NARROW GAP, UNDIVIDED ELECTROLYSIS CELL
20180187316 ยท 2018-07-05
Inventors
Cpc classification
C25B9/63
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
Abstract
An undivided electrolysis cell for electrolyzing a liquor is disclosed which has a narrow gap between the electrodes and improved energy efficiency. The electrolysis cell comprises a porous anode, a porous cathode, and an electrically insulating separator therebetween which are all permeable to the liquor. Electrolysis is performed while directing the liquor through the porous anode, the electrically insulating separator, and the porous cathode. Gas products generated during electrolysis are carried out with the liquor and do not remain between the electrodes thereby reducing gas blinding. The electrolysis cell is particularly suitable for chlorate electrolysis.
Claims
1. An undivided electrolysis cell for electrolyzing a liquor comprising: a porous anode permeable to the liquor; a porous cathode permeable to the liquor; an electrically insulating separator between the anode and cathode and permeable to the liquor; an anode compartment whose surface comprises the porous anode and an anode current carrier electrically connected to the porous anode; a cathode compartment whose surface comprises the porous cathode and a cathode current carrier electrically connected to the porous cathode; a liquor inlet at the bottom of an inlet compartment wherein the inlet compartment is one of the anode compartment and the cathode compartment; and a liquor and gas product outlet at the top of an outlet compartment wherein the outlet compartment is that one of the anode compartment and the cathode compartment other than the inlet compartment.
2. The electrolysis cell of claim 1 wherein the inlet compartment is the anode compartment and the outlet compartment is the cathode compartment.
3. The electrolysis cell of claim 1 wherein the electrolysis cell is a chlorate electrolysis cell and the liquor comprises NaCl and water.
4. The electrolysis cell of claim 1 wherein the porous anode is made of expanded metal or louvered metal.
5. The electrolysis cell of claim 4 wherein the anode metal is titanium.
6. The electrolysis cell of claim 1 wherein the porous cathode is made of expanded metal or louvered metal.
7. The electrolysis cell of claim 6 wherein the cathode metal is a nickel-free stainless or mild steel.
8. The electrolysis cell of claim 1 wherein the electrically insulating separator is selected from the group consisting of porous polymer sheet, polymer buttons, and a gap.
9. The electrolysis cell of claim 8 wherein the electrically insulating separator is a porous fluoropolymer sheet.
10. The electrolysis cell of claim 1 wherein the distance between the anode and the cathode is less than about 2 mm.
11. The electrolysis cell of claim 1 wherein the flow resistance of at least one of the separator and the cathode is greater than the flow resistance of the anode.
12. The electrolysis cell of claim 1 wherein the anode current carrier is pan shaped and comprises a set of formed features.
13. The electrolysis cell of claim 1 wherein the porous anode is electrically connected to the anode current carrier by a set of electrically conductive fingers.
14. The electrolysis cell of claim 1 wherein the cathode current carrier is pan shaped and comprises a set of formed features.
15. The electrolysis cell of claim 1 wherein the porous cathode is electrically connected to the cathode current carrier by a set of electrically conductive fingers.
16. The electrolysis cell of claim 1 wherein the cathode compartment comprises features for directing gas product upwards towards the gas product outlet.
17. The electrolysis cell of claim 1 comprising no other inlet in either the anode or the cathode compartments and no outlet in the anode compartment.
18. The electrolysis cell of claim 1 comprising a vent in the anode compartment.
19. The electrolysis cell of claim 1 comprising a drain in the cathode compartment.
20. An electrolyzer comprising a plurality of the electrolysis cells of claim 1 stacked in a bipolar arrangement.
21. The electrolyzer of claim 20 wherein the anode current carriers in the electrolysis cells are pan shaped and comprise a set of formed features, the cathode current carriers in the electrolysis cells are pan shaped and comprise a set of formed features, and the set of features in the anode current carriers nests with the set of features in adjacent cathode current carriers in the bipolar arrangement.
22. The electrolyzer of claim 20 wherein the electrolysis cells are stacked such that the anodes and cathodes in the cells are oriented at an angle greater than zero with the vertical.
23. The electrolyzer of claim 22 wherein the electrolysis cells are stacked such that the anodes and cathodes in the cells are oriented perpendicular to the vertical.
24. The electrolyzer of claim 20 wherein the electrolysis cells are modules and the electrolyzer is modular.
25. A method for the undivided electrolysis of a liquor comprising: providing the electrolysis cell of claim 1; directing the liquor to the liquor inlet in the inlet compartment and into the inlet compartment; directing the liquor in a direction through the porous anode, through the electrically insulating separator, and through the porous cathode; directing the liquor into the outlet compartment; applying an electrolysis voltage and current across the anode and cathode current carriers during the directing of the liquor; and directing the liquor and gas product out from the liquor outlet in the outlet compartment.
