WO2019194184A1 - 劣化次亜塩素酸塩から新規塩素酸化物組成物を得る製法 - Google Patents
劣化次亜塩素酸塩から新規塩素酸化物組成物を得る製法 Download PDFInfo
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- WO2019194184A1 WO2019194184A1 PCT/JP2019/014649 JP2019014649W WO2019194184A1 WO 2019194184 A1 WO2019194184 A1 WO 2019194184A1 JP 2019014649 W JP2019014649 W JP 2019014649W WO 2019194184 A1 WO2019194184 A1 WO 2019194184A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
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- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 title description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 543
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- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 372
- 239000007788 liquid Substances 0.000 claims abstract description 367
- -1 hypochlorite ions Chemical class 0.000 claims abstract description 168
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- 238000000034 method Methods 0.000 claims abstract description 135
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims abstract description 128
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 32
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- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
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Images
Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/157—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
- C01B11/068—Stabilisation by additives other than oxides, hydroxides, carbonates of alkali or alkaline-earth metals; Coating of particles; Shaping; Granulation
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/08—Alkali metal chlorides; Alkaline earth metal chlorides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/358—Inorganic compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0086—Processes carried out with a view to control or to change the pH-value; Applications of buffer salts; Neutralisation reactions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/04—Hypochlorous acid
- C01B11/06—Hypochlorites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/08—Chlorous acid
- C01B11/10—Chlorites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00177—Controlling or regulating processes controlling the pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
Definitions
- chlorine is decomposed during storage, and sodium hypochlorite that has generated chloride ions and chlorate ions is regenerated to obtain a new useful disinfectant.
- Sodium hypochlorite is a chlorinated liquid obtained through chlorine in sodium hydroxide solution and is known as a useful disinfectant for water supply, pools, and food additives, but it is unstable.
- the chlorine component decomposes during storage, and generates chloride ions (Cl ⁇ ) and chlorate ions (ClO 3 ⁇ ) by disproportionation, and loses its effectiveness.
- chlorate ions (ClO 3 ⁇ ) are dried and crystallized, accidents such as ignition and explosions are continually caused by friction.
- hypochlorite ion in sodium hypochlorite decreases and the content of chloride ion and chlorate ion increases, it becomes difficult to use normally. Or you will have the merchant pick it up and dispose of it.
- hypochlorite that has deteriorated during storage and reacting it again, it regenerates hypochlorous acid, and also reacts with chloric acid generated during storage to reduce hypochlorous acid and chlorous acid.
- the present inventor decided to produce a disinfectant having a new commercial value by reacting sodium hypochlorite whose quality was lowered.
- the disinfectant disinfects sodium hypochlorite with reduced concentration as chlorine gas, and also reacts with sodium chlorate, which is difficult to dispose of.
- hypochlorite ion, chlorate ion, chloride ion, etc. contained in the deteriorated sodium hypochlorite found the conditions for gasification by the reaction, and considered to obtain the recovered liquid.
- a large amount of various chlorine ion components are present simultaneously in the deteriorated sodium hypochlorite, and further, chlorate ions and chlorides are present. Since product ions are products accompanying the disappearance of available chlorine, they are less reactive than general chemical reaction methods using single products or saturated liquids as raw materials, and new reaction conditions and recovery methods are found. There was a need.
- the concentration of sulfuric acid to be added, the acidity in the reaction mother liquor, and the amount of chloride ions, which are products in the deteriorated sodium hypochlorite, are important. Since it is a product from sodium chlorite, it was difficult to adjust, and it was found that it was necessary to increase the yield by adjusting the reaction product amount by combining temperature, acidity, air blowing conditions and the like.
- chlorine gas and chlorine dioxide gas obtained by the reaction will be recovered with sodium hydroxide or calcium hydroxide, but if each is not recovered individually, the yield will be reduced and chlorate ions will be generated.
- a technique for gradually releasing chlorine gas and then chlorine dioxide gas from the reaction mother liquor to which deteriorated sodium hypochlorite and sulfuric acid were added was necessary.
- the first reaction in which chlorine gas is generated from a reaction mother liquor in which sulfuric acid is added to degraded sodium hypochlorite as a raw material.
- a second reaction in which chlorine dioxide gas is generated after adding sulfuric acid or the like and changing other conditions is performed.
- chloride ions and chlorate ions increase or decrease depending on reaction conditions such as acidity in the reaction mother liquor.
- One feature of this production method is that the reaction is adjusted to generate chlorine dioxide gas.
- the chlorine gas generated in the first reaction can be recovered with sodium hydroxide solution or calcium hydroxide solution, but the chlorine dioxide gas generated during the second reaction is mainly sodium hydroxide solution or calcium hydroxide solution only.
- chlorate ions are produced in large quantities. For this reason, it is necessary to prevent the formation of chlorate ions by using a sodium hydroxide solution or calcium hydroxide solution plus hydrogen peroxide solution as a recovery solution.
- the gas is decomposed and converted into chloride ions.
- the recovery liquid for the first reaction and the recovery liquid for the second reaction are provided with two recovery tanks, and the recovery liquid A mainly composed of chlorine gas and the recovery liquid B mainly composed of chlorine dioxide gas are individually recovered. It is also one of the characteristics of this production method that it is mixed and stabilized later.
- the solid disinfectant manufactured and dried in this way complies with the standard of high-quality powdered powder, which is a food additive, and the composition of the components changes even when stored at room temperature. It is also characterized by not.
- the disinfectant produced by this method is hypochlorous acid and chlorous acid. These sterilization characteristics are combined with each other, complying with the standards of food additives such as sodium hypochlorite and advanced smooth powder, and provided as a single agent.
- the reaction conditions are adjusted with low-grade sodium hypochlorite and general-grade sodium hypochlorite.
- the sulfuric acid concentration in the reaction mother liquor should be 4.0% to 4.5%.
- the sulfuric acid concentration should be 30.0% to 59.4%, and 30.0% to 40.0% in the case of advanced smooth powder.
- the sulfuric acid concentration is 50.0 w / w% to 70.0 w / w%.
- sodium hypochlorite In the case of general grade sodium hypochlorite, it should be 25.0% to 30.0%, and the sulfuric acid concentration to be used should be 65w / w%, and an intermediate trap tank should be installed to remove chlorine gas by washing. , Preventing contamination of the recovered liquid due to excessive generation of chlorine gas.
- the effective chlorine concentration ratio with the recovered liquid A being 1 is 1: 0.43.
- it meets the standard, and in order to satisfy the food additive standard of advanced powdered powder, it meets the standard in the range of the effective chlorine concentration ratio up to 1: 33.95.
- the present invention also provides the following.
- the solid is (1) Contains 60.0% or more of effective chlorine, (2) There is a smell of chlorine, (3) When 5 ml of water is added to 0.5 g of the solid and shaken and red litmus paper is immersed in this, the litmus paper turns blue and then fades. (4) When 2 ml of acetic acid (1 ⁇ 4) is added to 0.1 g of the solid, gas is generated and dissolved, and 5 ml of water added to the solution is filtered to give a calcium salt reaction. Item 4. The dry solid according to any one of Items 1 to 3. (Item 5) Item 5. The dry solid according to any one of Items 1 to 4, wherein the solid contains an SO 4 -based component at a detection limit of 8100 ppm or less.
- (Item 6) Item 6.
- (Item 7) The dry solid according to any one of items 1 to 6, wherein the effective chlorine concentration in the solid is in the range of 600,000 ppm to 900,000 ppm, and the free residual chlorine concentration is in the range of 900 ppm to 60,000 ppm. .
- (Item 8) A liquid obtained by dissolving the dry solid according to any one of items 1 to 7.
- (Item 9) Item 19.
- Item 10 Item 10.
- Item 11 Item 9.
- the liquid according to Item 8, wherein the ratio of hypochlorite ion to chlorite ion is 1 to 6 to 30 when diluted with water so that the effective chlorine concentration is 6%.
- Item 12 Item 12.
- Item 13 Item 9. The liquid according to Item 8, wherein the ratio of hypochlorite ion to chlorite ion is 1 to 6 to 30 when diluted with water so that the effective chlorine concentration is 12%.
- Item 14 14. The liquid according to item 8 or 13, wherein when diluted with water so that the effective chlorine concentration is 12%, the free residual chlorine concentration is in the range of 2,500 ppm to 12,000 ppm.
- a process for producing a dry solid comprising hypochlorite and chlorite comprising: Preparing a solution containing hypochlorite ions, chlorate ions and chloride ions; A first reaction step of adding sulfuric acid to the solution to generate chlorine gas; In the recovered liquid A, the generated chlorine gas is reacted with sodium hydroxide or calcium hydroxide and recovered as hypochlorite ions; A second reaction step in which sulfuric acid having a higher concentration than in the first reaction step is added to the reaction mother liquor after the first reaction step to generate chlorine dioxide gas; In the recovered liquid B, the generated chlorine dioxide gas is reacted with sodium hydroxide and hydrogen peroxide and recovered as chlorite ions; A step of mixing the recovered liquid A and the recovered liquid B; Drying and solidifying the obtained mixed solution.
- (Item 17) Item 17.
- (Item 18) In the step of mixing the recovered liquid A and the recovered liquid B, if the effective chlorine concentration of the recovered liquid A is 1, the effective chlorine concentration of the recovered liquid B is in the range of 9.6 to 33.95.
- (Item 19) 19 19. The method according to any one of items 15 to 18, wherein in the step of mixing the recovered liquid A and the recovered liquid B, the recovered liquid A and the recovered liquid B are each slurried and mixed.
- (Item 20) The step of mixing the recovered liquid A and the recovered liquid B pre-drys the recovered liquid A, forms granulation nuclei, slurries the recovered liquid B, and dries the recovered liquid A into the recovered liquid B slurry.
- 20. The method according to any one of items 15 to 19, comprising a step of charging an object.
- Item 21 Item 21.
- the method according to any one of Items 15 to 20, wherein the step of drying and solidifying includes a step of performing warm air drying for 20 minutes to 30 minutes.
- (Item 22) The method according to any one of items 15 to 21, wherein the drying and solidifying step includes reducing the water contents of the recovered liquid A and the recovered liquid B to 20% or less, respectively.
- the generated chlorine gas is reacted with sodium hydroxide or calcium hydroxide and recovered as hypochlorite ions;
- the second reaction step in which sulfuric acid having a higher concentration than in the first reaction step is added to the reaction mother liquor after the first reaction step to generate chlorine dioxide gas, and in the recovered solution B, the generated chlorine dioxide gas is added to water.
- the disinfectant is a solid product
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00 to 6.37%
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 30.00 to 40 26.
- the method according to item 25, wherein the sulfuric acid concentration used in the second reaction step is 0.000% and 50.0 w / w% to 70.0 w / w%.
- the disinfectant is a liquid product
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00 to 6.37%
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 30.00 to 59.
- 26. The method according to item 25, wherein the sulfuric acid concentration used in the second reaction step is 0.04% and 50.0 w / w% to 70.0 w / w%.
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00 to 4.50%, and the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 25.00 to 30.00%.
- the sulfuric acid concentration used in the step is 65 w / w%.
- (Item 34) The method according to any one of Items 23 to 33, wherein the second reaction step is performed while blowing air.
- (Item 35) The method according to any one of items 23 to 34, wherein an intermediate trap tank containing hydrogen peroxide is provided between the reaction tank and the recovery tank containing the recovery liquid B.
- (Item 36) 36.
- the effective chlorine concentration of the recovered liquid A is 1, and the effective chlorine concentration of the recovered liquid B is 0.43 to 0.6.
- the disinfectant is (1) Contains 4.0% or more of effective chlorine, (2) There is a smell of chlorine, (3) Presents the reaction of sodium salt and hypochlorite, (4) A solution obtained by adding 100 ml of a phosphate buffer (pH 8) to 4 ml of an aqueous solution (1 ⁇ 25) of this product has a maximum absorption part at a wavelength of 291 to 294 nm. (5) When red litmus paper is immersed in this product, the litmus paper turns blue and then fades. 39. A method according to item 38. (Item 40) 40.
- the disinfectant according to item 43 wherein the ratio of hypochlorite ion to chlorite ion is 1 to 0.24 to 0.3. (Item 45) 45.
- (Item 46) A liquid chlorine oxide produced using the dry solid according to any one of items 1 to 7, (A) dissolving the dry solid in water to prepare a solution having an increased pH; (B) while maintaining the pH of the solution prepared in step (a), the calcium salt is precipitated by adding a non-calcium inorganic alkaline agent to the solution, and includes a liquid phase and a solid phase containing the calcium salt, Forming a solid-liquid mixed phase with a reduced calcium ion concentration in the liquid phase; And (c) a liquid chlorine oxide prepared by a method comprising a step of taking only the liquid phase from the solid-liquid mixed phase formed in step (b) to obtain a liquid chlorine oxide.
- a liquid chlorine oxide produced using the dry solid according to any one of items 1 to 7, (A) a step of preparing a solution having a pH of 10.0 or more by dissolving the dry solid in water; (B) While maintaining the pH of the solution prepared in the step (a) at 10.0 or more, a calcium salt is precipitated by adding a non-calcium inorganic alkaline agent to the solution, and a solid phase containing the liquid phase and the calcium salt is precipitated.
- the generated chlorine gas is reacted with sodium hydroxide or calcium hydroxide and recovered as hypochlorite ions;
- the second reaction step in which sulfuric acid having a higher concentration than in the first reaction step is added to the reaction mother liquor after the first reaction step to generate chlorine dioxide gas, and in the recovered solution B, the generated chlorine dioxide gas is added to water.
- Item 54 Item 54.
- the method according to Item 53 which has one or more of the characteristics of the case where the disinfectant defined in Item 24 to Item 42 is replaced with a drug.
- Item 55 A drug produced by the method according to item 53 or 54.
- Item 56 56.
- the drug according to item 55 wherein the drug has one or more of the characteristics when the antiseptic agent defined in item 44 or 45 is replaced with a drug.
- Item 57 Use of the drug according to item 55 or 56 as a disinfectant.
- Item 58 Use of the drug according to item 55 or 56 as a food additive.
- Item 59 Use of a drug according to item 55 or 56 for sterilizing food.
- the present invention obtains a useful new disinfectant and disinfectant from sodium hypochlorite which has been reduced in quality and produced chloride ions and chlorate ions, and is a food additive sodium hypochlorite.
- the coexisting liquid of hypochlorite ion and chlorite ion is inferior in storage stability unless it is refrigerated, but has the advantage that long-term storage is possible by processing into a dry granular solid.
- sodium hypochlorite and high-quality salty powder that have been completed by this method have lower chlorine odor than liquids of the same concentration, have the advantage of reducing the burden on workers and being easy to use. Even if the regeneration method is used, it can be said that the manufacturing cost is absorbed and commercialization is possible.
- FIG. 1 shows the discoloration of permanganate K with respect to (mixed solution of recovered liquid A and recovered liquid B (sodium hypochlorite standard)). From the left, only sodium hypochlorite, hypochlorous acid The effective chlorine ratio of Na and sodium chlorite is 1: 0.6, the effective chlorine ratio of sodium hypochlorite and sodium chlorite is 1: 0.7, and only sodium chlorite is shown.
- FIG. 2 shows the absorbance of specimen 1 and specimen 2 (for a mixed solution of recovered liquid A and recovered liquid B (sodium hypochlorite standard)).
- hypochlorite a solution containing hypochlorite with degraded quality refers to sodium hypochlorite that has decomposed during storage and has produced chloride ions and chlorate ions. Means solution.
- hypochlorite is sometimes abbreviated as “hypochlorite”.
- low salt grade sodium hypochlorite solution means a sodium hypochlorite solution in which the amount of salt is reduced, The chlorate ion is 5000 to 6000 ppm, and at most 12000 ppm.
