This application is a U.S. National Stage Entry of International Patent Application No. PCT/JP2017/021864, filed Jun. 13, 2017, which claims priority to Japanese Patent Application No. JP 2016-118157, filed Jun. 14, 2016, the entire contents of both of which are incorporated herein by reference.
The present disclosure generally relates to electrolytic cells, including electrolytic cells with elastic members that cause little damage to membranes.
In an electrolytic cell used in electrolysis of an aqueous solution, the voltage necessary for electrolysis is influenced by various factors. Among such factors, the interval between the anode and the cathode greatly affects the electrolytic cell voltage. Thus, the amount of energy consumption required for electrolysis is reduced by decreasing the interval between the electrodes to decrease the electrolytic cell voltage. In an ion-exchange membrane electrolytic cell or the like used in electrolysis of a salt solution, the anode, ion-exchange membrane, and the cathode are arranged in a closely fitted state so as to reduce the electrolytic cell voltage. However, in a large electrolytic cell in which the electrode surface area may reach several square meters, in the case that the anode and the cathode are bonded to the electrode chambers by a rigid member, it has been difficult to closely fit the electrodes to the ion-exchange membrane and decrease the electrode interval to retain it at a prescribed value without applying excessive pressure to the ion-exchange membrane.
In order to overcome such problems, an electrolytic cell has been proposed in which a flexible electrode is used for at least one of the anode and the cathode so that the interval between the electrodes is adjustable.
Japanese Patent Publication No. JP 2004-2993 A proposes providing an elastic member and a flexible electrode in at least one of the electrode chambers. The elastic member has a structure including a support member disposed on an electrolytic partition wall and a plurality of pairs of comb-like flat spring-like bodies extending in an inclined manner from the support member, and the comb-like flat spring-like bodies of each pair are inserted so the adjacent flat spring-like bodies mutually oppose each other. By installing the above-described elastic body, the electrode surface can be kept smooth even when using an electrode with a large surface area, and damage to the ion-exchange membrane due to positional deviation of the electrode and excessive pressure applied to the surface of the ion-exchange membrane can be reduced.
However, even in the ion-exchange membrane electrolytic cell proposed in Japanese Patent Publication No. JP 2004-2993 A, it was difficult to completely prevent damage to the ion-exchange membrane. Further, due to the shape of the electrode, there were cases in which the voltage rose when the electrode was combined with the elastic member of Japanese Patent Publication No. JP 2004-2993 A. In addition, further reductions in the electrolytic voltage were desired in order to reduce the operational costs.
Thus a need exists for an electrolytic cell that prevents, or at least minimizes, damage to a membrane such as an ion-exchange membrane or a diaphragm and that can reduce the electrolytic voltage compared to conventional electrolytic cells.
Although certain example methods and apparatus have been described herein, the scope of coverage of this patent is not limited thereto. On the contrary, this patent covers all methods, apparatus, and articles of manufacture fairly falling within the scope of the appended claims either literally or under the doctrine of equivalents. Moreover, those having ordinary skill in the art will understand that reciting “a” element or “an” element in the appended claims does not restrict those claims to articles, apparatuses, systems, methods, or the like having only one of that element, even where other elements in the same claim or different claims are preceded by “at least one” or similar language. Similarly, it should be understood that the steps of any method claims need not necessarily be performed in the order in which they are recited, unless so required by the context of the claims. In addition, all references to one skilled in the art shall be understood to refer to one having ordinary skill in the art.
In some examples, an elastic member may be provided on an electrolytic partition wall of the electrolytic cell with a prescribed structure.
In some examples, an electrolytic cell may include an anode chamber accommodating an anode; a cathode chamber accommodating a cathode; an electrolytic partition wall that partitions the anode chamber and the cathode chamber; and an elastic member attached to the electrolytic partition wall within at least one of the anode chamber and the cathode chamber. The elastic member may have a spring retaining part including a bonding part that is bonded to the electrolytic partition wall; a pair of first support parts that extend from the bonding part in an opposite direction of the electrolytic partition wall, and that are arranged parallel to each other; a second support part that connects the ends of the pair of first support parts to each other; and two spring rows extending in a direction parallel to a parallel arrangement direction of the pair of first support parts. Each spring row may be formed by combining a plurality of first flat spring-like bodies which originate from the first support part as a starting point and extend toward the opposite direction of the electrolytic partition wall, and a plurality of second flat spring-like bodies which originate from the second support part as a starting point and extend toward the opposite direction of the electrolytic partition wall.
