CN103635609A - Electrolysis device - Google Patents
Electrolysis device Download PDFInfo
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- CN103635609A CN103635609A CN201280032007.0A CN201280032007A CN103635609A CN 103635609 A CN103635609 A CN 103635609A CN 201280032007 A CN201280032007 A CN 201280032007A CN 103635609 A CN103635609 A CN 103635609A
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- electrolyzer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
Abstract
An opening in the upper part of an electrolysis tank main body is closed by a first cover body with a sealing member sandwiched therebetween. An opening in the first cover body is closed by a second cover body with a sealing member sandwiched therebetween. The opening in the first cover body is smaller than the opening in the electrolysis tank main body. A partition wall that divides the inside of the electrolysis tank main body into a positive electrode chamber and a negative electrode chamber is provided integrally on the lower surface of the second cover body. The positive electrode chamber is disposed in an area on the inside of the sealing member. A positive electrode is attached to the second cover body inside of the positive electrode chamber, and the negative electrode is formed on the inside surface of the electrolysis tank main body. An electrolyte bath inside the electrolysis tank undergoes electrolysis, thereby generating fluorine gas in the positive electrode chamber. A plurality of round through holes may be formed in a liquid partition wall. Each through hole has an upper surface that extends upward at a slant from an end part on the positive electrode chamber side to an end part on the negative electrode chamber side. The diameter of the positive electrode side end of the through holes in the vertical direction is set to a size such that the electrolyte bath can pass through and bubbles of fluorine gas and hydrogen gas cannot pass through. The diameter of the through holes in the vertical direction on the negative electrode side end is larger than the diameter of the through holes on the positive electrode side end.
Description
Technical field
The present invention relates to possess the electrolyzer of electrolyzer.
Background technology
In the past, in semi-conductive manufacturing process etc., because of material clean and the various uses such as surfaction is used fluorine gas.Now, the situation of existing use fluorine gas self, also has and uses based on fluorine gas and the various fluorine such as synthetic NF3 (nitrogen trifluoride) gas, NeF (fluoridizing neon) gas and ArF (argon fluoride) gas are the situation of gas.
In order stably to supply fluorine gas, conventionally use HF (hydrogen fluoride) is carried out to electricity decomposition and the electrolyzer of generation fluorine gas.In such electrolyzer, for example, in electrolyzer, form the electrolytic bath of the fused salt mixt formation that is by KF-HF (potassium hydrogen fluoride).By the electrolytic bath in electrolyzer, by electricity, decomposed, thereby produce fluorine gas.
For example, the fused salt electrolysis apparatus of recording in patent documentation 1 has electrolyzer, and this electrolyzer consists of electrolyzer body and upper cover.By next door, the interior separation of electrolyzer is become to be positioned to the anolyte compartment and the cathode compartment that surrounds this anolyte compartment of electrolyzer central part.Anode is set in anolyte compartment, and negative electrode is set in cathode compartment.Substantial middle portion at upper cover is formed for anode to insert the intrinsic peristome of electrolyzer, and to cover the mode of peristome, lid is set.Between lid and upper cover, there is air seal material.In lid, the connective bar of holding anode is vertically set.
As mentioned above, in electrolyzer, together produce hydrogen with fluorine gas.Therefore, in electrolyzer, be provided for the next door of the fluorine gas producing and hydrogen separation.In the electrolyzer of recording at patent documentation 2, in order to prevent that gas from mixing, and uses the dividing plate with porousness or filamentary structure.Now, electrolytic bath can see through dividing plate.Therefore, prevent that the anode and the energising resistance between negative electrode that in electrolyzer, arrange from increasing.
Patent documentation 1: TOHKEMY 2005-48290 communique
Patent documentation 2: TOHKEMY 2000-104187 communique.
Summary of the invention
The problem that invention will solve
In the fused salt electrolysis apparatus of recording at patent documentation 1, by taking off lid from upper cover, easily upper cover and anode from the dismounting of electrolyzer body.Thus, even when anode consumption, also can easily change anode.
But in above-mentioned fused salt electrolysis apparatus, the air seal material requirements for existence between lid and upper cover is with respect to the erosion resistance of fluorine gas.In addition, even there is the air seal material of erosion resistance with respect to fluorine gas, also because contacting and corrode with fluorine gas chronically.Therefore, be necessary to change continually air seal material.Consequently increase maintenance cost.In addition, the frequency that the frequency ratio of replacing air seal material is changed anode is many, so the operating efficiency of safeguarding is poor.
In addition, the inventor finds in the electrolyzer of patent documentation 2, because the hole of the gas bubble blockage dividing plate that produces hinders seeing through of electrolytic bath.Thus, can not stably carry out the electrolytic reaction of electrolytic bath.
The object of the present invention is to provide the electrolyzer that can reduce maintenance cost and improve upkeep operation efficiency.
