WO2019124239A1 - Procédé et appareil de récupération de solvant à base de fluor, et procédé et système de nettoyage d'un objet à nettoyer. - Google Patents

Procédé et appareil de récupération de solvant à base de fluor, et procédé et système de nettoyage d'un objet à nettoyer. Download PDF

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Publication number
WO2019124239A1
WO2019124239A1 PCT/JP2018/046046 JP2018046046W WO2019124239A1 WO 2019124239 A1 WO2019124239 A1 WO 2019124239A1 JP 2018046046 W JP2018046046 W JP 2018046046W WO 2019124239 A1 WO2019124239 A1 WO 2019124239A1
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Prior art keywords
solvent
cleaning
fluorine
based solvent
water
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PCT/JP2018/046046
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English (en)
Japanese (ja)
Inventor
敬二 安藤
菅原　充
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日本ゼオン株式会社
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Publication of WO2019124239A1 publication Critical patent/WO2019124239A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C11D7/30—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents

Definitions

  • the present invention uses a method of recovering a fluorine-based solvent from a cleaning solvent composition used to clean objects to be cleaned such as precision machine parts, electric / electronic parts, and optical parts, and uses the method of recovering the fluorine-based solvent
  • the present invention relates to a cleaning method of the object to be cleaned.
  • the present invention also relates to an apparatus for recovering a fluorine-based solvent from a cleaning solvent composition used for cleaning an object to be cleaned such as a precision machine part, an electric / electronic part, or an optical part, and an apparatus for recovering the fluorine-based solvent.
  • the invention relates to a cleaning system for an object to be cleaned comprising the
  • processing oil for example, cutting oil, press oil, squeeze oil, rolling, etc.
  • rustproof oil for example, waxes, greases, fluxes, etc.
  • the cleaning solvent composition containing a fluorine-type solvent is used from a viewpoint of environmental impact reduction.
  • a fluorine-type solvent is collect
  • techniques are being used to re-use for cleaning of objects to be cleaned.
  • Patent Document 1 a used cleaning solution containing an aqueous cleaning solution and a fluorine-based cleaning agent is discharged when the object to be cleaned degreased with the aqueous cleaning solution is cleaned with a fluorine-based cleaning agent, After removing most of the aqueous cleaning solution (specifically water) by specific gravity separation, the used cleaning solution from which most of the aqueous cleaning solution has been removed is distilled at a distillation temperature lower than the boiling point of water to recover the fluorine-based cleaning agent , Are reused.
  • the cleaning solvent composition containing a fluorine-based solvent in which the soiling component is dissolved is precipitated from the cleaning solvent composition by addition of a poor solvent and cooling, By separating the deposited dirt components with a fiber separation filter, the cleaning solvent composition containing the fluorine-based solvent is recovered and reused.
  • an object of the present invention is to provide a method and apparatus for recovering a fluorinated solvent with high purity and high recovery rate from a used cleaning solvent composition.
  • Another object of the present invention is to provide a method and system for cleaning an object to be cleaned using a fluorinated solvent recovered from a used cleaning solvent composition.
  • the present inventors distill the mixture obtained by adding water to the used cleaning solvent composition, thereby obtaining a fluorinated solvent with high purity and high recovery rate. The inventors found that it was possible to recover, and completed the present invention.
  • the object of the present invention is to advantageously solve the above-mentioned problems, and according to the present invention, the following recovery methods (1) to (8), the following cleaning method (9), The recovery device of 10) and the cleaning system of (11) below are provided.
  • (1) A method of recovering a fluorine-based solvent from a used cleaning solvent composition containing a dirt component and a fluorine-based solvent, Adding water to the spent cleaning solvent composition to obtain a water mixture (A); A step (B) of distilling the water mixture to obtain a distillate containing water and a fluorinated solvent as main components; Removing water from the distillate (C); And a method of recovering a fluorinated solvent.
  • the used cleaning solvent composition further comprises a flammable organic solvent, The flammable organic solvent contains one or more selected from the group consisting of glycol ethers, glycol ether acetates, aliphatic alcohols, aromatic alcohols, ketones, carbonates, esters, and lactones.