Each first flat spring-like body is preferably bent toward the other first support part of the pair of first support parts at a position which is the same distance as that from the bonding part to a connecting part of the first support part and the second support part. Furthermore, each first flat spring-like body preferably extends parallel to a direction in which the first support parts extend in the opposite direction of the electrolytic partition wall to a position which is the same distance as that from the bonding part to the connecting part of the first support part and the second support part, and then is preferably bent toward the other first support part of the pair of first support parts at a position which is the same distance as that from the bonding part to the connecting part.
Each spring row preferably includes a spring unit in which the plurality of the first flat spring-like bodies and the plurality of second flat spring-like bodies are arranged alternately.
Distal ends of the first flat spring-like bodies and distal ends of the second flat spring-like bodies preferably form a bent shape which is convex toward the opposite direction of the electrolytic partition wall in a longitudinal direction cross-section view.
Distal ends of the first flat spring-like bodies and distal ends of the second flat spring-like bodies preferably form a bent shape which is convex toward the opposite direction of the electrolytic partition wall in a cross-section view of a plane that is orthogonal to the longitudinal direction.
The example electrolytic cells of the present disclosure cause little damage to a membrane such as an ion-exchange membrane or a diaphragm and simultaneously can suppress the damage of the electrodes compared to conventional electrolytic cells. Further, the surface pressure can be appropriately adjusted by the above-described elastic member, and thus the electrolytic voltage can be reduced.
The form of the anode 2 and the cathode 4 is not particularly limited. For example, expanded metal, a net-like body, and a woven body can be used. As the cathode 4, a cathode in which an electrode catalytic substance such as a platinum group metal-containing layer, a Raney nickel-containing layer, or an activated carbon-containing nickel layer is coated onto the surface of a substrate made of nickel or nickel alloy of the above-mentioned forms may be used. As the anode 2, an anode constituted by coating an electrode catalytic substance containing a platinum group metal or an oxide of a platinum group metal onto the surface of a substrate of the above-mentioned forms which is made of a thin-film-forming metal such as titanium, tantalum, or zirconium or an alloy thereof may be used.
In the electrolytic cell unit 1, an anode retaining member 7 is disposed within the anode chamber 3. The anode retaining member 7 is bonded by welding to the anode 2 and the electrolytic partition wall 6. Thereby, the anode 2 and the electrolytic partition wall 6 are electrically connected via the anode retaining member 7.
In the electrolytic cell unit 1, an elastic member 10 is disposed within the cathode chamber 5. The elastic member 10 is constituted by a plurality of spring retaining parts 30 and two spring rows 40 provided on each spring retaining part 30. The elastic member 10 contacts the electrolytic partition wall 6. The spring rows 40 contact the cathode 3. Thereby, the cathode 3 and the electrolytic partition wall 6 are electrically connected via the elastic member 10.
The electrolytic cell of a suitable embodiment of the present invention is assembled for use by laminating a plurality of the electrolytic cell units 1 via a membrane 8 such as an ion-exchange membrane or diaphragm.
In the example of
Each spring retaining part 30 has two spring rows 40. The spring rows 40 extend in the direction in which the pair of first support parts 31 are disposed parallel to each other. In other words, the spring rows 40 extend in a direction orthogonal to the direction in which the plurality of spring retaining parts 30 are arranged within the elastic member 10.
One spring row 40 is constituted by combining a plurality of first flat spring-like bodies 41 and a plurality of second flat spring-like bodies 42. The first flat spring-like bodies 41 and the second flat spring-like bodies 42 are arranged in a comb-like fashion in the direction in which the pair of first support parts 31 are disposed parallel to each other, i.e. in the direction orthogonal to the direction in which the plurality of spring retaining parts 30 are arranged. Within one spring row 40, a row of the first flat spring-like bodies 41 and a row of the second flat spring-like bodies 42 are parallel to each other.