Other object of the present invention is to provide the electrolyzer that can prevent that gas from mixing and stably carrying out electrolytic reaction.
For solving the means of problem
(1) electrolyzer that one aspect of the present invention relates to is to decompose by electrolytic bath being carried out to electricity the electrolyzer that produces fluorine gas and other gas, and there is the electrolyzer of accommodating electrolytic bath, electrolyzer has: electrolyzer body, has the first opening on top; The first lid, has second opening less than the first opening, and is arranged at electrolyzer body in the mode of inaccessible the first opening; The first sealing element, is arranged at the first lid to surround the mode of the second opening; The second lid, clips the first sealing element in the mode of inaccessible the second opening and is arranged on the first lid; The first electrode, is installed on the second lid; And next door, by being separated in electrolyzer body, produce the first Room of fluorine gas and the second Room that produces other gas, wherein, the mode that next door is arranged on the inside region of the first sealing element with the first Room forms.
In this electrolyzer, first opening on the top of electrolyzer body is inaccessible by the first lid.It is inaccessible by the second lid that the second opening of the first lid clips the first sealing element.The first electrode is installed on the second lid.Because second aperture efficiency the first opening is little, the second lid becomes the structure of and light weight more small-sized than the first lid.Therefore,, even when the first consumption of electrode, also can, by taking off the second lid from the first lid, easily change the first electrode.
In addition, by next door, the first Room is arranged on to the region of the inner side of the first sealing element.Now, because the fluorine producing in the first Room does not contact with the first sealing element, so prevent the corrosion of the first sealing element.Thus, reduce the frequency of changing the first sealing element.
Consequently reduce the maintenance cost of electrolyzer and improve the operating efficiency of safeguarding.
(2) next door also can be arranged at the first lid integratedly to surround the mode of the surrounding of the first electrode.Now, by taking off the second lid from the first lid, can easily check next door.Thus, more reduce the maintenance cost of electrolyzer and more improve the operating efficiency of safeguarding.
(3) electrolyzer body also can be used as the second electrode performance function.Now, without the second electrode is set individually.Thus, the structure of electrolyzer can be simplified.
(4) mode that electrolyzer also possesses to surround the first opening is arranged at the second sealing element of electrolyzer body, and the first lid also can clip the second sealing element and be arranged on electrolyzer body.
Now, can take off the first lid from electrolyzer body.Therefore, can, by taking off the first lid from electrolyzer body, check the inside of electrolyzer.
(5) electrolyzer that another aspect of the present invention relates to possesses: electrolyzer, accommodate electrolytic bath; Next door, so that the mode that is distinguished into anolyte compartment and cathode compartment in electrolyzer is arranged, and, there is the opening that the ion in electrolytic bath can pass through; Anode, is arranged on the anolyte compartment of electrolyzer; And negative electrode, be arranged on the cathode compartment of electrolyzer, wherein, the opening in next door has towards anolyte compartment and wherein at least one upper surface extending obliquely upward of cathode compartment.
In this electrolyzer, by next door, anolyte compartment and cathode compartment will be distinguished in electrolyzer.By applying voltage being arranged at the anode of anolyte compartment and being arranged between the negative electrode of cathode compartment, the electrolytic bath in electrolyzer is decomposed by electricity.In ， anolyte compartment and cathode compartment, produce gas thus.
The opening that ion in electrolytic bath can pass through is set in next door.Opening has towards anolyte compartment and wherein at least one upper surface extending obliquely upward of cathode compartment.Therefore, though the gas bubbles producing from anolyte compartment and cathode compartment above-mentioned at least one enter in opening, this bubble also can be back to along the upper surface of opening anolyte compartment or cathode compartment.Therefore, by the size of opening being set for to the bubble of generation, can't pass, thus the gas mixing that can prevent the gas producing in anolyte compartment and produce at cathode compartment, and can prevent the gas bubble blockage that opening is produced.Consequently, can prevent the mixing of gas and stably carry out the electrolytic reaction of electrolytic bath.
(6) in anolyte compartment, produce fluorine gas, and in cathode compartment, produce hydrogen, the upper surface of opening also can arrange in the mode of extending towards cathode compartment side direction oblique upper.
Because hydrogen is dissolved in electrolytic bath than fluorine gas difficulty, so bubble hydrogen is easily trapped in opening and occlusion of openings.Therefore, the upper surface by opening arranges in the mode of extending towards cathode compartment side direction oblique upper, even if the bubble hydrogen producing in cathode compartment enters in opening, this bubble also can be back to cathode compartment along the upper surface of opening.Thus, prevent because of hydrogen occlusion of openings.
(7) also the area of the end of the opening of comparable cathode compartment side is little for the area of the end of the opening of anolyte compartment's side.
Now, prevent that the fluorine gas producing from entering in opening in anolyte compartment.Thus, prevent that fluorine gas from moving to cathode compartment, and prevent that fluorine gas and hydrogen from mixing.