  • the fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane
  • the fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane
  • a step (a) of cleaning the object to be cleaned to which the dirt component adheres, using a cleaning solvent composition containing a fluorinated solvent The fluorine-based solvent recovery method according to any one of the above (1) to (8) is used from the used cleaning solvent composition containing the soil component and the fluorine-based solvent produced in the step (a) Recovering the solvent (b); And (c) cleaning the object to be cleaned to which the dirt component has been adhered using the fluorinated solvent obtained in the step (b). And a method of cleaning an object to be cleaned.
  • a fluorine-based solvent recovery device for recovering a fluorine-based solvent from a used cleaning solvent composition containing a dirt component and a fluorine-based solvent, A water mixing unit for adding water to the used cleaning solvent composition to obtain a water mixture; A distillation section for distilling the water mixture to obtain a distillate; A water removal unit for removing water from the distillate; Containing fluorine-based solvent recovery equipment.
  • a washing apparatus for washing an object to be cleaned having a dirt component attached thereto, using a cleaning solvent composition containing a fluorine-based solvent The recovery apparatus for a fluorine-based solvent according to the above (10), A recovery line for delivering a used cleaning solvent composition containing a dirt component and a fluorine-based solvent, which is discharged from the cleaning apparatus, to the fluorine-based solvent recovery apparatus; A recycling line for sending the fluorine-based solvent recovered by the fluorine-based solvent recovery device to the cleaning device;
  • containing water and a fluorine-based solvent as a main component means that the total content ratio of water and the fluorine-based solvent is 50% by mass or more.
  • the "flammable organic solvent” refers to an organic solvent having a flash point by any method when the flash point is measured by the tag sealing method and the Cleveland opening method according to JIS K2265. Point to.
  • the fluorine-based solvent can be recovered from the used cleaning solvent composition with high purity and high recovery rate.
  • the fluorine-based solvent recovered from the used cleaning solvent composition can be used to efficiently clean the object to be cleaned.
  • the method for cleaning an object to be cleaned according to the present invention is used when cleaning an object to be cleaned to which a dirt component adheres with a cleaning solvent composition.
  • the fluorine-based solvent recovered in the step (b) is reused to clean the object to be cleaned, so the cost required for cleaning the object to be cleaned is effectively achieved. It can be reduced.
  • the object to be cleaned is not particularly limited, and examples thereof include various materials such as metal materials, ceramic materials, plastics materials, intermediate products and final products.
  • the dirt component is not particularly limited, and, for example, processing oil (for example, cutting oil, press oil, throttling oil, rolling oil, etc.), lubricating oil, rust preventive oil, wax And greases, fluxes, and liquid crystals.
  • processing oil for example, cutting oil, press oil, throttling oil, rolling oil, etc.
  • lubricating oil for example, rust preventive oil, wax And greases, fluxes, and liquid crystals.
  • the cleaning solvent composition used in the present invention contains a fluorine-based solvent, and optionally, a flammable organic solvent, an alcohol azeotropically with the fluorine-based solvent, and a phenol-based antioxidant And at least one selected from the group consisting of Also, the cleaning solvent composition used in the present invention may optionally further contain an epoxy compound. Among them, from the viewpoint of enhancing the cleaning ability of the cleaning solvent composition, the cleaning solvent composition preferably contains at least a flammable organic solvent in addition to the fluorine-based solvent, and the flammable organic solvent and the fluorine-based solvent It is more preferable to contain boiling alcohols. And it is preferable that a washing
  • “does not have flammable” means that the flash point is measured by the tag sealing method and the Cleveland opening method according to JIS K2265, and the flash point is not recognized by any method. Point to.
  • fluorine-based solvent contained in the cleaning solvent composition are not particularly limited, and methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, ethyl perfluorobutyl ether, ethyl Hydrofluoroethers such as perfluoroisobutyl ether; Hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane; Hydrofluorochloroolefins such as 1-chloro-3,3,3-trifluoropropene And hydrofluorocyclocarbons such as 1,1,2,2,3,3,4 heptafluorocyclopentane; and the like.
  • fluoro solvents hydrofluorochloroolefins, hydrofluorocarbons and hydrofluorocyclocarbons are preferable, and 1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3. More preferred are 3-pentafluorobutane and 1,1,2,2,3,3,4-heptafluorocyclopentane.