The first flat spring-like bodies 41 originate from the first support part 31 as a starting point and extend toward the opposite direction of the electrolytic partition wall 6. In other words, the first flat spring-like bodies 41 extend toward the cathode. The first flat spring-like bodies 41 originate from the inside of the first support part 31 as a starting point 41A, and are bent toward the other first support part 31 (in other words, in the direction of the second flat spring-like bodies 42 within the same spring row 40) at a position (hereinafter referred to as the “bending point 41B”) which is the same distance as that from the bonding part 20 to a connecting part of the first support part 31 and the second support part 32. In the example of
The second flat spring-like bodies 42 originate from the second support part 32 as a starting point and extend toward the opposite direction of the electrolytic partition wall 6. In other words, the second flat spring-like bodies 42 extend toward the cathode. In the example of
The elastic modulus of the first flat spring-like bodies 41 can be changed by changing the overall length, length of the inclined portion, amount of bending, etc. of the first flat spring-like bodies 41. The elastic modulus of the second flat spring-like bodies 42 can be changed by the overall length, amount of bending, etc. of the second flat spring-like bodies 42. The dimensions of the first flat spring-like bodies 41 and the second flat spring-like bodies 42 can be appropriately designed in consideration of the surface pressure from the elastic member 10 pressing on the electrode (the cathode in the illustrated example). In the present embodiment, the first flat spring-like bodies 41 are preferably longer than the second flat spring-like bodies 42.
In the present embodiment, the first flat spring-like bodies 41 and the second flat spring-like bodies 42 are arranged alternately in at least a portion within the spring row 40. In the example of
As an alternative example, the second flat spring-like bodies 42 may be continuous between adjacent spring groups 43, or the first flat spring-like bodies 41 and the second flat spring-like bodies 42 may be arranged alternately over the entirety of the spring row 40.
In the example of
In
Since the length and shape of the first flat spring-like bodies differ from those of the second flat spring-like bodies, they each have a different elastic modulus. By changing the dimensions of the spring-like bodies, the ratio of the numbers of the first flat spring-like bodies and the second flat spring-like bodies, etc., the elastic modulus of the elastic member as a whole can be changed. Therefore, it is possible to control to a desired surface pressure.
For example, the number of contact points with the electrode (the cathode 4 in the illustrated example) can be increased by providing two spring rows on a single spring retaining part. As a result, compared to the conventional elastic member disclosed in Patent Literature 1, the load applied per each flat spring-like body can be reduced even though the surface area of the elastic member is the same.
Given the above, the elastic member of the present embodiment can suppress the application of excessive pressure on the membrane, and can suppress damage to the electrode itself. Further, by appropriately controlling the surface pressure, the electrolytic voltage can be reduced.
Further, in order to lower the electrolytic voltage, it is preferable to uniformly press the anode and the cathode to the membrane and retain both electrodes so that they are closely fitted to the membrane. In order to make the pressure on the electrodes uniform, it is necessary to increase the number of spring-like bodies. The elastic member of the present embodiment can also reduce the operation costs of the electrolytic cell because both electrodes can be more uniformly fitted to the membrane compared to Patent Literature 1. In addition, the elastic member of the present embodiment can increase the number of spring-like bodies without requiring any complicated machining, and thus is also advantageous in terms of manufacturing costs compared to the elastic member of Patent Literature 1.
As is clear from
In the present embodiment, the distal end portions of both of the flat spring-like bodies may be bent in only the longitudinal direction, and the cross-section orthogonal to the longitudinal direction may be flat.
By bending the distal ends of the first flat spring-like bodies 41 and the second flat spring-like bodies 42 as shown in
In the electrolytic cell of the present embodiment, the sizes of the elastic member 10 and the first flat spring-like bodies 41 and the second flat spring-like bodies 42 can be determined according to the electrode surface area of the electrolytic cell, etc. The elastic member 10 can be produced by, for example, punching a metal sheet having a thickness of 0.1 mm to 0.5 mm and then continuously bending with a press-molding machine, etc. The size of the first flat spring-like bodies 41 and the second flat spring-like bodies 42 is, for example, 1 mm to 10 mm wide and 20 mm to 50 mm long.
In the above example, only two spring rows are aligned. However, the shape of the elastic member of the present embodiment is not limited thereto. For example, in between the two spring rows 40, a separate spring row in which two rows of the second flat spring-like bodies are arranged opposing each other may be formed.
In the above-described embodiment, a bipolar-type electrolytic cell unit was used. However, the elastic member explained in the present embodiment may be applied to a monopolar-type electrolytic cell.
In the above-described embodiment, the elastic member was provided in the cathode chamber 5, but the elastic member may also be provided in the anode chamber 3.
If the elastic member is provided in the cathode chamber 5, the elastic member is made of a material exhibiting good corrosion resistance in the environment within the cathode chamber 5. Specifically, for the material of the elastic member, nickel, nickel alloy, stainless steel, etc. may be used.
If the elastic member is provided in the anode chamber 3, a thin-film-forming metal such as titanium, tantalum, or zirconium or an alloy thereof may be used for the material of the elastic member.
