WO2020026854A1 - 電解合成用陽極、及び、フッ素ガス又は含フッ素化合物の製造方法 - Google Patents
電解合成用陽極、及び、フッ素ガス又は含フッ素化合物の製造方法 Download PDFInfo
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Definitions
- the present invention relates to an anode for electrolytically synthesizing a fluorine gas or a fluorine-containing compound, and a method for producing a fluorine gas or a fluorine-containing compound.
- Fluorine gas and a fluorine-containing compound can be synthesized (electrosynthesis) by electrolyzing an electrolytic solution containing fluoride ions.
- a carbon electrode is generally used as an anode.
- the electrolytic cell voltage required to obtain a predetermined current is 12 V
- a problem that the pressure becomes higher than the maximum pressure may occur. This phenomenon is called the anodic effect.
- the causes of the anodic effect are as follows.
- Non-Patent Document 1 discloses that lithium fluoride and aluminum fluoride are added to an electrolyte solution containing hydrogen fluoride, and pre-electrolysis (conditioning) is performed using a nickel electrode to reduce the amount of water in the electrolyte solution. A technique has been disclosed in which the anode effect is suppressed.
- Patent Document 1 discloses a conductive substrate made of a conductive carbonaceous material, a conductive carbonaceous film having a diamond structure coated on a part of the conductive substrate, and a conductive substrate coated on another part of the conductive substrate. And a carbonaceous film made of (CF) n .
- the electrolyte contains a large amount of water, the water reacts with the non-diamond-structured carbonaceous material during the electrolysis to produce graphite oxide, which easily reacts with fluorine gas to form (CF)
- CF fluorine gas
- a carbonaceous film consisting of n is formed.
- a conductive carbonaceous film having a diamond structure does not generate a covalent carbon-fluorine bond, so that an insulating film is unlikely to be formed on the surface.
- Non-Patent Document 1 has a problem in that the nickel electrode needs to be switched to the carbon electrode after performing the pre-electrolysis, so that the process of electrolytic synthesis becomes complicated. Further, the anode for electrolysis disclosed in Patent Document 1 has a problem that it is expensive because it is necessary to form a coating with a special material such as conductive carbon having a diamond structure.
- the present invention provides an anode for electrolytic synthesis capable of electrolytically synthesizing a fluorine gas or a fluorine-containing compound in a simple process at low cost while suppressing the generation of the anode effect, and a method for producing a fluorine gas or a fluorine-containing compound. The task is to
- An anode for electrolytic synthesis of fluorine gas or a fluorine-containing compound An anode for electrolytic synthesis, comprising: an anode substrate formed of a carbonaceous material; and a metal film covering the anode substrate, wherein the metal forming the metal film is nickel.
- [4] A method for producing fluorine gas or a fluorine-containing compound, wherein the electrolytic solution containing hydrogen fluoride is electrolyzed using the anode for electrolytic synthesis according to any one of [1] to [3].
- [5] Using the anode for electrolytic synthesis according to any one of [1] to [3], after performing a pre-electrolysis step of electrolyzing moisture contained in an electrolyte solution containing hydrogen fluoride. And a method for producing a fluorine gas or a fluorine-containing compound by electrolyzing the electrolytic solution containing hydrogen fluoride.
- FIG. 2 is a cross-sectional view of the electrolytic device of FIG. 1, which is virtually cut along a plane different from that of FIG. 1.
- FIG. 1 is a cross-sectional view of the electrolysis apparatus virtually cut off on a plane perpendicular to the plate surfaces of the electrosynthesis anode 3 and the electrosynthesis cathode 5 of the electrolysis apparatus and parallel to the vertical direction.
- FIG. 2 is a cross-sectional view of the electrolysis apparatus virtually cut along a plane parallel to the plate surfaces of the electrosynthesis anode 3 and the electrosynthesis cathode 5 of the electrolysis apparatus and parallel to the vertical direction. .
- the electrolytic apparatus shown in FIGS. 1 and 2 includes an electrolytic cell 1 in which an electrolytic solution 10 is stored, an electrolytic synthesis anode 3 and an electrolytic synthesis cathode 5 arranged in the electrolytic bath 1 and immersed in the electrolytic solution 10. It has.
- the inside of the electrolytic cell 1 is divided into an anode chamber 12 and a cathode chamber 14 by a cylindrical partition wall 7 extending vertically downward from the lid 1a of the electrolytic cell 1. That is, the area inside the cylindrical partition 7 is the anode chamber 12, and the area outside the cylindrical partition 7 is the cathode chamber 14.
- the shape of the electrolytic synthesis anode 3 is not limited, and may be, for example, a column. However, in this example, the anode 3 has a plate shape and is disposed in the anode chamber 12 so that the plate surface is parallel to the vertical direction. Have been.
- the shape of the electrolytic synthesis cathode 5 is not limited to a particular shape, and may be, for example, a columnar shape. In this example, the shape is plate-like, and its plate surface is parallel to the plate surface of the electrolytic synthesis anode 3.
- the cathodes 5 are arranged in the cathode chamber 14 so as to sandwich the anode 3 for electrolytic synthesis between the two cathodes 5 for electrolytic synthesis.
- the electrosynthesis cathodes 5 and 5 and the electrolyte solution 10 are cooled on the plate surface opposite to the plate surface facing the electrosynthesis anode 3.
- a cooler is installed for In the example of the electrolyzer shown in FIGS. 1 and 2, a cooling pipe 16 through which a cooling fluid flows is mounted on the electrolytic synthesis cathodes 5 and 5 as a cooler.
- an electrode having the following configuration can be used. That is, an electrode including an anode substrate formed of a carbonaceous material and a metal film covering the anode substrate, wherein the metal forming the metal film is nickel.
- a specific example is an electrode in which both surfaces of a carbon electrode plate are covered with a metal film formed of nickel.
- a metal electrode can be used, and for example, an electrode made of a nickel plate can be used.
- a molten salt can be used.
- molten potassium fluoride (KF) containing hydrogen fluoride (HF) can be used.
