JP3278834B2 - Electrolysis cell for electrolysis - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to electrolysis of water.
The present invention relates to improvement of an electrolytic cell that can be used .

[0002]

2. Description of the Related Art Conventionally, an electrolysis cell, particularly an electrode plate used for electrolysis of water, has a conductive metal, in particular,
Gold, platinum, palladium, iron, stainless steel, zinc, titanium and the like are used. However, it is inevitable that these metals are ionized due to electricity used during electrolysis and worn away. Further, it is desirable to reduce the electric resistance generated during the electrolysis to improve the electrolysis efficiency. However, with these metals, the improvement for increasing the efficiency is limited. Furthermore, some of these conductive metals have poor workability or are expensive.
Depending on its performance and purpose, it may be necessary to use it while knowing these disadvantages. Further, in an electrolytic cell using a conventional electrode plate, at least two members of an insulator and a waterproof O-ring are interposed between each of the cathode and anode electrode plates. However, the interposition of these members has a limit in reducing the interval between the electrodes, and accordingly, the size of the electrolytic cell and the electrolytic tank containing the electrolytic cell are increased, and the improvement in the electrolytic efficiency is also limited. Was something. In addition, it is conceivable to reduce the distance between the electrodes by arranging these members in the radial direction instead of interposing them in the thickness direction. It is necessary to improve not only the accuracy but also the accuracy of the assembly.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an electrode
Prevents wear due to ionization and occurs during electrolysis
It is possible to reduce the electric resistance and improve the electrolytic efficiency.
And with an electrode for electrolysis with good processability
In both cases, the size of the electrolytic cell and the electrolytic cell can be reduced.
An electrolytic cell for electrolysis of water is provided.

[0004]

Means for Solving the Problems The first invention of the present application comprises:
Water, KOH, NaOH, H provided with an electrolytic cell 101 in the section
_{2 In} the electrolytic layer for electrolysis of electrolyte such as SO ₄
Electrolytic cell 101 has a cathode plate 102a and an anode plate 102b.
Electrode plates 102 are alternately arranged.
102 is a plate-shaped member formed of conductive metal
Formed a layer of proton conducting ceramic on the surface of the body
This electrode plate 102 is generated by electrolysis.
Flow hole 104 for flowing the gas and electrolytic water flow hole 1
06 are formed through the front and back, respectively.
And the respective electrode plates 10 of the cathode plate 102a and the anode plate 102b.
Insulation, waterproof, and pressure resistance between 2a and 102b
One spacer 111 is interposed and fixed.
111 is in contact with the entire circumference of the electrode plates 102a and 102b.
Ring-shaped, penetrating part formed in the center through the front and back
112, and the through portion 112
Size including the flow hole 104 and the electrolytic water flow hole 106
An electrode for electrolysis characterized by being formed
Provide delamination. The second invention of the present application is the above-mentioned water electricity
In the electrolytic layer for decomposition, formed on the surface of the cathode plate 102a
1) SrCeY
Ceramic sintered by blending bO ₃ , Mg and CaCO ₂
Click, 2) blended SrZrYbO ₃ Mg and CaCO ₂
3) SrCeYO ₃ , Mg and Ca
Select from the group consisting of ceramics mixed and sintered with CO ₂
At least one selected surface of the anode plate 102b
The layer of the proton conductive ceramic formed on
Sera sintered by blending ZrYO ₃ , Ce and CaCO ₂
Mick, 2) configuration of CaZrInO ₃ Ce and CaCO ₂
3) SrZrYbO ₃ and C
It is composed of a ceramic sintered by mixing e and CaCO ₂
Characterized in that it is at least one selected from the group
The present invention provides an electrolytic layer for electrolysis. Various types of proton conductive ceramics can be used for the electrolysis of water, etc., but the strontium serate-based and zirconate-based Is particularly effective.

