WO2015033887A1 - 二酸化塩素製造装置及び二酸化塩素製造方法 - Google Patents
二酸化塩素製造装置及び二酸化塩素製造方法 Download PDFInfo
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- WO2015033887A1 WO2015033887A1 PCT/JP2014/072910 JP2014072910W WO2015033887A1 WO 2015033887 A1 WO2015033887 A1 WO 2015033887A1 JP 2014072910 W JP2014072910 W JP 2014072910W WO 2015033887 A1 WO2015033887 A1 WO 2015033887A1
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- chlorine dioxide
- anode chamber
- aeration
- anolyte
- chamber
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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
- C25B1/26—Chlorine; 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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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
Definitions
- the present invention relates to an apparatus and method for producing chlorine dioxide by electrolyzing an anolyte containing chlorite using a diaphragm type electrolytic cell having an anode chamber and a cathode chamber.
- Examples of conventional chlorine dioxide production apparatuses and chlorine dioxide production methods include those shown in Patent Document 1 below.
- electrolytic treatment is carried out while supplying an anolyte containing chlorite and a catholyte containing sodium hydroxide or sodium chloride to the anode chamber and the cathode chamber of the diaphragm type electrolytic cell.
- An apparatus and method for generating chlorine dioxide is described.
- a chlorine dioxide production apparatus equipped with a diaphragm type electrolytic cell has a higher production efficiency of chlorine dioxide than a one-pack type chlorine dioxide production apparatus that does not use a diaphragm.
- the generated chlorine dioxide tends to be highly concentrated in the apparatus, and the risk of causing an explosion increases. Therefore, it is necessary to dilute the chlorine dioxide as quickly as possible.
- the chlorine dioxide production apparatus of Patent Document 1 is configured to recover and dilute chlorine dioxide by transferring an anolyte in which chlorine dioxide is dissolved to an aeration tank via a pipe and performing aeration treatment. During transfer to the aeration tank, chlorine dioxide may not be completely dissolved in the anolyte and may explode, and the apparatus configuration is complicated.
- An object of the present invention is to produce chlorine dioxide with a simpler configuration and method, to rapidly dilute the concentration of chlorine dioxide, and to easily carry out waste liquid treatment of each of anolyte and catholyte.
- An object of the present invention is to provide a chlorine dioxide production apparatus and a chlorine dioxide production method that can be used.
- a first characteristic configuration according to the chlorine dioxide production apparatus of the present invention has an anode chamber and a cathode chamber, and generates chlorine dioxide by electrolytic treatment of an anolyte containing chlorite supplied to the anode chamber.
- a diaphragm type electrolytic cell a flow passage section that communicates the anode chamber and the cathode chamber, a discharge section that communicates the cathode chamber and the outside, and an aeration that supplies aeration gas to the anode chamber so that the supply amount can be adjusted.
- Means, and a neutralizing means for supplying a neutralizing agent to at least one of the cathode chamber and the discharge section, and electrolyzing the anolyte in the anode chamber to generate chlorine dioxide, and the aeration
- the generated chlorine dioxide is recovered by supplying aeration gas to the anolyte in the anode chamber by means, and the anolyte after electrolytic treatment and aeration treatment in the anode chamber passes through the flow path section.
- the anolyte can be aerated by supplying the aerated gas to the anode chamber by the aeration means.
- This makes it possible to quickly dilute the chlorine dioxide concentration while avoiding the dissolution of the generated chlorine dioxide in the anolyte and avoid explosions, so that the generated chlorine dioxide can be recovered more efficiently and safely. be able to.
- it since it is the structure which supplies aeration gas directly to an anode chamber, it is not necessary to provide an aeration tank etc. separately, and an apparatus structure is simplified.
- the anolyte after electrolytic treatment and aeration treatment in the anode chamber can be transferred to the cathode chamber via the flow path portion and used as it is as the catholyte.
- the anolyte and the catholyte are supplied independently to the anode chamber and the cathode chamber, respectively. Therefore, a supply system such as a storage tank or a liquid feed pump for supplying the anolyte and the catholyte is used as an anode. It was necessary for each of the room and the cathode room. However, with this configuration, since only the supply system for the anode chamber is required, the apparatus configuration is simplified and various costs can be reduced.
- the anolyte after electrolytic treatment and aeration treatment in the anode chamber is transferred to the cathode compartment through the flow path portion and subjected to electrolytic treatment.