- the fluorine gas (F 2 ) Is produced as a main component
- a cathode gas containing hydrogen gas (H 2 ) as a main component is produced as a by-product in the electrolytic synthesis cathode 5.
- a fluorine-containing compound such as nitrogen trifluoride (NF 3 ) can be electrolytically synthesized at the electrolytic synthesis anode 3 by appropriately selecting the type of the electrolytic solution 10.
- the anode gas accumulates in a space above the liquid level of the electrolyte 10 in the anode chamber 12, and the cathode gas accumulates in a space above the liquid level of the electrolyte 10 in the cathode chamber 14. Since the space above the liquid surface of the electrolytic solution 10 is partitioned by the partition walls 7 into a space in the anode chamber 12 and a space in the cathode chamber 14, the anode gas and the cathode gas are not mixed. On the other hand, the electrolytic solution 10 is partitioned by the partition 7 at a portion above the lower end of the partition 7, but is not partitioned by the partition 7 at a portion below the lower end of the partition 7 and is continuous. ing.
- the anode chamber 12 is provided with an exhaust port 21 for discharging the anode gas generated by the anode for electrolytic synthesis 3 from the inside of the anode chamber 12 to the outside of the electrolytic cell 1.
- An exhaust port 23 is provided for discharging the cathode gas generated by the synthesis cathodes 5 and 5 from the inside of the cathode chamber 14 to the outside of the electrolytic cell 1.
- the anode for electrolytic synthesis 3 of the present embodiment includes the anode substrate formed of the carbonaceous material and the metal coating covering the anode substrate. And the metal film is formed of nickel.
- both pre-electrolysis and electrolytic synthesis can be performed. Therefore, when performing electrolytic synthesis after performing pre-electrolysis, the electrolytic synthesis anode is used from the anode for pre-electrolysis. It is not necessary to switch to the anode for use, and pre-electrolysis and electrolytic synthesis can be performed continuously. Therefore, if the electrolytic synthesis anode 3 of the present embodiment is used, the electrolytic synthesis of fluorine gas or a fluorine-containing compound can be performed in a simple process.
- the use of the electrolytic synthesis anode 3 of the present embodiment makes it possible to electrolytically synthesize fluorine gas or a fluorine-containing compound at low cost. Can be.
- the fluorine gas or the fluorine-containing compound for example, three Nitrogen fluoride
- the fluorine gas or the fluorine-containing compound can be electrolytically synthesized.
- a fluorine-containing compound such as uranium hexafluoride (UF 6 ), sulfur hexafluoride (SF 6 ), carbon tetrafluoride (CF 4 ), or nitrogen trifluoride is used. It can also be chemically synthesized. Fluorine-containing compounds such as fluorine gas, uranium hexafluoride, sulfur hexafluoride, carbon tetrafluoride, and nitrogen trifluoride are useful in the nuclear industry, semiconductor industry, medical and agricultural chemicals, and consumer applications. is there.
- Electrolyzer The material of the electrolyzer for electrosynthesis is not particularly limited, but it is preferable to use copper, mild steel, nickel alloys such as Monel (trademark), fluororesins, etc. from the viewpoint of corrosion resistance. .
- an anode chamber provided with the anode for electrolytic synthesis and a cathode for electrolytic synthesis It is preferable that all or a part of the cathode chamber in which is disposed is partitioned by a partition wall, a diaphragm, or the like, as in the electrolysis apparatus shown in FIGS.
- Electrolytic Solution An example of an electrolytic solution used when electrolytically synthesizing fluorine gas will be described.
- a mixed molten salt of hydrogen fluoride and potassium fluoride can be used as the electrolytic solution.
- the molar ratio between hydrogen fluoride and potassium fluoride in the electrolytic solution is preferably 1.8 or more and 2.2 or less as a value of (moles of hydrogen fluoride) / (moles of potassium fluoride). It is more preferably 1.9 or more and 2.1 or less, for example, 2: 1.
- an electrolytic solution used for electrolytically synthesizing a fluorine-containing compound will be described.
- a mixed molten salt of a compound having a chemical structure before fluorination of a fluorine-containing compound to be synthesized, hydrogen fluoride, and potassium fluoride can be used as an electrolytic solution.
- the compound having the chemical structure before fluorination may be gasified and electrolytic synthesis may be performed while blowing into a mixed molten salt of hydrogen fluoride and potassium fluoride, or the compound having the chemical structure before fluorination may be fluorinated.
- Electrosynthesis may be performed using an electrolytic solution dissolved in a mixed molten salt of hydrogen and potassium fluoride.
- the compound having the chemical structure before fluorination reacts with the fluorine gas generated by the reaction at the anode for electrolytic synthesis to become a fluorine-containing compound.
- a mixed molten salt of hydrogen fluoride and ammonium fluoride (NH 4 F) or a mixed molten salt of hydrogen fluoride, potassium fluoride, and ammonium fluoride is electrolyzed. It can be used as a liquid.
- a mixed molten salt of hydrogen fluoride and cesium fluoride (CsF) or a mixed molten salt of hydrogen fluoride, potassium fluoride, and cesium fluoride is also used for the synthesis of nitrogen trifluoride by adding ammonium fluoride. It can be used as an electrolyte.
- the molar ratio of hydrogen fluoride and ammonium fluoride in the electrolytic solution is represented by the value of (moles of hydrogen fluoride) / (moles of ammonium fluoride).
- 1.8 to 2.2 Preferably 1.8 to 2.2, more preferably 1.9 to 2.1, for example, 2: 1.
- the total molar ratio of hydrogen fluoride in the electrolytic solution to potassium fluoride and ammonium fluoride is (moles of hydrogen fluoride) /
- the value of (total mole number of potassium fluoride and ammonium fluoride) is preferably 1.8 or more and 2.2 or less, more preferably 1.9 or more and 2.1 or less, for example, 2: 1. can do.
- the molar ratio between potassium fluoride and ammonium fluoride is 1/9 or more and 1/1 or less as the value of (mol number of potassium fluoride) / (mol number of ammonium fluoride).