[0005] More specifically, an oxide conductive material containing a plurality of types of elements shown below is used as the proton conductive ceramic. That is, as a main component of this proton conductive ceramic,
1) Sr (strontium), Ba of group IIIa of the periodic table
(1) Group consisting of (barium) and Zr (zirconium)
Group) is adopted. It may be carried out only with this main component, but in addition, 2) Y (yttrium), Gd (gadolinium), Yb
(Ytterbium), Eu (eurobium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Lu
One or more elements selected from the group consisting of (lutetium), Sc (scandium) and other lanthanoids (group (2)); 3) Mg (magnesium), Be (beryllium), Al
(Aluminum), Fe (iron), Co (cobalt), N
i (nickel), Cr (chromium), Ti (titanium), M
It is preferable to mix one or more elements selected from the group consisting of n (manganese) (group (3)).
It is preferable to mix at least two kinds of at least one kind selected from group 2) and at least one kind selected from group 3), but only at least one kind selected from group 2) and group 3). At least one selected from the above may be blended.
Further, other components in the 1) group, which were not selected as the main components of the 1) group, may be blended as a composite material in a small amount. For example, Sr (strontium) may be compounded as a main component, and a small amount of Zr (zirconium) may be compounded as a composite material.

Particularly, in direct current electrolysis, since the temperature of the electrolyte solution and the effective function for increasing the conductivity are both positive factors, the above-mentioned 1) such as strontium oxide serate is used. The oxide of at least one element selected from the group is desirably 60 to 95% by weight of the ceramic component, and the other components are the above-mentioned composite materials, particularly iron, aluminum, copper, gold, silver and the like. It is preferable to use the conductive metal. These components can be appropriately selected and used in consideration of electric conductivity and corrosion resistance of the electrolytic solution.

The substrate on which this ceramic is coated to form a layer may be any substrate provided that it has pressure resistance and heat resistance to electrolysis pressure and heat, and for example,
In the case of water electrolysis, a pressure resistance of about 2.5 atm.
It is only necessary to have a heat resistance of about 0 ° C., and a metal such as iron or stainless steel, or a plate material of a synthetic resin can be adopted, and it does not matter whether or not there is conductivity. In addition, other metals such as platinum and gold as in the prior art can be used for the substrate, but it is not necessary to use a noble metal in order to suppress an increase in manufacturing cost.

The above-mentioned oxide conductive material is sintered at an appropriate sintering temperature of about 1300 ° C. in accordance with a conventional method for producing a ceramic. This sintering may be performed after the application to the substrate, but may also be performed before the application to the substrate. When iron or the like having heat resistance to the sintering temperature is used as the base, sintering may be performed at any stage after or before the application of the oxide conductive material to the base. When a synthetic resin or the like having no heat resistance to the sintering temperature is used as the base, the sintering may be performed before applying the oxide conductive material to the base. As an example of a method of sintering after application, a method of adding a liquid such as water to the above-mentioned oxide conductive material in the form of fine particles, applying the slurry to the surface of the substrate, and then sintering can be used. As a method of sintering before application, the above-mentioned oxide conductive material in the form of fine particles is sintered as it is and laminated on the surface of the base by arc spraying or the like.

As a method of coating the proton conductive ceramic, any method can be selected as appropriate, and the above-mentioned substrate of the electrode plate is annealed with a proton conductive oxide ceramic in an oxidizing atmosphere, and then subjected to a sputtering method, a printing method, or the like. It is desirable to form by a screen printing method, a spray method, a plasma spray method, an electrified beam evaporation method, a plasma and VD method, or other methods.

The proton conductive ceramic can be laminated on the surface of the substrate using a binder according to a coating method. When a non-proton conductor is used, 1 to 15% by volume is added to the material as the binder. In particular, an organic resin soluble in an organic solvent was used as a binder for surface coating by a screen printing method or a spray method.
At this time, the film thickness is required to be 10 μm or more, and a thickness up to 30 μm is desirable. A thickness of 6 μm or more is required even in a sputtering method or the like, and a thickness up to 10 μm is desirable.

Next, at least the above-mentioned electrode for electrolysis is used.
There is also a pair of yin and yang, between these electrodes, insulation, waterproof,
An electrode fixed with one pressure-resistant spacer interposed
The solution cell is coordinated inside the electrolytic cell.