(8) next door comprises the liquid next door being immersed in electrolytic bath, and in liquid next door, opening is set, and liquid next door also can be formed by perfluorinated resin.
Now, prevent that liquid next door from being corroded by electrolytic bath.In addition, the processing in the liquid next door when forming opening becomes easy.And, reduce the material cost in liquid next door.
(9) also can carry out the processing of conductive diamond coating on the surface of anode.Now, because anode is difficult to polarize, so improve the luminous efficiency of gas.Even if the generating capacity of gas is more, also because the opening that prevents next door is by gas bubble blockage, thereby can stably carry out electrolytic reaction.
Invention effect
According to the present invention, can reduce the maintenance cost of electrolyzer and improve the operating efficiency of safeguarding.
In addition, according to the present invention, can prevent the mixing of gas and stably carry out electrolytic reaction.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of the electrolyzer that relates to of the first embodiment of the present invention.
Fig. 2 is the exploded perspective view of the electrolyzer of Fig. 1.
Fig. 3 is the lower surface figure of the second lid.
Fig. 4 is the schematic sectional view of the electrolyzer that relates to of the second embodiment of the present invention.
Fig. 5 is the stereoscopic figure in liquid next door.
Fig. 6 is the expanded view that is formed at the through hole in liquid next door.
Fig. 7 means the figure of other example of the through hole that is formed at liquid next door.
Fig. 8 is for the sectional view of other example in liquid next door is described.
Embodiment
[1] first embodiment
Below, with reference to the accompanying drawings of the electrolyzer (gas generating unit) that the first embodiment of the present invention relates to.
(1) structure of electrolyzer
Fig. 1 is the schematic sectional view of the electrolyzer that relates to of the first embodiment of the present invention.The electrolyzer 10 of Fig. 1 is the gas generating units that produce fluorine gas.As shown in Figure 1, electrolyzer 10 possesses electrolyzer 11.Electrolyzer 11 consists of electrolyzer body 11a, the first lid 11b, sealing element 11c, the second lid 11d and sealing element 11e.At the lower surface of the second lid 11d, to surround the mode in the space of the central part in electrolyzer body 11a, next door 13 is set integratedly.Electrolyzer body 11a, the first and second lid 11b, 11d and next door 13 are formed by metal or alloy such as Ni (nickel), Monel, pure iron or stainless steel.
In electrolyzer 11, apply the electric power of high electric current.In addition, while there is the gases such as hydrogen in cathode compartment 14b, the electric discharge in the cathode compartment 14b that is necessary to prevent to cause because of static or electric discharge.Therefore, the first lid 11b of cathode compartment 14b is by ground wire E1 ground connection.Thus, can prevent electric shock causing because of the electric leakage from electrolyzer 11 etc., and prevent the gaseous detonations such as hydrogen.
In the interior formation of electrolyzer 11, by KF-HF (potassium hydrogen fluoride), be the electrolytic bath (electrolytic solution) 12 that fused salt mixt forms.In electrolyzer 11, the 14a of formation anolyte compartment, inner side of next door 13, and the outside of next door 13 forms cathode compartment 14b.
Anode 15a is set in the 14a of anolyte compartment.The part in next door 13 and anode 15a are immersed in electrolytic bath 12.Internal surface at electrolyzer body 11a forms negative electrode 15b.As the material of negative electrode 15b, preferably use for example Ni.
For supplying the HF supply pipe 18a of HF, be connected with the first lid 11b.HF supply pipe 18a is covered with well heater 18b by temperature adjustment.Thus, prevent that HF from liquefying at HF supply pipe 18a place.The height of the liquid level of electrolytic bath 12 is detected by liquid level sensor (not shown).If the liquid level being detected by liquid level sensor lower than set-point, passes through FH supply pipe 18a to the interior supply of electrolyzer 11 HF.
This electrolyzer 10 possesses control part 23.Electrolytic bath 12 in electrolyzer 11 is in room temperature and under atmospheric pressure become solid state.Therefore, in order to carry out the electricity of electrolytic bath 12, decompose, be necessary electrolytic bath 12 to be heated to 80 to 90 ℃, make it be dissolved into liquid state.The temperature of the electrolytic bath 12 of control part 23 based on being detected by temperature sensor (not shown) is controlled temperature control part (not shown), and the temperature of electrolytic bath 12 is maintained to 80 to 90 ℃.
By control part 23, between anode 15a and negative electrode 15b, apply voltage.Thus, the electrolytic bath in electrolyzer 11 12 is decomposed by electricity.Consequently in the 14a of ， anolyte compartment, mainly produce fluorine gas.In addition, the main hydrogen that produces in cathode compartment 14b.