- the composition of the electrolytic solution containing cesium fluoride may be as follows. That is, the molar ratio between cesium fluoride and hydrogen fluoride in the electrolytic solution may be 1: 1.0 to 4.0. Further, the molar ratio of cesium fluoride, hydrogen fluoride, and potassium fluoride in the electrolyte may be 1: 1.5 to 4.0: 0.01 to 1.0.
- the electrolyte containing hydrogen fluoride generally contains 0.1% by mass or more and 5% by mass or less of water.
- the amount of water contained in the electrolyte containing hydrogen fluoride is determined by, for example, the method described in JP-A-7-2515.
- the water content may be reduced to 3% by mass or less and then used for the electrolyte.
- it is difficult to easily reduce the amount of water in an electrolytic solution containing hydrogen fluoride so when industrially synthesizing fluorine gas or a fluorine-containing compound, the water content is low in terms of cost. It is preferable to use an electrolyte solution of 3% by mass or less.
- Electrode for Electrosynthesis As described above, a metal electrode can be used as the cathode for electrosynthesis. Examples of the type of metal forming the metal electrode include iron, copper, and nickel alloy. (4) Anode for Electrosynthesis The anode for electrosynthesis of the present embodiment will be described in detail by taking an anode for electrosynthesis suitable for electrolytic synthesis of fluorine gas as an example. When electrolytic synthesis is performed using a conventional electrolytic synthesis anode made of a carbonaceous material such as graphite or amorphous carbon in an electrolytic solution made of a molten salt containing water, fluorine gas is generated at the anode. On the other hand, water contained in the electrolytic solution is electrolyzed to generate oxygen gas.
- Oxygen gas is recovered in gaseous form like fluorine gas, but some oxygen gas reacts with the carbonaceous material on the surface of the anode before being recovered. Then, the oxygen that has reacted with the carbonaceous material is replaced with fluorine and is recovered as oxygen gas. As a result of this reaction, an insulating film having a covalent carbon-fluorine bond is formed on the surface of the carbonaceous material, and an anodic effect occurs.
- the anode for electrolytic synthesis of the present embodiment has a portion formed of a carbonaceous material covered with a metal coating made of nickel, but oxygen gas does not react with metal as much as a carbonaceous material, Even if it reacts, it will subsequently react with fluorine gas and is thus recovered as oxygen gas.
- the metal film of the anode for electrolytic synthesis becomes a metal fluoride as electrolytic synthesis is continued. Then, the generated metal fluoride desorbs from the surface of the anode for electrolytic synthesis.
- the water contained in the electrolytic solution is decomposed and recovered as oxygen gas at the anode for electrolytic synthesis and as hydrogen gas at the cathode for electrolytic synthesis, so that it is removed from the electrolytic solution.
- no insulating film is formed on the metal film of the anode for electrolytic synthesis of the present embodiment, and the metal film peels off.
- the electrolytic synthesis of fluorine gas is continued in this manner, the metal film is sufficiently peeled off, and the underlying carbonaceous material appears on the surface (this step corresponds to the pre-electrolysis described in Non-Patent Document 1). ).
- the amount of water in the electrolytic solution has been sufficiently reduced. That is, if the pre-electrolysis is performed using the anode for electrolytic synthesis of the present embodiment, the amount of water in the electrolytic solution can be sufficiently reduced by the simple operation as described above.
- a metal coating with a metal having a property of forming no passivation even when reacting with fluorine gas and detaching from the anode for electrolytic synthesis.
- Nickel is effective as such a metal.
- the metal for forming the metal film nickel may be used alone, or two or more types obtained by adding another type of metal to nickel may be used in combination.
- a metal coating may be formed from an alloy of those metals, or a metal coating formed from each metal may be coated on the surface of the anode substrate of the anode for electrolytic synthesis. You may.
- the metal film may be formed with an alloy containing a transition element in nickel. The addition of the transition element can suppress the consumption of the anode for electrolytic synthesis.
- a metal film is formed on the surface of the anode substrate formed of a carbonaceous material, but the method for forming the metal film is not particularly limited, and the method for forming the metal film is not limited.
- a vacuum film forming method such as an evaporation method or a sputtering method can be used. Among these methods, electrolytic plating and electroless plating are preferred because they are simple.
- the metal coating is preferably formed so as to cover at least a part of the portion formed of the carbonaceous material of the anode substrate, and more preferably formed so as to cover all of the portion formed of the carbonaceous material. .
- the electrolytic synthesis anode is present even in the power supply unit that receives the electric power, the effect of preventing the contact resistance can be expected. If there is a portion of the surface of the anode for electrolytic synthesis that is in contact with the electrolytic solution and has no metal coating, the carbonaceous material composed of (CF) n A film forms and becomes insulated. On the other hand, if the metal film is formed, the portion where the metal film is formed is energized, so that the electrolysis proceeds. As a result, the metal coating peels off when the amount of water in the electrolyte decreases, and the underlying carbonaceous material appears on the surface. Then, since the electrolytic synthesis proceeds on the surface of the newly appearing carbonaceous material, the electrolytic synthesis can be continued without any problem.
- the carbonaceous material used for the anode substrate graphite, amorphous carbon, carbon nanotube, graphene, conductive single-crystal diamond, conductive polycrystalline diamond, conductive diamond-like carbon, and the like, which are usually used for electrolysis, can be used.
- the shape of the carbonaceous material is not particularly limited, it is preferable that the carbonaceous material has a plate shape because the power supply unit can be easily attached. If the portion made of the carbonaceous material exists in the lower layer of the metal coating, there may be a portion made of a material having a low resistance in the anode substrate further below the portion made of the carbonaceous material, or in order to impart strength. There may be a portion made of another material.
