non-metallic material that is electrically conductive, such as carbon, and in particular from graphite. Alternatively, the non-metallic material may be a polymer such as carbon filled fluoropolymer. An example of such polymer such as carbon filled fluoropolymer is graphite filled PTFE.
[0049] In a preferred embodiment, the plurality of electrically conductive granules may fill the entire the electrolyte compartment or may fill a part of the electrolyte compartment.
[0050] In a preferred embodiment, the spacer element for maintaining the plurality of electrically conductive granules at least at a distance d from the separator element shields essentially the entire surface of the electrolyte-facing side of the separator element where the working electrode granules are comprised. This may be of particular advantage in an electrochemical cell in which a dragged bed of working electrode granules is used and in which the direction of flow of the electrolyte in the electrolyte compartment is periodically inverted during operation of the electrochemical reactor. In general, the electrolyte compartment is then filled in part with electrically conductive granules. Such separator element configuration may nonetheless be used in a packed bed electrochemical reactor, for example when the entire electrolyte compartment is essentially filled up with electrically conductive granules of the working electrode.
[0051] In a preferred embodiment, the spacer element for maintaining the plurality of electrically conductive granules at least at a distance d from the separator element shields an upper and/or lower surface of the electrolyte-facing side of the separator element where the working electrode granules are comprised. This may be of advantage in terms of material used in in an electrochemical cell in which a dragged bed of working electrode granules is used and in which the direction of flow of the electrolyte in the electrolyte compartment is periodically inverted during operation of the electrochemical reactor.
[0052] The aqueous electrolyte may be an aqueous solution or an aqueous dispersion. In the case of a vat dye such as for example indigo, the electrolyte is an aqueous dispersion or solution of the vat dye such as for example an aqueous dispersion of indigo.
[0053] In the case where the aqueous electrolyte is an aqueous solution or an aqueous dispersion of a vat dye, the aqueous electrolyte preferably has a basic pH.
[0054] The non-aqueous electrolyte may be a non-aqueous solution or a non-aqueous dispersion.
[0055] The plurality of electrically conductive granules forming a working electrode may be formed by granules having a diameter of at least or of from 0.25 to 1.5 mm, preferably of from 0.5 mm to 1 mm.
[0056] It is understood that the spacer element, in its various forms, is chosen such that the porosity of the spacer element is such that it does not allow the granules of the working electrode to penetrate into the bulk of the spacer element.
[0057] In a much preferred embodiment of the electrochemical reactor for carrying out an electrochemical main reaction, the at least one electrolyte compartment for receiving an aqueous or non-aqueous electrolyte is formed by an electrode forming one side wall of said electrolyte compartment and a separator fluoropolymer membrane forming an opposite side wall, where the said opposed side walls are connected through a polymer or ceramic frame and the working electrode if formed by granules of anode-grade coke granules for the electrochemical reduction of a vat dye such as indigo enclosed in the electrolyte compartment and the electrochemical reactor further comprises a graphite felt spacer element on the electrolyte-facing side of the fluoropolymer membrane for maintaining the anode-grade coke granules at a distance of at least 2 mm or 2 mm to 10 mm; or at least 5 mm or of from 5 mm to 10 mm, from the fluoropolymer membrane separator element.
[0058] In an embodiment, the electrochemical reactor according to the present invention, can be assembled by placing a side wall comprising or consisting of a separator element in a horizontal plane, fastening the connecting frame to the separator element such as to form a recess, filling the recess essentially to the brim with a plurality of electrically conductive granules that will form the working electrode, and fastening a side wall forming an electrode.
[0059] An electrochemical reactor is capable of carrying out several electrochemical reactions, depending on the chemical nature of the electrolyte, and on the voltage and/or current applied. Exemplary reactions include the reduction or oxidation of vat dyes. A common vat dye is indigo, which can be reduced to leuco-indigo.
Example
Comparative Setup
[0060] An electrochemical reactor having an anolyte compartment and a catholyte compartment, which compartments are separated by a cation-exchange separator membrane of fluoropolymer (commercially available under the trademark NAFION) is used.
[0061] The anolyte compartment is formed by a stainless steel plate acting as anode, acting as feeder electrode, which forms one wall of the anolyte compartment and by the membrane of fluoropolymer which forms the opposite wall of the anolyte compartment. The dimensions of both anode and membrane are 12.5 cm by 40 cm, and the distance between membrane and anode is of 2 cm. The anolyte compartment has thus a volume of, 12.5×40×2 cm and an anolyte of aqueous 3 M NaOH solution is circulated.
[0062] The catholyte compartment is formed by a stainless steel plate acting as supply cathode for supplying the working cathode consisting of a dragged bed of carbon granules made from anode-grade coke with current. Depending on the direction of flow of the catholyte, the dragged bed is formed against the top or the bottom of the catholyte compartment. Each five minutes, the direction of flow is inverted. The stainless steel plate acting as feeder electrode forms one wall of the catholyte compartment and the membrane of fluoropolymer forms the opposite wall of the catholyte compartment. The dimensions of both supply cathode and membrane are 12.5 cm by 40 cm, and the distance between membrane and supply cathode is of 4 cm. The catholyte compartment has thus a volume of, 12.5×40×4 cm, in which an catholyte of aqueous 1.3 M NaOH solution containing 10 weight percent of particulate indigo is circulated at a flow rate of 1 l/min.
[0063] The potential applied between the anode and the supply cathode is increased until gaseous hydrogen is formed. The onset of hydrogen formation indicates the maximum permissible voltage at which the electrochemical cell can be operated to ensure that the main reaction, i.e. the reduction of indigo towards leuco-indigo, can be run efficiently and stably.
[0064] In this comparative setup, the voltage at which the hydrogen formation started was 2.6 V for a current of 20 A.
Inventive Setup
[0065] The same electrochemical reactor was used, except that the electrochemical reactor was equipped with a non-woven graphite textile (a felt) mat having a thickness of 5 mm on the cation-exchange membrane on the side facing the catholyte compartment, thereby impeding the granules of the working electrode to come into a proximity of less than essentially 5 mm of the membrane.
[0066] In this setup according to the present invention, the voltage at which the hydrogen formation started was 2.6 V for a current of 20 A.
[0067] It is apparent that the insertion of a spacer element made from an electrochemically inert material, such as a mat of carbon felt, preventing the granules of the working electrode from coming into proximity of the separator membrane, while at the same being electrically conductive and porous such as to allow for mass transfer allows to dramatically increase the performance of the electrochemical cell.
[0068]
[0069] As can be seen from
[0070] In contrast, when a spacer element is used according to the inventive setup, the electrochemical reactor could be stably run at approximately 90% of the maximum settings of 36 A/3.3 V. As can be seen from
[0071] Thus, an electrochemical reactor according to the inventive setup can in general be run more effectively than an electrochemical reactor according to the comparative setup.
LIST OF REFERENCE SIGNS
[0072]
TABLE-US-00001 1 electrode 2 separator membrane 3 electrolyte inlet 4 electrolyte compartment 5 spacer element 6 working electrode granules 7 electrolyte outlet 8 frame 9 gasket 10 electrochemical reator