- the “general grade sodium hypochlorite solution” means a sodium hypochlorite solution in which the amount of sodium chloride is not reduced, and in a general grade sodium hypochlorite 12% solution. About 14,000 to 26000 ppm of chlorate ions are produced at the time of distribution.
- effective chlorine or “effective chlorine concentration” refers to the concentration of chlorine effective for bleaching action, which is contained in a disinfectant such as salash powder.
- Effective chlorine is, for example, potassium iodide added to sodium hypochlorite of the sample, and iodine released by the formula Cl 2 + KI ⁇ I 2 + KCl (1) is redox titrated with sodium thiosulfate (I 2 + 2Na 2 S 2 O 3 ⁇ 2NaI + Na 2 S 4 O 6 (Equation (2)) can be used to determine the effective chlorine concentration.
- free chlorine means “free residual chlorine and binding determined by the Minister of Health, Labor and Welfare in accordance with Article 17, Paragraph 2 of the Water Supply Law Enforcement Regulations”. It is a value measured by the attached table 3 (hereinafter referred to as a colorimetric method (DPD indicator)) of “Chlorine Inspection Method”, and is a value obtained by oxidizing the DPD indicator.
- DPD indicator colorimetric method
- SO 4 -based component means a component derived from sulfuric acid, and means sulfuric acid, sulfate or the like.
- warm air drying as drying conditions, the storage room environment temperature of 50 ⁇ 60 ° C., the internal humidity is 10% or less, the air volume to feed the warm air 1.9m 3 / s Is done.
- chlorine oxide refers to any oxide of chlorine. Examples thereof include hypochlorous acid, chlorous acid, chloric acid, perchloric acid, and salts thereof. Also included are dichlorine heptoxide, dichlorine hexaoxide, dichlorine trioxide, chlorine dioxide, dichlorine monoxide and the like.
- “advanced smooth powder” satisfies the standard stipulated in the 8th edition Food Additive Official Document. Specifically: (1) Contains 60.0% or more of effective chlorine, (2) There is a smell of chlorine, (3) When 5 ml of water is added to 0.5 g of the solid and shaken and red litmus paper is immersed in this, the litmus paper turns blue and then fades. (4) When 2 ml of acetic acid (1 ⁇ 4) is added to 0.1 g of the solid, a gas is generated and dissolved, and 5 ml of water added thereto and filtered are reacted with calcium salt.
- T.AL is used to measure the alkalinity in a sample by titrating a 0.1 mol / L hydrochloric acid-acid standard solution until the sample reaches pH 4.0, and adjusting the pH of 100 g of the sample to 4
- the alkalinity (T.AL) is set to 1 when 0.1 mol / L hydrochloric acid required to make 0.0 is 1 mL.
- pH 4.0 is the second neutralization point of sodium carbonate.
- high-grade powders have a wide range of specifications, and generally chlorine oxides differ depending on the combination of pH adjusters and the like at each company. AL is often not described in the standard. However, since chlorine is contained, high T.I. It shows AL value and is highly alkaline.
- non-calcium inorganic alkaline agent refers to a (drug) agent having an inorganic alkaline substance having a cation other than calcium. It is understood that any material can be used as long as it has an inorganic alkaline substance having a cation other than calcium. Examples include, but are not limited to, sodium carbonate, disodium hydrogen phosphate, sodium sulfate, and sodium hydroxide.
- the “bivalent or higher inorganic alkali agent” refers to a non-calcium inorganic alkaline agent having a valence of 2 or higher.
- a sodium-containing alkaline agent is preferred but not limited thereto.
- divalent or higher inorganic alkali agent those having the ability to adjust the pH to 10 or less are advantageous. This is because the pH of the advanced smooth powder can be lowered. Examples of such can include, but are not limited to, sodium carbonate, disodium hydrogen phosphate, and sodium sulfate.
- less than divalent inorganic alkaline agents, such as sodium hydroxide can optionally be used.
- the input amount of sodium sulfate is usually around 0.1 with respect to the input amount 1 of the other inorganic alkaline agent, and may be any other amount as long as the object can be achieved, preferably 10% or less, preferably 5%.
- 2% or less, 1% or less, etc. can be mentioned.
- recovered liquid A refers to a recovered liquid in which the gas generated in the first reaction step is recovered in the method for treating a solution containing hypochlorite of the present invention.
- recovered liquid B refers to a recovered liquid in which the gas generated in the second reaction step is recovered in the method for treating a solution containing hypochlorite of the present invention.
- the present invention provides a dry solid comprising hypochlorite and chlorite.
- the hypochlorite includes alkali metal salts or alkaline earth metal salts of hypochlorous acid, and examples thereof include sodium salts, potassium salts, calcium salts, and magnesium salts.
- Examples of chlorite include alkali metal salts or alkaline earth metal salts of chlorous acid, and examples thereof include sodium salts, potassium salts, calcium salts, and magnesium salts.
- the solid sterilizing disinfectant of the present invention does not change the composition of the content components even when stored at room temperature, and when it is a calcium salt, it can conform to the standard of high-quality powdered food additive. Salts such as potassium and magnesium salts can be obtained by using an alkali solution of the corresponding alkali metal or alkaline earth metal in the recovered solution or by exchanging the sodium salt or calcium salt with the corresponding metal. it can.
- the solid is dry granular.
- the solid comprises calcium hypochlorite.
- the solid meets the standard specified in the 8th edition Food Additives official high-grade powder. Specifically, the solid is (1) Contains 60.0% or more of effective chlorine, (2) There is a smell of chlorine, (3) When 5 ml of water is added to 0.5 g of the solid and shaken and red litmus paper is immersed in this, the litmus paper turns blue and then fades. (4) When 2 ml of acetic acid (1 ⁇ 4) is added to 0.1 g of the solid, a gas is generated and dissolved, and 5 ml of water added thereto and filtered are reacted with calcium salt.
- the solid contains a SO 4 -based component at a detection limit or more and 8100 ppm or less.
- the SO 4 -based component may be 8000 ppm or less, 7000 ppm or less, 6000 ppm or less, 5000 ppm or less, 4000 ppm or less, 3000 ppm or less, 2000 ppm or less, or 1000 ppm or less.
- the SO 4 -based component may be 100 ppm or more, 200 ppm or more, 300 ppm or more, 400 ppm or more, 500 ppm or more, 600 ppm or more, 700 ppm or more, 800 ppm or more, 900 ppm or more, 1000 ppm or more, 1100 ppm or more.
- This SO 4 -based component is entrainment of sulfuric acid contained in the reaction tank, and the amount of SO 4 -based component can be one of the indicators that the chlorine oxide is produced according to the present invention.
- the ratio of hypochlorite to chlorite in the solid is 1 to 5-25. This ratio is obtained by drying and solidifying the mixed solution obtained by preliminarily drying the recovered liquid A and recovered liquid B used to obtain the solid to obtain a water content of about 20%. It is a value about the thing.
- free residual chlorine concentration effective chlorine concentration
- the concentration of hypochlorite ions can be derived from the free residual chlorine concentration.
- the chlorite ion concentration can be measured by ion chromatography.
- the ratio of hypochlorite to chlorite is derived from the ratio of each ion.
- the ratio of hypochlorite to chlorite in the solid may be 1 to 9-25.
- the ratio of hypochlorite to chlorite in the solid may be 1 to 5-9.
- the ratio of hypochlorite to chlorite in the solid may be any value or value range between 5 and 25, where hypochlorite is 1.
- hypochlorite is 1, chlorite is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, Can be 21, 22, 23, 24, or 25, and can be any numerical value or range between them.
- the ratio of hypochlorite to chlorite in the solid is 1: 5.53 to 23.59.
- the ratio of hypochlorite to chlorite in the solid may be 1 to 8.92-23.59.
- the ratio of hypochlorite to chlorite in the solid can be 1 to 5.53 to 8.92.
- a dry solid having such a ratio has high purity, long-term preservation, high bactericidal effect, and low chlorine odor.
- calcium salt it conforms to the standard standard of advanced smooth powder. If necessary, a solid having a value outside the above range may be produced.
- the effective chlorine concentration in the solid is in the range of 600,000 ppm to 900,000 ppm, and the free residual chlorine concentration is in the range of 900 ppm to 60,000 ppm.
- the effective chlorine concentration in the solid may be in any numerical value or numerical range within the range of 600,000 ppm to 900,000 ppm.
- the effective chlorine concentration in the solid can be 600,000 ppm, 650,000 ppm, 700,000 ppm, 750,000 ppm, 800,000 ppm, 850,000 ppm, 900,000 ppm, and within any combination of these numbers. possible.
- the free residual chlorine concentration in the solid may be in any numerical value or numerical range within the range of 900 ppm to 60,000 ppm.
- the concentration of free residual chlorine in the solid is 900 ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, 5,000 ppm, 6,000 ppm, 7,000 ppm, 8,000 ppm, 9,000 ppm, 10,000 ppm. 15,000 ppm, 20,000 ppm, 25,000 ppm, 30,000 ppm, 35,000 ppm, 40,000 ppm, 45,000 ppm, 50,000 ppm, 55,000 ppm, 60,000 ppm, any of these numbers It can be within a combination.
- the effective chlorine concentration in the solid is in the range of 606,811 ppm to 881,677 ppm, and the free residual chlorine concentration is in the range of 901 ppm to 58,728 ppm.
- the effective chlorine concentration in the solid may be in the range of 606,811 ppm to 881,677 ppm.
- the effective chlorine concentration in the solid may be 606,811 ppm, 616,877 ppm, 632,513 ppm, 647,265 ppm, 781,019 ppm, 782,210 ppm, 824,064 ppm, or 881,667 ppm.
- the free residual chlorine concentration in the solid may range from 901 ppm to 58728 ppm.
- the free residual chlorine concentration in the solid can be 901 ppm, 2,145 ppm, 2,625 ppm, 20,785 ppm, 49,314 ppm, 55,916 ppm, or 58,728 ppm.
- a dry solid having such a concentration has high purity, long-term storage, high bactericidal effect, and low chlorine odor.
- calcium salt it conforms to the standard standard of advanced smooth powder. If necessary, a solid having a value outside the above range may be produced.
- the present invention provides a liquid obtained by dissolving the dry solid.
- the solvent for dissolving include water, alcohol, ether and the like.
- water include arbitrary water such as tap water, well water, seawater, ion exchange water, and purified water.
- the ratio of hypochlorite ion to chlorite ion is 1 to 7-35, and hypochlorite ion is Assuming 1, chlorite ions are 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, and any numerical value or range between them.
- the ratio of hypochlorite ions to chlorite ions is 1: 7.16 to 34.36.
- the free residual chlorine concentration is in the range of 150 ppm to 900 ppm, and the free residual chlorine concentration is 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, It can be 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm and can be within any numerical value or numerical range between these numerical values. As one specific example, when diluted with water so that the effective chlorine concentration is 1%, the free residual chlorine concentration is within the range of 187.07 ppm to 836.70 ppm.
- the ratio of hypochlorite to chlorite ions can vary depending on the degree of dilution.
- a liquid having such a ratio has a high purity, a high bactericidal effect, and a low chlorine odor.
- the ratio of hypochlorite ion to chlorite ion is 1 to 6-30. If hypochlorite ion is 1, Acid ions are 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and any numerical value or range between them. As one specific example, when diluted with water so that the effective chlorine concentration is 6%, the ratio of hypochlorite ion to chlorite ion is 1: 6.31 to 29.54.
- the free residual chlorine concentration is in the range of 1,000 ppm to 6,000 ppm, and the free residual chlorine concentration is 1,000 ppm, 1,500 ppm, 2, 000ppm, 2,500ppm, 3,000ppm, 3,500ppm, 4,000ppm, 4,500ppm, 5,000ppm, 5,500ppm, 6,000ppm, within any number or range between these numbers It can be.
- the free residual chlorine concentration is within the range of 1296.01 ppm to 5624.20 ppm.
- the ratio of hypochlorite to chlorite ions can vary depending on the degree of dilution.
- a liquid having such a ratio has a high purity, a high bactericidal effect, and a low chlorine odor.
- the ratio of hypochlorite ion to chlorite ion is 1 to 6-30. If hypochlorite ion is 1, Acid ions are 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and any numerical value or range between them. As one specific example, when diluted with water so that the effective chlorine concentration is 12%, the ratio of hypochlorite ions to chlorite ions is 1: 6.39 to 28.16.
- the free residual chlorine concentration is in the range of 2,500 ppm to 12,000 ppm, and the free residual chlorine concentration is 2,500 ppm, 3,000 ppm, 3, 500 ppm, 4,000 ppm, 4,500 ppm, 5,000 ppm, 6,000 ppm, 6,500 ppm, 7,000 ppm, 7,500 ppm, 8,000 ppm, 8,500 ppm, 9,000 ppm, 9,500 ppm, 10,000 ppm, It can be 10,500 ppm, 11,000 ppm, 11,500 ppm, 12,000 ppm, and can be within any value or range between these values.
- the free residual chlorine concentration when diluted with water so that the effective chlorine concentration is 12%, the free residual chlorine concentration is in the range of 2736.70 ppm to 11378.81 ppm. Since free residual chlorine can be decomposed during operation, the ratio of hypochlorite to chlorite ions can vary depending on the degree of dilution. A liquid having such a ratio has a high purity, a high bactericidal effect, and a low chlorine odor.
- the present invention is a method of producing a dry solid containing hypochlorite and chlorite, comprising providing a solution containing hypochlorite ions, chlorate ions and chloride ions.
- a first reaction step in which sulfuric acid is added to the solution to produce chlorine gas, and the produced chlorine gas is reacted with sodium hydroxide or calcium hydroxide in the recovered liquid A to produce hypochlorite ions.
- the second reaction step in which sulfuric acid having a higher concentration than in the first reaction step is added to the reaction mother liquor after the first reaction step to generate chlorine dioxide gas,
- the generated chlorine dioxide gas is reacted with sodium hydroxide and hydrogen peroxide to recover it as chlorite ions, the recovery liquid A and the recovery liquid B are mixed, and the resulting mixed solution is dried.
- This method regenerates quality-deteriorated sodium hypochlorite and provides a new useful disinfectant.
- the solid disinfectant manufactured and dried by this method does not change the composition of the content components even when stored at room temperature, and when it is made into a calcium salt, it can conform to the standard of advanced smooth powder that is a food additive .
- the dry solids completed by this method have the advantage of low chlorine odor, reducing the burden on workers, and being easy to use. It can be said that commercialization is possible.
- the recovery liquid A contains calcium hydroxide.
- the method further includes a step of adding hydrogen peroxide to the reaction mother liquor after the first reaction. It is possible to suppress the generation of chlorine gas by the step of adding hydrogen peroxide.
- the effective chlorine concentration of the recovered liquid B is 9.6 to 33.95. Is within the range.
- the effective chlorine concentration of the recovered liquid A is 1, whereas the effective chlorine concentration of the recovered liquid B is 9.6 or higher, 9.7 or higher, 9.8 or higher, 9.9 or higher, 10.0 or higher, 11 or higher, 12 or more, 13 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more, 19 or more, 20 or more, 21 or more, 22 or more, 23 or more, 24 or more, 25 or more, 26 or more, 27 or more, 28 or more 29 or more, 30 or more, 31 or more, 32 or more, 33 or more, 33.95 or less, 33.9 or less, 33.8 or less, 33.7 or less, 33.6 or less, 33.5 or less, 33 4 or less, 33.3 or less, 33.2 or less, 33.1 or less, 33 or less, 32 or less, 31 or
- the effective chlorine concentration of the recovered liquid A is 1, whereas the effective chlorine concentration of the recovered liquid B is 9.6, 9.7, 9.8, 9.9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33.
- the effective chlorine concentration of the recovered liquid B is 20 with respect to the effective chlorine concentration of the recovered liquids A and 1.