In the second lid 11d, gas discharge outlet 16a is set, and in the first lid 11b, gas discharge outlet 16b is set.Vapor pipe 17a is connected with gas discharge outlet 16a, and vapor pipe 17b is connected with gas discharge outlet 16b.The gas discharge outlet 16aYu 14a of anolyte compartment is communicated with, and gas discharge outlet 16b is communicated with cathode compartment 14b.The gas producing in the 14a of anolyte compartment is discharged by vapor pipe 17a from gas discharge outlet 16a, and the gas producing in cathode compartment 14b is discharged by vapor pipe 17b from gas discharge outlet 16b.
(2) electrolyzer is detailed
Fig. 2 is the exploded perspective view of the electrolyzer 11 of Fig. 1.Fig. 3 is the lower surface figure of the second lid 11d.
As shown in Figure 2, electrolyzer body 11a has bottom surface sections and four side surface part, and on top, has the opening H1 of rectangle.Sealing element 11c is arranged on the upper surface of four side surface part to surround the mode of opening H1.Sealing element 11c is for example the O type ring being formed by viton.The first lid 11b has rectangular shape, and has the size that ratio open H1 is larger.This first lid 11b is arranged on sealing element 11c in the mode of the opening H1 of inaccessible electrolyzer body 11a.Thus, electrolyzer body 11a and the first lid 11b are by sealing element 11c electrically insulated from one another and sealed.
The first lid 11b has the opening H2 of rectangle in substantial middle portion.Sealing element 11e is arranged on the upper surface of the first lid 11b with the edge of the first lid 11b along opening H2 and the mode that surrounds opening H2.Sealing element 11e is the O type ring for example being formed by viton.The second lid 11d has rectangular shape, and has the size that ratio open H2 is larger.This second lid 11d is arranged on sealing element 11e in the mode of the opening H2 of inaccessible the first lid 11b.Thus, the first lid 11b and the second lid 11d are by sealing element 11e electrically insulated from one another and sealed.The HF supply orifice 18c that can insert HF supply pipe 18a is set in the first lid 11b.
(3) effect
Arranged outside sealing element 11c, the 11e of the electrolyzer 10Zhong， 14a of anolyte compartment of the Fig. 1 relating in present embodiment.Therefore the fluorine gas producing in the 14a of ， anolyte compartment does not contact with sealing element 11c, 11e.Thus, can prevent the corrosion of sealing element 11c, 11e.Its result, reduces sealing element 11c, the inspection of 11e and the frequency of replacing.
In addition, by the second lid 11d from the first lid 11b dismounting, anode 15a can easily dismantling together with the second lid 11d from electrolyzer body 11a.Thus, even when anode 15a consumes, also can easily change anode 15a.Particularly, when electrolyzer 11 maximizes, electrolyzer body 11a and the first lid 11b maximize, and weight.Even under these circumstances, owing to not needing to make the second lid 11d to maximize, so the second lid 11d from the first lid 11b dismounting easily.
And, when life-time service electrolyzer 10, be necessary to check whether next door 13 consumes.Even in these cases, by from the second lid 11d of the first lid 11b dismounting, also can be from the first lid 11b dismantles next door 13.Thus, can easily check next door 13.
Consequently, can reduce the maintenance cost of electrolyzer 10, and improve the operating efficiency of safeguarding.
(4) other embodiment
In the above-described embodiment, electrolyzer body 11a has bottom surface sections and four side surface part, and on top, has the opening H1 of rectangle, but is not defined in this.For example, electrolyzer body 11a also can have bottom surface sections and side surface part cylindraceous, and on top, has circular opening.Now, it is inaccessible that the opening of electrolyzer body 11a is had the first round-shaped lid 11b.
The first lid 11b has the opening H2 of rectangle, but is not defined in this.For example, the first lid 11b also can have circular opening.Now, it is inaccessible that the opening of the first lid 11b is had the second round-shaped lid 11d.
If guarantee and the second lid 11d between stopping property, and the resistance to air loss of holding anode chamber 14a, next door 13 also can arrange dividually with the second lid 11d.Now, preferably, by between next door 13 and the second lid 11d, the sealing material that the erosion resistances such as metallic seal are high being set, guarantee stopping property.
(5) corresponding relation of each integrant of claim and the each several part of embodiment
Below, the corresponding example of each integrant of claim and the each several part of embodiment is described, but the present invention is not defined in following example.
In the above-described embodiment, electrolytic bath 12 is examples of electrolytic bath, and electrolyzer 10 is electrolyzers, and hydrogen is the example of other gas, and electrolyzer 11 is examples of electrolyzer, and electrolyzer body 11a is the example of electrolyzer body.Opening H1 is the example of the first opening, opening H2 is the example of the second opening, and the first lid 11b is the example of the first lid, and the second lid 11d is the example of the second lid, sealing element 11e is the example of the first sealing element, and sealing element 11c is the example of the second sealing element.Anode 15a is the example of the first electrode, and negative electrode 15b is the example of the second electrode, and the 14a of anolyte compartment is the example of the first Room, and cathode compartment 14b is the example of the second Room, the example in 13Shi next door, next door.