- the mass of nickel which is a metal forming the metal coating, is preferably 0.01 g or more and 0.1 g or less per 1 cm 2 of the surface of the anode substrate formed of the carbonaceous material. If the mass of nickel is within the above range, since the nickel does not dissolve before the water in the electrolytic solution is pre-electrolyzed and the underlying carbonaceous material appears, the anodic oxidation phenomenon occurs on the surface of the carbonaceous material. And the formation of a covalent carbon-fluorine bond that causes anodic polarization. Moreover, the possibility that the amount of dissolved nickel becomes too large and the dissolved nickel is reduced at the cathode and deposited as fluoride sludge in the electrolytic cell is also reduced. For this purpose, the mass of nickel is more preferably 0.03 g or more and 0.07 g or less per 1 cm 2 of the surface of the anode substrate formed of the carbonaceous material.
- the mass of nickel which is the metal forming the metal coating, is preferably 0.03% by mass or more and 0.4% by mass or less of the mass of the electrolytic solution used for electrolytic synthesis. If the mass of nickel is within the above range, since the nickel does not dissolve before the water in the electrolytic solution is pre-electrolyzed and the underlying carbonaceous material appears, the anodic oxidation phenomenon occurs on the surface of the carbonaceous material. And the formation of a covalent carbon-fluorine bond that causes anodic polarization. Moreover, the possibility that the amount of dissolved nickel becomes too large and the dissolved nickel is reduced at the cathode and deposited as fluoride sludge in the electrolytic cell is also reduced. For this purpose, the mass of nickel is more preferably 0.1% by mass or more and 0.2% by mass or less.
- the surface area (apparent surface area determined by measurement) of a portion through which current flows in electrolytic synthesis is 20 cm 2 or more and 100 cm 2 or less per 1 L of the electrolytic solution. Is preferred. If the surface area of the portion where the current flows is within the above range, the time until the water in the electrolytic solution is dehydrated by the pre-electrolysis is not lengthened, and the possibility that the economic efficiency is reduced is reduced. Further, the distance between the anode for electrolytic synthesis and the cathode for electrolytic synthesis can be kept at an appropriate level, and current efficiency and economic efficiency are not easily reduced.
- anode for electrolytic synthesis to be installed in the electrolytic cell it is preferable to install an electrode whose entire surface is covered with nickel.
- a nickel-coated electrode and a non-nickel-coated electrode are installed.
- a method may be adopted in which, after the termination, the electrode not covered with nickel is energized.
- the electrolysis may be performed at a current density of 0.001 A / cm 2 or more and 5 A / cm 2 or less.
- the water in the electrolytic solution is removed.
- Completion of the removal of water from the electrolyte can be known by measuring the amount of oxygen gas in the generated fluorine gas.
- FIGS. 1 and 2 An electrolytic device having the same configuration as the electrolytic device shown in FIGS. 1 and 2 was prepared. However, two carbon electrode plates were used for the anode. The dimensions of the carbon electrode plate are 45 cm long, 28 cm wide, and 7 cm thick. The anode and the lid of the electrolytic cell are electrically insulated. Further, the main body of the electrolytic cell and the metal plate made of Monel are used as a cathode, and both are electrically connected (not shown). Further, the main body and the lid of the electrolytic cell are electrically insulated.
- a cooling pipe is welded to the metal plate made of Monel, and a Teflon (registered trademark) plate is laid on the bottom surface to prevent generation of hydrogen from the bottom surface inside the main body of the electrolytic cell. . Furthermore, the area of the portion of the anode through which current flows is 2800 cm 2 (25 cm ⁇ 28 cm ⁇ 4). Since hydrogen fluoride in the electrolytic solution is consumed by the electrolysis, the electrolytic solution is supplied to the electrolytic cell so that the level of the electrolytic solution is constant. At this time, by controlling the water content of the supplied electrolytic solution to a low level, the water content in the system can be hardly increased.
- a mixed molten salt of potassium fluoride and hydrogen fluoride (KF ⁇ 2HF) was used as the electrolytic solution.
- the amount of water in the electrolyte is measured by the Karl Fischer method and is 2.4% by mass (2.66 kg).
- the electrolytic solution was placed in the electrolytic cell, and the temperature of the electrolytic solution was controlled at 90 ° C. by heating with an external heater and cooling with a cooling pipe through which hot water at 65 ° C. was passed.
- a sheet made of Viton which is a fluorinated hydrocarbon polymer, is 1 cm long, 2 cm wide, and has a thickness of 0. 5 cm
- the composition of the generated gas can be estimated from the change in the state of the sheet. In other words, when sufficient fluorine gas and an appropriate amount of oxygen gas coexist in the electrolysis temperature atmosphere, the sheet is burned out, and almost no oxygen gas is present even when the amount of fluorine gas is small or sufficient fluorine gas is present. It has been empirically found that if not, the seat will not change.
- Comparative Example 2 Pre-electrolysis was performed in the same manner as in Comparative Example 1 except that a carbon electrode plate whose surface was coated with a conductive diamond film was used as an anode. First, a DC current of 280 A (current density: 0.1 A / cm 2 ) was passed through the electrolysis apparatus. However, since the cell voltage did not exceed 12 V, electrolysis was continued for 31 hours, and 8680 Ah of electricity was supplied.
- a DC current of 280 A current density: 0.1 A / cm 2
- Comparative Example 3 Pre-electrolysis was performed in the same manner as in Comparative Example 1 except that a nickel plate was used as an anode. The distance between the electrodes was the same as in the case of the carbon electrode plate. First, a DC current of 280 A (current density: 0.1 A / cm 2 ) was passed through the electrolysis apparatus. However, since the cell voltage did not exceed 12 V, electrolysis was continued for 31 hours, and 8680 Ah of electricity was supplied.
- the anode was changed from a nickel plate to a new carbon electrode plate, and the test piece was placed on the carbon electrode plate. Then, when the electrolysis was performed again by passing a direct current of 280 A (current density: 0.1 A / cm 2 ) into the electrolysis apparatus, the cell voltage became 12 V or more when the electric current of 500 kAh was applied. When the lid of the electrolytic cell was opened after the current of 500 kAh was applied, the test piece placed on the carbon electrode plate was burned out, and it was presumed that moisture was mixed in by the replacement work of the anode.