26. The method of claim 25 comprising recirculating the liquor from the liquor outlet in the outlet compartment to the liquor inlet in the inlet compartment.
27. The method of claim 25 for the production of sodium chlorate wherein the liquor comprises NaCl and water, and wherein the gas product is hydrogen.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
DETAILED DESCRIPTION
[0029] Unless the context requires otherwise, throughout this specification and claims, the words comprise, comprising and the like are to be construed in an open, inclusive sense. The words a, an, and the like are to be considered as meaning at least one and not limited to just one.
[0030] In addition, the following definitions are intended. In a numerical context, the word about is to be construed as meaning plus or minus 10%.
[0031] As mentioned before, an electrolysis cell may either be a divided type or an undivided type of cell. In both, certain ions may travel between the electrodes. A divided cell however is one in which the cathode and anode sides of the cell are separated (divided) in some manner such that most or all of the reactants and products on each side of the cell are kept separate. An undivided cell is one in which the cathode and anode sides of the cell are not separated (undivided) and the reactants and products on each side of the cell can mix.
[0032] Herein, the term electrically insulating separator is used in the context of an undivided electrolysis cell and refers to any of the various materials, components, or means for providing electrical separation between the anode and cathode electrodes. It thus can include porous sheet materials, spacers such as buttons, or simply a gap (i.e. a space) between the electrodes.
[0033] The term louvered is used in the context of the porous cell electrodes and refers to an electrode comprising a series of angled openings (thereby rendering the electrode porous) which are typically spaced at regular intervals (e.g. suggestive of window blinds).
[0034] The present invention relates to improved designs and methods for operating undivided electrolysis cells in order to obtain better energy efficiency. It is particularly suitable for use in chlorate electrolysis.
[0035] A schematic of a cell unit for an exemplary bipolar chlorate electrolyzer in the prior art is shown in
[0036] A bipolar electrolyzer is then made by combining two or more cell units 1 in a series stack, i.e. the flat side of anode carrier plate 2 from one cell unit is attached to the flat side of cathode carrier plate 3 from a second cell unit. (Typically, the carrier plates are welded together, for instance by explosive bonding because dissimilar metals are used for each polarity.) This kind of bipolar arrangement is known in the art as a multi-monopolar configuration.
[0037] The liquor for chlorate electrolysis primarily contains sodium chloride in aqueous solution. However, the liquor is usually recirculated and thus comprises a certain amount of the products of electrolysis and also products of subsequent chemical reaction (e.g. sodium hypochlorite, sodium chlorate, chlorine and hydrogen gases). Further, certain additives (e.g. sodium dichromate) are also usually included to enhance chlorate formation. In operation, this liquor is supplied at the bottom of the numerous electrolysis cells (indicated by arrow 6 in
[0038]
2NaCl.fwdarw.Cl.sub.2+2e.sup.+2Na.sup.|1)
[0039] At cathode plate 5, electrochemical reaction 2) occurs:
2H.sub.2O+2e.sup..fwdarw.H.sub.2+2OH.sup.2)
[0040] Because the electrolysis products and liquor are not kept apart or divided, while the liquor travels between the cell electrodes, the chlorine produced by electrolysis reacts quickly with components in the liquor according to chemical reaction 3):
2Na.sup.++2OH.sup.+Cl.sub.2.fwdarw.Na.sup.+Cl.sup.+Na.sup.+OC.sup.+H.sub.2O 3)
[0041] As illustrated in
NaCl+3H.sub.2O.fwdarw.NaClO.sub.3+3H.sub.24)
[0042] To a certain extent, hydrogen bubbles 8 interfere with the electrolysis process by increasing the effective resistance of the liquor electrolyte between the electrodes and/or by gas blinding (wherein access to the cathode surface is blocked). Thus, the gap between anode plate 4 and cathode plate 5 cannot be made too small without experiencing a substantial negative effect due to these effects.
[0043] In a chlorate electrolysis cell of the invention however, the generated hydrogen gas is quickly removed from between the anode and cathode electrodes and out of the electrolysis region. Any increase in electrolyte resistance and gas blinding is significantly reduced and the electrodes can be brought much closer together, thereby reducing the liquor electrolyte resistance between the electrodes and increasing energy efficiency. In order to further reduce any negative effects arising from the presence of hydrogen bubbles between the electrodes, it can be beneficial to increase the pressure drop across the electrolysis cell which in turn can advantageously prevent back migration of hydrogen into the spaces between the electrodes. Such an increased pressure drop can be engineered into the electrolysis cell generally by selecting the cell components such that the flow resistance of at least one of the separator and the cathode is greater than the flow resistance of the anode. As will be readily apparent to those in the art, this can be achieved for instance via appropriate modifications to the relative pore characteristics in these various components.