In the spacer in this electrolytic cell,
The conditions required for insulation, waterproofing, and pressure resistance between electrodes are not performed by separate members, but are satisfied by one member. More specifically, a cork material is pulverized, mixed with a heat-resistant resin, and molded to obtain a spacer having functions of pressure resistance, heat resistance, insulation, and water resistance. That is, by selecting the type of resin and adjusting the mixing ratio with the pulverized cork material, a spacer having appropriate functions of pressure resistance, heat resistance, insulation, and water resistance is obtained. 80 ° C as heat resistant temperature
As described above, more desirably, a heat resistance of 100 ° C. or more is sufficient. If this heat resistance can be satisfied, any of a thermoplastic synthetic resin and a thermosetting synthetic resin can be used. It is sufficient that the pressure resistance is at least about 2.5 atm.

The spacer is arranged between at least a pair of electrode plates. The spacer is formed in a ring shape that comes into contact with the entire circumference of both electrode plates, and a bolt insertion hole for inserting a fixing bolt is provided as necessary. Then, the required pressure resistance, required heat resistance, and required elasticity are obtained by arbitrarily adjusting the material such as resin and the mixing ratio. Also, the elasticity can be arbitrarily adjusted by the pressing pressure at the time of molding.

[0014]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1A is a perspective view of an electrode plate according to the embodiment of the present invention, and FIG. 1B is a perspective view of a spacer. 2 and 3 are longitudinal sectional views of the electrolytic cell. FIG. 2 is a sectional view taken along the line II-II of FIG.
Is along the line III-III in FIG.

The electrolytic cell according to this embodiment includes an electrolytic cell 101 therein. The electrolytic cell 101 has at least one pair, in this example, a large number of electrode plates 102 arranged. In this example, a large number of cells are arranged in the horizontal direction, but the arrangement direction is arbitrary, and an electrolytic cell arranged in the vertical direction can be used. The electrode plate 102 includes a cathode plate 102a and an anode plate 102b.
Are alternately arranged, and a spacer 111 is arranged between each of the electrode plates 102a and 102b.
The specific shape and configuration of a and the anode plate 102b are the same, and in the following description, the electrode plate 102 will be described unless otherwise required.

The electrode plate 102 is formed by coating a surface of a plate-shaped body made of a conductive metal such as iron or stainless steel with a proton conductive ceramic.
The electrode plate 102 has a rectangular shape, and through holes 105 for bolts are formed at four corners of the electrode plate 102 so as to penetrate the front and back. Further, a gas flow hole 104 through which gas (hydrogen and oxygen) generated by electrolysis flows is formed above the center, and an electrolyzed water flow hole 106 is formed below the center through the front and back.

Examples of the proton conductive ceramic coated on the cathode plate 102a include the following. 1) Ceramic sintered by mixing SrCeYbO ₃ , Mg and CaCO ₂ 2) Ceramic sintered by mixing SrZrYbO ₃ , Mg and CaCO ₂ 3) Sintered by mixing SrCeYO ₃ , Mg and CaCO ₂ ceramic

Examples of the proton conductive ceramic coated on the anode plate 102b include the following. 1) A ceramic sintered by blending CaZrYO ₃ , Ce and CaCO ₂ 2) A ceramic sintered by blending CaZrInO ₃ , Ce and CaCO ₂ 3) A ceramic sintered by blending SrZrYbO ₃ , Ce and CaCO ₂ ceramic

Next, the spacer 111 arranged between the negative and positive electrode plates 102a and 102b will be described. The spacer 111 is embodied as a ring that comes into contact with the entire periphery of both electrode plates 102a and 102b. More specifically, the spacer 111 has an outer shape substantially equal to that of the electrode plate 102, and has a penetrating portion 112 formed at the center thereof so as to penetrate the front and back surfaces. The penetrating portion 112 is provided in the electrode plate 1
No. 02 is formed in a size including the gas flow hole 104 and the electrolytic water flow hole 106. Further, at the four corners of the spacer 111, projections 113 that fit into the bolt through holes 105 of the electrode plate 102 are formed.
A bolt insertion hole 114 is formed through the front and back.