- Example 1 Pre-electrolysis was performed in the same manner as in Comparative Example 1, except that a carbon electrode plate whose surface was coated with a metal film formed of nickel was used as an anode. The metal coating was applied only to the portion of the carbon electrode plate that was in contact with the electrolyte (that is, the portion that was immersed in the electrolyte). The metal film was coated on the carbon electrode plate by nickel electrolytic plating, and after nickel electrolytic plating, washed with water and sufficiently dried was used as the electrode.
- the one carbon electrode plates and 100g of nickel is coated, the effective electrode area is 2800 cm 2, the plating weight of about 0.07g per 1 cm 2. Since there are two carbon electrode plates, the total amount of nickel plated on the carbon electrode plate is 200 g, which corresponds to 0.18% by mass of the mass of the electrolytic solution.
- the electrolysis was continued by passing a DC current of 280 A (current density: 0.1 A / cm 2 ) into the electrolysis apparatus.
- a DC current of 280 A current density: 0.1 A / cm 2
- the anode gas generated at the anode during the electrolysis was analyzed, most of the anode gas was fluorine gas, and the concentration of oxygen in the anode gas was 0.05% by volume or less. Also, the current efficiency of fluorine gas generation was found to be 90%.
- the energization was temporarily stopped, and the lid of the electrolytic cell was opened to check the state of the test piece. However, no change was observed, and the metal coating formed of nickel was dissolved.
- the method for analyzing the anode gas is as follows. Fluorine gas in the anode gas is absorbed into an aqueous solution of potassium iodide, and liberated iodine (I 2 ) is titrated with a sodium thiosulfate (Na 2 S 2 O 3 ) solution to identify and generate fluorine gas. was measured. Further, after passing the anode gas through a sodium fluoride packed tower to remove hydrogen fluoride in the anode gas, the fluorine gas is converted into chlorine gas by sodium chloride, and the chlorine gas in the obtained gas is adsorbed (NaOH). ). Then, the residual gas was analyzed by gas chromatography to calculate the concentration of oxygen gas in the anode gas.
- Example 2 Pre-electrolysis was performed in the same manner as in Example 1 except that the conditions of nickel electroplating performed when manufacturing the carbon electrode plate serving as the anode were different.
- the two effective area portion of the carbon electrode plates and 33g of nickel is coated, the effective electrode area is 2800 cm 2, the plating weight of about 0.01g per 1 cm 2.
- the total amount of nickel plated on the carbon electrode plate was 33 g, which corresponds to 0.03% by mass of the electrolyte solution.
- the electrolysis was continued by passing a DC current of 280 A (current density: 0.1 A / cm 2 ) into the electrolysis apparatus.
- a DC current of 280 A current density: 0.1 A / cm 2
- the anode gas generated at the anode during the electrolysis was analyzed, most of the anode gas was fluorine gas, and the concentration of oxygen in the anode gas was 0.05% by volume or less. Also, the current efficiency of fluorine gas generation was found to be 90%.
- the energization was temporarily stopped, and the lid of the electrolytic cell was opened to check the state of the test piece. However, no change was observed, and the metal coating formed of nickel was dissolved.
- Example 3 Pre-electrolysis was performed in the same manner as in Example 1 except that the conditions of nickel electroplating performed when manufacturing the carbon electrode plate serving as the anode were different.
- the one of the effective area portion of the carbon electrode plates and 10g of nickel is coated, the effective electrode area is 2800 cm 2, the plating weight of about 0.007g per 1 cm 2. Since there are two carbon electrode plates, the total amount of nickel plated on the carbon electrode plate is 20 g, which corresponds to 0.018% by mass of the mass of the electrolytic solution.
- Example 1 As in Example 1, first, a DC current of 280 A (current density: 0.1 A / cm 2 ) was passed through the electrolysis apparatus, but after the electrolysis was continued for 10 hours, the cell voltage gradually started to rise and exceeded 11 V. Therefore, electrolysis was temporarily stopped. The amount of energization was 2800 Ah. The current value was reduced to 200 A (current density 0.07 A / cm 2 ), electrolysis was continued for 29 hours while the cell voltage did not exceed 12 V, and 5800 Ah was supplied. A total of 8600 Ah of electricity was supplied. When the amount of water in the electrolytic solution was measured by sampling the electrolytic solution, it decreased by 1.66 kg to 1.00 kg, and it was found that 57% of the amount of electricity was used for the electrolysis of water.
- 280 A current density: 0.1 A / cm 2
- the electrolysis was continued by passing a DC current of 280 A (current density: 0.1 A / cm 2 ) into the electrolysis apparatus. Since the cell voltage exceeded 11 V but was 12 V or less, 500 kAh of electricity was applied.
- the anode gas generated at the anode during the electrolysis was analyzed, most of the anode gas was fluorine gas, and the concentration of oxygen in the anode gas was 0.05% by volume or less. Also, the current efficiency of fluorine gas generation was found to be 90%.
- the energization was temporarily stopped, and the lid of the electrolytic cell was opened to check the state of the test piece. However, no change was observed, and the metal coating formed of nickel was dissolved.
- Example 4 Pre-electrolysis was performed in the same manner as in Example 1 except that the conditions of nickel electroplating performed when manufacturing the carbon electrode plate serving as the anode were different.
- the two effective area portion of the carbon electrode plates and 500g of nickel is coated, the effective electrode area is 2800 cm 2, the plating weight of about 0.18g per 1 cm 2.
- the total amount of nickel plated on the carbon electrode plate was 500 g, which corresponds to 0.45% by mass of the mass of the electrolytic solution.
- the electrolysis was continued by passing a DC current of 280 A (current density: 0.1 A / cm 2 ) into the electrolysis apparatus. Further, when the anode gas generated at the anode during the electrolysis was analyzed, most of the anode gas was fluorine gas, and the concentration of oxygen in the anode gas was 0.05% by volume or less. Also, the current efficiency of fluorine gas generation was found to be 90%. At this time, the current was stopped once, the lid of the electrolytic cell was opened, and the state of the test piece was checked. However, no change was observed, and the metal film formed by nickel was dissolved, but the nickel film was Was deposited.