As each integrant of claim, also can use and there are the structure of record in the claims or other various key elements of function.
[2] second embodiments
Below, with reference to the accompanying drawings of the electrolyzer that the second embodiment of the present invention relates to.
(1) structure of electrolyzer
Fig. 4 is the schematic sectional view of the electrolyzer that relates to of the second embodiment of the present invention.The electrolyzer 10 of Fig. 4 is the electrolyzers that produce fluorine gas.As shown in Figure 4, electrolyzer 10 possesses electrolyzer 11.Electrolyzer 11 comprises electrolyzer body 11a and upper cover 11f.
In electrolyzer 11, accommodating by KF-HF (potassium hydrogen fluoride) is the electrolytic bath 12 that fused salt mixt forms.The mode that extends to below with the lower surface from upper cover 11f arranges next door 13 cylindraceous.Next door 13 is comprised of gas cylindraceous next door 13A and liquid cylindraceous next door 13B.Gas next door 13A is arranged at upper cover 11f integratedly.The height of the bottom of gas next door 13A is set to become with the liquid level of electrolytic bath 12 mode about equally.As the material of gas next door 13A, preferably use the metal or alloy such as Ni (nickel), nickelalloy, Monel, pure iron or stainless steel.Now, suppress the corrosion of the gas next door 13A that causes because of fluorine gas and hydrogen fluoride steam.Gas next door 13A also can be arranged to dismantle from upper cover 11f.
Liquid next door 13B is installed on the bottom of gas next door 13A impregnated in the mode of electrolytic bath 12.In the 13B of liquid next door, be formed for guaranteeing a plurality of through hole H (Fig. 5 described later) of the perviousness of electrolytic bath 12.Describe afterwards liquid next door 13B in detail.As the material of liquid next door 13B, preferably use the perfluorinated resins such as PTFE (tetrafluoroethylene) or PFA (tetrafluoroethylene and perfluorinated alkoxy vinyl ether copolymer), and preferably use especially PTFE.Now, compare as the situation of the material of liquid next door 13B with using metal, suppress the corrosion of the liquid next door 13B that causes because of electrolytic bath 12.Processing while in addition, forming above-mentioned through hole H becomes easy.And, the material cost of reduction liquid next door 13B.
In electrolyzer 11, the 14a of formation anolyte compartment, inner side of next door 13, and the outside of next door 13 forms cathode compartment 14b.In the 14a of anolyte compartment, impregnated in the mode of electrolytic bath 12, anode 15a is set.As the material of anode 15a, preferably use for example hypopolarization carbon dioxide process carbon electrode.
On the surface of anode 15a, preferably carry out the processing of conductive diamond coating.Particularly, by using the mixed gas of hydrogen and carbon source as diamond raw material, and the element that indium addition valence is different from carbon in this mixed gas (hereinafter referred to as hotchpotch), thereby can form the diamond coatings with electroconductibility.As hotchpotch, preferably use boron, phosphorus or nitrogen, particularly preferably use boron.The weight of the hotchpotch adding is preferably all wts with respect to diamond coatings below the above 30000ppm of 1ppm, more preferably below the above 10000ppm of 100ppm.By the surface at anode 15a, carry out the processing of conductive diamond coating, at anode 15a place, be difficult to polarize.Therefore, improve the formation efficiency of fluorine gas.In the present embodiment, the side surface part of electrolyzer body 11a is brought into play function as negative electrode.
For the HF supply pipe 18a at the interior supply of electrolyzer 11 HF, be connected in upper cover 11f.HF supply pipe 18a is covered with well heater 18b by temperature adjustment.Thus, prevent from liquefying at the HF supply pipe 18a HF of place.The liquid level of electrolytic bath 12 is detected by liquid level sensor (not shown).If the height of the liquid level being detected by liquid level sensor, lower than set-point, is supplied to HF in electrolyzer 11 by HF supply pipe 18a.
In upper cover 11f, be provided with gas discharge outlet 16a, 16b.At gas discharge outlet 16a, be connected with vapor pipe 17a, and be connected with vapor pipe 17b at gas discharge outlet 16b.The gas discharge outlet 16aYu 14a of anolyte compartment is communicated with, and gas discharge outlet 16b is communicated with cathode compartment 14b.
By apply voltage between anode 15a and electrolyzer body 11a, thereby being carried out to electricity, decomposes electrolytic bath 12.Now, on the surface of anode 15a, produce fluorine gas, and produce hydrogen on the internal surface of the side surface part of electrolyzer body 11a.Because the upper surface of the bottom surface sections of electrolyzer body 11a is insulated parts 11g, cover, so do not carry out the electrolytic reaction of electrolytic bath 12 on the upper surface of bottom surface sections, do not produce hydrogen.