When assembling the electrolytic cell, the electrode plate 10
The protrusion 113 of the spacer 111 is fitted into the through hole 105 for the second bolt. Then, a predetermined number of electrode plates 102 are arranged by alternately arranging cathodes and anodes via spacers 111. Then, a fixing bolt 121 is passed through a bolt insertion hole 114 that penetrates the protrusion 113 of each spacer 111, and is tightened and fixed with a nut 122. Further, a cathode plate 102a located at both ends of the electrolytic cell and an anode plate 102b
Have terminals 107 such as stud bolts, respectively.
a, 107b are formed, and a current for electrolysis is supplied.

The spacer 111 is integrally formed as a material having insulation, waterproof, pressure resistance, heat resistance and elasticity properties by crushing a cork material, mixing with a heat-resistant synthetic resin and molding. . That is, the insulation between the electrode plates 102 is achieved by the spacer 111, and in this embodiment, the insulation between the fixing bolt 121 and each electrode plate 102 is also achieved. In addition, waterproofness between the electrode plates 102 is also achieved, and water and generated gas (hydrogen, oxygen) from between the electrode plates 102 are prevented from leaking to the outside. In addition, the performance can be maintained by an appropriate heat resistance that is not affected even when the temperature of the electrolytic solution rises.

Next, as shown in FIG. 4, the electrolytic cell 101 is arranged in an electrolytic cell 1. The electrolytic cell 1 is filled with water or an electrolytic solution such as KOH, NaOH, and H ₂ SO ₄ . The water level of the electrolyte is sensed by sensors (not shown) provided at the upper and lower positions, and the water level is adjusted by opening and closing a valve (not shown). As shown in FIG. 2, the electrolytic solution is supplied from the electrolyzed water flow hole 106 below the center of each electrode plate 102 to the spacer 1 between the electrode plates 102.
The electrode extends between the electrode plates 102 through the 11 through portions 112. Then, an electric current is passed and oxygen and hydrogen are generated by electrolysis. Although the generated hydrogen and oxygen may be separately collected, in this embodiment, oxygen and hydrogen are extracted as a mixed gas. That is, the gas flows out of the electrolytic cell from the penetrating part 112 of the spacer 111 between the electrode plates 102 through the gas flow holes 104 below the center of each electrode plate 102. The mixed gas of oxygen and hydrogen that has flowed out is collected in a collection tank above the electrolytic cell.

The mixed gas taken out can be used as cooking gas, heating, heating and combustion energy gas as combustion gas. As described above, in this embodiment, since the mixed gas is taken out without using the separation membrane between the cathode plate and the anode plate, the electric resistance can be reduced accordingly, and the space between the electrode plates can be reduced. Requires only a minimum space, and the production cost of hydrogen and oxygen can be reduced. Of course, it is also possible to separate the cathode chamber and the anode chamber by using a separation membrane or the like, and to separately extract hydrogen and oxygen.

Further, referring to FIG. 4, an example of utilization as a combustion gas will be described. This electrolytic cell 1 is formed by vaporizing means 2 for vaporizing a hydrocarbon fuel and decomposition of water ( Mixing means 3 for obtaining combustion gas by mixing H ₂ , O ₂ ) and vaporized hydrocarbon fuel at a predetermined ratio, and combustion means 4 for burning this combustion gas.
Used in conjunction with

An electrolytic solution supplied by a pump 12 or the like is supplied to the electrolytic cell 1, and electricity is supplied from a DC power supply 13 between the electrodes to perform electrolysis. Hydrogen and oxygen (H ₂ , O ₂ ) generated by the decomposition are sent to the mixing means 3 through a transfer path such as a pipe 51.

A liquid fossil fuel heating device such as a regulator tank 22 provided with a heating means 21 such as a jacket is used as the vaporizing means 2, and a liquid fossil fuel such as heavy oil, light oil, kerosene or the like is supplied to a pump 23 or the like. By regulator tank 2
2. The supplied liquid fossil fuel is vaporized by heating, and is sent to the mixing means 3 through a transfer path such as the pipe 52.

The mixing means 3 comprises hydrogen, oxygen (H ₂ , O ₂ )
And the mixing ratio of the flow rate with the vaporized fuel is adjusted to a predetermined value and mixed.
A pressure regulator 31 and a flow regulating valve 32 provided in a transfer path such as a pipe 51 from
And a flow control valve 33 provided on a transfer path such as a pipe 52 from a liquid fossil fuel heating device such as the second.