- 280 A current density: 0.1 A / cm 2
- Example 4 Pre-electrolysis was performed in the same manner as in Example 1 except that the conditions of nickel electroplating performed when manufacturing the carbon electrode plate serving as the anode were different.
- the one carbon electrode plates and 10g of nickel is coated, the effective electrode area is 2800 cm 2, the plating weight of about 0.007g per 1 cm 2. Since there are two carbon electrode plates, the total amount of nickel plated on the carbon electrode plate is 20 g, which corresponds to 0.018% by mass of the mass of the electrolytic solution.
- Example 1 As in Example 1, a DC current of 280 A (current density: 0.1 A / cm 2 ) was passed through the electrolysis apparatus. However, when electrolysis was continued for 10 hours, the cell voltage gradually started to rise and exceeded 12 V. Interrupted. This is presumed to have caused the anode effect. The amount of energization was 2800 Ah. The electrolytic solution was sampled, and the amount of water in the electrolytic solution was measured. As a result, it was 1.8% by mass. Thus, it was found that 70% of the amount of electricity was used for electrolysis of the moisture. Subsequently, an attempt was made to conduct electrolysis through a DC current of 280 A through the electrolysis apparatus, but the electrolysis could not be continued because the cell voltage exceeded 12 V.
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Abstract
Description
陽極効果が発生する原因は、以下の通りである。電解液の電気分解を行うと、陽極の表面で発生したフッ素ガスが、陽極を形成する炭素と反応するため、陽極の表面に、共有結合性の炭素-フッ素結合を有する被膜が形成される。この被膜は絶縁性で電解液との濡れ性も悪いため、陽極に電流が流れにくくなり、陽極効果が発生する。そして、陽極効果が進行すると、継続した電気分解が不可能になる場合がある。表面が絶縁性の被膜で覆われた陽極を、電解合成に使用可能とするためには、表面を研磨して被膜を除去する必要がある。
また、特許文献1には、導電性炭素質材料からなる導電性基体と、導電性基体の一部に被覆されたダイヤモンド構造を有する導電性炭素質被膜と、導電性基体の他部に被覆された(CF)nからなる炭素質被膜と、を有する電解用陽極が開示されている。
電解液中に水分が多い場合は、電解中に水分と非ダイヤモンド構造の炭素質材料部分とが反応して酸化グラファイトが生成し、この酸化グラファイトがフッ素ガスと容易に反応して、(CF)nからなる炭素質被膜が生成する。ダイヤモンド構造を有する導電性炭素質被膜は、非ダイヤモンド構造の炭素電極とは異なり、共有結合性の炭素-フッ素結合が生成しないため、表面に絶縁性の被膜が生成しにくい。
本発明は、陽極効果の発生を抑制しつつ簡易な工程で且つ安価にフッ素ガス又は含フッ素化合物を電解合成することができる電解合成用陽極、及び、フッ素ガス又は含フッ素化合物の製造方法を提供することを課題とする。
[1] フッ素ガス又は含フッ素化合物を電解合成するための陽極であって、
炭素質材料で形成された陽極基体と、前記陽極基体を被覆する金属被膜と、を備え、前記金属被膜を形成する金属がニッケルである電解合成用陽極。
[2] 前記金属被膜を形成するニッケルの質量が、前記電解合成に用いられる電解液の質量の0.03質量%以上0.4質量%以下である[1]に記載の電解合成用陽極。
[3] 前記金属被膜を形成するニッケルの質量が、前記陽極基体の表面1cm2当たり0.01g以上0.1g以下である[1]又は[2]に記載の電解合成用陽極。
[5] [1]~[3]のいずれか一項に記載の電解合成用陽極を用いて、フッ化水素を含有する電解液に含有される水分を電気分解する前電解工程を行った後に、前記フッ化水素を含有する電解液を電気分解する、フッ素ガス又は含フッ素化合物の製造方法。
電解液10としては、溶融塩を用いることができ、例えば、フッ化水素(HF)を含有する溶融フッ化カリウム(KF)を用いることができる。
一方、電解液10は、隔壁7の下端よりも上方側の部分については隔壁7によって区画されているが、隔壁7の下端よりも下方側の部分については隔壁7によって区画されておらず連続している。
上記のように、本実施形態の電解合成用陽極3は、炭素質材料で形成された陽極基体と、陽極基体を被覆する金属被膜と、を備えている。そして、金属被膜がニッケルで形成されている。
以上のように、本実施形態の電解合成用陽極3を用いて電解液の電気分解を行えば、陽極効果の発生を抑制しつつ簡易な工程で且つ安価にフッ素ガス又は含フッ素化合物(例えば三フッ化窒素)を電解合成することができる。
(1)電解槽
電解合成を行う電解槽の材質は特に限定されるものではないが、耐食性の点から、銅、軟鋼、モネル(商標)等のニッケル合金、フッ素樹脂等を使用することが好ましい。
電解合成用陽極で電解合成されたフッ素ガス又は含フッ素化合物と、電解合成用陰極で生成した水素ガスとの混合を防止するために、電解合成用陽極が配された陽極室と電解合成用陰極が配された陰極室は、図1、2に示す電解装置のように、隔壁、隔膜等によって、その全部又は一部が区画されていることが好ましい。
フッ素ガスを電解合成する場合に用いる電解液の一例について説明する。フッ素ガスを電解合成する場合には、フッ化水素とフッ化カリウムの混合溶融塩を、電解液として用いることができる。電解液中のフッ化水素とフッ化カリウムのモル比は、(フッ化水素のモル数)/(フッ化カリウムのモル数)の値として、好ましくは1.8以上2.2以下であり、より好ましくは1.9以上2.1以下であり、例えば2:1とすることができる。