The fluorine gas producing at 14a place, anolyte compartment is directed to the outside of electrolyzer 11 by vapor pipe 17a from gas discharge outlet 16a.The hydrogen producing at cathode compartment 14b place is directed to the outside of electrolyzer 11 by vapor pipe 17b from gas discharge outlet 16b.
(2) liquid next door is detailed
Fig. 5 is the stereoscopic figure of liquid next door 13B, and Fig. 6 is the enlarged view that is formed at the through hole H of liquid next door 13B.Fig. 6 (a) is the longitdinal cross-section diagram of through hole H, the side-view of the being seen through hole H of Fig. 6 (b) Shi Cong 14a of anolyte compartment, and Fig. 6 (c) is the side-view from the being seen through hole H of cathode compartment 14b.The A-A line cross section of Fig. 6 (a) presentation graphs 6 (b) and Fig. 6 (c).
As shown in Figure 5, in the 13B of liquid next door, form the through hole H of a plurality of circles.In the example of Fig. 5, a plurality of through hole H circumferentially become two row along liquid next door 13B's.Now, the ion in electrolytic bath 12 can move by a plurality of through hole H between the 14a of anolyte compartment and cathode compartment 14b.In the 14a of ， anolyte compartment and cathode compartment 14b, stablize and carry out swimmingly thus electrolytic reaction.
Now, if the fluorine gas being produced by electrolytic reaction and hydrogen move in the 14a of ，Ze anolyte compartment or cathode compartment 14b by through hole H, fluorine gas and hydrogen mix.Thus, fluorine gas and hydrogen reaction, the formation efficiency of fluorine gas reduces, and also with good grounds fluorine gas and hydrogen ratio and generate the possibility of volatile mixed gas.
Therefore, the diameter of each through hole H is configured to the size that the bubble of fluorine gas and hydrogen does not pass through.But, therefore also exist bubble to be trapped in through hole H, and stop up the situation of through hole H.Particularly, because hydrogen is dissolved in electrolytic bath 12 than fluorine gas difficulty, therefore, the bubble of hydrogen is easily trapped in through hole H, and easily stops up through hole H.If through hole H is blocked, electrolytic bath 12 can not move by through hole H.Thus, can not stably carry out electrolytic reaction.
Therefore, in the present embodiment, as shown in Figure 6, each through hole H has the upper surface L1 that extends to obliquely upward the end of cathode compartment 14b side from 14aCe end, anolyte compartment.The end of the through hole H of the following ，Jiang 14a of anolyte compartment side is called anode side, and the end of the through hole H of cathode compartment 14b side is called to negative electrode side.The lower surface L2 of through hole H flatly extends to negative electrode side from anode side.At this, the upper surface of so-called through hole H refers in the inner peripheral surface of through hole region downward, and the lower surface of so-called through hole H refers in the inner peripheral surface of through hole H the region towards top.
The diameter D1 of the above-below direction of the anode side of through hole H be configured to electrolytic bath can by and the size do not passed through of the bubble of fluorine gas and hydrogen.Diameter D1 is for example below the above 3mm of 1mm, and preferably below the above 2mm of 1mm.The diameter D2 diameter group D1 of the above-below direction of the negative electrode side of through hole H is large.Diameter D2 is for example below the above 10mm of 5mm, and preferably below the above 8mm of 5mm.The thickness T H of liquid next door 13B is for example below the above 10mm of 5mm, and preferably below the above 8mm of 5mm.
In the electrolyzer 10 relating in present embodiment, even if the bubble of hydrogen enters in through hole H from cathode compartment 14b, this bubble is also back to cathode compartment 14b along the upper surface of through hole H, and floating upper to liquid level.Therefore, prevent from entering from cathode compartment 14b the gas bubble blockage through hole H of the hydrogen in through hole H.
In addition, the diameter of the above-below direction of the through hole H of the 14a of anolyte compartment side is less than the diameter of the above-below direction of the through hole H of cathode compartment 14b side.And as mentioned above, fluorine gas is dissolved in electrolytic bath 12 than hydrogen is easy.Therefore the bubble that, prevents fluorine gas enters in through hole H from the 14a of anolyte compartment.
With which, prevent that the bubble of fluorine gas and hydrogen from moving by through hole H, and prevent the gas bubble blockage through hole H of fluorine gas and hydrogen.Thus, can be in the situation that do not reduce the formation efficiency of fluorine gas, stable and carry out swimmingly electrolytic reaction.
(3) other example of through hole
(3-1)
The shape of the through hole H of liquid next door 13B is not limited to the example of Fig. 5 and Fig. 6.Fig. 7 means the figure of other example of the through hole H forming in the 13B of liquid next door.About the example of Fig. 7 (a) and Fig. 7 (b), the point that explanation is different from the example of Fig. 5 and Fig. 6.
In the example of Fig. 7 (a), the upper surface L1 of through hole H flatly extends to the intermediate point P1 of anode side and cathode side section from anode side, and extends to obliquely upward negative electrode side from intermediate point P1.Now, also prevent from entering from cathode compartment 14b the gas bubble blockage through hole H of the hydrogen in through hole H, and prevent that the bubble of fluorine gas from entering in through hole H from the 14a of anolyte compartment.