- electrolytic treatment even if a part of the generated chlorine dioxide remains in the anolyte without being collected in the anode chamber, it is cathodic reduced in the cathode chamber to become chlorite.
- the catholyte having a high pH after being electrolyzed in the cathode chamber is neutralized in at least one of the cathode chamber and the discharge section by the neutralizing agent supplied from the neutralizing means. .
- the anolyte after electrolytic treatment and aeration treatment in the anode chamber is used as the catholyte as it is, and the catholyte after electrolytic treatment in the cathode chamber is neutralized.
- each waste liquid treatment of anolyte containing residual chlorine dioxide and catholyte having high pH is not performed separately but collectively from the cathode chamber until it is discharged through the discharge part Therefore, the waste liquid treatment is simplified.
- the second characteristic configuration is that the diaphragm type electrolytic cell, the flow path part, and the discharge part are integrated.
- the third characteristic configuration is that a deaeration tank is provided in the flow path portion, and the aeration means is configured to supply aeration gas to the anode chamber and the deaeration tank.
- the fourth characteristic configuration is that a neutralization tank is provided in the discharge part, and the neutralization means supplies the neutralizing agent to the neutralization tank.
- the neutralization treatment is performed more efficiently by providing a dedicated neutralization tank for neutralization treatment.
- a characteristic configuration according to the chlorine dioxide production method of the present invention is a chlorine dioxide production method using a diaphragm-type electrolytic cell having an anode chamber and a cathode chamber, wherein the anode chamber of the diaphragm-type electrolytic cell contains chlorite.
- the anolyte can be aerated by supplying the aerated gas to the anode chamber by the aeration process. This makes it possible to quickly dilute the chlorine dioxide concentration while avoiding the dissolution of the generated chlorine dioxide in the anolyte and avoid explosions, so that the generated chlorine dioxide can be recovered more efficiently and safely. be able to.
- the anolyte after electrolytic treatment and aeration treatment in the anode chamber is subjected to electrolytic treatment in the cathode chamber as a catholyte, a part of the generated chlorine dioxide is generated in the anode chamber. Even if it is not recovered and remains in the anolyte, it is cathodically reduced in the cathode chamber to chlorite or the like. Furthermore, the catholyte having a high pH after being electrolyzed in the cathode chamber is neutralized in at least one of the cathodic electrolysis step and the discharge step.
- the anolyte after electrolytic treatment and aeration treatment in the anode chamber is used as the catholyte as it is, and the catholyte after electrolytic treatment in the cathode chamber is neutralized.
- the effluent treatment of the anolyte containing residual chlorine dioxide and the catholyte having a high pH are carried out collectively before being discharged from the cathode chamber, not separately. Therefore, the waste liquid treatment is simplified.
- a chlorine dioxide production apparatus 1 includes a diaphragm type electrolytic cell 2 having an anode chamber 3 and a cathode chamber 5, and an anolyte containing chlorite.
- Supply means 8 a degassing tank 9, a first drainage tank 10, a neutralization tank 11 for neutralizing the catholyte after electrolytic treatment, a neutralizing means for supplying a neutralizing agent 12, the 2nd drainage tank 13, and the aeration means 14 which supplies aeration gas are comprised.
- the anode chamber 3 and the deaeration tank 9 are communicated with each other by the first communication path P1, and the deaeration tank 9 and the first drainage tank 10 are communicated by the second communication path P2, and the first drainage tank 10 and the cathode chamber are communicated with each other.
- 5 is communicated by the third communication path P3, the cathode chamber 5 and the neutralization tank 11 are communicated by the fourth communication path P4, and the neutralization tank 11 and the second drainage tank 13 are communicated by the fifth communication path P5. It is communicated. That is, the chlorine dioxide production apparatus 1 uses the first to fifth communication passages P1 to P5 to provide the anode chamber 3, the deaeration tank 9, the first drainage tank 10, the cathode chamber 5, the neutralization tank 11, and the second drainage liquid. The tank 13 is connected in series.
- the flow path portion C that communicates the anode chamber 3 and the cathode chamber 5 includes the first communication path P1, the degassing tank 9, the second communication path P2, the first drainage tank 10, and the first drainage tank 10. It is formed by a triple communication path P3.
- the flow path portion C is not limited to this configuration.
- the flow path portion C is configured only by the first communication path P1 without providing the deaeration tank 9 and the first drainage tank 10, and the anode chamber 3 and the cathode. It is good also as a structure which communicates with the chamber 5 directly.