  • fluorine-type solvent mentioned above can be used individually by 1 type or in mixture of 2 or more types.
  • the fluorine-based solvent contained in the cleaning solvent composition used in the present invention is preferably capable of forming an azeotropic composition or an azeotrope-like composition with water.
  • the aliphatic alcohol preferably has 6 or more carbon atoms.
  • the flammable organic solvent glycol ethers and aromatic alcohols are preferable, and 3-methoxy-3-methylbutanol, benzyl alcohol and phenethyl alcohol are more preferable.
  • the flammable organic solvent preferably has a boiling point higher than that of the fluorinated solvent.
  • the fluorinated solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane
  • the flammable organic solvent is particularly preferably an aromatic alcohol, and benzyl alcohol and It is more preferable to contain / or phenethyl alcohol.
  • the flammable organic solvent mentioned above can be used individually by 1 type or in mixture of 2 or more types.
  • the alcohol which can be used in the cleaning solvent composition and which forms an azeotropic mixture with the fluorine-based solvent is not particularly limited, and any alcohol such as tert-amyl alcohol can be used.
  • the fluorinated solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane
  • the cleaning solvent composition is a tert-amyl alcohol as an alcohol which is azeotroped with the fluorinated solvent. Is preferred.
  • the phenol-based antioxidant that can be used for the cleaning solvent composition is not particularly limited, and phenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p- Cresol, butyl hydroxyl anisole etc. can be mentioned. Among these, 2,6-di-t-butyl-p-cresol is preferable as a phenol-based antioxidant from the viewpoint of a high antioxidant effect.
  • the phenolic antioxidant mentioned above can be used individually by 1 type or in mixture of 2 or more types.
  • epoxy compounds which can be used for the cleaning solvent composition are not particularly limited, and butylene oxide, penten oxide, hexene oxide, heptene oxide, octene oxide, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide And cyclooctene oxide, glycidol, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether and the like.
  • the epoxy compound mentioned above can be used individually by 1 type or in mixture of 2 or more types.
  • the proportions of the fluorine-based solvent contained in the cleaning solvent composition, the flammable organic solvent which is an optional component, the alcohol which forms an azeotropy with the fluorine-based solvent, the phenolic antioxidant and the epoxy compound are It can be appropriately set according to the type of component and the like.
  • the cleaning of the object to be cleaned to which the dirt component adheres and the object to be cleaned is immersed in the cleaning solvent composition, or the cleaning solvent composition is sprayed onto the object to be cleaned, By dissolving or dispersing the soil components.
  • the temperature of the cleaning solvent composition to be used can be appropriately set according to the solubility or dispersibility of the dirt component, and the cleaning solvent composition used for cleaning may be boiling. .
  • the rinse of the object to be cleaned washed with the cleaning solvent composition is not particularly limited, and the object to be cleaned is dipped in the rinse solution, or the rinse liquid is sprayed onto the object to be washed and adheres to the object to be cleaned. It can be carried out by replacing the cleaning solvent composition and / or the cleaning solvent composition containing the soil component with a rinse solution.
  • the temperature of the rinse solution used is preferably kept as low as possible.
  • the temperature of the rinse solution is 20 times higher than the temperature of the steam used in steam cleaning. It is preferable that the temperature be lower than ° C.
  • the object to be cleaned in the rinse may be irradiated with ultrasonic waves, or physical force such as jet flow or peristalsis is used. You may add it.
  • the rinse solution is not particularly limited, and it is preferable to use a solvent containing the above-mentioned fluorine-based solvent as a main component (that is, a solvent containing 50 mass% or more of the fluorine-based solvent).
  • a solvent containing the fluorine-based solvent as a main component does not impair the rinse property and the vapor cleaning property, and in addition to the fluorine-based solvent, the solvent which forms an azeotropic film with the flammable organic solvent and / or the fluorine-based solvent You may include the kind.
  • the solvent which has a fluorine-type solvent as a main component may further contain the epoxy-type compound mentioned above in the range which does not inhibit rinse property and steam cleaning property.
  • the solvent which has a fluorine-type solvent as a main component forms an azeotropic composition from a viewpoint of the predictability of flash point.