In the example of Fig. 7 (b), the upper surface L1 of through hole H oliquely downward extends to intermediate point P1 from anode side, and extends to obliquely upward negative electrode side from intermediate point P1.Now, also prevent from entering from cathode compartment 14b the gas bubble blockage through hole H of the hydrogen in through hole H.In addition, even if fluorine gas bubble enters in through hole H from the 14a of anolyte compartment, this bubble is also back to the 14a of anolyte compartment along the upper surface L1 of through hole H, and floating upper to liquid level.Therefore, prevent from entering from the 14a of anolyte compartment the gas bubble blockage through hole H of the fluorine gas in through hole H.
(3-2)
In above-mentioned example, through hole H has circular longitudinal cross-section, but through hole H also can have the longitudinal cross-section of other shapes such as elliptical shape, trilateral or tetragon.
(3-3)
In above-mentioned example, the upper surface L1 of through hole H arranges in the mode of extending obliquely upward towards negative electrode side linearity, but is not limited to this, and for example the upper surface L1 of through hole H also can arrange in the mode of extending agley obliquely upward towards negative electrode side.
(4) other the example in liquid next door
Fig. 8 is for the sectional view of other example of liquid next door 13B is described.The bottom of gas next door 13A and the upper end of liquid next door 13B in Fig. 8, have been shown.About the example of Fig. 8, the point that explanation is different from the example of Fig. 5 and Fig. 6.
In the example of Fig. 8, the upper end of liquid next door 13B arranges in the mode of the bottom of the periphery (surface of cathode compartment 14b side) of blanketing gas next door 13A.While carrying out the electrolytic reaction of electrolytic bath 12 under the bottom of gas next door 13A impregnated in the state of electrolytic bath 12, in electrolytic bath 12, gas next door 13A polarization, and at the periphery of gas next door 13A with positive electric charge.Now, metal is from the periphery ionization of the gas next door 13A with positive charge, and stripping is in electrolytic bath 12, and the periphery of gas next door 13A is easily corroded.Therefore, in the present example, the part that impregnated in the periphery of the gas next door 13A in electrolytic bath 12 is covered by liquid level next door 13B.Thus, prevent the periphery of electrolytic bath 12 contact gas next door 13A, and prevent from impregnated in the partial corrosion of the periphery of the gas next door 13A in electrolytic bath 12.
In addition, the upper end of liquid level next door 13B preferably extends to the top of the liquid level of electrolytic bath 12.Now, can prevent effectively the periphery of electrolytic bath 12 contact gas next door 13A.And, because the upper-end part of driving of liquid level next door 13B is in cathode compartment 14b side, so even if the upper end of liquid level next door 13B extends to the top of the liquid level of electrolytic bath 12, fluorine gas and hydrogen fluoride steam do not contact with liquid level next door 13B.Therefore, prevent the corrosion of liquid level next door 13B.
(5) other embodiment
(5-1)
In the above-described embodiment, gas next door 13A and liquid next door 13B divide and are arranged, but when the corrosion of gas next door 13A and liquid next door 13B is prevented from or when the corrosion of gas next door 13A and liquid next door 13B does not become problem, gas next door 13A and liquid next door 13B also can arrange integratedly.
(5-2)
In the above-described embodiment, gas next door 13A and liquid next door 13B are respectively cylindric, but are not limited to this, and gas next door 13A and liquid next door 13B can be respectively also other shapes such as square tube shape or tabular.
(5-3)
Above-mentioned embodiment is the present invention to be applicable to produce the example of the electrolyzer of fluorine gas, but similarly also the present invention can be applicable to the electrolyzer of other gases such as producing oxygen.
(6) corresponding relation of each integrant of claim and the each several part of embodiment
Below, the corresponding example of each integrant of claim and the each several part of embodiment is described, but the present invention is not defined to following example.
In the above-described embodiment, electrolytic bath 12 is examples of electrolytic bath, electrolyzer 11 is examples of electrolyzer, and through hole H is the example of opening, and upper surface L1 is the example of upper surface, the example in 13Shi next door, next door, the example of 14aShi anolyte compartment, anolyte compartment, anode 15a is the example of anode, cathode compartment 14b is the example of cathode compartment, negative electrode 15b is the example of negative electrode, and liquid next door 13B is the example in liquid next door.
As each integrant of claim, also can use and there are the structure of record in the claims or other various key elements of function.
In industry, utilize possibility
The present invention can effectively utilize in various electrolyzers such as gas generating units.