フッ化水素とフッ化カリウムとフッ化アンモニウムの混合溶融塩の場合、電解液中のフッ化水素と、フッ化カリウム及びフッ化アンモニウムの合計のモル比は、(フッ化水素のモル数)/(フッ化カリウム及びフッ化アンモニウムの合計のモル数)の値として、好ましくは1.8以上2.2以下であり、より好ましくは1.9以上2.1以下であり、例えば2:1とすることができる。この場合、フッ化カリウムとフッ化アンモニウムのモル比は、(フッ化カリウムのモル数)/(フッ化アンモニウムのモル数)の値として、1/9以上1/1以下である。
前述したように、電解合成用陰極として金属製電極を用いることができる。金属製電極を形成する金属の種類としては、例えば、鉄、銅、ニッケル合金があげられる。
(4)電解合成用陽極
本実施形態の電解合成用陽極について、フッ素ガスを電解合成する際に好適な電解合成用陽極を例にして、詳細に説明する。
水分を含有する溶融塩からなる電解液中で、黒鉛や無定形カーボンのような炭素質材料からなる従来の電解合成用陽極を用いて電解合成を行った場合は、陽極においてフッ素ガスが発生する一方で、電解液に含有される水分が電解されて酸素ガスが発生する。
金属被膜は、陽極基体の炭素質材料で形成された部分の少なくとも一部分を被覆するように形成することが好ましく、炭素質材料で形成された部分の全部を被覆するように形成することがより好ましい。
炭素質材料からなる部分が金属被膜の下層に存在していれば、陽極基体において炭素質材料からなる部分のさらに下層に抵抗の少ない材質からなる部分があってもよいし、強度を持たせるための他の材質からなる部分があってもよい。
〔比較例1〕
図1、2に示す電解装置と同様の構成の電解装置を用意した。ただし、陽極には、2枚の炭素電極板を用いた。この炭素電極板の寸法は、縦45cm、横28cm、厚さ7cmである。陽極と電解槽の蓋とは電気的に絶縁されている。また、電解槽の本体とモネル製の金属板とが陰極とされ、両者は導通している(図示せず)。さらに、電解槽の本体と蓋とは電気的に絶縁されている。モネル製の金属板には冷却管が溶接されており、また、電解槽の本体の内側の底面からの水素の発生を防止するために、底面にはテフロン(登録商標)板が敷かれている。さらに、陽極のうち電流が流れる部分の面積は、2800cm2(25cm×28cm×4)である。電解によって電解液中のフッ化水素が消費されるので、電解液の液レベルが一定になるように電解槽に電解液が供給されるようになっている。このとき、供給される電解液の水分量を低いレベルに制御することによって、系内の水分量をほとんど増加させないことができる。
導電性ダイヤモンド被膜で表面を被覆した炭素電極板を陽極として用いた点以外は、比較例1と同様にして前電解を行った。
まず、電解装置に280A(電流密度0.1A/cm2)の直流電流を通じたが、槽電圧は12Vを超えることはなかったので、31時間電解を継続し8680Ahの通電を行った。
比較例1に比べて前電解の時間を短縮することはできたが、電解初期に発生する燃焼性の高いガス組成(十分なフッ素ガスと適当量の酸素ガスとが共存)は変わらず、異常反応を抑えることはできなかった。
ニッケル板を陽極として用いた点以外は、比較例1と同様にして前電解を行った。極間の距離は、炭素電極板の場合と同じになるようにした。
まず、電解装置に280A(電流密度0.1A/cm2)の直流電流を通じたが、槽電圧は12Vを超えることはなかったので、31時間電解を継続し8680Ahの通電を行った。
ニッケルにより形成された金属被膜で表面を被覆した炭素電極板を陽極として用いた点以外は、比較例1と同様にして前電解を行った。なお、金属被膜は、炭素電極板のうち電解液に接触する部分(すなわち、電解液に浸漬される部分)のみに被覆した。金属被膜はニッケル電解メッキにより炭素電極板に被覆し、ニッケル電解メッキを行った後に水洗して十分に乾燥したものを電極として用いた。
陽極である炭素電極板を製造する際に行うニッケル電解メッキの条件が異なる点以外は、実施例1と同様にして前電解を行った。
2枚の炭素電極板の有効面積部位には33gのニッケルが被覆されており、有効な電極面積は2800cm2であるので、メッキ量は1cm2当たり約0.01gである。炭素電極板にメッキされたニッケルの総量は33gであり、電解液の質量の0.03質量%に当たる。
陽極である炭素電極板を製造する際に行うニッケル電解メッキの条件が異なる点以外は、実施例1と同様にして前電解を行った。
1枚の炭素電極板の有効面積部位には10gのニッケルが被覆されており、有効な電極面積は2800cm2であるので、メッキ量は1cm2当たり約0.007gである。炭素電極板は2枚であるので、炭素電極板にメッキされたニッケルの総量は20gであり、電解液の質量の0.018質量%に当たる。
陽極である炭素電極板を製造する際に行うニッケル電解メッキの条件が異なる点以外は、実施例1と同様にして前電解を行った。
2枚の炭素電極板の有効面積部位には500gのニッケルが被覆されており、有効な電極面積は2800cm2であるので、メッキ量は1cm2当たり約0.18gである。炭素電極板にメッキされたニッケルの総量は500gであり、電解液の質量の0.45質量%に当たる。
陽極である炭素電極板を製造する際に行うニッケル電解メッキの条件が異なる点以外は、実施例1と同様にして前電解を行った。
1枚の炭素電極板には10gのニッケルが被覆されており、有効な電極面積は2800cm2であるので、メッキ量は1cm2当たり約0.007gである。炭素電極板は2枚であるので、炭素電極板にメッキされたニッケルの総量は20gであり、電解液の質量の0.018質量%に当たる。
電解液をサンプリングして、電解液中の水分量を測定したところ1.8質量%であったので、通電量の70%が水分の電気分解に使用されたことが分かった。引き続いて電解装置に280Aの直流電流を通じて電解を試みたが、槽電圧が12Vを超えるため電解を継続することはできなかった。
3 電解合成用陽極
5 電解合成用陰極
10 電解液
Claims (5)
- フッ素ガス又は含フッ素化合物を電解合成するための陽極であって、
炭素質材料で形成された陽極基体と、前記陽極基体を被覆する金属被膜と、を備え、前記金属被膜を形成する金属がニッケルである電解合成用陽極。 - 前記金属被膜を形成するニッケルの質量が、前記電解合成に用いられる電解液の質量の0.03質量%以上0.4質量%以下である請求項1に記載の電解合成用陽極。
- 前記金属被膜を形成するニッケルの質量が、前記陽極基体の表面1cm2当たり0.01g以上0.1g以下である請求項1又は請求項2に記載の電解合成用陽極。
- 請求項1~3のいずれか一項に記載の電解合成用陽極を用いて、フッ化水素を含有する電解液を電気分解する、フッ素ガス又は含フッ素化合物の製造方法。
- 請求項1~3のいずれか一項に記載の電解合成用陽極を用いて、フッ化水素を含有する電解液に含有される水分を電気分解する前電解工程を行った後に、前記フッ化水素を含有する電解液を電気分解する、フッ素ガス又は含フッ素化合物の製造方法。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60221591A (ja) * | 1984-04-17 | 1985-11-06 | Central Glass Co Ltd | フツ素の製造方法 |