  • a component other than a fluorine-based solvent it is preferable to use a solvent containing a fluorine-based solvent and an alcohol which forms an azeotrope with the fluorine-based solvent as the rinse solution. It is more preferable to use a solvent having a total content ratio of 98% by mass or more of a system solvent and an alcohol which is azeotroped.
  • the fluorine-based solvent, the flammable organic solvent as an optional component, the alcohol which forms an azeotropy with the fluorine-based solvent, and the epoxy-based compound contained in the solvent containing the above-mentioned fluorine-based solvent as a main component It is preferred to use the same ones contained in the cleaning solvent composition used to wash the wash.
  • the vapor cleaning of the object to be cleaned rinsed with the rinse solution is not particularly limited, and can be performed by exposing the object to be cleaned to the vapor of the fluorine-based solvent described above as the main component. Then, in the vapor cleaning, due to the temperature difference between the vapor and the object to be cleaned, the vapor mainly composed of the vapor of the fluorine-based solvent becomes a condensate on the surface of the object to be cleaned, and the cleaning solvent composition etc. Be done.
  • the steam cleaning can be finished at the timing when the surface temperature of the object to be cleaned becomes the same as the temperature of the steam and the condensation of the vapor mainly composed of the vapor of the fluorinated solvent stops.
  • cleaning of a to-be-cleaned thing which has as a main component the vapor
  • the change in the composition of the cleaning solvent composition used for cleaning the object to be cleaned is evaporation of a solvent mainly composed of a fluorine-based solvent such as a rinse solution. This can be suppressed by feeding the cleaning solvent composition in an amount approximately equal to the amount.
  • cleaning arbitrarily can be dried using a well-known drying method, without being limited.
  • Process (b) Contamination components are mixed into the cleaning solvent composition used in the step (a) by cleaning the object to be cleaned. Then, since the cleaning solvent composition in which the dirt component is mixed has a reduced detergency, if the cleaning solvent composition is continued to be used for washing as it is, the dirt component tends to remain on the object to be washed. Therefore, it is necessary to replace the cleaning solvent composition used in step (a) with a new cleaning solvent composition at an appropriate timing, or to withdraw a part thereof to replenish a new cleaning solvent composition.
  • a fluorine-based solvent according to the present invention which will be described later from the cleaning solvent composition (used cleaning solvent composition) containing dirt components, generated in step (a) It is recovered using a recovery method so that it can be reused for washing the object to be washed.
  • the concentration of the soiling component in the used cleaning solvent composition from which the fluorinated solvent is recovered in step (b) can be appropriately set according to the cleaning power required for the cleaning solvent composition. That is, the used cleaning solvent composition may be one in which the removing power of the dirt component is completely lost, or may be one having a removing power of the dirt component to some extent.
  • the fluorine-based solvent recovered in the step (b) is not particularly limited, and if necessary, a flammable organic solvent, alcohols which azeotrope with the fluorine-based solvent, a phenolic antioxidant and an epoxy compound
  • the fluorine-based solvent recovered in the step (b) may be used to wash the object to be cleaned by using the recovered fluorine-based solvent as a rinse liquid to rinse the object to be cleaned.
  • recovered at the process (b) can be performed like the process (a) mentioned above.
  • the fluorinated solvent is recovered from the cleaning solvent composition containing the dirt component generated in the step (c) in the same manner as the step (b). It is more preferable to repeatedly carry out the step (d) of conducting and the step (e) of washing the object to be washed using the fluorinated solvent recovered in the step (d). As described above, if the steps (b) and (c) are repeated and the steps (d) and (e) are repeated, the object to be cleaned can be washed continuously and efficiently.
  • a fluorine-based solvent is used from a used cleaning solvent composition in which a dirt component is dissolved or dispersed in a cleaning solvent composition containing a fluorine-based solvent. Water is added to the used cleaning solvent composition to obtain a water mixture, and the water mixture obtained in step (A) is distilled to obtain mainly water and a fluorinated solvent.
  • a step (B) of obtaining a distillate containing as a component, and a step (C) of removing water from the distillate obtained in the step (B) are characterized.