Hydrogen, oxygen (H ₂ , O ₂ ) and vaporized fuel (mainly hydrocarbon gas) adjusted to a predetermined molar ratio by the two flow control valves 32 and 33 are mixed by a static mixer 34, and ideally mixed. Is sent to the combustion means 4 via a transfer path such as a pipe 53.

As the combustion means 4, a normal boiler or the like can be employed, and a furnace 41 having a refractory such as a refractory brick on its inner wall, and a burner 42 having a continuous vent refractory provided in the furnace.
And the like. As described above, the mixed combustion gas supplied from the burner 42 explosively burns in the furnace. The exhaust gas is exhausted to the outside from an exhaust pipe 43 provided in the furnace 41.
It can also be used as a part of the heat source of the heating means 21 such as the above-mentioned jacket.

In this embodiment, the electrolysis of water has been described as an example. However, the present invention can be applied to other electrolysis electrodes or electrolytic cells. Although the shape of the electrode is a rectangular plate, the shape may be changed to an appropriate shape such as a disk shape.

[0031]

As described above , the present invention is based on the ionization of the electrode.
To reduce the electrical resistance that occurs during electrolysis.
And improve the electrolysis efficiency.
Equipped with an electrode for electrolysis with good workability,
An electrolytic cell for electrolysis that can reduce the size of the electrolytic cell
Was provided.

[Brief description of the drawings]

FIG. 1A is a perspective view of an electrode plate according to an embodiment of the present invention, and FIG. 1B is a perspective view of a spacer.

FIG. 2 shows an electrolytic cell according to an embodiment of the present invention.
It is sectional drawing which follows the II-II line of (A).

FIG. 3 shows an electrolytic cell according to an embodiment of the present invention.
FIG. 3A is a cross-sectional view along the line III-III.

FIG. 4 is an explanatory diagram of a fossil fuel combustion apparatus using an electrolytic cell according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Electrolysis cell 102 Electrode plate 102a Cathode plate 102b Anode plate 104 Gas flow hole 105 Through hole 106 Electrolyzed water flow hole 111 Spacer 112 Penetrating part 113 Projecting part 114 Bolt insertion hole

Claims (2)

(57) [Claims] 1. Water, KO having an electrolytic cell 101 therein
H, NaOH, electricity for electrolysis of the electrolytic solution such as H ₂ SO ₄
In the delamination, the electrolytic cell 101 includes a cathode plate 102a and an anode plate 102b.
Electrode plates 102 are alternately arranged , and each electrode plate 102 is formed of a conductive metal.
A layer of proton conductive ceramic on the surface of the plate
Are those that form, the electrode plate 102, the flow of gas generated by electrolysis
The gas flow hole 104 and the electrolytic water flow hole 106 to be passed are
Each of the electrode plates 102 of the cathode plate 102a and the anode plate 102b is formed through the front and back sides.
a, 102b having insulation, waterproofness, and pressure resistance
A plurality of spacers 111 are interposed and fixed, and the spacers 111 are provided all around the electrode plates 102a and 102b.
It has a ring shape that abuts and is formed through the front and back at the center.
The through-hole 112 is formed on the electrode plate 1.
02 including a gas flow hole 104 and an electrolytic water flow hole 106
An electric component characterized by being formed in a size.
Electrolytic layer for solution. 2. A profile formed on the surface of the cathode plate 102a.
The layers of conductive ceramics are: 1) SrCeYbO ₃ and M
g ) and ceramic sintered by mixing CaCO ₂ 2) S
rZrYbO ₃ , Mg and CaCO ₂ were mixed and sintered
Distribution ceramic ₃₎ SrCeYO 3 Mg and CaCO ₂
Selected from the group consisting of ceramics sintered together.
At least one kind of proton conductive ceramic is formed on the surface of the anode plate 102b.
Layer of click is, 1) a CaZrYO ₃ and Ce and CaCO ₂
2) CaZrInO ₃ with ceramic sintered and blended
Ceramic sintered by mixing Ce and CaCO ₂ 3)
SrZrYbO ₃ , Ce and CaCO ₂ are mixed and sintered
At least one selected from the group consisting of ceramics
2. The electrode for electrolysis according to claim 1, wherein
Delamination.