- the effective chlorine concentration of the recovered liquid B is less than 9.6, the effective chlorine is considered to fall below 60%, and the effective chlorine ratio falls under the lower limit since it is not suitable for high-quality powder. If the effective chlorine ratio of the recovered liquid B exceeds 33.95, it does not meet the standards for free residual chlorine and calcium.
- the recovered liquid A and the recovered liquid B are each made into a slurry and mixed.
- the entire operation time is shortened and the loss of effective chlorine and the change of the composition can be prevented as compared with the case where the slurry is not slurryed.
- the step of mixing the recovered liquid A and the recovered liquid B pre-drys the recovered liquid A, forms granulation nuclei, slurries the recovered liquid B, and recovers the recovered liquid B.
- the step of drying and solidifying includes the step of performing hot air drying for 20 minutes to 30 minutes.
- the internal environmental temperature is 50 to 60 ° C.
- the internal humidity is 10% or less.
- warm air is sent at an air volume of 1.9 m 3 / s.
- the step of drying and solidifying includes reducing the water contents of the recovered liquid A and the recovered liquid B to 20% or less, respectively.
- the moisture content is 26% or less, 25% or less, 24% or less, 23% or less, 22% or less, 21% or less, 20% or less, 19% or less, 18% or less, 17% or less, It can be 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less. If the water content is 26% or more, the free residual chlorine (hypochlorite ion) in the recovered liquid A reacts with the chlorite ion, the effective chlorine concentration decreases, and the chlorate ion increases. Purity and drying rate are also reduced.
- the present invention provides a method for producing a new disinfectant from a solution containing hypochlorite ions, chlorate ions, and chloride ions, the concentration of hypochlorite ions in the solution, A step of quantifying the chlorate ion concentration and the chloride ion concentration, a first reaction step of adding sulfuric acid to the solution to generate chlorine gas, and the generated chlorine gas in sodium hydroxide or A step of reacting with calcium hydroxide and collecting it as hypochlorite ions, and adding a higher concentration of sulfuric acid to the reaction mother liquor after the first reaction step than in the first reaction step to produce chlorine dioxide gas.
- the generated chlorine dioxide gas is reacted with sodium hydroxide and hydrogen peroxide and recovered as chlorite ions;
- Mixing the liquid B, comprising the steps, a to obtain a new disinfectant it provides a method.
- the mixture of the recovery liquid A and the recovery liquid B can be used as a disinfectant.
- This method regenerates quality-deteriorated sodium hypochlorite and provides a new useful disinfectant.
- the disinfectant produced by this method is a sodium salt, it can meet the standard standard as a food additive of sodium hypochlorite.
- the solution containing hypochlorite ion, chlorate ion and chloride ion is a solution containing hypochlorite whose quality has deteriorated.
- the solution containing the deteriorated hypochlorite is derived from a low salt grade sodium hypochlorite solution.
- the solution containing degraded hypochlorite is derived from a general grade sodium hypochlorite solution.
- the chlorine dioxide gas mixed in the recovered liquid A it is important to control the chlorine dioxide gas mixed in the recovered liquid A by adjusting the sulfuric acid concentration, and the acidity in the reaction mother liquor during the first reaction should not decompose chlorate ions. is important.
- the sulfuric acid during the second reaction depends on two factors: the sulfuric acid concentration used and the sulfuric acid concentration in the reaction mother liquor during the second reaction. Moreover, it is better that the sulfuric acid concentration used in the second reaction is high. In the second reaction, only the sulfuric acid concentration in the reaction mother liquor is not important.
- the solution containing the deteriorated hypochlorite is derived from a low salt grade sodium hypochlorite solution
- the disinfectant is a solid product
- the reaction in the first reaction step The sulfuric acid concentration in the mother liquor is 4.00 to 6.37%
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 30.00 to 40.00%
- the sulfuric acid concentration used in the second reaction step Is 50.0 w / w% to 70.0 w / w%.
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00%, 4.10%, 4.20%, 4.30%.
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step may be 30.0%, 31.0%, 32.0%, 33.0%, 34.0%, 35.0%. %, 36.0%, 37.0%, 38.0%, 39.0% or 40.0%, and the sulfuric acid concentration used in the second reaction step is 50.0 w / w%.
- the solution containing the deteriorated hypochlorite is derived from a low salt grade sodium hypochlorite solution
- the disinfectant is a liquid product
- the reaction in the first reaction step The sulfuric acid concentration in the mother liquor is 4.00 to 6.37%
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 30.00 to 59.04%
- the sulfuric acid concentration used in the second reaction step Is 50.0 w / w% to 70.0 w / w%.
- the disinfectant is a liquid product
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00, 4.10%, 4.20%, 4.30%, 40%, 4.50%, 4.60%, 4.70%, 4.80%, 4.90%, 5.00%, 5.10%, 5.20%, 5.30%, 5 .40%, 5.50%, 5.60%, 5.70%, 5.80%, 5.90%, 6.00%, 6.10%, 6.20%, 6.30% or 6
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step was 30.0%, 31.0%, 32.0%, 33.0%, 34.0%, 35.0%, 36 0.0%, 37.0%, 38.0%, 39.0%, 40.0%, 41.0%, 42.0%, 43.0%, 44.0%, 45.0%, 46 0.0%, 47 0%, 48.0%, 49.0%, 50.0%, 51.0%, 52.0%, 53.0%, 54.0%, 55.0%, 56.0%, 57.
- the sulfuric acid concentration used in the second reaction step was 50.0 w / w%, 51.0 w / w%, 52.0 w / w%, 53.0 w / w%, 54.0 w / w%, 55.0 w / w%, 56.0 w / w%, 57.0 w / w%, 58.0 w / w%, 59.0 w / w %, 60.0 w / w%, 61.0 w / w%, 62.0 w / w%, 63.0 w / w%, 64.0 w / w%, 65.0 w / w%, 66.0 w / w% 67.0 w / w%, 68.0 w / w%, 69.0 w / w%, or 70.0 w / w%.
- the solution containing the deteriorated hypochlorite is derived from a general grade sodium hypochlorite solution
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00-4.
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 25.00 to 30.00%, and the sulfuric acid concentration used in the second reaction step is 65 w / w%.
- the sulfuric acid concentration in the reaction mother liquor in the first reaction step is 4.00%, 4.10%, 4.20%, 4.30%, 4.40%, or 4.50%.
- the sulfuric acid concentration in the reaction mother liquor in the second reaction step is 25.0%, 26.0%, 27.0%, 28.0%, 29.0% or 30.00%
- the sulfuric acid concentration used in the reaction step is 65 w / w%.
- the recovery liquid A contains sodium hydroxide or calcium hydroxide.
- the recovery liquid B contains sodium hydroxide and hydrogen peroxide.
- the reaction step can be performed while blowing air. Air serves to prevent chlorine gas and chlorine dioxide gas generated in the reaction tank from returning to the solution and preventing the reverse reaction from proceeding.
- the first reaction step is performed while blowing air.
- the second reaction step is performed while blowing air.
- an intermediate trap tank containing hydrogen peroxide is provided between the reaction tank and the recovery tank containing the recovery liquid B.
- the intermediate trap tank prevents chlorine gas from being mixed into the recovered liquid B.
- the method further includes a step of adding hydrogen peroxide to the reaction mother liquor after the first reaction.
- a step of adding hydrogen peroxide during the second reaction chlorine gas generation is suppressed.
- the effective chlorine concentration of the recovery liquid A is 0.43 to 0.6, where the effective chlorine concentration of the recovery liquid A is 1. . In one embodiment, the effective chlorine concentration of the recovered liquid A is 1, and the effective chlorine concentration of the recovered liquid B is 0.43 or higher, 0.44 or higher, 0.45 or higher, 0.46 or higher, 0.47 or higher.
- the disinfectant contains sodium hypochlorite.
- the disinfectant is a food additive, a standard conforming product of sodium hypochlorite.
- the disinfectant is (1) Contains 4.0% or more of effective chlorine, (2) There is a smell of chlorine, (3) Presents the reaction of sodium salt and hypochlorite, (4) A solution obtained by adding 100 ml of a phosphate buffer (pH 8) to 4 ml of an aqueous solution (1 ⁇ 25) of this product has a maximum absorption part at a wavelength of 291 to 294 nm. (5) When red litmus paper is immersed in this product, the litmus paper turns blue and then fades.
- the sterilizing agent comprises SO 4 system components below the detection limit or 8100Ppm.
- the SO 4 -based component may be 8000 ppm or less, 7000 ppm or less, 6000 ppm or less, 5000 ppm or less, 4000 ppm or less, 3000 ppm or less, 2000 ppm or less, or 1000 ppm or less.
- the SO 4 -based component may be 100 ppm or more, 200 ppm or more, 300 ppm or more, 400 ppm or more, 500 ppm or more, 600 ppm or more, 700 ppm or more, 800 ppm or more, 900 ppm or more, 1000 ppm or more, 1100 ppm or more.
- This SO 4 -based component is entrainment of sulfuric acid contained in the reaction tank, and the amount of SO 4 -based component can be one of the indicators that the chlorine oxide is produced according to the present invention.
- the ratio of hypochlorite ion to chlorite ion in the disinfectant is 1: 0.24 to 0.3.
- the chlorite ion derived from the recovered liquid B is obtained by ion chromatography, converted to effective chlorine, and the total effective chlorine Deducted from. Further, the remaining effective chlorine was determined as effective chlorine derived from the recovered liquid A, and a coefficient was multiplied to obtain hypochlorite ions to obtain a final ion ratio.
- the ratio of hypochlorite ion to chlorite ion in the disinfectant is such that the hypochlorite is an arbitrary numerical value or a numerical range between 0.24 and 0.3, where hypochlorite is 1. Can be within. For example, if hypochlorite is 1, the chlorite is 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 or 0.30.
- the disinfectant having such a ratio has high purity, high bactericidal effect, and low chlorine odor.
- the effective chlorine concentration in the disinfectant is about 60,000 ppm and the free residual chlorine concentration is in the range of about 60,000 ppm.
- the effective chlorine concentration in the disinfectant is 55,000 ppm, 56,000 ppm, 57,000 ppm, 58,000 ppm, 59,000 ppm, 60,000 ppm, 61,000 ppm, 62,000 ppm, 63,000 ppm, 64,000 ppm, 65 Can be within the range of any combination of these numbers.
- the effective chlorine concentration in the disinfectant is 60,114 ppm, 60,814 ppm.
- the free residual chlorine concentration in the disinfectant is 55,000 ppm, 56,000 ppm, 57,000 ppm, 58,000 ppm, 59,000 ppm, 60,000 ppm, 61,000 ppm, 62,000 ppm, 63,000 ppm, 64,000 ppm, It can be 65,000 ppm and can be within the range of any combination of these numbers. As one specific example, they are 58,157 ppm and 59,380 ppm. A disinfectant having such a concentration has a high purity, a high bactericidal effect, and a low chlorine odor.
- the present invention provides a bactericidal disinfectant produced by any of the above methods.
- the ratio of hypochlorite ion to chlorite ion in the disinfectant is 1 to 0.24 to 0.3.
- the ratio of hypochlorite ion to chlorite ion in the disinfectant is such that the hypochlorite is an arbitrary numerical value or a numerical range between 0.24 and 0.3, where hypochlorite is 1.
- the disinfectant having such a ratio has high purity, high bactericidal effect, and low chlorine odor.
- the effective chlorine concentration in the disinfectant is about 60,000 ppm and the free residual chlorine concentration is about 60,000 ppm.
- the effective chlorine concentration in the disinfectant is 55,000 ppm, 56,000 ppm, 57,000 ppm, 58,000 ppm, 59,000 ppm, 60,000 ppm, 61,000 ppm, 62,000 ppm, 63,000 ppm, 64,000 ppm, 65 Can be within the range of any combination of these numbers. Specific examples are 60, 114 ppm and 60, 814 ppm.
- the free residual chlorine concentration in the disinfectant is 55,000 ppm, 56,000 ppm, 57,000 ppm, 58,000 ppm, 59,000 ppm, 60,000 ppm, 61,000 ppm, 62,000 ppm, 63,000 ppm, 64,000 ppm, It can be 65,000 ppm and can be within the range of any combination of these numbers. As one specific example, they are 58,157 ppm and 59,380 ppm. A disinfectant having such a concentration has a high purity, a high bactericidal effect, and a low chlorine odor.
- a liquid chloroxide produced using the dry solid comprising: (a) dissolving the dry solid in water to prepare an elevated pH solution.
- the pH of step (a) can be 10.0 or higher.
- the pH of step (b) can be 10.0 or higher.
- This method may be the method shown in Japanese Patent No. 593253.
- the calcium salt may remain as a residue, and there is a concern about the problem of foreign matter contamination in the food for the end processor who performs food processing.
- processing of a large amount of calcium salt is very troublesome.
- This liquid chlorine oxide is useful because calcium is removed. Even in long-term storage, there is an effect of not precipitating calcium salt.
- the product completed by this method has the advantage that it has a lower chlorine odor than the sodium hypochlorite solution of the same concentration, which reduces the burden on workers and is easy to use.
- the liquid or liquid chloroxide having a calcium concentration substantially below the detection limit is provided.
- the calcium concentration in the chlorine oxide-containing liquid is 24 ppm or less.
- the calcium concentration in the chlorine oxide-containing liquid is more preferably 23 ppm or less, 22 ppm or less, 21 ppm or less, 20 ppm or less, 19 ppm or less, 18 ppm or less, 17 ppm or less, 16 ppm or less, 15 ppm or less, 14 ppm or less, 13 ppm or less, 12 ppm or less, 11 ppm or less, 10 ppm or less, 9 ppm or less, 8 ppm or less, 6 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, 1 ppm or less, 0.9 ppm or less, 0.8 ppm or less, 0.7 ppm or less 0.6 ppm or less, 0.5 ppm or less
- use of the dry solid, the liquid, or the liquid or liquid chloroxide as a disinfectant is provided.
- use of the dry solid, the liquid, the disinfectant, or the liquid or liquid chloroxide as a food additive is provided.
- use of the dry solid, the liquid, the disinfectant, or the liquid or liquid chloroxide for sterilizing food is provided.
- a method for producing a new drug from a solution comprising hypochlorite ions, chlorate ions and chloride ions comprising the concentration of hypochlorite ions in the solution, chlorine A step of quantifying the acid ion concentration and the chloride ion concentration, a first reaction step of adding sulfuric acid to the solution to generate chlorine gas, and the generated chlorine gas in sodium hydroxide or water in the recovered liquid A A step of reacting with calcium oxide and recovering it as hypochlorite ions, and adding a higher concentration of sulfuric acid to the reaction mother liquor after the first reaction step to produce chlorine dioxide gas.
- the generated chlorine dioxide gas is reacted with sodium hydroxide and hydrogen peroxide to recover it as chlorite ions, and the recovered liquid A Mixing the liquid B, comprising a step of obtaining a new drugs.
- This method may have one or more of the characteristics of replacing the germicide as defined above with a drug.
- a medicament produced by this method is provided.
- the drug may have one or more of the characteristics of replacing the disinfectant as defined above with a drug.
- Use of the drug as a disinfectant, use as a food additive, and use for disinfecting food can be provided.
- the chlorine oxide produced according to the present invention uses sodium hypochlorite with reduced quality as a raw material, and therefore can contain various components in the raw material. Also in the step of treating sodium, various reactions can proceed to produce various components including various chlorine oxides. Therefore, although the recovered liquid A and the recovered liquid B can contain hypochlorite and chlorite as main components, respectively, not all components can be identified. Therefore, the disinfectant of the present invention produced by mixing the recovered liquid A and the recovered liquid B may contain components that cannot be identified, although they satisfy the standards of sodium hypochlorite and the standards of high-quality powder. . There is a possibility that such unidentified components may contribute to the improvement of the bactericidal effect and the stability, and the effect is different from the case of simply combining hypochlorite and chlorite. It is assumed that it will be obtained.