- the discharge part D that communicates the cathode chamber 5 with the outside is constituted by the fourth communication path P4, the neutralization tank 11, the fifth communication path P5, the second drainage tank 13, and the drainage pipe 17. Is formed.
- the discharge part D is not limited to this configuration.
- the discharge part D is constituted only by the drainage pipe 17 without providing the neutralization tank 11 and the second drainage tank 13, and the cathode chamber 5 and the outside are connected. It is good also as a structure connected directly.
- the neutralizing means 12 is configured to supply a neutralizing agent to the cathode chamber 5.
- Diaphragm electrolytic cell As the diaphragm type electrolytic cell 2, a conventionally known electrolytic cell in which the anode chamber 3 and the cathode chamber 5 are partitioned by a cation exchange membrane 7 can be used.
- an anode 4 and a cathode 6 are provided as electrodes.
- the cathode material includes titanium, stainless steel, nickel, nickel-chromium alloy, or other valve metal.
- the anode material includes platinum, gold, palladium, iridium, rhodium, ruthenium and other precious metals, graphite, graphite felt, multilayer graphite cloth, graphite woven cloth, carbon, or platinum coating material obtained by electroplating platinum on titanium.
- An electrode composed of a valve metal oxide of titanium, tantalum, niobium, or zirconium, and the like, and those coated with an electrode catalyst are preferably used.
- a conventionally known one can be used, but a fluorocarbon cation exchange membrane 7 having excellent permselectivity, durability and the like is preferable.
- the neutralization means 12 in this embodiment is configured to supply a neutralizing agent to at least one of the cathode chamber 5 and the neutralization tank 11.
- the neutralization means 12 is not limited to this configuration, and may be configured to neutralize at least one of the cathode chamber 5 and the discharge part D.
- the fourth communication path P4, the fifth communication path P5, the second drainage tank 13, and the drainage pipe constituting the discharge part D are not limited to the neutralization tank 11.
- a neutralizing agent may be supplied to any of 17.
- the neutralization means 12 a conventionally well-known structure, for example, a thing provided with the storage tank which stores a neutralizer, a liquid feeding pump, a liquid feeding pipe, etc. can be used.
- neutralizing agent examples include hydrochloric acid, sulfuric acid, citric acid, fumaric acid, formic acid, lactic acid, phosphoric acid, tartaric acid, butyric acid, and various phosphates. These may be used alone or in combination of two or more.
- a conventionally known structure for example, a storage tank that stores an anolyte containing chlorite, a liquid feed pump, a liquid feed pipe, and the like can be used.
- Usable chlorites include, for example, alkali metal chlorites and alkaline earth metal chlorites.
- the alkali metal chlorite include sodium chlorite, potassium chlorite, and lithium chlorite.
- the alkaline earth metal chlorite include calcium chlorite, magnesium chlorite, Barium chlorite is mentioned. Of these, sodium chlorite and potassium chlorite are preferable and sodium chlorite is most preferable from the viewpoint of easy availability.
- These chlorites may be used individually by 1 type, and may use 2 or more types together.
- the concentration of chlorite in the anolyte is preferably 1% by weight to 25% by weight in consideration of the generation efficiency of chlorine dioxide, safety, stability, prevention of crystal precipitation of chlorite.
- aeration means 14 As the aeration means 14, for example, a conventionally known apparatus including an aeration pump capable of adjusting the supply amount of the aeration gas and an introduction pipe for introducing the aeration gas from the aeration pump into each tank can be used. .
- the aeration means 14 in this embodiment is configured to supply aeration gas to each of the anode chamber 3, the deaeration tank 9, and the neutralization tank 11 of the diaphragm type electrolytic cell 2.
- Examples of aeration gas that can be used include air or an inert gas such as nitrogen or argon.
- Chlorine dioxide production method A method for producing chlorine dioxide using the chlorine dioxide production apparatus 1 will be described below.
- an anolyte containing chlorite chlorite aqueous solution
- the catholyte or the anolyte diluted twice is supplied in advance to the cathode chamber 5 of the diaphragm type electrolytic cell 2 and stored.
- the anolyte supplied to the anode chamber 3 is subjected to electrolytic treatment. That is, since chlorite ions (ClO 2 ⁇ ) and cations (sodium ions when sodium chlorite is used as a chlorite) are present in the anode chamber 3, direct current is supplied to the diaphragm-type electrolytic cell 2. When a direct current is applied from a power supply (not shown), chlorite ions emit electrons (e) at the anode, as shown in the following formula (1), and chlorine dioxide (ClO 2 ) is generated ( Anodic electrolysis step). ClO 2 ⁇ ⁇ ClO 2 + e (1) On the other hand, the cation passes through the cation exchange membrane 7 and enters the cathode chamber 5.