  • the used washing solvent composition was not distilled as it is, but the obtained water solvent obtained by adding water to the used washing solvent composition was distilled. Since water is removed from the distillate, the fluorinated solvent can be recovered with high purity and high recovery rate (for example, a recovery rate of 80% or more). Although the reason why the fluorinated solvent can be recovered with high purity and high recovery rate by distilling the water mixture formed by adding water is not clear, the boiling point depression of the fluorinated solvent is caused by the addition of water. It is guessed that it is to happen.
  • the method for recovering a fluorine-based solvent of the present invention can be particularly suitably used when recovering a fluorine-based solvent in the step (b) and the step (d) of the method for cleaning an object to be washed of the present invention described above.
  • the method for recovering a fluorine-based solvent according to the present invention may be used for applications other than the method for cleaning an object to be cleaned according to the present invention described above.
  • step (A) water is added to the used cleaning solvent composition to obtain a mixture (water mixture) containing the used cleaning solvent composition and water.
  • the amount of water added is not particularly limited, but from the viewpoint of improving the recovery rate and the purity of the fluorinated solvent recovered in the step (B), it is included in the used cleaning solvent composition.
  • the amount is preferably 8 parts by mass or more, and more preferably 10 parts by mass or more per 100 parts by mass of the fluorinated solvent.
  • the amount of water added is such that free water can be present in the system at the distillation temperature when distilling the water mixture in step (B) (ie, from the solubility of water in the used cleaning solvent composition at the distillation temperature) It is preferable to use a large amount of
  • the amount of water added is usually such that the amount of water contained in the water mixture is equal to or less than the amount of the fluorinated solvent contained in the water mixture.
  • water it is preferable to use water which does not contain chlorine for sterilization, such as pure water.
  • step (B) the water mixture obtained in step (A) is distilled to obtain a distillate containing water and a fluorinated solvent as main components.
  • step (B) distillation may be performed while water is continuously added.
  • the distillation temperature (temperature of the liquid phase) at the time of distilling the water mixture is not particularly limited as long as a distillate containing the water and the fluorinated solvent as the main components can be obtained, but usually the soiling It is below the boiling point of the component (if the soil component forms an azeotropic or azeotrope-like composition with the component contained in the cleaning solvent composition and / or water).
  • the distillation temperature is the boiling point of the fluorinated solvent (when the fluorinated solvent forms an azeotropic composition or an azeotrope-like composition with water
  • the distillation temperature is preferably not less than the azeotropic point), and the distillation temperature is preferably not less than the boiling point of water from the viewpoint of further improving the recovery of the fluorinated solvent to be recovered.
  • the fluorinated solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane capable of forming an azeotropic composition or an azeotrope-like composition with water, distillation is performed.
  • the temperature is preferably 105 ° C. or less.
  • the distillation temperature is the boiling point of the flammable organic solvent (the flammable organic solvent is a cleaning solvent When forming an azeotropic composition or an azeotrope-like composition with other components contained in the composition and / or water, it is preferable to be less than the azeotropic point).
  • the distillate may contain other components such as flammable organic solvents, alcohols which azeotrope with fluorinated solvents, phenolic antioxidants, epoxy compounds and dirt components.
  • the distillate does not contain a dirt component (that is, the content of the dirt component is below the lower limit of detection).
  • other components may be removed by known methods, such as water washing, as needed before or after a process (C).
  • step (C) water is removed from the distillate obtained in the step (B) to obtain a recovered product containing a fluorinated solvent.
  • the fluorine-based solvent generally has low compatibility with water, water can be easily removed in the step (C) to obtain a recovered product containing the high-purity fluorine-based solvent.
  • the removal of water from the distillate is not particularly limited, and may be performed using a known water separator or water separation membrane (for example, U-TEC Membrane (registered trademark) manufactured by Asahi Kasei Co., Ltd.). it can.
  • a known water separator or water separation membrane for example, U-TEC Membrane (registered trademark) manufactured by Asahi Kasei Co., Ltd.
  • the cleaning system for object to be cleaned cleans the object to be cleaned to which the dirt component adheres with the cleaning solvent composition containing fluorine-based solvent
  • recovery apparatus can be sent to a cleaning apparatus and reused, the cost required to wash
  • the fluorine solvent recovery device of the present invention is used when recovering a fluorine solvent from a used cleaning solvent composition containing a dirt component and a fluorine solvent, and water is added to the used cleaning solvent composition.