- the amount of sulfate ion was measured by the following test method (ion chromatography).
- Preparation of the sample solution The sample is diluted by adding water, and adjusted to 0 to 40 mg / L as sulfate ions.
- Preparation of standard solution for calibration curve Reagent anion mixed standard IV manufactured by Kanto Chemical Co., Ltd. is used as the standard solution. (1 mL of this solution contains about 40 ⁇ g of sulfate ions).
- Measurement conditions Use an ion chromatograph with an electrical conductivity detector (suppressor system) and measure under the following conditions.
- Degraded sodium hypochlorite contains hypochlorite ion, chloride ion, and chlorate ion.
- chlorate ion which is expected to be difficult to decompose, was reacted with sulfuric acid. A preliminary verification of the case was performed. Moreover, the sodium chlorate section was set in order to compare the reactivity.
- chlorine dioxide gas was easily generated by reacting sodium chlorate with sulfuric acid, and chlorite ions could be obtained through sodium hydroxide.
- the yield of chlorite ions was improved by adding hydrogen peroxide to sodium hydroxide.
- chlorite ions could not be recovered from deteriorated sodium hypochlorite, only chloride ions could be recovered. Furthermore, when hydrogen peroxide was added to sodium hydroxide, chloride ions were recovered. As a result, the amount of recovered material increased.
- this production method uses degraded sodium hypochlorite as the reaction mother liquor, but from this one reaction mother liquor, it is necessary to recover the chlorine gas as the first reaction and then to recover the chlorine dioxide gas. In addition, it has been found that it is necessary to separate and collect these gases and combine them later.
- the reaction model is a first reaction in which chlorine gas is generated from a reaction mother liquor in which deteriorated sodium hypochlorite and a sulfuric acid solution are added, and hypochlorite ions are recovered with sodium hydroxide or calcium hydroxide.
- hypochlorite ions are recovered with sodium hydroxide or calcium hydroxide.
- Degradation following reaction 2 The amount of chlorate ion in the deteriorated sodium hypochlorite is small, and the reactivity is poor just by adding sulfuric acid dropwise little by little, so the batch type reaction is performed, and the sulfuric acid concentration to be added is increased to 65 w / w%. Furthermore, it was considered to generate chlorine gas and chlorine dioxide gas stepwise by raising the temperature during the reaction. Also, two types of recovery liquid A and recovery liquid B are prepared. In the first reaction, hypochlorite ions are recovered by the recovery liquid A, and after completion of the first reaction, the piping is switched. Thought to recover.
- reaction 3 In order to confirm the sulfuric acid concentration necessary for generating chlorine gas preferentially during the first reaction, the reaction was carried out with the sulfuric acid concentration set to 50 w / w%. The sulfuric acid concentration in the reaction mother liquor at this time is 25.0%.
- the chlorine gas recovery in the first reaction and the chlorine dioxide gas recovery in the second reaction could be further controlled stepwise.
- the recovery rate of chlorite ions in the recovery liquid B to which sodium hydroxide and hydrogen peroxide were added was improved.
- chlorite ions were also recovered in the recovered liquid A, possibly due to chlorine dioxide gas contamination, and generation of chlorate ions occurred because hydrogen peroxide could not be added. For this reason, it turned out that it is necessary to examine not only the concentration of sulfuric acid but also the method of adding sulfuric acid.
- the concentration and amount of sulfuric acid in the first reaction and the second reaction, and the temperature were set, and the chlorine gas and the chlorine dioxide gas were separately collected and recovered by adding sulfuric acid twice.
- the sulfuric acid concentration used in the first reaction was 50 w / w%, and the input amount was 25 g, so that the sulfuric acid concentration in the reaction mother liquor was 5.6%.
- the sulfuric acid concentration was 65 w / w%, and the input amount was 250 g, so that the sulfuric acid concentration in the reaction mother liquor was 36.8%.
- chlorine dioxide gas mixed in the recovered liquid A could be reduced, and chlorite ions and chlorate ions could be reduced.
- the amount of chlorite ions recovered in the recovered liquid B increased by 20% from the previous level, exceeding the expected value of 60%.
- chlorate ions are decomposed. It turned out that it was important not to let it.
- each of the recovery liquids A and B was provided with a preliminary recovery tank. In addition, the timing of blowing air was advanced so that air was blown into the reaction vessel immediately after the raw materials were added, and the air volume was gradually increased.
- reaction mother liquid after the first reaction contained 24378.5 ppm to 33990.4 ppm of chlorate ions. It turned out that it has increased to. Conversely, it was also found that the chloride ion decreased from 50079.5ppm to 23532.4ppm. This increase in chlorate ion is thought to be due to the increase in chlorate ion due to the re-proportionation reaction in the strong acidification by the addition of sulfuric acid, and hydrochloric acid is also generated due to the decrease in chloride ion during the addition of sulfuric acid. It was thought that it contributed to the reaction.
- Chloride ions formed in the deteriorated sodium hypochlorite form hydrochloric acid in the presence of sulfuric acid. Then, in the second reaction, chlorine dioxide gas is formed from hydrochloric acid and chloric acid. Will occur.
- the recovery rate of recovered liquid B increased from 63.04% to 74.48% recovery rate for effective chlorine and 71.03% to 78.91% recovery rate for chlorite ion. It was thought that it was doing. Also in this test, it was also confirmed that the reaction mother liquor after completion of the first reaction had increased chlorate ions and decreased chloride ions.
- the sulfuric acid at the first reaction depends on the sulfuric acid concentration in the reaction mother liquor at the first reaction, regardless of the sulfuric acid concentration to be added.
- the sulfuric acid during the second reaction depends on two factors: the sulfuric acid concentration used and the sulfuric acid concentration in the reaction mother liquor during the second reaction. Moreover, it is better that the sulfuric acid concentration used in the second reaction is higher, and 70% w / w is at least 65% w / w or higher. In the second reaction, only the sulfuric acid concentration in the reaction mother liquor is not important. I understood that.
- the recovery rate of recovered liquid B exceeds 80% and is very good, but chloride ions are higher in concentration than chlorite ions, and this composition can only be used with sodium hypochlorite standards. .
- general grade sodium hypochlorite is characterized by a lower chemical unit price than low-sodium sodium hypochlorite, a large amount of chloride ions in the composition, and high chlorate ions from the beginning. is there.
- the chloride ion in the raw material was excessive, so the sulfuric acid concentration in the reaction mother liquor during the first reaction was set to a low 4.47%. Furthermore, during the second reaction, chlorate ions in the reaction mother liquor were set. In order to completely decompose, sodium chloride was additionally added to actively promote hydrochloric acid formation.
- the recovery liquid A uses 10% calcium hydroxide, and when the recovery rate of the recovery liquid B is obtained excessively, the tendency of increasing chloride ions in the recovery liquid B has been confirmed. Therefore, it was recovered after passing through an intermediate trap tank (containing hydrogen peroxide). In addition, about the chloride ion at this time, it was considered that hydrochloric acid was entrained from the reaction tank or chlorine gas was mixed.
- the recovery rate of recovered liquid B is in the 20% range, a large amount of chloride ions are recovered in the chloride ion recovery trap tank (containing hydrogen peroxide), and the chloride ions in recovered liquid B are also high. showed that.
- the reaction for decomposing chlorate ions has a main reaction and a side reaction, and the reaction ratio varies depending on the reaction conditions.
- the side reaction is considered to proceed easily.
- the sulfuric acid concentration in the reaction mother liquor during the second reaction was set to 30%. This is because when the sulfuric acid concentration is about 20%, about 20% of chlorate ions remain, and the total decomposition has not been achieved.
- hydrogen peroxide was added before adding sulfuric acid. Originally, hydrogen peroxide is often added for the purpose of suppressing generation of chlorine dioxide, or generates chlorine dioxide gas at a low sulfuric acid concentration, and often exhibits different reactions depending on conditions. This time, it tried adding for the purpose of side reaction suppression by hydrogen peroxide addition.
- the effective chlorine in the recovered liquid B was measured every hour, a recovery graph of effective chlorine was prepared, and at the same time, the change in the composition in the recovered liquid B was confirmed.
- the intermediate trap tank by performing the chlorine gas cleaning by passing the hydrogen peroxide solution through the intermediate trap tank, it plays the role of removing chloride ions, and as a result, the high-purity recovered liquid B can be recovered, and then the drying step By carrying out, it reaches a level that can be concentrated to a high concentration.
- both chlorine dioxide gas and chlorine gas are always generated as shown in the reaction formulas (13) and (14).
- hydrogen gas is used, so that chlorine gas Even if chlorine dioxide gas is allowed to pass through by washing, only half the amount of chlorine gas generated can be removed by reaction formulas (15) and (16).
- chlorine dioxide gas which is also an oxidizing agent, reacts. Therefore, the recovery liquid in the present invention using sodium hypochlorite as a raw material must be chlorinated. Contain ions.
- the amount of sodium hydroxide in the recovered liquid B in the second reaction is examined.
- the amount of alkali in the second reaction is preferably excessive in order to prevent omission of recovery, but if there are a large number of inorganic alkali salts, the concentration rate when dried is lowered and the final concentration is also lowered.
- the T.O. AL is 515.46, and after the reaction is 149.25, the T. of 366.21. It was found that AL was consumed in the reaction. And although the recovery rate of the recovery liquid B tends to decrease somewhat, the drying efficiency increases, so that it can be dried to a powder containing very high concentration of effective chlorine.
- the chlorate ion after the first reaction was decomposed by 5.15%, and for the chloride concentration of 43429 ppm in the raw material, there was still excessive sulfuric acid, and the decomposition rate of the chlorate ion varied somewhat. I was able to confirm that.
- the reaction was carried out at a sulfuric acid concentration of 30% against the chloride concentration of 18225 ppm in the reaction mother liquor after the completion of the first reaction, but almost all chloride ions and chlorate ions were produced in the recovered solution B. Because there was no reaction, the main reaction could be mainly performed, and it could be recovered with high purity.
- the sulfuric acid concentration that can be input is determined by the chloride concentration in the raw material, and if sulfuric acid for completely decomposing effective chlorine in the raw material is input, depending on the chloride concentration, chloric acid Since ions may decrease and the yield thereafter decreases, the sulfuric acid concentration during the first reaction is determined by the chloride concentration in the raw material. If the chloride concentration is excessive, it is effective. Even if the chlorine concentration is high, a large amount of sulfuric acid cannot be added.
- the chlorate ion concentration after the completion of the first reaction was increased to 118.24%, and the recovery rate of the recovered liquid B after the second reaction was 93.7%.
- the chloride ion in the collection liquid B increased to 3827 ppm, and it was confirmed that increasing the sulfuric acid concentration to increase the recovery rate causes a by-product of chloride ion.
- the concentration of chloride in the recovered liquid B may be high.
- the concentration rate during drying will decrease. As a result, it becomes impossible to produce high-concentration high-quality powder.
- chloride concentration in the raw material is already excessive for the reaction.
- Chlorine gas-derived chloride ions are generated in the recovered liquid B. This event occurs when the sulfuric acid concentration is high, or when the chloride concentration in the raw material is high, but when producing a solid product by this method, the chloride ion in the recovered solution B must be about 4000 ppm. Since it cannot be concentrated to a high concentration, 40.0% is the upper limit. (However, since it is not necessary to consider the concentration rate when manufacturing a liquid product, it is not limited to this, and it is good up to 59.4%.)
- Appropriate sulfuric acid concentration during the first reaction requires that effective chlorine be converted to chlorine gas without decomposing chlorate ions in the raw material.
- the reaction mother liquor The sulfuric acid concentration in is determined.
- the reaction mother liquor after the completion of the first reaction is the raw material, but the raw material contains a sufficient amount of chloride for the reaction and is often somewhat excessive. If the sulfuric acid concentration in the reaction mother liquor is increased too much, the side reaction proceeds to generate only chlorine gas, and a large amount of chloride ions are generated in the recovered liquid B. The same applies if the sulfuric acid concentration is too low.
- an appropriate sulfuric acid concentration at the time of the second reaction is that the chlorate ions in the reaction mother liquor are totally decomposed, side reactions are controlled, and a large amount of chloride ions are not generated in the recovered solution B.
- the sulfuric acid concentration in the reaction mother liquor of the second reaction is as follows.
- Recovered liquid A and recovered liquid B were obtained while reacting with deteriorated sodium hypochlorite as a raw material, while preventing the regeneration of chlorate ions.
- the effective chlorine concentration of the recovered liquid A is 1 and the effective chlorine concentration of the recovered liquid B is 0.6 as the upper limit, and 0.7 is hypochlorous acid in the confirmation test (1).
- the item (3) was nonconforming. Therefore, considering the configuration for the purpose of the present invention, it is desirable to combine them at an effective chlorine concentration ratio of 0.43 to 0.6.
- the disinfectant manufactured with this effective chlorine concentration ratio conformed to the standard standard as sodium hypochlorite by analysis of an external organization.
- the free residual chlorine concentration is measured with a DPD reagent, but it is measured at 58,157 to 59,380 ppm, and since an effective chlorine concentration and an approximate value are obtained, a reaction is shown in addition to hypochlorous acid. It is possible.
- the concentration of chlorite ion derived from the recovered liquid B was obtained by ion chromatography, converted to an effective chlorine concentration, and subtracted from the total effective chlorine concentration. Further, the remaining effective chlorine concentration was determined as the effective chlorine concentration derived from the recovered liquid A, and the hypochlorite ion concentration was obtained by multiplying by a coefficient to obtain the final ion ratio.
- Effective chlorine concentration ⁇ 0.476 chlorite ion concentration (ClO 2 -)
- Effective chlorine concentration ⁇ 0.726 hypochlorite ion concentration (ClO -)
- This conversion formula was obtained by using a known concentration of chlorite ion or hypochlorite ion to derive a relationship with the effective chlorine concentration.
- the initial effective chlorine concentration produced about 6.94% disinfectant, but even at refrigeration temperature (6 °C), the effective chlorine concentration is about 5% (about 72%) at D + 30. At 40 ° C, the effective chlorine concentration decreased to about 3.8% (about 54%) at D + 3, and sterilization that contained both hypochlorite and chlorite ions. It has been found that disinfectants (liquids) are very poor in preservability and are difficult to sell at room temperature, and are preferably sold refrigerated.
- the effective chlorine concentration of the recovered liquid A is set to 1, and the effective chlorine concentration of the recovered liquid B is adjusted within the range of 9.6 to 33.95, and the drying process is performed.
- the recovered liquids B and 9.6 are mainly used for the recovered liquids A and 1.
- the yield deteriorates depending on the drying process and the order of charging.
- free residual chlorine is easily decomposed, granulated nuclei are formed in advance only with the recovered liquid A, and then the recovered liquid B is A certain amount of concentration is advanced to make a slurry.
- the recovered liquid B is A certain amount of concentration is advanced to make a slurry.
- the advanced smooth powder produced by this method has a special composition compared to the commercially available advanced smooth powder, so it is not sold as a single advanced powder, but a sterilizer (food additive formulation). Or consider selling it as a disinfectant formulation.
- the drying condition is that the internal environmental temperature is 50-60 ° C. and the internal humidity is 10% or less. Moreover, warm air is sent in at 1.9 m3 / s. The hot air at this time does not need to be directly applied to the liquid in the drying chamber, and the purpose is to maintain the temperature and humidity in the chamber.
- the yield and content composition after drying are more stable when the granulation nucleus of the recovered liquid A and the slurry of the recovered liquid B are respectively formed and mixed.
- hypochlorite ions and chlorite ions are mixed, effective chlorine is decomposed, and simultaneously chloride ions and chlorate ions are generated. In this case, not only the effective chlorine concentration of the final product is lowered, but also the purity is lowered by the subsidiary components.