- Chlorine dioxide generated by the above formula (1) dissolves in the anolyte due to its high solubility, but the aeration gas blown in by the aeration means 14 lowers the concentration in the liquid according to the vapor-liquid equilibrium relationship and is driven out of the liquid. It is.
- the expelled chlorine dioxide is recovered from the collection tube 15 by the supplied aeration gas while being diluted to a concentration lower than the concentration at which explosion can be avoided (approximately 10% v / v) (aeration step).
- the anolyte after electrolytic treatment in the anode chamber 3 is transferred to the deaeration tank 9 through the first communication path P1. Also in the deaeration tank 9, the aeration process is again performed by the aeration gas blown by the aeration means 14, and chlorine dioxide remaining in the anolyte is driven out of the liquid. The expelled chlorine dioxide returns to the anode chamber 3 again through the sixth communication passage P6 that communicates the anode chamber 3 and the deaeration tank 9, and is collected from the collection tube 15. Also in the deaeration tank 9, the purged chlorine dioxide is diluted with the aerated gas to a concentration lower than the concentration at which explosion can be avoided (approximately 10% v / v).
- the supply amount of aeration gas to the anode chamber 3 and the deaeration tank 9 is configured to be adjustable so that the chlorine dioxide concentration is controlled, and at the same time as the dilution, the chlorine dioxide having a concentration desired by the user. You may comprise so that it may manufacture.
- the anolyte after the aeration treatment in the deaeration tank 9 is transferred to the first drainage tank 10 through the second communication path P2. Then, the anolyte transferred to the first drainage tank 10 passes through the third communication path P3, and is then supplied as the catholyte into the cathode chamber 5 of the diaphragm type electrolytic cell 2.
- the cathode chamber 5 if a part of chlorine dioxide remains in the anolyte supplied as the catholyte without being collected in the anode chamber 3 or the deaeration tank 9, the residual chlorine dioxide is Cathodic reduction by the cathode 6 of the chamber 5 becomes chlorite.
- the remaining hydroxide ions become alkali (for example, sodium hydroxide when the cation is a sodium ion). Accordingly, the catholyte after electrolytic treatment in the cathode chamber 5 has a high pH because it contains a large amount of alkali. This catholyte having a high pH is neutralized by the neutralizing agent supplied from the neutralizing means 12 (neutralization step).
- the neutralization means 12 in this embodiment is configured to supply a neutralizing agent to at least one of the cathode chamber 5 and the neutralization tank 11, the catholyte having a high pH is Neutralization is performed in at least one of the neutralization tanks 11.
- the high pH catholyte after being electrolyzed in the cathode chamber 5 passes through the fourth communication path P4 and the neutralization tank 11. Since the aeration gas blown in by the aeration means 14 is vigorously stirred and mixed together with the neutralizing agent supplied from the neutralization means 12, efficient neutralization processing is performed.
- the aerated gas supplied to the neutralization tank 11 is then transferred to the cathode chamber 5 through a seventh communication path P7 that communicates the cathode chamber 5 and the neutralization tank 11.
- the aerated gas thus transferred is discharged from the exhaust pipe 16 together with the hydrogen gas while diluting the hydrogen gas generated in the cathode chamber 5 to a concentration lower than the concentration at which explosion can be avoided (approximately 4% v / v).
- the catholyte after neutralization in the neutralization tank 11 is transferred to the second drainage tank 13 through the fifth communication path P5. Then, the catholyte transferred to the second drainage tank 13 is discharged from the drainage pipe 17 to the outside of the apparatus.
- a cation exchange membrane is used as a diaphragm that partitions the anode chamber and the cathode chamber, but the present invention is not limited to this, and a neutral diaphragm may be used. .
- the chlorine dioxide production kit K includes the first to fourth members A1 to A4, the first to fourth gasket members G1 to G4, the cation exchange membrane 7, and an outside not shown.
- a frame member is provided.
- the first to fourth members A1 to A4, the first to fourth gasket members G1 to G4, and the cation exchange membrane 7 are all rectangular members, and their width and height are set to the same dimensions. ing.
- the first to fourth members A1 to A4 are all rectangular plate-like members, and are made of a durable material such as polyvinyl chloride, for example.
- each thickness of 1st member A1 and 4th member A4 is set thinner than each thickness of 2nd member A2 and 3rd member A3.
