JPWO2019093251A1 - Recycling method and reclaiming device for cleaning solvent composition, and cleaning method and cleaning system for objects to be cleaned - Google Patents

Abstract

The present invention provides a method for regenerating a cleaning solvent composition capable of efficiently separating stain components. A method for regenerating a cleaning solvent composition in which a stain component is dissolved. The cleaning solvent composition contains a fluorine-based solvent and a flammable organic solvent, and the stain component is precipitated from the cleaning solvent composition in which the stain component is dissolved. From the step (A) of obtaining a mixture containing the precipitated stain component and the cleaning solvent composition, the step of contacting the mixture with the stain component compatible material (B), and the mixture contacting with the stain component compatible material. This is a method for regenerating a cleaning solvent composition, which comprises a step (C) of removing a stain component to obtain a regenerated cleaning solvent composition.

Description

The present invention relates to a method for regenerating a cleaning solvent composition used for cleaning an object to be cleaned such as precision mechanical parts, electrical / electronic parts, and optical parts, and a method for cleaning the object to be cleaned using the regenerating method. Is.
The present invention also relates to a regenerating device for a cleaning solvent composition used for cleaning an object to be cleaned such as precision mechanical parts, electrical / electronic parts, and optical parts, and a cleaning system for the object to be cleaned including the regenerating device. It is a thing.

Conventionally, in the precision machine parts industry, the electronic / electrical parts industry, the optical parts industry, etc., processing oils (for example, cutting oils, press oils, drawing oils, rolling) have been used for processing and storing metal materials, ceramics materials, plastics materials, etc. Oil etc.), rust preventive oil, waxes, greases, fluxes, etc. are used. Then, these components (hereinafter, may be referred to as "dirt components") adhering to the surface of various materials during processing or storage are usually used as a cleaning solvent composition when making an intermediate product or a final product. It has been removed by washing with.

Here, as the cleaning solvent composition used when removing the dirt component, a mixed solution containing a fluorine-based solvent and a predetermined organic solvent is used from the viewpoint of realizing high cleaning performance with a low environmental load. (See, for example, Patent Documents 1 to 4).

Then, in the cleaning of the object to be cleaned using the cleaning solvent composition, from the viewpoint of preventing the dirt components from accumulating in the cleaning solvent composition and deteriorating the cleaning power of the cleaning solvent composition due to repeated cleaning, the cleaning power is deteriorated. It has been proposed to clean the object to be cleaned while regenerating the cleaning solvent composition in which the stain component is dissolved.

Specifically, for example, in Patent Documents 1 and 2, after the stain component is precipitated from the cleaning solvent composition by adding or cooling a poor solvent in the stain removal tank, the precipitated stain component is floated in the stain removal tank. The cleaning solvent composition is regenerated by separating the components. Then, the regenerated cleaning solvent composition obtained in the stain removing tank is sent from the stain removing tank to the cleaning tank for cleaning the object to be cleaned and reused for cleaning the object to be cleaned.

Further, for example, in Patent Documents 3 and 4, after the stain component is precipitated from the cleaning solvent composition by adding and cooling a poor solvent in the stain separation tank, the precipitated stain component is connected to the stain separation tank and the cleaning tank. By sending the regenerated cleaning solvent composition obtained by separating with a fiber separation filter installed in the liquid feeding path and separating the dirt components with the separation filter, the dirt components are dissolved. The solvent composition is recycled and reused.

Japanese Unexamined Patent Publication No. 2000-8095 Japanese Unexamined Patent Publication No. 2006-289173 JP-A-2003-333730 Japanese Unexamined Patent Publication No. 2011-116909

However, in the above-mentioned conventional technique in which the dirt component precipitated in the dirt removing tank is directly floated and separated in the dirt removing tank, the separability of the precipitated dirt component is low, and the precipitated dirt component and the cleaning solvent composition There was a problem that it could not be separated well.

In addition, the above-mentioned conventional technique for separating precipitated dirt components with a separation filter has a problem that workability and economy are low because the separation filter is clogged and the filter needs to be cleaned or replaced frequently. It was.

Therefore, an object of the present invention is to provide a method and an apparatus for regenerating a cleaning solvent composition capable of efficiently separating stain components.
Another object of the present invention is to provide a cleaning method and a cleaning system for an object to be cleaned using a regenerated cleaning solvent composition obtained by efficiently separating stain components.

As a result of intensive studies to achieve the above object, the present inventors have precipitated the stain component from the cleaning solvent composition in which the stain component is dissolved, and then applied the cleaning solvent composition containing the precipitated stain component to the stain component. We have found that by contacting a stain component-affinitive material having a higher affinity than the cleaning solvent composition, the stain component can be coarse-grained and the stain component can be efficiently separated, and the present invention has been completed. I let you.