- the stability when liquid A and liquid B are mixed and dried is affected by two factors: the amount of water retained before drying, and the effective chlorine ratio when recovered liquid A and recovered liquid B are mixed. It was.
- the formation of granulated nuclei with the recovered liquid A and the formation of the slurry with the recovered liquid B have resulted in improved workability and stability if dried to some extent in advance. As a guideline, it is better to pre-dry each until the total water content before drying becomes 20% or less.
- the effective chlorine ratio when mixing the recovered liquid A and the recovered liquid B 1:20 is the highest in purity because no secondary component is generated, so that the recovered liquid A and the recovered liquid B exist stably.
- the effective chlorine ratio was set to 1:20, and the water content was most preferably 20% or less.
- Chlorite ion contains 1: 5.53-23.18.
- composition of recovered liquids A and B and combined drying result (1: 33.95) It is a measurement result when the recovered liquid A is set to 1 in the effective chlorine ratio, and the recovered liquid B is mixed at 33.95 and dried. However, if the effective chlorine ratio of the recovered liquid B becomes too high, free residual chlorine and calcium Cases that do not conform to the standard are assumed. As a result of this ratio, the calcium ion concentration after drying is 5.64%, which is the lower limit of the condition that the amount of calcium in the high-quality salty powder is suitable, so this effective chlorine ratio is almost the upper limit.
- composition of recovered liquids A and B and combined drying results (list) Composition of recovered liquids A and B and combined drying results (list)
- (1) if there is a large amount of free residual chlorine, hypochlorite ions and chlorite ions react to reduce effective chlorine, and chloride ions and chlorate ions are generated. In this case, not only the decomposition of effective chlorine but also subcomponents that do not contribute to effective chlorine are generated, so that the dry concentration rate also decreases and the effective chlorine concentration becomes the lowest.
- this production method is obtained from the reaction of chlorine gas, it contains about 1140 ppm or more of sulfate ions, and these sulfate ions are entrained with sulfuric acid contained in the reaction tank, and the recovered liquid contains calcium hydroxide. Because it exists in excess, it is mainly in the form of sodium sulfate.
- composition when calcium is removed from the solid product Add ion-exchanged water and dissolve so that the effective chlorine concentration after dilution of the recovered solution after removal of Ca is 1%, 6%, and 12% based on the following recipe and Ca removal formula (*) Stirring was performed for 15 minutes with a stirrer so that there was no residue. (The 20% sodium carbonate solution obtained from the relational expression was added and the mixture was stirred for 1 minute.) Next, the mixture was allowed to stand in an incubator at 10 ° C. for 19 hours (to obtain a clear supernatant) and the precipitate was sucked Collect the supernatant so that it does not.
- 0.05mol / L EDTA solution 1ml 3.705mgCa (OH) 2 ⁇ Standards for Food, Additives, etc.
- Direct titration method with EDTA solution (first method) and after adding excess EDTA, acetic acid
- second method back titration method
- titration is performed with a zinc solution.
- first method direct titration method with EDTA solution
- second method back titration method
- 10 ml of the test solution specified by the first method add 50 ml of water, add 10 ml of potassium hydroxide solution (1 ⁇ 10) and leave it for about 1 minute, then add about 0.1 g of NN indicator and immediately add 0.05 mol.
- Titrate with / LEDTA solution The end point is when the reddish purple color of the liquid completely disappears and becomes blue.
- the specimen was preliminarily dried from the collected liquid A to form granulated nuclei, and the preliminarily dried collected liquid B was mixed and dried.
- the ORP oxidation-reduction potential
- chlorine gas concentration The ORP (oxidation-reduction potential) and chlorine gas concentration were measured for the specimen (1) and specimen (2), which were the prepared mixed solution (hypochlorous acid Na standard). Further, a sodium hypochlorite solution having the same concentration was used as a comparative control. As a result, the ORP (oxidation-reduction potential) did not change even when sodium hypochlorite was diluted, whereas the oxidizing power increased by diluting both the specimens (1) and (2). Further, with respect to the chlorine gas concentration, almost no chlorine gas was released even when it was brought into contact with an organic substance, and the superiority that only about 1/31 to 1/50 was measured was confirmed.
- the liquid product can confirm the superiority of the bactericidal effect for both the number of general viable bacteria and the number of coliforms. It was.
- the solid product it was confirmed in the 2nd section before and after calcium removal in the high-quality salty powder, the bactericidal effect on the coliform group can be confirmed as well, and the overall characteristics of the bactericide in the present invention are as follows. It confirmed that the bactericidal effect with respect to was high.
- the recovery rate may be improved by adding sodium chloride to the reaction mother liquor as in the R2 method. If this happens, it may be possible to reduce the cost of using sulfuric acid, so the second reaction is carried out using the reaction mother liquor (deteriorated sodium hypochlorite + sulfuric acid) that has finished the first reaction. 50% sulfuric acid and sodium chloride were added, and the decomposition rate of chlorate ions and the recovery rate in the recovered liquid B were confirmed.
- the temperature condition for the primary reaction is preferably to react at room temperature around 30 ° C. I understood. Further, it is considered that raising the temperature too much is not preferable because steam is generated and entrainment of sulfuric acid, hydrochloric acid or the like increases in the recovered liquid.
- the chlorate ion increased as the acidity increased rather than the influence of temperature.
- the generation of hydrochloric acid is considered to progress, and as a result, chlorite ions and chlorate ions are detected in the recovered liquid A, and the recovery rate may be deteriorated. It is not preferable to excessively increase the sulfuric acid concentration.
- reaction conditions differ depending on the grade of sodium hypochlorite (low salt grade and general grade) used as a raw material.
- the recovered solution is recovered only with sodium hydroxide or calcium hydroxide in the first reaction, and is recovered by adding hydrogen peroxide to sodium hydroxide in the second reaction.
- an intermediate tank is provided between the reaction tank and the recovery tank to prevent backflow.
- hydrogen peroxide water is added to prevent chlorine gas from entering. It is good to add.
- the effective chlorine in the recovery liquid A is set to 1, and the effective chlorine in the recovery liquid B should not exceed 0.6, and is preferably adjusted within the range of 0.43 to 0.6 from the features of the present invention.
- the effective chlorine of the recovered liquid A is set to 1 and the effective chlorine of the recovered liquid B to 33.95 or less, but considering the characteristics of this product, 1: 9 .6 is desirable.
- the dry solid produced by these methods has a very low decomposition of free residual chlorine, and becomes a chlorine oxide solid in a state where the composition of the content liquid is maintained for a long period of time.
- the invention makes it possible not only to dispose of the deteriorated sodium hypochlorite as a raw material, but to dispose of it or restore it to inexpensive sodium hypochlorite, as well as add value to the end consumer. It can be regenerated to a certain disinfectant.
- composition of the present invention is useful as a disinfectant.
- the method of the present invention regenerates degraded sodium hypochlorite and provides a new useful disinfectant.
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Abstract