In the case that the electrolytic cell of the present embodiment is used for electrolysis of an aqueous solution of an alkali metal halide, e.g. electrolysis of a salt solution, a saturated salt solution is supplied to the anode chamber 3, water or a weak sodium hydroxide aqueous solution is supplied to the cathode chamber 5, electrolysis is carried out at a predetermined decomposition rate, and then the solution after electrolysis is removed from the electrolytic cell. In electrolysis of a salt solution using an ion-exchange membrane electrolytic cell, the electrolysis is carried out in a state in which the pressure of the cathode chamber 5 is retained higher than the pressure of the anode chamber 3 so that the membrane 8 is closely fitted to the anode 2. In the present embodiment, the cathode 4 is retained by the elastic member 10, and thus the electrolysis can be carried out with the cathode 4 positioned close to the surface of the membrane 8 by a predetermined distance. Further, the elastic member 10 according to the present embodiment has a large restoring force, and thus even if the pressure on the anode chamber 3 side has increased during an abnormality, operation in which the predetermined interval is maintained after the pressure has been removed is possible.
Examples of the present invention will be explained in detail below, but these examples are merely for the purpose of suitably explaining the present invention, and the present invention is not limited in any way to these examples.
An elastic member of the type shown in
Elastic Member
Bonding part: 9 mm
First support part: 12 mm
Second support part: 47 mm
Number of flat spring-like bodies per electrode unit surface area (total number of first flat spring-like bodies and second flat spring-like bodies): 9600/m2
First Flat Spring-Like Bodies
Length from starting point (reference sign 41A in
Length of parallel portion (portion parallel to second support part; reference sign 51 in
Length of inclined portion (portion inclined relative to second support part; reference sign 52 in
Inclination angle of inclined portion: 40° relative to second support part
Curvature radius in longitudinal direction cross-section of distal end: 2 mm
Curvature radius in cross-section of direction orthogonal to longitudinal direction of distal end: 1.5 mm
Second Flat Spring-Like Bodies
Length of parallel portion (portion parallel to second support part; reference sign 51 in
Length of inclined portion (portion inclined relative to second support part; reference sign 52 in
Inclination angle of inclined portion: 40° relative to second support part
Curvature radius in longitudinal direction cross-section of distal end: 2 mm
Curvature radius in cross-section of direction orthogonal to longitudinal direction of distal end: 1.5 mm
An elastic member of a comparative example was produced by punching and bending a pure nickel flat sheet having a thickness of 0.2 mm. The elastic member of the comparative example has a shape corresponding to FIG. 7 of Patent Literature 1. Therein, a single spring row in which flat spring-like bodies corresponding to the second flat spring-like bodies are arranged alternately in two rows opposing each other is formed on the spring retaining part. The distal ends have the shape shown in
Elastic Member
Bonding part: 9 mm
First support part: 12 mm
Second support part: 47 mm
Number of flat spring-like bodies per electrode unit surface area: 3200/m2
Spring-Like Bodies
Length of parallel portion (portion parallel to second support part): 7 mm
Length of inclined portion (portion inclined relative to support part): 28.5 mm
Inclination angle of inclined portion: 20° relative to second support part
Curvature radius in longitudinal direction cross-section of distal end: 2 mm
The amount of compression and the contact surface pressure of the elastic member were measured using the elastic members that were produced in the example and the comparative example.
As shown in
The voltage between the electrodes was measured upon operating electrolytic cells in which the elastic members of the example and the comparative example were installed within the cathode chamber. This experiment was conducted using a plain weave mesh (material: pure nickel; catalyst: platinum group metal-containing layer) as the cathode and with a current density during operation of 6.0 kA/m2. In the results, the voltage between the electrodes was 2.9 V when using the elastic member of the example, whereas the voltage between the electrodes was higher at 2.96 V when using the elastic member of the comparative example. It can be said that this result was due to the greater number of spring-like bodies in the elastic member of the example compared to the elastic member of the comparative example, which allowed the electrodes to be closely fitted to the membrane more uniformly.
Number | Date | Country | Kind |
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JP2016-118157 | Jun 2016 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2017/021864 | 6/13/2017 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/217427 | 12/21/2017 | WO | A |
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Number | Date | Country |
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1442512 | Sep 2003 | CN |
101074481 | Nov 2007 | CN |
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2015068579 | May 2015 | WO |
Entry |
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International Search Report issued in PCT/JP2017/021864, dated Aug. 24, 2017. |
Number | Date | Country | |
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20190226100 A1 | Jul 2019 | US |