- the second member A ⁇ b> 2 is provided with three rectangular parallelepiped through spaces penetrating in the thickness direction, and each of the three through spaces includes the anode chamber 3 and the deaeration.
- a tank 9 and a first drain tank 10 are configured.
- the anode 4 is disposed in the anode chamber 3 of the second member A2.
- An anolyte introduction pipe 20 is provided.
- the anolyte introduction pipe 20 is provided below the collection pipe 15.
- a first gas introduction pipe 21 for introducing aeration gas from the aeration means 14 (see FIG. 1) into the anode chamber 3 passes through the upper side wall of the second member A2, and its tip is the lower space of the anode chamber 3. It is provided so as to open.
- a second gas introduction pipe 22 for introducing aeration gas from the aeration means 14 into the deaeration tank 9 passes through the upper side wall of the second member A2, and its tip opens into the lower space of the deaeration tank 9. It is provided as follows.
- the upper and lower portions of the partition wall between the anode chamber 3 and the deaeration tank 9 are respectively provided with a sixth communication path P6 and a first communication path P1 that connect the anode chamber 3 and the deaeration tank 9. Yes.
- a second communication path P ⁇ b> 2 that connects the deaeration tank 9 and the first drainage tank 10 is provided at the lower part of the partition wall between the deaeration tank 9 and the first drainage tank 10.
- An L-shaped communication passage 30 that leads from the inner wall surface of the first drainage tank 10 to the mating surface with the second gasket member G2 is provided on the lateral wall of the second member A2 on the first drainage tank 10 side. Yes.
- the third member A3 is provided with three rectangular parallelepiped through spaces penetrating in the thickness direction.
- a tank 11 and a second drain tank 13 are configured.
- the cathode 6 is disposed in the cathode chamber 5 of the third member A3.
- An exhaust pipe 16 for discharging the hydrogen gas generated in the cathode chamber 5 is provided on the lateral side wall of the third member A3 on the cathode chamber 5 side.
- a first neutralizing agent introduction tube 24 for introducing the neutralizing agent from the neutralizing means 12 into the cathode chamber 5 passes through the upper side wall of the third member A3, and the tip thereof enters the lower space of the cathode chamber 5. It is provided to open.
- the sump introduction pipe 25 is provided so as to penetrate the upper side wall of the third member A ⁇ b> 3, and each tip opens into the lower space of the neutralization tank 11.
- a seventh communication path P7 and a fourth communication path P4 that connect the cathode chamber 5 and the neutralization tank 11 are provided in the upper and lower portions of the partition wall between the cathode chamber 5 and the neutralization tank 11, respectively. Yes.
- a fifth communication passage P ⁇ b> 5 that communicates the neutralization tank 11 and the second drainage tank 13 is provided at the lower part of the partition wall between the neutralization tank 11 and the second drainage tank 13.
- a drainage pipe 17 for discharging the catholyte in the second drainage tank 13 to the outside of the apparatus and a communication passage 31 penetrating in the thickness direction are provided on the side wall of the third member A3 on the second drainage tank 13 side. Is provided.
- the communication path 31 is provided below the drainage pipe 17.
- the fourth member A4 has through holes 32 and 33 penetrating in the thickness direction at both end portions in the width direction, and these through holes 32 and 33 are U-shaped. Communication connection is established via a pipe 34.
- the first to fourth gasket members G1 to G4 are rectangular plate-shaped members made of a chemical resistant material such as ethylene-propylene-diene rubber (EPDM), for example.
- EPDM ethylene-propylene-diene rubber
- the second gasket member G ⁇ b> 2 has a through-hole 26 that penetrates in the thickness direction at one end in the width direction and has a rectangular parallelepiped penetration space 27 that penetrates in the thickness direction at the other end.
- the third gasket member G3 has a through hole 35 that penetrates in the thickness direction at one end in the width direction, and has a rectangular parallelepiped shape that penetrates in the thickness direction at the other end.
- a through space 38 is provided.
- the width and height of the through space 27 of the second gasket member G2 are set to be the same as or smaller than the width and height of the anode chamber 3 of the second member A2.
- the width and height of the through space 38 of the third gasket member G3 may be the same as the width and height of the cathode chamber 5 of the third member A3, or the width and height of the cathode chamber 5 of the third member A3. It may be set smaller than the height.
- the fourth gasket member G4 has through holes 36 and 37 penetrating in the thickness direction at both ends in the width direction.