Description
本発明はまた、以下を提供する。
(項目1)
次亜塩素酸塩および亜塩素酸塩を含む乾燥固体。
(項目2)
前記固体が、乾燥粒状である、項目1に記載の乾燥固体。
(項目3)
前記固体が、次亜塩素酸カルシウムを含む、項目1または2に記載の乾燥固体。
(項目4)
前記固体が、
(1)有効塩素60.0%以上含み、
(2)塩素のにおいがあり、
(3)該固体0.5gに水5mlを加えて振り混ぜ、これに赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色し、
(4)該固体0.1gに酢酸(1→4)2mlを加えるとき、ガスを発生して溶け、これに水5mlを加えてろ過した液は、カルシウム塩の反応を呈する、
項目1~3のいずれか一項に記載の乾燥固体。
(項目5)
前記固体が、SO4系成分を検出限界以上8100ppm以下で含む、項目1~4のいずれか一項に記載の乾燥固体。
(項目6)
前記固体における次亜塩素酸塩と亜塩素酸塩の比が、1対5~25である、項目1~5のいずれか一項に記載の乾燥固体。
(項目7)
前記固体における有効塩素濃度が600,000ppm~900,000ppmの範囲内であり、遊離残留塩素濃度が900ppm~60,000ppmの範囲内である、項目1~6のいずれか一項に記載の乾燥固体。
(項目8)
項目1~7のいずれか一項に記載の乾燥固体を溶解させて得られた液体。
(項目9)
有効塩素濃度が1%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対7~35である、項目8に記載の液体。
(項目10)
有効塩素濃度が1%となるように水で希釈した場合、遊離残留塩素濃度が150ppm~900ppmの範囲内である、項目8または9に記載の液体。
(項目11)
有効塩素濃度が6%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対6~30である、項目8に記載の液体。
(項目12)
有効塩素濃度が6%となるように水で希釈した場合、遊離残留塩素濃度が1,000ppm~6,000ppmの範囲内である、項目8または11に記載の液体。
(項目13)
有効塩素濃度が12%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対6~30である、項目8に記載の液体。
(項目14)
有効塩素濃度が12%となるように水で希釈した場合、遊離残留塩素濃度が2,500ppm~12,000ppmの範囲内である、項目8または13に記載の液体。
(項目15)
次亜塩素酸塩および亜塩素酸塩を含む乾燥固体を製造する方法であって、
次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液を用意する工程と、
該溶液に硫酸を添加し、塩素ガスを生成させる第一反応工程と、
回収液A中において、該生成した塩素ガスを水酸化ナトリウムまたは水酸化カルシウムと反応させて次亜塩素酸イオンとして回収する工程と、
第一反応工程後の反応母液に、第一反応工程におけるよりも高い濃度の硫酸を添加し、二酸化塩素ガスを生成させる第二反応工程と、
回収液B中において、該生成した二酸化塩素ガスを水酸化ナトリウムおよび過酸化水素と反応させて亜塩素酸イオンとして回収する工程と、
回収液Aと回収液Bとを混合する工程と、
得られた混合溶液を乾燥させ固体化させる工程と
を包含する、方法。
(項目16)
前記回収液Aが水酸化カルシウムを含む、項目15に記載の方法。
(項目17)
第1反応後の反応母液に、過酸化水素を添加する工程をさらに包含する、項目15または16に記載の方法。
(項目18)
前記回収液Aと前記回収液Bとを混合する工程において、該回収液Aの有効塩素濃度を1とすると、回収液Bの有効塩素濃度が9.6~33.95の範囲内である、項目15~17のいずれか一項に記載の方法。
(項目19)
前記回収液Aと前記回収液Bとを混合する工程において、該回収液Aおよび該回収液Bが、それぞれスラリー化されて混合される、項目15~18のいずれか一項の方法。
(項目20)
前記回収液Aと回収液Bとを混合する工程が、前記回収液Aを予備乾燥し、造粒核を形成し、回収液Bをスラリー化させ、そして、回収液Bスラリーに回収液A乾燥物を投入する工程を包含する、項目15~19のいずれか一項に記載の方法。
(項目21)
前記乾燥させ固体化させる工程が、20分~30分間の温風乾燥を行う工程を包含する、項目15~20のいずれか一項に記載の方法。
(項目22)
前記乾燥させ固体化させる工程が、回収液Aおよび回収液Bの水分量をそれぞれ20%以下に減少させることを含む、項目15~21のいずれか一項に記載の方法。
(項目23)
次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液から新たな殺菌消毒剤を製造する方法であって、
該溶液中の次亜塩素酸イオン濃度、塩素酸イオン濃度および塩化物イオン濃度を定量する工程と、
該溶液に硫酸を添加し、塩素ガスを生成させる第一反応工程と、
回収液A中において、該生成した塩素ガスを水酸化ナトリウムまたは水酸化カルシウムと反応させて次亜塩素酸イオンとして回収する工程と、
第一反応工程後の反応母液に、第一反応工程におけるよりも高い濃度の硫酸を添加し、二酸化塩素ガスを生成させる第二反応工程と
回収液B中において、該生成した二酸化塩素ガスを水酸化ナトリウムおよび過酸化水素と反応させて亜塩素酸イオンとして回収する工程と、
回収液Aと回収液Bとを混合し、新たな殺菌消毒剤を得る工程と、
を包含する、方法。
(項目24)
前記次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液が、品質劣化した次亜塩素酸塩を含む溶液である、項目23に記載の方法。
(項目25)
前記品質劣化した次亜塩素酸塩を含む溶液が、低食塩級の次亜塩素酸ナトリウム溶液に由来する、項目24に記載の方法。
(項目26)
前記品質劣化した次亜塩素酸塩を含む溶液が、一般級の次亜塩素酸ナトリウム溶液に由来する、項目24に記載の方法。
(項目27)
前記殺菌消毒剤が固体品であり、第一反応工程における反応母液中の硫酸濃度が4.00~6.37%であり、第二反応工程における反応母液中の硫酸濃度が30.00~40.00%であり、第二反応工程において使用される硫酸濃度が、50.0w/w%~70.0w/w%である、項目25に記載の方法。
(項目28)
前記殺菌消毒剤が液体品であり、第一反応工程における反応母液中の硫酸濃度が4.00~6.37%であり、第二反応工程における反応母液中の硫酸濃度が30.00~59.04%であり、第二反応工程において使用される硫酸濃度が、50.0w/w%~70.0w/w%である、項目25に記載の方法。
(項目29)
第一反応工程における反応母液中の硫酸濃度が4.00~4.50%であり、第二反応工程における反応母液中の硫酸濃度が25.00~30.00%であり、第二反応工程において使用される硫酸濃度が、65w/w%である、項目26に記載の方法。
(項目30)
第一反応において、原料中の塩化物濃度をX%とし、反応母液中の硫酸濃度をY%としたとき、
(1)Y=-1.2676X+9.84393
(2)X≦4
を満たす、項目23~29にいずれか一項に記載の方法。
(項目31)
前記回収液Aが、水酸化ナトリウムまたは水酸化カルシウムを含む、項目23~30のいずれか一項に記載の方法。
(項目32)
前記回収液Bが、水酸化ナトリウムおよび過酸化水素を含む、項目23~31のいずれか一項に記載の方法。
(項目33)
前記第一反応工程が、エアーを吹き込みながら行われる、項目23~32のいずれか一項に記載の方法。
(項目34)
前記第二反応工程が、エアーを吹き込みながら行われる、項目23~33のいずれか一項に記載の方法。
(項目35)
反応槽と回収液Bを含む回収槽との間に、過酸化水素を含む中間トラップ槽が設けられている、項目23~34のいずれか一項に記載の方法。
(項目36)
第1反応後の反応母液に、過酸化水素を添加する工程をさらに包含する、項目23~35のいずれか一項に記載の方法。
(項目37)
前記回収液Aと回収液Bとを混合する工程において、回収液Aの有効塩素濃度を1として、回収液Bの有効塩素濃度が、0.43~0.6である、項目23~36のいずれか一項に記載の方法。
(項目38)
前記殺菌消毒剤が、次亜塩素酸ナトリウムを含む、項目23~37のいずれか一項に記載の方法。
(項目39)
前記殺菌消毒剤が、
(1)有効塩素4.0%以上含み、
(2)塩素のにおいがあり、
(3)ナトリウム塩の反応及び次亜塩素酸塩の反応を呈し、
(4)本品の水溶液(1→25)4mlにリン酸緩衝液(pH8)100mlを加えた液は、波長291~294nmに極大吸収部があり、
(5)本品に赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色する、
項目38に記載の方法。
(項目40)
前記殺菌消毒剤が、SO4系成分を検出限界以上8100ppm以下で含む、項目23~39のいずれか一項に記載の方法。
(項目41)
前記消毒剤における次亜塩素酸イオンと亜塩素酸イオンの比が、1対0.24~0.3である、項目23~40にいずれか一項に記載の方法。
(項目42)
前記消毒剤における有効塩素濃度が約60,000ppmであり、遊離残留塩素濃度が約60,000ppmである、項目23~41のいずれか一項に記載の方法。
(項目43)
項目23~42のいずれか一項に記載の方法により製造された殺菌消毒剤。
(項目44)
次亜塩素酸イオンと亜塩素酸イオンの比が、1対0.24~0.3である、項目43に記載の殺菌消毒剤。
(項目45)
前記消毒剤における有効塩素濃度が約60,000ppmであり、遊離残留塩素濃度が約60,000ppmである、項目43または44に記載の殺菌消毒剤。
(項目46)
項目1~7のいずれか一項に記載の乾燥固体を用いて製造された液体塩素酸化物であって、
(a)該乾燥固体を水に溶解し、pHの上昇した溶液を調製する工程;
(b)工程(a)で調製した溶液のpHを維持しつつ、該溶液に非カルシウム無機アルカリ剤を加える事でカルシウム塩を沈殿させて、液相とカルシウム塩を含む固相を含む、該液相中のカルシウムイオン濃度が低下した固液混合相を形成する工程;
および
(c)工程(b)で形成された固液混合相から液相のみを取り出して、液体塩素酸化物を得る工程
を包含する方法によって調製される、液体塩素酸化物。
(項目47)
項目1~7のいずれか一項に記載の乾燥固体を用いて製造された液体塩素酸化物であって、
(a)該乾燥固体を水に溶解してpH10.0以上の溶液を調製する工程;
(b)工程(a)で調製した溶液のpHを10.0以上に維持しつつ、該溶液に非カルシウム無機アルカリ剤を加える事でカルシウム塩を沈殿させて、液相とカルシウム塩を含む固相を含む、該液相中のカルシウムイオン濃度を24ppm以下とする固液混合相を形成する工程;および
(c)工程(b)で形成された固液混合相から液相のみを取り出して、液体塩素酸化物を得る工程
を包含する方法によって調製される、液体塩素酸化物。
(項目48)
カルシウム濃度が実質的に検出限界以下である、項目8~14、46および47のいずれか一項に記載の液体または液体塩素酸化物。
(項目49)
カルシウム濃度が24ppm以下である、項目8~14、46および47のいずれか一項に記載の液体または液体塩素酸化物。
(項目50)
項目1~7のいずれか一項に記載の乾燥固体、項目8~14のいずれか一項に記載の液体、または項目46~49のいずれか一項に記載の液体または液体塩素酸化物の殺菌消毒剤としての使用。
(項目51)
項目1~7のいずれか一項に記載の乾燥固体、項目8~14のいずれか一項に記載の液体、項目43~45のいずれか一項に記載の殺菌消毒剤、または項目46~49のいずれか一項に記載の液体または液体塩素酸化物の食品添加物としての使用。
(項目52)
食品を殺菌消毒するための、項目1~7のいずれか一項に記載の乾燥固体、項目8~14のいずれか一項に記載の液体、項目43~45のいずれか一項に記載の殺菌消毒剤、または項目46~49のいずれか一項に記載の液体または液体塩素酸化物の使用。
(項目53)
次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液から新たな薬剤を製造する方法であって、
該溶液中の次亜塩素酸イオン濃度、塩素酸イオン濃度および塩化物イオン濃度を定量する工程と、
該溶液に硫酸を添加し、塩素ガスを生成させる第一反応工程と、
回収液A中において、該生成した塩素ガスを水酸化ナトリウムまたは水酸化カルシウムと反応させて次亜塩素酸イオンとして回収する工程と、
第一反応工程後の反応母液に、第一反応工程におけるよりも高い濃度の硫酸を添加し、二酸化塩素ガスを生成させる第二反応工程と
回収液B中において、該生成した二酸化塩素ガスを水酸化ナトリウムおよび過酸化水素と反応させて亜塩素酸イオンとして回収する工程と、
回収液Aと回収液Bとを混合し、新たな薬剤を得る工程と、
を包含する、方法。
(項目54)
項目24~項目42に規定される殺菌消毒剤を薬剤に置き換えた場合の特徴のうちの1個または複数の特徴を有する、項目53に記載の方法。
(項目55)
項目53または54に記載の方法により製造された薬剤。
(項目56)
項目44または項目45に規定される殺菌消毒剤を薬剤に置き換えた場合の特徴のうちの1個または複数の特徴を有する、項目55に記載の薬剤。
(項目57)
項目55または56に記載の薬剤の殺菌消毒剤としての使用。
(項目58)
項目55または56に記載の薬剤の食品添加物としての使用。
(項目59)
食品を殺菌消毒するための、項目55または56に記載の薬剤の使用。
本明細書における用語について以下に説明する。
をチオ硫酸ナトリウムで酸化還元滴定(I2+2Na2S2O3→2NaI+Na2S4O6 (2)式)して有効塩素濃度を定量することができる。
(1)有効塩素60.0%以上含み、
(2)塩素のにおいがあり、
(3)該固体0.5gに水5mlを加えて振り混ぜ、これに赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色し、
(4)該固体0.1gに酢酸(1→4)2mlを加えるとき、ガスを発生して溶け、これに水5mlを加えてろ過した液は、カルシウム塩の反応を呈する。
以下に本発明の好ましい実施形態を説明する。以下に提供される実施形態は、本発明のよりよい理解のために提供されるものであり、本発明の範囲は以下の記載に限定されるべきではないことが理解される。従って、当業者は、本明細書中の記載を参酌して、本発明の範囲内で適宜改変を行うことができることは明らかである。また、本発明の以下の実施形態は単独でも使用され、あるいはそれらを組み合わせて使用することができることが理解される。
(1)有効塩素60.0%以上含み、
(2)塩素のにおいがあり、
(3)該固体0.5gに水5mlを加えて振り混ぜ、これに赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色し、
(4)該固体0.1gに酢酸(1→4)2mlを加えるとき、ガスを発生して溶け、これに水5mlを加えてろ過した液は、カルシウム塩の反応を呈する。
(1)Y=-1.2676X+9.84393
(2)X≦4
を満たす。この式は、原料中の塩素酸イオンが分解されない、もしくは増加するということを上限とし、かつ、安全率を考慮して、塩素酸イオンが110%以上に増加することを条件とし、そして、この時、原料中の塩化物濃度が高ければ、添加可能な硫酸濃度は低下することを考慮して導かれる。
(1)有効塩素4.0%以上含み、
(2)塩素のにおいがあり、
(3)ナトリウム塩の反応及び次亜塩素酸塩の反応を呈し、
(4)本品の水溶液(1→25)4mlにリン酸緩衝液(pH8)100mlを加えた液は、波長291~294nmに極大吸収部があり、
(5)本品に赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色する。
試料液の調製
試料に水を加えて希釈し、硫酸イオンとして、0~40mg/L調整する。
検量線用標準液の調製
関東化学(株)製の試薬 陰イオン混合標準IVを標準液とする。
(この液1mLは硫酸イオン約40μgを含む)。
測定条件
電気伝導検出器付イオンクロマトグラフ(サプレッサ方式)を用い、次の条件で測定する。
充填剤:エチレンビニルベンゼン-ジビニルベンゼンポリマー系陰イオン交換樹脂
カラム管:内径4.0mm、長さ250mm
溶離液:12mmol/L炭酸ナトリウム、5mmol/L重炭酸ナトリウムの混合液
カラム温度:室温
流速:1.0mL/分
試料液注入量:250μL
検量線
標準液を250μLずつ正確に、イオンクロマトグラフに注入し、得られたピーク面積から、硫酸イオンの検量線を作成する。
定量
試料液から得られたピーク面積と、検量線によって試料液中の硫酸イオンの濃度(A)を求め、次式によって試料原液中の硫酸イオンの含有量(X)〔mg/L〕を計算する。
(X)=A×K
A:試料液中の硫酸イオンの濃度(mg/L)
K:試料液を調製した時の希釈倍率
食品添加物として流通している次亜塩素酸ナトリウム12%液には大きく低食塩級と一般級の2種類があるが、低食塩級の塩素酸イオン生成量としては、約20000~25000ppmであり、一般級の塩素酸イオン生成量としては約30000~42000ppmであった。また、理論値として有効塩が1%減少するごとに塩素酸イオンは約3500ppm増加すると考えられているが、次亜塩素酸ナトリウムの品質の違いによって、塩素酸イオン初発値が高い場合があることと、さらに、理論値以上に生成されている場合があることもわかった。
劣化次亜塩素酸ナトリウム中には、次亜塩素酸イオン、塩化物イオン、塩素酸イオンがそれぞれ含まれているが、まず、分解反応が難しいと予想される塩素酸イオンを硫酸で反応させた場合の予備検証を行った。また、反応性を比較するため塩素酸ナトリウム区を設定した。
・Cl2+2NaOH+H2O2→NaCl+NaClO+H2O
NaClO+H2O2→NaCl+H2O+O2・・・・・(2)
・2ClO2+2NaOH→NaClO2+NaClO3+H2O・・・・・(3)
・2ClO2+2NaOH+H2O2→2NaClO2+O2+2H2O・・・・・(4)
劣化次亜塩素酸ナトリウム中の塩素酸イオンは少量であり、硫酸を少量ずつ滴下するだけでは反応性が悪い為、バッチ式での反応を行い、投入する硫酸濃度を65w/w%に上げ、さらに反応時の温度を上昇させることによって、塩素ガス、二酸化塩素ガスを段階的に発生させることを考えた。また、回収液A、回収液Bの2種類を用意し、第一反応では回収液Aで次亜塩素酸イオンを回収し、第一反応終了後に配管を切り替え、回収液Bで亜塩素酸イオンを回収することを考えた。その結果、二酸化塩素が発生し始め、亜塩素酸イオンの回収が出来始めたことから、反応母液中の温度と酸度の影響が重要であることがわかった。しかし、亜塩素酸イオンの大部分は過酸化水素を添加していない回収液A中で回収されたため収率が悪く、また過酸化水素がないために塩素酸イオンも生成されてしまった。このため、塩素ガス、二酸化塩素ガスをさらに段階的に発生させるための条件を確立し、それぞれの回収液中に吹き込む必要があるということがわかった。