[0044] An improved chlorate electrolysis cell of the invention is shown in the schematic of
[0045] Further, electrolysis cell 10 comprises seals 21 at both top and bottom which seal to anode pan 12, anode 14, cathode 15, and cathode pan 13. The sealed anode 14 and anode pan 12 thus form the surface of an anode compartment for the chlorate liquor. In a like manner, the sealed cathode 15 and cathode pan 13 form the surface of a cathode compartment for the chlorate liquor. In the embodiment shown in
[0046] In electrolysis cell 10, the liquor is forced through porous anode 14 and then porous cathode 15 instead of travelling upwards between anode plate 4 and cathode plate 5 as in the prior art cell of
[0047] Both anode 14 and cathode 15 are desirably quite permeable to the liquor. As mentioned previously however, it may be advantageous for the former to be more permeable than the latter to introduce a desirable pressure drop in the cell. While various design options are available, use of expanded metals for either or both of these electrodes is a convenient choice. Alternatively, and as more clearly shown for both anode 14 and cathode 15 in
[0048] Porous, electrically insulating separator 11 is also desirably quite permeable to the liquor. Further, it should be compatible with the chemical reactants and products. And any means for achieving a reliable, insulating separation may be employed. For instance, separator 11 can simply be a gap between the electrodes. However, to obtain narrow gaps while still maintaining reliable electrical separation between the electrodes, it is generally desirable to employ some porous, electrically insulating spacing material. For instance, a number of polymer buttons may be used to space anode 14 and cathode 15 apart. Or, in one desirable embodiment, a porous polymer sheet is used because such sheets can be made quite thin yet robust and allow for distances between the anode and cathode of less than about 2 mm (a typical minimum in conventional chlorate electrolysis cells relying on a gap). A variety of fluoropolymers can be used as suitable materials for separator 11 because they are capable of withstanding the corrosive, demanding environment in the electrolyzes. Alternatively, certain ceramics can be used as suitable materials for separator 11. Materials may have hydrophobic surface properties. Alternatively, hydrophilic materials may further improve performance by reducing hydrogen disengagement.
[0049] In
[0050] Anode pan 12 and cathode pan 13 can comprise sets of complementary features which have been formed therein for purposes of providing structural strength and of locating and electrically connecting cells during assembly into a multi-cell bipolar electrolyzer. In
[0051]
[0052] Operation of the chlorate electrolysis cells of
[0053] Electrolysis cells of the type shown in
[0054] In bipolar electrolyzer 30, four chlorate electrolysis cells 10 are stacked such that the anodes 14 and cathodes 15 in the cells therein are oriented vertically. Additionally, electrolysis cells 10 are stacked such that complementary features 12a in anode pans 12 nest with features 13a in adjacent cathode pans 13 and thereby ensure that the cells are located well with respect to each other and are well connected electrically. An advantage of the invention is that the electrolysis cells can be made as modules and thus may be readily removed and exchanged as desired.
[0055] In the embodiment shown in
[0056] A different exemplary orientation for the cells in a bipolar electrolyzer of the invention is shown in
[0057] Electrolyzers of the type shown in
[0058] Merchant chlorate production system 50 is relatively complex and in sequence comprises salt and water feed 51, brine saturator 52, guard filter 53, ion exchange subsystem 54, brine line 55, chlorate reactor 56, liquor inlet line 57, chlorate electrolyzer 58 of the invention, collected liquor outlet line 59, chlorate crystallization subsystem 61 and line 62 which are interconnected as shown. Brine for electrolysis is prepared in brine saturator 52. A suitable source of salt (e.g. evaporated salt) and a supply of demineralised water is provided at salt and water feed 51. From there, brine is directed via brine line 55 to guard filter 53, then to ion exchange subsystem 54 and finally to chlorate reactor 56 where it is mixed with the product from chlorate electrolyzer 58 to maintain the salt content in the electrolyzer feed. Chlorate reactor 56 directs an electrolyte solution for electrolysis comprising both chlorate and brine to chlorate electrolyzer 58 via liquor inlet line 57. And electrolyzed chlorate solution from chlorate electrolyzer 58 is directed back to chlorate reactor 56 via collected liquor outlet line 59. The hydrogen gas produced is removed via line 60.