- the cation exchange membrane 7 has a through hole (not shown) penetrating in the thickness direction at one end in the width direction.
- the first to fourth members A1 to A4, the first to fourth gasket members G1 to G4, and the cation exchange membrane 7 are arranged as shown in FIG. That is, the first gasket member G1 is disposed between the first member A1 and the second member A2, and the second gasket member G2, the cation exchange membrane 7, and the second member A2 and the third member A3.
- the third gasket member G3 is arranged in this order, and the fourth gasket member G4 is arranged between the third member A3 and the fourth member A4.
- the second gasket member G2 is disposed such that the through space 27 faces the anode chamber 3 of the second member A2, and the third gasket member G3 is disposed of the cathode space of the third member A3. 5 so as to face 5.
- the fourth gasket member G4 is arranged such that one through hole 36 faces the communication path 31 of the third member A3 and the other through hole 37 faces the cathode chamber 5 of the third member A3. Further, the fourth member A4 is arranged so that the two through holes 32 and 33 respectively face the two through holes 36 and 37 of the fourth gasket member G4.
- a rectangular parallelepiped or cubic chlorine dioxide production kit K is completed.
- the 3rd communication path P3 connected from the 1st drainage tank 10 of 2nd member A2 to the cathode chamber 5 of 3rd member A3 is formed.
- the anode chamber 3 of the second member A2 and the through space 27 of the second gasket member G2 communicate with each other
- the cathode chamber 5 of the third member A3 and the through space 38 of the third gasket member G3 communicate with each other.
- the anode chamber 3 of the two member A2 and the cathode chamber 5 of the third member A3 are arranged to face each other with the cation exchange membrane 7 interposed therebetween, so that the diaphragm type electrolytic cell 2 is formed.
- the configuration of the chlorine dioxide production apparatus can be made compact.
- a chlorine dioxide production kit K having a width of 73 mm, a height of 148 mm, and a thickness of 45 mm, comprising an anode 4 and a cathode 5 having an electrode size of width 18 mm, height 46 mm, and thickness 1 mm was produced.
- the aeration means 14 is connected to the first and second gas introduction pipes 21 and 22 of the chlorine dioxide production kit K, the supply means 8 is connected to the anolyte introduction pipe 20 of the chlorine dioxide production kit K, and the chlorine dioxide production kit
- the chlorine dioxide production apparatus 1 was configured by connecting the neutralizing means 12 to the second neutralizing agent introduction pipe 25 of K.
- An anolyte was prepared by dissolving 800 mL of 25 wt% sodium chlorite and 50 g of potassium chloride in water to 1 L. This anolyte was fed at 14 mL / hour by a feed pump of the supply means 8.
- the anode 4 and the cathode 6 are energized at 800 mA. Further, air is supplied to the anode chamber 3 and the deaeration tank 9 by the aeration pump of the aeration means 14, and chlorine dioxide released from the sampling tube 15 is supplied. Absorbed with a potassium iodide solution for a predetermined time, and liberated iodine was titrated with a predetermined aqueous sodium thiosulfate solution. As a result, it was confirmed that 1.2 g / hour of chlorine dioxide was generated. Further, the drainage discharged from the drainage pipe 17 contained almost no chlorine dioxide and had a pH of 7.8, which could be safely discarded.
- the chlorine dioxide production apparatus and chlorine dioxide production method according to the present invention can be suitably used in industrial fields related to environmental sterilization and deodorization by chlorine dioxide.