第一反応時に塩素ガスを優先的に発生させる時に必要な硫酸濃度を確認するため、硫酸濃度を50w/w%に設定し反応を行った。また、この時の反応母液中の硫酸濃度は25.0%である。
劣化次亜塩素酸ナトリウムの反応を行い、反応母液中から2段階で回収を行うためには、反応温度や硫酸による酸度が重要であるが、初期硫酸濃度が高すぎると塩素ガスと二酸化塩素ガスの両方が発生してしまい、回収液の切り替えを行う事が出来ない。そこで、硫酸濃度を下げるだけではなく、2回に分けて添加し反応させたところ、収率の大きな変化は見られなかったが、50w/w%硫酸を200g投入するよりも、65w/w%硫酸100gを2回に分けて投入した場合の方が、第一反応時の二酸化塩素ガス発生量が多くなることがわかった。この事から、第一反応時における反応母液中の硫酸濃度は依然として過剰であることと、投入時の硫酸の設定濃度によっても反応性が異なっていることがわかった。
第一反応と第二反応の硫酸濃度と量、温度をそれぞれ設定し、さらに硫酸の2回投入を行うことで塩素ガスと二酸化塩素ガスを分別回収することを検討した。第一反応時に使用する硫酸濃度は50w/w%とし、投入量は25gとすることで反応母液中の硫酸濃度を5.6%とした。また、二次反応は硫酸濃度を65w/w%とし、投入量は250gとすることで反応母液中の硫酸濃度を36.8%とした。その結果、回収液A中に混入する二酸化塩素ガスを減少させることが出来、亜塩素酸イオン、塩素酸イオンをそれぞれ減少させることができた。
第一反応時と第二反応時の硫酸濃度と量が判明してきたので、処理量を5倍に上げた時の回収率の変化を確認した。また、ガスの回収漏れの有無を確認するため回収液A、Bにはそれぞれ予備回収槽を設けた。さらに、エアーを吹き込むタイミングを早め、原料投入後、すぐにエアーを反応槽に吹き込むようにし、徐々にエアー量を上げていった。
トラップ槽を設置し、それ以外の大きな変更点は無い状態で、エアーの送り込むタイミングによって回収率が向上するのかを再検証したところ、やはり、エアーを反応初期段階から送り込むほうが有効塩素の回収率が良いということがわかった。また、回収液Aには亜塩素酸イオン、塩素酸イオンが減少し、回収液Bには、塩化物イオンが減少していることから、回収液A、Bの分別回収が可能となった。
エアーの開始タイミングにおける回収率の違いを再検証するため、あえてエアー開始時間を遅らせた場合の回収率を確認することにした。
有用な殺菌消毒剤を検討した場合に、薬品濃度は重要である。そして、これまでは原料である劣化次亜塩素酸ナトリウムの投入量に対して、およそ等量の回収液を設定してきたが、この回収液の量を1/2にした場合にも、回収率が低下しないかどうかの濃縮回収試験を行った。
2NaCl+H2SO4→2HCl+Na2SO4・・・・・(6)第一反応、第二反応
NaClO+2HCl→NaCl+Cl2+H2O・・・・・(7)第一反応
3NaClO→2NaClO+NaClO3・・・・・(8)第一反応
2NaClO3+H2SO4→2HClO3+Na2SO4・・・・・(9)第二反応
HClO3+HCl→HClO2+HClO・・・・・(10)第二反応
HClO3+HClO2→2ClO2+H2O・・・・・(11)第二反応
第一反応、第二反応での反応母液中の硫酸濃度の上限を確認するため、酸度を調整し、ともに反応母液中の硫酸濃度を6.37%と37.03%に設定した試験を実施した。また、濃縮回収も実施することにした。
これまでの反応方法は劣化次亜塩素酸ナトリウムに対して、ほぼ同じ重量の硫酸液を用いて第二反応を行ってきた。しかし、劣化次亜塩素酸ナトリウム中に生成されている塩素酸イオンは第一反応を経て増加しているものの反応性が高くなる濃度としては不足している。
そして、生成された塩酸が反応前に分解されれば、回収率が低下するだけでなく、発生した塩素ガスが回収液Bに混入し、回収液B中の過酸化水素で分解され、塩化物イオンが多量に生成されてしまうことがわかった。
第二反応時における反応母液中の硫酸濃度の下限値を確認するため、反応母液中の硫酸濃度を35.7%にし、再度回収率を確認してみた。また反応終了後の反応母液をそれぞれ測定し、第一反応、第二反応終了後における残渣成分を確認してみた。
低食塩級次亜塩素酸ナトリウムを原料に用いて、第一反応、第二反応時の反応母液に投入する硫酸濃度をすべて70w/w%とし、その上で、第一反応時の反応母液中の硫酸濃度は6.37%に設定し、第二反応時の硫酸濃度を35.7%で製造を実施してみた。
低食塩次亜塩素酸ナトリウムだけではなく、一般級次亜塩素酸ナトリウム12%液が品質低下した劣化次亜塩素酸ナトリウムを用いて、本製法における反応性と回収率を確認した。
NaClO3+6HCl→3Cl2+NaCl+3H2O・・・・・(14)副反応
※特に一般級の劣化次亜反応の場合、酸性度、塩酸の生成量によって、主副反応の進行が変わりやすい。
一般級の劣化次亜塩素酸ナトリウムを用いた場合、低食塩劣化次亜塩素酸ナトリウムと比較して、主反応と副反応の進行が逆転しやすいということが確認出来ている。例えば、第一反応時点ですでに塩素酸イオンが分解しやすい傾向にあり、それは劣化次亜塩素酸ナトリウム中に生成している多量の塩化物イオンと硫酸との反応による塩酸過剰生成に原因があるが、原料中の生成物である塩化物イオンは事前に除去することは難しい。
一般級の劣化次亜塩素酸ナトリウムの第一反応の硫酸条件を確認するため、反応母液中の硫酸濃度を4.0%に設定した。これは、硫酸濃度を4.5%に設定すると、第一反応時点でやや過剰に塩酸が生成されてしまった結果、塩素酸イオンが分解されてしまったと考えられたからである。
一般級次亜塩素酸ナトリウムの場合、塩化物イオンが多量に含まれていることから、反応条件が過剰になりすぎると主副反応が入れ替わりやすい。
第二反応時の反応母液中の硫酸濃度が40.0%の場合は副反応が進行し、塩素ガス由来の塩化物イオンが多量に生成されてしまい回収率が悪化した。
一般級次亜塩素酸ナトリウムを用いた場合の反応条件の確認として、一般級劣化次亜塩素酸ナトリウムを原料に、50w/w%硫酸を用いて、反応母液中の硫酸濃度を4.0%に設定し、エアーを投入しながら、第一反応を実施する。この時の反応時間は1時間行った。そして、回収液Aでは水酸化ナトリウム(あるいは水酸化カルシウム)で回収する。
NaClO3+6HCl→3Cl2+NaCl+3H2O・・・・・(14)副反応
Cl2+3H2O2→2HCl+2H2O+2O2・・・・・(15)
2HCl+H2O2→2H2O+Cl2・・・・・(16)
これまで第二反応時には温度を60~70℃にして反応を行っていた。しかし、一般級次亜塩素酸ナトリウムを用いた場合の反応性は高く、低食塩級次亜塩素酸ナトリウムと同様の反応条件では塩化物イオンが多量に生成され過剰であるため、反応母液中の硫酸濃度を下げるなどの調整を必要としていた。
第二反応における回収液B中の水酸化ナトリウム量の検討を行う。第二反応におけるアルカリ量は回収漏れを防止するにはアルカリは過剰な方が良いが、無機アルカリ塩が多ければ、乾燥した場合の濃縮率が低下し、最終濃度が低下することにも繋がる。
第一反応、第二反応における硫酸濃度が原料組成によって決定されているかどうかを検証するための試験を実施するため、塩化物が多い別メーカーの低食塩級次亜塩素酸ナトリウムを原料に用いて、反応条件の検証を行った。また、原料中の塩化物濃度の測定にはモール法を用いることで、次亜塩素酸ナトリウム中の塩素イオンとの分別定量を行うことにし、塩化物濃度と硫酸濃度との反応条件を確認することにした。
第一反応条件については、(劣化次亜の反応23)と同じにすることで再現性を確認することとし、第二反応時の反応母液中の硫酸濃度を30.0%に設定した。
原料中の塩化物濃度41983ppmに対し、第一反応時の反応母液中の硫酸濃度を4.00%に設定し、製造を行った。
原料中の塩化物濃度41416ppmに対し、第一反応時の反応母液中の硫酸濃度を5.00%に設定し、製造を行った。その結果、第一反応終了後の反応母液中には有効塩素が13281ppm残存し、塩素酸イオンは1.36%減少しており、やや過多であることが確認された。
原料中の塩化物濃度41416ppmに対し、第一反応時の反応母液中の硫酸濃度を6.00%に設定し、製造を行った。その結果、第一反応終了後の反応母液中には有効塩素が13281ppm残存し、塩素酸イオンは3.6%減少しており、過多であることが確認された。また、塩素酸イオンが減少した分、
回収液Bの回収率も低下した。
原料中の塩化物濃度42614ppmに対し、第一反応時の反応母液中の硫酸濃度を4.50%に設定し、製造を行った。また、第一反応終了後の反応母液中に有効塩素が残存することが予測できたため、エアーを含めた反応時間を2時間に設定した。
これまで、原料中の塩化物濃度約42000ppmに対して、硫酸濃度は4.5%が適正範囲内であるとしたが、別Lotで原料中の塩化物濃度が約35000ppmの原料を用いて反応試験を実施した。また、硫酸濃度としては、42000÷35000=1.2となるため、4.5%×1.2=5.4%が適正値と試算できたが、この条件は塩素酸イオンが約110%以上に増加する、反応上のバラつきを考慮した安全数値である。このため、初回は、6.0%に設定し反応を行った。
第一反応時の反応母液中の硫酸濃度の添加式としては、原料中の塩素酸イオンが分解されない、もしくは増加するということを上限とし、かつ、安全率を考慮して、塩素酸イオンが110%以上に増加することを条件としていた。
(1)Y=-1.2676X+9.84393
(2)X≦4
(Y 反応母液中の硫酸濃度、X 原料中の塩化物濃度)
そこで、第一反応時には計算式どおりの5.4%の硫酸を添加し、第二反応時には40.0%硫酸濃度とした上で試験を実施した。
なお、回収液B中の塩化物イオンは3827ppmに増加しており、回収率を高めるために硫酸濃度を増加させることは塩化物イオンの副生を招くことが確認された。仮に最終製品が次亜塩素酸ナトリウム溶液であれば回収液B中の塩化物濃度が高くとも良いが、高度サラシ粉の場合には、4000ppmを超えてくると乾燥時の濃縮率が低下してしまい、結果として、高濃度の高度サラシ粉を製造できなくなってしまう。
低食塩級次亜塩素酸ナトリウムを原料に用いて、第二反応時の反応母液中の硫酸濃度を45.0%に設定し、反応を行った。その結果、回収液B中の塩化物イオンが増加し始め、また、回収率も悪化した。これは、反応母液中の塩素酸イオンが分解される際に、塩素ガスとなる副反応が進行し始めたことを現す。以上のことから、第二反応における硫酸濃度は45%を超えると急激に塩素ガスが生じるため、固体品を製造する場合には濃縮率が低下してしまうということがわかった。
低食塩級次亜塩素酸ナトリウムを原料に用いて、第二反応時の反応母液中の硫酸濃度を40.0%に設定し、反応を行った。
原料である劣化次亜塩素酸ナトリウムは、低食塩級と一般級の2種類があり、それぞれ塩化物イオンや塩化物濃度が異なっており、その濃度に応じて適切な硫酸濃度も変化する。
(1)Y=-1.2676X+9.84393
(2)X≦4
(Y 反応母液中の硫酸濃度、X 原料中の塩化物濃度)
劣化次亜塩素酸ナトリウムを原料として再反応させ、塩素酸イオンの再生成防止を行いながら回収液Aと回収液Bを得ていたが、これらを混合し、食品添加物である次亜塩素酸ナトリウムの規格基準に適合させるためには、有効塩素濃度が4%以上であることと、その他の確認試験に合格する必要がある。
※は以下の換算式で計算した
(換算式)
有効塩素濃度×0.476=亜塩素酸イオン濃度(ClO2 -)
有効塩素濃度×0.726=次亜塩素酸イオン濃度(ClO-)
この換算式は、既知の濃度の亜塩素酸イオンまたは次亜塩素酸イオン濃度を使用して、有効塩素濃度との関係を導くことにより得られた。
本製法に基づき製造された殺菌消毒剤(食品添加物、次亜塩素酸ナトリウムの規格基準適合品)の保存性を確認した。
第一反応における回収液を水酸化カルシウムにし、乾燥させ固体化させることによって保存性と有効塩素濃度の向上を検討することにした。その結果、劣化次亜塩素酸ナトリウム1に対して、20%水酸化カルシウムを1で回収した場合と、劣化次亜塩素酸ナトリウム2に対して、20%水酸化カルシウムを1で回収した場合において、大きな回収率の変化は見られず、濃縮回収を行えることがわかった。
劣化次亜塩素酸ナトリウムを原料として再反応させ、塩素酸イオン生成防止のために回収液Aと回収液Bを得ていたが、これらを混合し、食品添加物である高度サラシ粉の規格基準に遵守させる必要があり、有効塩素濃度が60%以上であることと、その他、確認試験に適合する必要がある。
回収液Aと回収液Bを混合して乾燥させると、それぞれの乾燥時の濃縮率が異なるため、最終製品では有効塩素比を測定することができなくなる。このため、回収液Aと回収液Bの有効塩素比率の下限を確認するため、予備試験として、回収液A、回収液Bそれぞれを単体で乾燥させたものを使用し、それぞれの有効塩素濃度を測定の上、検体を作成した。
乾燥条件は、庫内環境温度を50~60℃とし、庫内湿度は10%以下とする。また、風量は1.9m3/sで温風を送り込む。この時の温風は直接乾燥庫内の液体へ直接当てる必要はなく、庫内の温度と湿度を維持させることが目的である。
No.1法に比べ、No.2法の方が遊離残留塩素の減少が極めて少なく、副成分である塩化物イオン、塩素酸イオンの生成も少ない。
また、予備乾燥後の水分量20%区における固体品の測定値から、乾燥後の有効塩素比とイオン比を計算した。次亜塩素酸イオン:亜塩素酸イオンは、1:5.53~23.18を含有する。
有効塩素比で回収液Aを1とし、回収液Bを9.61で混合し、乾燥した場合の測定結果であるが、この有効塩素比の場合、以下の反応が過多となり、塩化物と塩素酸イオンが生成される。
ClO-+ClO2 - → ClO3 - + Cl-
有効塩素比で回収液Aを1とし、回収液Bを33.95で混合し、乾燥した場合の測定結果であるが、回収液Bの有効塩素比率があまりに高くなると、遊離残留塩素とカルシウムの規格に適合しない場合が想定される。この比率の結果では、乾燥後のカルシウムイオン濃度が5.64%となり、高度サラシ粉中のカルシウム量が適合する条件の下限にあるため、この有効塩素比がほぼ上限にあたる。
(1)区の場合、遊離残留塩素が多いと次亜塩素酸イオンと亜塩素酸イオンが反応し、有効塩素が減少するとともに、塩化物イオンと塩素酸イオンが生成される。この場合、有効塩素の分解だけではなく、有効塩素に寄与しない副成分も生成されるため、乾燥濃縮率も低下し、有効塩素濃度は最も低くなる。
下記の配合表に基づき、希釈後の有効塩素濃度が1%、6%、12%になるように、イオン交換水を加え、溶け残りが無いようにスターラーで15分間の攪拌を行った。次に、10℃のインキュベーター内で1時間静置させ(清澄な上澄み液を得る)、沈殿物を吸い込まないように上澄み液を回収する。そして、上澄み液の遊離残留塩素濃度、有効塩素濃度、各種イオン濃度(イオンクロマトグラフィー)の測定を行った。
下記の配合表とCa除去の関係式(※)に基づき、Ca除去後の回収液を希釈後の有効塩素濃度が1%、6%、12%になるように、イオン交換水を加え、溶け残りが無いようにスターラーで15分間の攪拌を行った。(関係式から求めた20%炭酸ナトリウム溶液を加え、1分間の攪拌を行った。)次に、10℃のインキュベーター内で19時間静置させ(清澄な上澄み液を得る)、沈殿物を吸い込まないように上澄み液を回収する。そして、上澄み液の遊離残留塩素濃度、有効塩素濃度、各種イオン濃度(イオンクロマトグラフィー)の測定を行った。
※高度サラシ粉中のカルシウムイオン濃度(%)<X1>と、20%炭酸水素Na液の添加量(g)<Y1>の関係式(1)は、Y1=14.042X1+0.0185
0.05mol/L EDTA溶液1ml=3.705mgCa(OH)2×カルシウムイオンの分子量(40.08)/水酸化カルシウムの分子量(74.08)
=0.05mol/L EDTA溶液1ml=2.005mgCa2+
<食品、添加物等の規格基準 第2 添加物 D 成分規格・保存基準各条 水酸化カルシウム>
定量法
本品約2gを正確に量り、塩酸(1→4)30mlを加えて溶かし、更に水を加えて正確に250mLとし、検液とし、カルシウム塩定量法中の第1法により定量する。
0.05mol/L EDTA溶液1ml=3.705mgCa(OH)2
<食品、添加物等の規格基準 第2 添加物 B 一般試験法 8.カルシウム塩定量法>
カルシウム塩定量法は、カルシウム塩類の含量を、エチレンジアミン四酢酸二ナトリウム(EDTA)を用いて定量する方法で、EDTA溶液による直接滴定法(第1法)と、過剰のEDTAを加えた後、酢酸亜鉛溶液で滴定する逆滴定法(第2法)がある。
操作法
別に規定するもののほか、次のいずれかの方法による。
第1法
別に規定する検液10mlを正確に量り、水50mlを加え、水酸化カリウム溶液(1→10)10mlを加えて約1分間放置した後、NN指示薬約0.1gを加え、直ちに0.05mol/LEDTA溶液で滴定する。終点は、液の赤紫色が完全に消失して青色となるときとする。
第2法
別に規定する検液20mlを正確に量り、0.02mol/LEDTA溶液25mLを正確に量って加え、次に水50ml及びアンモニア・塩化アンモニウム緩衝液(pH10.7)5mlを加えて約1分間放置した後、エリオクロムブラックT・塩化ナトリウム指示薬0.025gを加え、直ちに過剰のEDTAを0.02mol/L酢酸亜鉛溶液で滴定する。終点は、液の青色が青紫色となるときとする。別に空試験を行う。
0.05mol/L EDTA溶液1ml=3.705mgCa(OH)2×カルシウムイオンの分子量(40.08)/水酸化カルシウムの分子量(74.08)
=0.05mol/L EDTA溶液1ml=2.005mgCa2+
比較対照のため、市販品の高度サラシ粉(「トヨクロン-PTGIII」)と、本製法で生産した高度サラシ粉(「高度サラシ粉A」)を25℃と40℃とで保存試験を行ってみた。保存試験項目としては、「高度サラシ粉」公定規格試験を実施し、水分、過酸化水素水の反応による気泡の確認(遊離残留塩素)、膨張を測定することにした。
作製した混合溶液(次亜塩素酸Na規格)である検体(1)と検体(2)について、ORP(酸化還元電位)と塩素ガス濃度を測定した。また、比較対照として同濃度の次亜塩素酸ナトリウム溶液を用いた。その結果として、ORP(酸化還元電位)については、次亜塩素酸ナトリウムは希釈しても変化が無いのに対し、検体(1)、(2)ともに希釈することによって酸化力が上昇した。また、塩素ガス濃度については、有機物と接触させてもほとんど塩素ガスの放出が見られず、約1/31~1/50程度しか測定されないという優位性を確認することができた。
<使用器具・備品>
(株)ガステック製の気体採集器 GV-100S
(株)ガステック製の検知管 No.8LL:測定範囲 0.025~2.0ppm