  • a water mixing part for obtaining a water mixture, a distillation part for distilling a water mixture obtained in the water mixing part to obtain a distillate, and a water removal part for removing water from the distillate obtained in the distillation part It is characterized by having.
  • the recovery apparatus of the fluorine-type solvent of the present invention since the water mixing part, the distillation part and the water removal part are provided, the fluorine-type solvent can be recovered with high purity and high recovery rate.
  • the fluorine-based solvent recovery device of the present invention can be particularly suitably used as a recovery device of the cleaning system for the object to be cleaned of the present invention described above, but the fluorine-based solvent recovery device of the present invention is It may be used in cleaning systems other than the cleaning system for objects to be cleaned of the present invention, or may be used alone without being incorporated in the cleaning system.
  • recovery apparatus of a fluorine-type solvent is not specifically limited, For example, it has a structure as shown in FIG.
  • the cleaning system 100 for the object to be cleaned shown in FIG. 1 is the used cleaning device 10 for cleaning the object to be cleaned to which the dirt component adheres, the recovery device 20 for the fluorine-based solvent, and the used device discharged from the cleaning device 10
  • a recovery line 18 for sending the cleaning solvent composition to the recovery device 20 and a recycling line 26 for sending the fluorinated solvent recovered by the recovery device 20 to the cleaning device 10 are provided.
  • the cleaning system 100 is for adjusting the composition for adjusting the composition of the cleaning solvent composition used in the storage tank 30 and the cleaning apparatus 10, which are provided in the recycling line 26 and store the recovered fluorinated solvent.
  • a tank 40 is provided.
  • the cleaning device 10 is not particularly limited, and is, for example, a two-tank type cleaning device, in which the cleaning solvent composition is stored, the cleaning tank 11 for cleaning the object to be cleaned, and the rinse liquid is stored. And 11 a rinse tank 12 for rinsing the object to be cleaned.
  • the cleaning apparatus 10 further includes an overflow pipe 13 for feeding the rinse liquid from the rinse tank 12 to the cleaning tank 11 and a heater 14 for heating the cleaning solvent composition in the cleaning tank 11.
  • a cooling coil 16 is provided above the cleaning tank 11 and the rinse tank 12 in the cleaning apparatus 10, and the upper part of the cleaning tank 11 and the rinse tank 12, more specifically, the cleaning tank 11 and the rinse tank 12
  • a vapor phase 15 is formed between the cooling coil 16 and the vapor heated by the heater 14 and accumulated therein.
  • the cleaning apparatus 10 further includes a water separator 17 that removes water from the condensate of the steam cooled by the cooling coil 16 and sends the obtained liquid to the rinse tank 12. Even if the cleaning tank 11 of the cleaning apparatus 10 is provided with a sensor (for example, a thermometer, a hydrometer, a liquid level meter, etc.) for controlling the concentration of the component contained in the cleaning solvent composition. Good.
  • a sensor for example, a thermometer, a hydrometer, a liquid level meter, etc.
  • the vapor obtained by heating the cleaning solvent composition with the heater 14 usually contains the vapor of the fluorinated solvent as the main component. And the condensate of the said vapor has a fluorine system solvent as a main component, and may contain water.
  • the recovery apparatus 20 distills the water mixture obtained in the water mixing tank 21 as a water mixing unit which adds water to the used cleaning solvent composition to obtain a water mixture, and obtains a distillate.
  • the distillation tank 22 as a distillation part and the water separator 25 as a water removal part which removes water from the distillate obtained in the distillation tank 22 are provided.
  • the water mixing tank 21 of the recovery device 20 is connected to the lower portion of the cleaning tank 11 of the cleaning device 10 via the recovery line 18. Then, in the water mixing tank 21, the used cleaning solvent composition flowing from the cleaning tank 11 through the regeneration line 18 is stored, and water is added to the used cleaning solvent composition to use the used cleaning solvent composition.
  • a water mixture is prepared comprising water and water. In addition, it is preferable to use the water which does not contain the chlorine for sterilization, such as a pure water, as water.