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Abstract
Description
本構成によれば、曝気手段によって曝気気体を陽極室に供給して陽極液を曝気処理することができる。これにより、発生した二酸化塩素の陽極液への溶解を抑えながら、二酸化塩素濃度を速やかに希釈して爆発を回避することが可能となるため、発生した二酸化塩素をより効率的且つ安全に回収することができる。さらに、曝気気体を陽極室に直接供給する構成であることから、別に曝気槽等を設ける必要がなく、装置構成が簡素化される。
本構成によれば、隔膜式電解槽、前記流路部、及び前記排出部が一体化されているため、二酸化塩素製造装置の構成をコンパクト化することができる。
本構成によれば、曝気処理が陽極室だけでなく、脱気槽においても実施されることになる。そのため、生成された二酸化塩素のうち、陽極室で回収されなかった二酸化塩素を、脱気槽で回収することができるようになり、生成された二酸化塩素をより確実に回収することができる。
本構成のごとく、中和処置する専用の中和槽を設けることによって、より効率的に中和処理が実施される。
本構成によれば、曝気工程によって曝気気体を陽極室に供給して陽極液を曝気処理することができる。これにより、発生した二酸化塩素の陽極液への溶解を抑えながら、二酸化塩素濃度を速やかに希釈して爆発を回避することが可能となるため、発生した二酸化塩素をより効率的且つ安全に回収することができる。
〔実施形態〕
〔1〕二酸化塩素製造装置
図1に示すように、本実施形態に係る二酸化塩素製造装置1は、陽極室3と陰極室5とを有する隔膜式電解槽2、亜塩素酸塩を含む陽極液を隔膜式電解槽2に供給する供給手段8、脱気槽9、第1排液槽10、電解処理後の陰極液を中和処理する中和槽11、中和剤を供給する中和手段12、第2排液槽13、及び曝気気体を供給する曝気手段14を備えて構成される。
隔膜式電解槽2としては、陽極室3と陰極室5とが陽イオン交換膜7によって仕切られている従来公知の電解槽を使用することができる。
本実施形態における中和手段12は、陰極室5及び中和槽11の少なくともいずれか一方に中和剤を供給するように構成されている。しかし、中和手段12は、この構成に限定されるものではなく、陰極室5及び排出部Dの少なくともいずれか一方で中和処理する構成とすれば良い。排出部Dで中和処理する場合、例えば、中和槽11に限らず、排出部Dを構成する、第4連通路P4、第5連通路P5、第2排液槽13、及び排液管17のいずれかに中和剤を供給するようにしても良い。
中和手段12としては、従来公知の構成、例えば、中和剤を貯留する貯留タンク、送液ポンプ、及び送液管等を備えるものを使用することができる。使用可能な中和剤としては、例えば、塩酸、硫酸、クエン酸、フマル酸、ギ酸、乳酸、リン酸、酒石酸、酪酸、各種リン酸塩などが挙げられる。これらは1種を単独で用いてもよいし、2種以上を併用しても構わない。
供給手段8としては、従来公知の構成、例えば、亜塩素酸塩を含む陽極液を貯留する貯留タンク、送液ポンプ、及び送液管等を備えるものを使用することができる。使用可能な亜塩素酸塩としては、例えば亜塩素酸アルカリ金属塩や亜塩素酸アルカリ土類金属塩が挙げられる。亜塩素酸アルカリ金属塩としては、例えば、亜塩素酸ナトリウム、亜塩素酸カリウム、亜塩素酸リチウムが挙げられ、亜塩素酸アルカリ土類金属塩としては、亜塩素酸カルシウム、亜塩素酸マグネシウム、亜塩素酸バリウムが挙げられる。なかでも、入手が容易という点から、亜塩素酸ナトリウム、亜塩素酸カリウムが好ましく、亜塩素酸ナトリウムが最も好ましい。これら亜塩素酸塩は1種を単独で用いてもよいし、2種以上を併用しても構わない。陽極液における亜塩素酸塩の濃度は、二酸化塩素の発生効率、安全性、安定性、亜塩素酸塩の結晶析出防止などを考慮すると、1重量%~25重量%であることが好ましい。
曝気手段14は、例えば、曝気気体の供給量を調節することのできる曝気ポンプと、曝気ポンプからの曝気気体を各槽に導入する導入管等とを備える従来公知の装置を使用することができる。
本実施形態における曝気手段14は、隔膜式電解槽2の陽極室3、脱気槽9、及び中和槽11のそれぞれに曝気気体を供給するように構成されている。また使用可能な曝気気体としては、例えば、空気、あるいは窒素やアルゴンなどの不活性ガスが挙げられる。
上記二酸化塩素製造装置1を用いて二酸化塩素を製造する方法について以下に説明する。供給手段8を作動させることによって、亜塩素酸塩を含む陽極液(亜塩素酸塩水溶液)を隔膜式電解槽2の陽極室3に連続的に供給する(供給工程)。また最初のうちだけ、陰極液又は2倍希釈した陽極液を、隔膜式電解槽2の陰極室5に予め供給して貯めておく。
ClO2 -→ClO2+e・・・・・式(1)
一方、陽イオンは、陽イオン交換膜7を通過して陰極室5に入る。
2H++2e→H2・・・・・式(2)
上述の実施形態の隔膜式電解槽において、陽極室と陰極室とを仕切る隔膜として陽イオン交換膜を使用しているが、これに限定されるものではなく、中性隔膜を使用しても良い。