(株)ガステック製の検知管 No.8La:測定範囲 0.1~16ppm
(株)ガステック製の検知管 No.8H:測定範囲 25~1000ppm
作製した高度サラシ粉液体品を用いて、同濃度の次亜塩素酸ナトリウムと比較した場合の有機物接触時の塩素ガス濃度を測定した。その結果、高度サラシ粉液体品は、有機物と接触させても急激に塩素ガスを発生させることなく、1/1000~1/6000程度の塩素ガスしか測定されることはなかった。そして、この事は殺菌対象食品に塩素臭の付着を低減させることにも繋がる。
<試験区>
・次亜塩素酸ナトリウム 200ppm、1000ppm
・高度サラシ粉液体品 200ppm、1000ppm
上記の各液50gを測り取り、カットキャベツ5g(液比 1:10)の条件で浸漬し、密閉した。その後、25℃で1時間浸漬を行い、塩素ガス濃度の測定を行った。
<使用器具・備品>
(株)ガステック製の気体採集器 GV-100S
(株)ガステック製の検知管 No.8LL:測定範囲 0.025~2.0ppm
(株)ガステック製の検知管 No.8La:測定範囲 0.1~16ppm
(株)ガステック製の検知管 No.8H:測定範囲 25~1000ppm
本発明によって作成された液体品(次亜塩素酸Na規格)と固体品(高度サラシ粉規格)を用いて、原料菌数が高いことで知られている青ネギに対して殺菌効果を確認した。
原料が劣化次亜塩素酸ナトリウムではないが、類似した反応方法にR2法がある。
第一反応終了後の反応母液に塩化ナトリウムを添加することで、硫酸を過剰投入しなくても塩素酸イオンの分解率を100%に到達するということがわかったが、塩素酸イオンの分解率は向上するが、逆に収率を悪化させた。
第一反応終了後の反応母液に塩化ナトリウムを投入することで塩酸が生成し、硫酸を過剰投入しなくても塩素酸イオンの分解率を100%に到達させる事がわかった。
劣化次亜塩素酸ナトリウムを用いて第一反応を行った後に塩化物イオンと塩素酸イオンがどの程度増減するのかを確認してみた。また、通常の第一反応は常温で実施しており、20℃~30℃、高くても反応時の発熱で40℃である。
先の試験の再検証とし、さらに65w/w%硫酸を追加することで第一反応における酸度の影響を確認した。
品質低下した次亜塩素酸ナトリウムである劣化次亜塩素酸ナトリウムを再反応させ、次亜塩素酸ナトリウムを再製造すること自体は目新しい技術ではないが、再製造のコストを製品単価に付加することが出来ないという問題がある。
Claims (52)
- 次亜塩素酸塩および亜塩素酸塩を含む乾燥固体。
- 前記固体が、乾燥粒状である、請求項1に記載の乾燥固体。
- 前記固体が、次亜塩素酸カルシウムを含む、請求項1または2に記載の乾燥固体。
- 前記固体が、
(1)有効塩素60.0%以上含み、
(2)塩素のにおいがあり、
(3)該固体0.5gに水5mlを加えて振り混ぜ、これに赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色し、
(4)該固体0.1gに酢酸(1→4)2mlを加えるとき、ガスを発生して溶け、これに水5mlを加えてろ過した液は、カルシウム塩の反応を呈する、
請求項1~3のいずれか一項に記載の乾燥固体。 - 前記固体が、SO4系成分を検出限界以上8100ppm以下で含む、請求項1~4のいずれか一項に記載の乾燥固体。
- 前記固体における次亜塩素酸塩と亜塩素酸塩の比が、1対5~25である、請求項1~5のいずれか一項に記載の乾燥固体。
- 前記固体における有効塩素濃度が600,000ppm~900,000ppmの範囲内であり、遊離残留塩素濃度が900ppm~60,000ppmの範囲内である、請求項1~6のいずれか一項に記載の乾燥固体。
- 請求項1~7のいずれか一項に記載の乾燥固体を溶解させて得られた液体。
- 有効塩素濃度が1%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対7~35である、請求項8に記載の液体。
- 有効塩素濃度が1%となるように水で希釈した場合、遊離残留塩素濃度が150ppm~900ppmの範囲内である、請求項8または9に記載の液体。
- 有効塩素濃度が6%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対6~30である、請求項8に記載の液体。
- 有効塩素濃度が6%となるように水で希釈した場合、遊離残留塩素濃度が1,000ppm~6,000ppmの範囲内である、請求項8または11に記載の液体。
- 有効塩素濃度が12%となるように水で希釈した場合、次亜塩素酸イオンと亜塩素酸イオンの比が、1対6~30である、請求項8に記載の液体。
- 有効塩素濃度が12%となるように水で希釈した場合、遊離残留塩素濃度が2,500ppm~12,000ppmの範囲内である、請求項8または13に記載の液体。
- 次亜塩素酸塩および亜塩素酸塩を含む乾燥固体を製造する方法であって、
次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液を用意する工程と、
該溶液に硫酸を添加し、塩素ガスを生成させる第一反応工程と、
回収液A中において、該生成した塩素ガスを水酸化ナトリウムまたは水酸化カルシウムと反応させて次亜塩素酸イオンとして回収する工程と、
第一反応工程後の反応母液に、第一反応工程におけるよりも高い濃度の硫酸を添加し、二酸化塩素ガスを生成させる第二反応工程と、
回収液B中において、該生成した二酸化塩素ガスを水酸化ナトリウムおよび過酸化水素と反応させて亜塩素酸イオンとして回収する工程と、
回収液Aと回収液Bとを混合する工程と、
得られた混合溶液を乾燥させ固体化させる工程と
を包含する、方法。 - 前記回収液Aが水酸化カルシウムを含む、請求項15に記載の方法。
- 第1反応後の反応母液に、過酸化水素を添加する工程をさらに包含する、請求項15または16に記載の方法。
- 前記回収液Aと前記回収液Bとを混合する工程において、該回収液Aの有効塩素濃度を1とすると、回収液Bの有効塩素濃度が9.6~33.95の範囲内である、請求項15~17のいずれか一項に記載の方法。
- 前記回収液Aと前記回収液Bとを混合する工程において、該回収液Aおよび該回収液Bが、それぞれスラリー化されて混合される、請求項15~18のいずれか一項の方法。
- 前記回収液Aと回収液Bとを混合する工程が、前記回収液Aを予備乾燥し、造粒核を形成し、回収液Bをスラリー化させ、そして、回収液Bスラリーに回収液A乾燥物を投入する工程を包含する、請求項15~19のいずれか一項に記載の方法。
- 前記乾燥させ固体化させる工程が、20分~30分間の温風乾燥を行う工程を包含する、請求項15~20のいずれか一項に記載の方法。
- 前記乾燥させ固体化させる工程が、回収液Aおよび回収液Bの水分量をそれぞれ20%以下に減少させることを含む、請求項15~21のいずれか一項に記載の方法。
- 次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液から新たな殺菌消毒剤を製造する方法であって、
該溶液中の次亜塩素酸イオン濃度、塩素酸イオン濃度および塩化物イオン濃度を定量する工程と、
該溶液に硫酸を添加し、塩素ガスを生成させる第一反応工程と、
回収液A中において、該生成した塩素ガスを水酸化ナトリウムまたは水酸化カルシウムと反応させて次亜塩素酸イオンとして回収する工程と、
第一反応工程後の反応母液に、第一反応工程におけるよりも高い濃度の硫酸を添加し、二酸化塩素ガスを生成させる第二反応工程と
回収液B中において、該生成した二酸化塩素ガスを水酸化ナトリウムおよび過酸化水素と反応させて亜塩素酸イオンとして回収する工程と、
回収液Aと回収液Bとを混合し、新たな殺菌消毒剤を得る工程と、
を包含する、方法。 - 前記次亜塩素酸イオン、塩素酸イオンおよび塩化物イオンを含む溶液が、品質劣化した次亜塩素酸塩を含む溶液である、請求項23に記載の方法。
- 前記品質劣化した次亜塩素酸塩を含む溶液が、低食塩級の次亜塩素酸ナトリウム溶液に由来する、請求項24に記載の方法。
- 前記品質劣化した次亜塩素酸塩を含む溶液が、一般級の次亜塩素酸ナトリウム溶液に由来する、請求項24に記載の方法。
- 前記殺菌消毒剤が固体品であり、第一反応工程における反応母液中の硫酸濃度が4.00~6.37%であり、第二反応工程における反応母液中の硫酸濃度が30.00~40.00%であり、第二反応工程において使用される硫酸濃度が、50.0w/w%~70.0w/w%である、請求項25に記載の方法。
- 前記殺菌消毒剤が液体品であり、第一反応工程における反応母液中の硫酸濃度が4.00~6.37%であり、第二反応工程における反応母液中の硫酸濃度が30.00~59.04%であり、第二反応工程において使用される硫酸濃度が、50.0w/w%~70.0w/w%である、請求項25に記載の方法。
- 第一反応工程における反応母液中の硫酸濃度が4.00~4.50%であり、第二反応工程における反応母液中の硫酸濃度が25.00~30.00%であり、第二反応工程において使用される硫酸濃度が、65w/w%である、請求項26に記載の方法。
- 第一反応において、原料中の塩化物濃度をX%とし、反応母液中の硫酸濃度をY%としたとき、
(1)Y=-1.2676X+9.84393
(2)X≦4
を満たす、請求項23~29にいずれか一項に記載の方法。 - 前記回収液Aが、水酸化ナトリウムまたは水酸化カルシウムを含む、請求項23~30のいずれか一項に記載の方法。
- 前記回収液Bが、水酸化ナトリウムおよび過酸化水素を含む、請求項23~31のいずれか一項に記載の方法。
- 前記第一反応工程が、エアーを吹き込みながら行われる、請求項23~32のいずれか一項に記載の方法。
- 前記第二反応工程が、エアーを吹き込みながら行われる、請求項23~33のいずれか一項に記載の方法。
- 反応槽と回収液Bを含む回収槽との間に、過酸化水素を含む中間トラップ槽が設けられている、請求項23~34のいずれか一項に記載の方法。
- 第1反応後の反応母液に、過酸化水素を添加する工程をさらに包含する、請求項23~35のいずれか一項に記載の方法。
- 前記回収液Aと回収液Bとを混合する工程において、回収液Aの有効塩素濃度を1として、回収液Bの有効塩素濃度が、0.43~0.6である、請求項23~36のいずれか一項に記載の方法。
- 前記殺菌消毒剤が、次亜塩素酸ナトリウムを含む、請求項23~37のいずれか一項に記載の方法。
- 前記殺菌消毒剤が、
(1)有効塩素4.0%以上含み、
(2)塩素のにおいがあり、
(3)ナトリウム塩の反応及び次亜塩素酸塩の反応を呈し、
(4)本品の水溶液(1→25)4mlにリン酸緩衝液(pH8)100mlを加えた液は、波長291~294nmに極大吸収部があり、
(5)本品に赤色リトマス紙を浸すとき、リトマス紙は青変し、次に退色する、
請求項38に記載の方法。 - 前記殺菌消毒剤が、SO4系成分を検出限界以上8100ppm以下で含む、請求項23~39のいずれか一項に記載の方法。
- 前記消毒剤における次亜塩素酸イオンと亜塩素酸イオンの比が、1対0.24~0.3である、請求項23~40にいずれか一項に記載の方法。
- 前記消毒剤における有効塩素濃度が約60,000ppmであり、遊離残留塩素濃度が約60,000ppmである、請求項23~41のいずれか一項に記載の方法。
- 請求項23~42のいずれか一項に記載の方法により製造された殺菌消毒剤。
- 次亜塩素酸イオンと亜塩素酸イオンの比が、1対0.24~0.3である、請求項43に記載の殺菌消毒剤。
- 前記消毒剤における有効塩素濃度が約60,000ppmであり、遊離残留塩素濃度が約60,000ppmである、請求項43または44に記載の殺菌消毒剤。
- 請求項1~7のいずれか一項に記載の乾燥固体を用いて製造された液体塩素酸化物であって、
(a)該乾燥固体を水に溶解し、pHの上昇した溶液を調製する工程;
(b)工程(a)で調製した溶液のpHを維持しつつ、該溶液に非カルシウム無機アルカリ剤を加える事でカルシウム塩を沈殿させて、液相とカルシウム塩を含む固相を含む、該液相中のカルシウムイオン濃度が低下した固液混合相を形成する工程;
および
(c)工程(b)で形成された固液混合相から液相のみを取り出して、液体塩素酸化物を得る工程
を包含する方法によって調製される、液体塩素酸化物。 - 請求項1~7のいずれか一項に記載の乾燥固体を用いて製造された液体塩素酸化物であって、
(a)該乾燥固体を水に溶解してpH10.0以上の溶液を調製する工程;
(b)工程(a)で調製した溶液のpHを10.0以上に維持しつつ、該溶液に非カルシウム無機アルカリ剤を加える事でカルシウム塩を沈殿させて、液相とカルシウム塩を含む固相を含む、該液相中のカルシウムイオン濃度を24ppm以下とする固液混合相を形成する工程;
および
(c)工程(b)で形成された固液混合相から液相のみを取り出して、液体塩素酸化物を得る工程
を包含する方法によって調製される、液体塩素酸化物。 - カルシウム濃度が実質的に検出限界以下である、請求項8~14、46および47のいずれか一項に記載の液体または液体塩素酸化物。
- カルシウム濃度が24ppm以下である、請求項8~14、46および47のいずれか一項に記載の液体または液体塩素酸化物。
- 請求項1~7のいずれか一項に記載の乾燥固体、請求項8~14のいずれか一項に記載の液体、または請求項46~49のいずれか一項に記載の液体または液体塩素酸化物の殺菌消毒剤としての使用。
- 請求項1~7のいずれか一項に記載の乾燥固体、請求項8~14のいずれか一項に記載の液体、請求項43~45のいずれか一項に記載の殺菌消毒剤、または請求項46~49のいずれか一項に記載の液体または液体塩素酸化物の食品添加物としての使用。
- 食品を殺菌消毒するための、請求項1~7のいずれか一項に記載の乾燥固体、請求項8~14のいずれか一項に記載の液体、請求項43~45のいずれか一項に記載の殺菌消毒剤、または請求項46~49のいずれか一項に記載の液体または液体塩素酸化物の使用。
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JP2020512262A JP7291958B2 (ja) | 2018-04-03 | 2019-04-02 | 劣化次亜塩素酸塩から新規塩素酸化物組成物を得る製法 |
CN201980034372.7A CN112153900B (zh) | 2018-04-03 | 2019-04-02 | 由劣化次氯酸盐得到新型氯氧化物组合物的制造方法 |
CN202210903946.3A CN115316399A (zh) | 2018-04-03 | 2019-04-02 | 干燥固体以及由其制造的液体氯氧化物 |
KR1020207031287A KR20200139740A (ko) | 2018-04-03 | 2019-04-02 | 열화 차아염소산염으로부터 신규 염소 산화물 조성물을 얻는 제법 |
EP19781264.7A EP3777537A4 (en) | 2018-04-03 | 2019-04-02 | MANUFACTURING PROCESS FOR OBTAINING A NEW COMPOSITION OF CHLORINE OXIDE FROM DEGRADED HYPOCHLORITE |
US17/044,863 US20210206636A1 (en) | 2018-04-03 | 2019-04-02 | Manufacturing method for obtaining novel chlorine oxide composition from degraded hypochlorite |
AU2019248959A AU2019248959B2 (en) | 2018-04-03 | 2019-04-02 | Manufacturing method for obtaining novel chlorine oxide composition from degraded hypochlorite |
IL277759A IL277759B2 (en) | 2018-04-03 | 2020-10-02 | Create a method for obtaining an innovative chlorine oxide compound from degraded hypochlorite |
AU2024202489A AU2024202489A1 (en) | 2018-04-03 | 2024-04-16 | Manufacturing Method For Obtaining Novel Chlorine Oxide Composition From Degraded Hypochlorite |
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JP7301055B2 (ja) * | 2018-09-06 | 2023-06-30 | 富士フイルム株式会社 | 薬液、基板の処理方法 |
CN115947442A (zh) * | 2021-10-08 | 2023-04-11 | 香港科技大学 | 在高氯水环境中原位形成一氧化二氯的方法 |
CN114534288B (zh) * | 2022-02-22 | 2023-08-04 | 沧州华宇特种气体科技有限公司 | 一种含盐混合溶液的分离及溶剂回收方法 |
CN115436558A (zh) * | 2022-08-03 | 2022-12-06 | 浙江衢化氟化学有限公司 | 一种用离子色谱测定氯系氧化物含量的方法 |
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IL277759B1 (en) | 2023-03-01 |
CN112153900B (zh) | 2022-09-13 |
JP7291958B2 (ja) | 2023-06-16 |
AU2019248959A1 (en) | 2020-11-26 |
AU2019248959B2 (en) | 2024-05-09 |
IL277759A (en) | 2020-11-30 |
IL277759B2 (en) | 2023-07-01 |
US20210206636A1 (en) | 2021-07-08 |
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JPWO2019194184A1 (ja) | 2021-05-13 |
JP2023107815A (ja) | 2023-08-03 |
AU2024202489A1 (en) | 2024-05-09 |
CN112153900A (zh) | 2020-12-29 |
EP3777537A1 (en) | 2021-02-17 |
EP3777537A4 (en) | 2022-01-05 |
KR20200139740A (ko) | 2020-12-14 |
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