Claims (9)
1. an electrolyzer, produces fluorine gas and other gas by electrolytic bath being carried out to electricity decomposition,
There is the electrolyzer of accommodating electrolytic bath,
Described electrolyzer has:
Electrolyzer body, has the first opening on top;
The first lid, has second opening less than described the first opening, and is arranged at described electrolyzer body in the mode of described the first opening of obturation;
The first sealing element, is arranged at described the first lid to surround the mode of described the second opening;
The second lid, clips described the first sealing element in the mode of described the second opening of obturation and is arranged on described the first lid;
The first electrode, is installed on described the second lid; And
Next door, produces the first Room of fluorine gas and the second Room that produces other gas by being separated in described electrolyzer body,
Wherein, the mode in region that described next door is arranged on the inner side of described the first sealing element with described the first Room forms.
2. electrolyzer according to claim 1, is characterized in that, described next door is arranged at described the first lid integratedly to surround the mode of the surrounding of described the first electrode.
3. electrolyzer according to claim 1 and 2, is characterized in that, described electrolyzer body is as the second electrode performance function.
4. according to the electrolyzer described in any one in claims 1 to 3, it is characterized in that, the mode that also possesses to surround described the first opening is arranged at the second sealing element of described electrolyzer body,
Described the first lid clips described the second sealing element and is arranged on described electrolyzer body.
5. an electrolyzer, possesses:
Accommodate the electrolyzer of electrolytic bath;
Next door, so that the mode that is distinguished into anolyte compartment and cathode compartment in described electrolyzer is arranged, and has the opening that the ion in described electrolytic bath can pass through;
Anode, is arranged on the described anolyte compartment of described electrolyzer; And
Negative electrode, is arranged on the described cathode compartment of described electrolyzer,
Wherein, the described opening in described next door has at least one upper surface extending obliquely upward in described anolyte compartment and described cathode compartment.
6. electrolyzer according to claim 5, is characterized in that, in described anolyte compartment, produces fluorine gas, and produces hydrogen in described cathode compartment,
The described upper surface of described opening arranges in the mode of extending towards described cathode compartment side direction oblique upper.
7. electrolyzer according to claim 6, is characterized in that, the area of the end of the described opening of cathode compartment side is little described in the Area Ratio of the end of the described opening of described anolyte compartment side.
8. according to the electrolyzer described in any one in claim 5 to 7, it is characterized in that, described next door comprises the liquid next door impregnated in described electrolytic bath,
Described opening is arranged at described liquid next door,
Described liquid next door is formed by perfluorinated resin.
9. according to the electrolyzer described in any one in claim 5 to 8, it is characterized in that, on the surface of described anode, apply the processing of conductive diamond coating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011143908A JP5824256B2 (en) | 2011-06-29 | 2011-06-29 | Electrolyzer |
| JP2011-143908 | 2011-06-29 | ||
| JP2011155066A JP2013019035A (en) | 2011-07-13 | 2011-07-13 | Gas generator |
| JP2011-155066 | 2011-07-13 | ||
| PCT/JP2012/004145 WO2013001800A1 (en) | 2011-06-29 | 2012-06-27 | Electrolysis device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103635609A true CN103635609A (en) | 2014-03-12 |
Family
ID=47423720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280032007.0A Pending CN103635609A (en) | 2011-06-29 | 2012-06-27 | Electrolysis device |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR20140035957A (en) |
| CN (1) | CN103635609A (en) |
| DE (1) | DE112012002702T8 (en) |
| TW (1) | TW201311935A (en) |
| WO (1) | WO2013001800A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111183247A (en) * | 2017-10-31 | 2020-05-19 | 关东电化工业株式会社 | Electrolytic cell for producing nitrogen trifluoride gas and partition wall thereof |
| CN112752869A (en) * | 2018-10-24 | 2021-05-04 | 昭和电工株式会社 | Fluorine gas production device |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015162868A1 (en) * | 2014-04-24 | 2015-10-29 | 東洋炭素株式会社 | Reaction device |
| JP6096258B1 (en) * | 2015-09-11 | 2017-03-15 | 株式会社ウォーターエージェンシー | Ozone water production equipment |
| KR101771862B1 (en) * | 2015-10-02 | 2017-08-28 | 후성정공 주식회사 | Collector of electrolyzer for manufacturing nitrogen trifluoride and manufacturing method the same |
| ITUB20155211A1 (en) | 2015-10-22 | 2017-04-22 | Pasquale Impero | DEFORMATION DRIVING SYSTEM FOR A ROAD SAFETY DEVICE AND ROAD SAFETY DEVICE GROUP |
| JPWO2021131815A1 (en) * | 2019-12-27 | 2021-07-01 |
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- 2012-06-27 DE DE112012002702.7T patent/DE112012002702T8/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| DE112012002702T8 (en) | 2014-04-10 |
| TW201311935A (en) | 2013-03-16 |
| DE112012002702T5 (en) | 2014-03-20 |
| KR20140035957A (en) | 2014-03-24 |
| WO2013001800A1 (en) | 2013-01-03 |
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Application publication date: 20140312 |