[0059] Concentrated product chlorate solution from chlorate reactor 56 is directed to chlorate crystallization subsystem 61 where chlorate product is crystallized out from the more concentrated chlorate solution and removed at 62. The leftover solution after crystallizing is recirculated back to chlorate reactor 56 via recirculation line 63. Over time, impurities can accumulate in recirculation line 56. These impurities may be removed in a variety of ways. For instance, chlorate electrolysis system 50 in
[0060] Electrolyzers of the invention may also be employed in chlorate production systems or subsystems other than merchant chlorate production systems like that shown in
[0061] The method of the invention is particularly suitable for use in chlorate electrolysis. However, any process involving undivided electrolysis may benefit from the designs and methods of the invention, e.g. hypochlorite production, perchlorate production, potassium permanganate production. Further, use of the invention can provide greater flexibility in the design and/or configuration of the electrolyzers employed. For instance, conventional chlorate electrolyzers have practical limits on cell height arising from the amount of generated hydrogen gas. However, such limitations may not apply to electrolyzers of the invention, and thus higher cells may be considered in practical embodiments.
[0062] The following Examples have been included to illustrate certain aspects of the invention but should not be construed as limiting in any way.
EXAMPLES
[0063] Laboratory type chlorate electrolysis cells were made and operated to compare the characteristics of a cell of the invention to those of a conventional cell.
[0064] An inventive electrolysis cell was made comprising a pan-shaped anode compartment and a pan-shaped cathode compartment. Both compartments were made of grade 2 titanium and had dimensions of about 38 cm in width, 23 cm in height and 2.2 cm in depth. A cell assembly comprising a porous anode, a porous cathode, and an electrically insulating separator therebetween was sandwiched together between the lips of the pan-shaped anode and cathode compartments. The lips of the anode and cathode compartments directly contacted the edges of the anode and cathode respectively and thus were electrically connected thereto to serve as anode and cathode current carriers respectively. The separator extended slightly beyond the edges of the anode and cathode. The electrolysis cell was sealed by bolting together suitably shaped gaskets between the extended separator edge and the lips of the anode and cathode compartments.
[0065] Both the anode and cathode employed substrates which were made of expanded titanium mesh (approximately 1 mm thick, with diamond shaped openings in which the diamond dimensions were about 3 mm by 1.5 mm, and an open area 50%) thus rendering both anode and cathode permeable to cell liquor. Prior to assembly, both substrates were treated by sandblasting and an acid etching process, and then coated with catalyst comprising mixed metal oxides (mainly RuO.sub.2, IrO.sub.2, and TiO.sub.2).
[0066] An expanded PTFE mesh was used as the cell separator, thus rendering the separator permeable to cell liquor. The PTFE mesh was about 0.95 mm thick and had diamond shaped openings whose dimensions were about the size of those of the anode and cathode substrates. In addition however, to improve flow and performance, additional larger openings were cut out from the separator. Specifically, nine evenly-spaced rectangular openings (about 32 mm by 83 mm in size) were cut out from the separator surface.
[0067] The active surface of the cell assembly (i.e. the surface within the seal of the electrolysis cell) had dimensions of about 10 cm by 25 cm. The electrolysis cell was oriented vertically and had three liquor inlets at the bottom of the anode compartment, and three liquor and gas product outlets at the top of the cathode compartment. These liquor inlets and outlets were evenly spaced and about 13 mm in diameter. Liquor distributors were employed within each of the anode and cathode compartments to achieve a more even flow of cell liquor into and out from the electrolysis cell. The anode and cathode distributors were located in the compartments immediately adjacent the liquor inlets and outlets respectively. Both distributors were about 16 mm22 mm25 cm in size and each comprised 8 evenly spaced distribution holes about 6 mm in diameter.
[0068] A comparative electrolysis cell was constructed in a similar manner to a conventional chlorate electrolysis cell (e.g. to operate as represented by
[0069] The electrolyte used for test purposes was a convention chlorate solution having a composition of NaClO.sub.3/NaCl/Na.sub.2Cr.sub.2O.sub.7 in concentrations of 450/110/5 gpl. In the inventive electrolysis cell, electrolyte flowed in the liquor inlets at the bottom of the anode compartment, through the liquor distributor therein, through the porous anode, the porous separator, and the porous cathode, and then out through the liquor distributor in the cathode compartment, and finally out the top of the cathode compartment. In the comparative cell, electrolyte flowed in from the liquor inlet at the cell bottom, through the gap between anode and cathode, and then out the liquor outlet at the cell top. The cells were initially conditioned for 4.5 days by operating at a current density of 3 kA/m.sup.2 (based on active area of electrodes), a pH of 6, and a temperature of 80 C. Thereafter, the temperature of the electrolyte was raised to 90 C. and polarization results (i.e. voltage versus current density) were obtained for each cell over a range of current densities from 0.5 to 5 kA/m.sup.2. The electrolyte flow rate used was about 100 l/h.
[0070]
[0071] All of the above U.S. patents, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification, are incorporated herein by reference in their entirety.
[0072] While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood, of course, that the invention is not limited thereto since modifications may be made by those skilled in the art without departing from the spirit and scope of the present disclosure, particularly in light of the foregoing teachings. Such modifications are to be considered within the purview and scope of the claims appended hereto.