  • the distillation tank 22 of the recovery apparatus 20 is provided with a heater 23 for heating the water mixture flowing from the water mixing tank 21 and a cooling coil 24 provided in the upper part in the distillation tank 22, and the distillation tank A vapor phase is formed between the water mixture stored in the housing 22 and heated by the heater 23 and the cooling coil 24. The vapor of the water mixture heated and vaporized by the heater 23 is retained. Moreover, the distillation tank 22 is equipped with the discharge line 27 which discharges a distillation residual liquid at the bottom.
  • the distillation tank 22 may be provided with a water supply mechanism for supplying water into the distillation tank 22.
  • the water separator 25 removes water from the condensate (distillate) of the steam cooled by the cooling coil 24, and sends the recovered material containing the fluorinated solvent to the rinse tank 12.
  • the recovered material containing the fluorine-based solvent is stored in the storage tank 30 and then sent to the rinse tank 12.
  • the recovered matter may be purified by a purification mechanism (not shown) as necessary to remove unnecessary components and then sent to the rinse tank 12 it can.
  • the cleaning of the object to be cleaned, the recovery of the fluorinated solvent, and the reuse of the recovered fluorinated solvent can be performed as follows.
  • the object to be cleaned to which the dirt component has been attached can be washed by immersing it in the washing solvent composition in the washing tank 11 and dissolving or dispersing the dirt component in the washing solvent composition.
  • cleaning solvent composition in the washing tank 11 can be suitably set according to the solubility or the dispersibility of a dirt component, and the washing
  • the object to be cleaned may be irradiated with ultrasonic waves, or physical force such as jet flow or peristalsis may be applied.
  • the temperature of the rinse solution in the rinse tank 12 is not particularly limited, but is preferably kept as low as possible to enhance the steam cleaning property, and is preferably 20 ° C. or more lower than the temperature of the steam of the vapor phase 15 .
  • the object to be cleaned is pulled from the rinse tank 12 to the vapor phase 15 and is vapor cleaned. And the to-be-washed
  • the cleaning solvent composition (the used cleaning solvent composition) in which the dirt component is mixed by the cleaning of the object to be cleaned (spent cleaning solvent composition) is sent from the cleaning tank 11 to the recovery device 20 via the recovery line 18
  • the fluorinated solvent is recovered from the used cleaning solvent composition.
  • the cleaning solvent composition in the cleaning tank 11 is sent to the water mixing tank 21 via the recovery line 18, and water is added to the water mixing tank 21.
  • the water mixture containing the dirt component, the cleaning solvent composition, and the water is sent to the distillation tank 22 and then distilled to obtain a distillate containing water and the fluorinated solvent as main components, and the distillation It is separated into residual liquid.
  • the distillate is separated from the water by the water separator 25 and the obtained recovered product (the recovered product containing the fluorinated solvent) is sent to the rinse tank 12 through the reuse line 26 and the storage tank 30. , It is reused for washing of the to-be-cleaned material. Further, the residual distillation solution is discharged to a waste liquid tank or the like through the discharge line 27 and disposed of.
  • the distillation residue may be discharged at a predetermined timing such as a timing when the distillation temperature reaches a predetermined temperature, or may be always discharged.
  • the composition and the amount of the cleaning solvent composition and the rinse liquid are generated by the vapor of the fluorinated solvent generated by heating by the heater 14 as the main component by the cooling coil 16 It is cooled to form a condensate, which is removed by the water separator 17 and returned to the rinse tank 12 so that the rinse solution mainly composed of a fluorinated solvent having an amount substantially equivalent to the amount of evaporation overflows the overflow pipe 13 By flowing into the cleaning tank 11 through the, it can be maintained substantially uniform.
  • the change of the composition of the cleaning solvent composition by sending the recovered material containing the fluorine-based solvent to the rinse tank 12 can be obtained from the composition adjustment tank 40 by the alcohol which azesates with the flammable organic solvent and the fluorine-based solvent It can prevent by supplying 1 or more types selected from the group which consists of a phenolic antioxidant and an epoxy-type compound as needed, and adjusting the composition of the washing
  • recovery apparatus of the fluorine-type solvent of this invention were demonstrated using an example, the washing
  • the number of cleaning tanks and rinsing tanks may be two or more as needed.
  • the return destination of the recovered fluorine-based solvent is not limited to the rinse tank 12, and the recovered fluorine-based solvent is used for cleaning the cleaning object in the cleaning tank 11 or a separately prepared cleaning device. It is also good.