JPH04100262U (ja) * | 1991-01-29 | 1992-08-31 | ||
JPH072515A (ja) | 1993-01-19 | 1995-01-06 | British Nuclear Fuels Plc | フッ化物混合物の脱水 |
US5744022A (en) * | 1997-02-19 | 1998-04-28 | Miller; Jorge | Method and apparatus for producing sulfur hexafluoride |
JP2000313981A (ja) * | 1999-04-27 | 2000-11-14 | Toyo Tanso Kk | フッ素電解用炭素電極 |
JP3893397B2 (ja) | 2005-03-14 | 2007-03-14 | ペルメレック電極株式会社 | 電解用陽極および該電解用陽極を使用するフッ素含有物質の電解合成方法 |
JP2009001877A (ja) * | 2007-06-22 | 2009-01-08 | Permelec Electrode Ltd | 導電性ダイヤモンド電極構造体及びフッ素含有物質の電解合成方法 |
JP2009215578A (ja) * | 2008-03-07 | 2009-09-24 | Toyohashi Univ Of Technology | フッ素電解装置 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2534638A (en) * | 1947-12-17 | 1950-12-19 | Harshaw Chem Corp | Electrolytic production of fluorine |
GB2135335B (en) * | 1983-02-24 | 1986-11-19 | British Nuclear Fuels Plc | Supports for carbon electrodes |
DE69415025T2 (de) * | 1993-09-03 | 1999-08-05 | Minnesota Mining And Mfg. Co., Saint Paul, Minn. | Fluor-zelle |
GB9418598D0 (en) | 1994-09-14 | 1994-11-02 | British Nuclear Fuels Plc | Fluorine cell |
CN100590229C (zh) * | 2007-10-17 | 2010-02-17 | 中南大学 | 制氟碳阳极化学气相沉积热解碳抗极化涂层制备方法 |
JP5772102B2 (ja) * | 2011-03-17 | 2015-09-02 | セントラル硝子株式会社 | フッ素化合物の電解合成用電極 |
-
2019
- 2019-07-19 CN CN201980050052.0A patent/CN112513333A/zh active Pending
- 2019-07-19 US US17/263,616 patent/US20210292923A1/en active Pending
- 2019-07-19 KR KR1020217002515A patent/KR102617579B1/ko active IP Right Grant
- 2019-07-19 EP EP19844681.7A patent/EP3831984A4/en active Pending
- 2019-07-19 WO PCT/JP2019/028482 patent/WO2020026854A1/ja unknown
- 2019-07-19 JP JP2020533430A patent/JP7428126B2/ja active Active
- 2019-07-26 TW TW108126536A patent/TWI720556B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60221591A (ja) * | 1984-04-17 | 1985-11-06 | Central Glass Co Ltd | フツ素の製造方法 |
JPH04100262U (ja) * | 1991-01-29 | 1992-08-31 | ||
JPH072515A (ja) | 1993-01-19 | 1995-01-06 | British Nuclear Fuels Plc | フッ化物混合物の脱水 |
US5744022A (en) * | 1997-02-19 | 1998-04-28 | Miller; Jorge | Method and apparatus for producing sulfur hexafluoride |
JP2000313981A (ja) * | 1999-04-27 | 2000-11-14 | Toyo Tanso Kk | フッ素電解用炭素電極 |
JP3893397B2 (ja) | 2005-03-14 | 2007-03-14 | ペルメレック電極株式会社 | 電解用陽極および該電解用陽極を使用するフッ素含有物質の電解合成方法 |
JP2009001877A (ja) * | 2007-06-22 | 2009-01-08 | Permelec Electrode Ltd | 導電性ダイヤモンド電極構造体及びフッ素含有物質の電解合成方法 |
JP2009215578A (ja) * | 2008-03-07 | 2009-09-24 | Toyohashi Univ Of Technology | フッ素電解装置 |
Non-Patent Citations (2)
Title |
---|
INDUSTRIAL & ENGINEERING CHEMISTRY'', (U.S., vol. 39, 1947, pages 259 - 262 |
See also references of EP3831984A4 |
Also Published As
Publication number | Publication date |
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TWI720556B (zh) | 2021-03-01 |
CN112513333A (zh) | 2021-03-16 |
KR102617579B1 (ko) | 2023-12-27 |
EP3831984A4 (en) | 2021-09-29 |
EP3831984A1 (en) | 2021-06-09 |
JPWO2020026854A1 (ja) | 2021-08-05 |
JP7428126B2 (ja) | 2024-02-06 |
TW202024400A (zh) | 2020-07-01 |
KR20210024110A (ko) | 2021-03-04 |
US20210292923A1 (en) | 2021-09-23 |
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