第2部材A2における陽極室3側の横側壁には、陽極室3の二酸化塩素を回収するための採取管15、及び供給手段8(図1参照)から陽極液を陽極室3に導入するための陽極液導入管20が設けられている。尚、陽極液導入管20は、採取管15の下側に設けられる。
第3部材A3における陰極室5側の横側壁には、陰極室5で発生した水素ガスを排出するための排気管16が設けられている。
電極寸法が幅18mm、高さ46mm、厚さ1mmの陽極4及び陰極5を備える、幅73mm、高さ148mm、厚さ45mmの二酸化塩素製造キットKを作製した。そしてその二酸化塩素製造キットKの第1及び第2気体導入管21,22に曝気手段14を接続し、二酸化塩素製造キットKの陽極液導入管20に供給手段8を接続し、二酸化塩素製造キットKの第2中和剤導入管25に中和手段12を接続して二酸化塩素製造装置1を構成した。
2 隔膜式電解槽
3 陽極室
4 陽極
5 陰極室
6 陰極
7 陽イオン交換膜
8 供給手段
9 脱気槽
10 第1排液槽
11 中和槽
12 中和手段
13 第2排液槽
14 曝気手段
15 採取管
16 排気管
17 排液管
P1~P7 第1~第7連通路
C 流路部
D 排出部
Claims (5)
- 陽極室と陰極室とを有し、前記陽極室に供給された亜塩素酸塩を含む陽極液を電解処理して二酸化塩素を発生させる隔膜式電解槽と、
前記陽極室と前記陰極室とを連通する流路部と、
前記陰極室と外部とを連通する排出部と、
供給量調節自在に曝気気体を前記陽極室に供給する曝気手段と、
前記陰極室及び前記排出部の少なくともいずれか一方に中和剤を供給する中和手段と、を備え、
前記陽極室において前記陽極液を電解処理して二酸化塩素を発生させ、
前記曝気手段により曝気気体を前記陽極室の陽極液に供給することによって、発生した二酸化塩素を回収し、
前記陽極室にて電解処理及び曝気処理された後の陽極液が、前記流路部を通って前記陰極室に移流して陰極液として電解処理された後、前記陰極室及び前記排出部の少なくともいずれか一方で中和処理されるように構成される二酸化塩素製造装置。 - 前記隔膜式電解槽、前記流路部、及び前記排出部が一体化されている請求項1に記載の二酸化塩素製造装置。
- 前記流路部に脱気槽を設け、前記曝気手段が前記陽極室及び前記脱気槽に曝気気体を供給するように構成される請求項2に記載の二酸化塩素製造装置。
- 前記排出部に中和槽を設け、前記中和手段が前記中和槽に中和剤を供給するように構成される請求項2又は3に記載の二酸化塩素製造装置。
- 陽極室と陰極室とを有する隔膜式電解槽を用いる二酸化塩素製造方法であって、
前記隔膜式電解槽の陽極室に亜塩素酸塩を含む陽極液を供給する供給工程と、
前記陽極液を電解処理して二酸化塩素を発生させる陽極電解工程と、
曝気気体を前記陽極室の陽極液に供給することによって、発生した二酸化塩素を回収する曝気工程と、
前記陽極室にて電解処理及び曝気処理された後の陽極液を、陰極液として前記陰極室にて電解処理する陰極電解工程と、
前記陰極室にて電解処理された後の陰極液を排出する排出工程と、
前記陰極電解工程、及び前記排出工程の少なくともいずれか一方において陰極液を中和処理する中和工程と、を包含する二酸化塩素製造方法。
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CN201480049450.8A CN105683417B (zh) | 2013-09-09 | 2014-09-01 | 二氧化氯制造装置及二氧化氯制造方法 |
EP14843084.6A EP3045568A4 (en) | 2013-09-09 | 2014-09-01 | Chlorine dioxide production device and chlorine dioxide production method |
US14/911,931 US10094029B2 (en) | 2013-09-09 | 2014-09-01 | Chlorine dioxide production device and chlorine dioxide production method |
JP2015535457A JP6448540B2 (ja) | 2013-09-09 | 2014-09-01 | 二酸化塩素製造装置及び二酸化塩素製造方法 |
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CN111621803A (zh) * | 2020-06-05 | 2020-09-04 | 池晓雷 | 一种二氧化氯发生装置及应用 |
CN114921799A (zh) * | 2022-05-11 | 2022-08-19 | 上海交通大学 | 单原子阴阳极同时合成高纯二氧化氯气体的方法及其装置 |
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