  • the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.
  • the composition of the distillate and the distillation residue, and the purity and recovery of the recovered fluorinated solvent were analyzed or evaluated as follows.
  • Example 1 As a used cleaning solvent composition, 383 g of 1,1,2,2,3,3,4-heptafluorocyclopentane as a fluorine-based solvent, 500 g of benzyl alcohol as a flammable organic solvent, and a fluorine-based solvent 17 g of tert-amyl alcohol as a boiling alcohol and Lilia cut DS-10 as a dirt component (manufactured by JX Nippon Mining & Energy Co., Ltd., density (15 ° C.): 0.86 g / cm 3 , dynamic viscosity (40 ° C.) : 11.8 mm 2 / s) A mixture with 100 g was prepared.
  • the used cleaning solvent composition described above and 120 g of water are put into a 1000 ml round bottom flask equipped with a cooling pipe, and the round bottom flask is immersed in an oil bath heated to 120 ° C. Distilled. Distillation was stopped when the liquid phase temperature (distillation temperature) of the round bottom flask reached 100 ° C., and the compositions of the distillate and the distillation residue were examined immediately. In addition, the purity and recovery rate of the recovered fluorinated solvent were determined. The results are shown in Table 1.
  • Example 1 The used cleaning solvent composition was prepared and distilled in the same manner as in Example 1 except that water was not added. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.
  • the fluorine-based solvent can be recovered from the used cleaning solvent composition with high purity and high recovery rate.
  • the fluorine-based solvent recovered from the used cleaning solvent composition can be used to efficiently clean the object to be cleaned.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

La présente invention concerne un procédé de récupération d'un solvant à base de fluor à partir d'une composition de solvant de nettoyage utilisée ayant une pureté élevée et un taux de récupération élevé. Un procédé de récupération d'un solvant à base de fluor selon la présente invention est configuré pour récupérer un solvant à base de fluor à partir d'une composition de solvant de nettoyage utilisée qui contient une composante sale et le solvant à base de fluor; et ce procédé de récupération d'un solvant à base de fluor comprend une étape (A) pour obtenir un mélange d'eau par ajout d'eau à la composition de solvant de nettoyage utilisée, une étape (B) pour obtenir un distillat liquide qui contient de l'eau et le solvant à base de fluor en tant que composantes principales par distillation du mélange d'eau, et une étape (C) pour éliminer l'eau du distillat liquide.
PCT/JP2018/046046 2017-12-20 2018-12-14 Procédé et appareil de récupération de solvant à base de fluor, et procédé et système de nettoyage d'un objet à nettoyer. WO2019124239A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0663303A (ja) * 1992-08-14 1994-03-08 Ashizawa Supuree Plant Kk 洗浄装置の溶剤濃縮回収法
JP2006083308A (ja) * 2004-09-16 2006-03-30 Nippon Zeon Co Ltd 洗浄剤組成物
JP2015174014A (ja) * 2014-03-13 2015-10-05 東京エレクトロン株式会社 分離再生装置および基板処理装置
WO2015174487A1 (fr) * 2014-05-14 2015-11-19 株式会社カネコ化学 Système de nettoyage et procédé de nettoyage à l'aide d'une composition d'agent de nettoyage non-azéotropique
WO2016181922A1 (fr) * 2015-05-14 2016-11-17 日本ゼオン株式会社 Composition de solvant de démoulage, procédé de démoulage, et composition de solvant de nettoyage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0663303A (ja) * 1992-08-14 1994-03-08 Ashizawa Supuree Plant Kk 洗浄装置の溶剤濃縮回収法
JP2006083308A (ja) * 2004-09-16 2006-03-30 Nippon Zeon Co Ltd 洗浄剤組成物
JP2015174014A (ja) * 2014-03-13 2015-10-05 東京エレクトロン株式会社 分離再生装置および基板処理装置
WO2015174487A1 (fr) * 2014-05-14 2015-11-19 株式会社カネコ化学 Système de nettoyage et procédé de nettoyage à l'aide d'une composition d'agent de nettoyage non-azéotropique
WO2016181922A1 (fr) * 2015-05-14 2016-11-17 日本ゼオン株式会社 Composition de solvant de démoulage, procédé de démoulage, et composition de solvant de nettoyage

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