That is, the present invention is intended to advantageously solve the above problems, and according to the present invention, the following (1) to (10) regeneration method, the following (11) cleaning method, and the following ( The regenerators (12) to (13) and the cleaning system (14) below are provided.
(1) A method for regenerating a cleaning solvent composition in which a stain component is dissolved.
The cleaning solvent composition contains a fluorine-based solvent and a flammable organic solvent.
The step (A) of precipitating the stain component from the cleaning solvent composition in which the stain component is dissolved to obtain a mixture containing the precipitated stain component and the cleaning solvent composition.
In the step (B) of bringing the mixture into contact with the stain component-affinity material,
A step (C) of removing a stain component from the mixture in contact with the stain component-affinity material to obtain a regenerated cleaning solvent composition.
A method for regenerating a cleaning solvent composition, which comprises.
(2) The above steps (B) and (C) are carried out while circulating the mixture between a contact portion having the stain component compatible material and a separation portion for removing the stain component from the mixture. The method for regenerating the cleaning solvent composition according to (1).
(3) The method for regenerating a cleaning solvent composition according to (1) or (2) above, wherein the stain component affinity material contains at least one of an ion exchange resin and a polyethylene resin.
(4) Any of the above (1) to (3), wherein the fluorocarbon solvent contains one or more solvents selected from hydrofluoroethers, hydrofluorocarbons, hydrofluorochloroolefins, and hydrofluorocyclocarbons. A method for regenerating a cleaning solvent composition according to the above.
(5) One or more of the flammable organic solvents selected from the group consisting of glycol ethers, glycol ether acetates, aliphatic alcohols, aromatic alcohols, ketones, carbonic acid esters, esters, and lactones. The method for regenerating a cleaning solvent composition according to any one of (1) to (4) above, which comprises.
(6) The fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane.
The method for regenerating a cleaning solvent composition according to any one of (1) to (5) above, wherein the flammable organic solvent is an aromatic alcohol.
(7) The method for regenerating a cleaning solvent composition according to any one of (1) to (6) above, wherein the flammable organic solvent contains at least one of benzyl alcohol and phenethyl alcohol.
(8) The method for regenerating a cleaning solvent composition according to any one of (1) to (7) above, wherein the cleaning solvent composition further contains alcohols that azeotrope with the fluorine-based solvent.
(9) The fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane.
The method for regenerating a cleaning solvent composition according to (8) above, wherein the alcohols are tert-amyl alcohol.
(10) The method for regenerating a cleaning solvent composition according to any one of (1) to (9) above, wherein the cleaning solvent composition further contains a phenolic antioxidant.
(11) The step (a) of cleaning the object to be cleaned to which the dirt component is attached using a cleaning solvent composition containing a fluorine-based solvent and a flammable organic solvent.
The step (b) of regenerating the cleaning solvent composition in which the stain component generated in the step (a) is dissolved by using the method for regenerating the cleaning solvent composition according to any one of (1) to (10) above.
The step (c) of cleaning the object to be cleaned to which the stain component is attached using the regenerated cleaning solvent composition obtained in the step (b).
A method of cleaning an object to be cleaned, including.
(12) A regenerating device for regenerating a cleaning solvent composition in which a stain component is dissolved.
The cleaning solvent composition contains a fluorine-based solvent and a flammable organic solvent.
A precipitation portion for precipitating the stain component from the cleaning solvent composition in which the stain component is dissolved,
A contact portion obtained in the precipitation portion, which brings the mixture containing the precipitated stain component and the cleaning solvent composition into contact with the stain component affinity material, and the contact portion.
A separation part for removing the dirt component from the mixture brought into contact with the dirt component-affinity material at the contact part,
A device for regenerating a cleaning solvent composition.
(13) The washing solvent composition regenerating apparatus according to (12) above, further comprising a circulation line for circulating the mixture between the contact portion and the separation portion.
(14) A cleaning device for cleaning the object to be cleaned to which dirt components are attached using a cleaning solvent composition containing a fluorine-based solvent and a flammable organic solvent.
With the regenerating apparatus for the cleaning solvent composition according to (12) or (13) above,
A regeneration line that sends a cleaning solvent composition in which dirt components are dissolved, which is discharged from the cleaning apparatus, to the regeneration apparatus.
A reuse line that sends the regenerated cleaning solvent composition discharged from the regenerating device to the regenerating device, and
A cleaning system for objects to be cleaned.

Here, in the present invention, the "flammable organic solvent" is 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 in accordance with JIS K2265. Point to.
Further, in the present invention, the "dirt component compatible material" is a cleaning solvent composition in which a stain component is dissolved so as to have a concentration of 6% by mass, and the turbidity value measured by a turbidity meter is 5 or more. After cooling until the temperature rises to obtain 50 ml of a cleaning solvent composition in which stain components are precipitated, 25 ml of a stain component affinity material is added while maintaining the temperature, mixed at a stirring speed of 300 rpm, and then immersed for 30 minutes. Refers to a material in which the reduction rate of the concentration of dirt components is 10% or more. The stain component-affinity material preferably has a reduction rate of 30% or more in the concentration of the stain component when immersed for 30 minutes.

According to the cleaning solvent composition regeneration method and the recycling apparatus of the present invention, the stain component can be efficiently separated from the cleaning solvent composition in which the stain component is dissolved, and the cleaning solvent composition can be efficiently regenerated.
Further, according to the cleaning method and cleaning system of the object to be cleaned of the present invention, the object to be cleaned is efficiently cleaned by using the regenerated cleaning solvent composition obtained by efficiently separating the stain components. Can be done.

It is explanatory drawing which shows the schematic structure of an example of the cleaning system of the object to be cleaned according to this invention. It is explanatory drawing which shows the schematic structure of the test apparatus used in an Example.

Hereinafter, (1) a method for cleaning the object to be cleaned, (2) a method for regenerating the cleaning solvent composition, (3) a system for cleaning the object to be cleaned, and a device for regenerating the cleaning solvent composition according to the present invention will be described in detail. ..

(1) Cleaning method of the object to be cleaned The cleaning method of the object to be cleaned of the present invention is used when cleaning the object to be cleaned with the stain component with the cleaning solvent composition, and the object to be cleaned to which the stain component is attached is used. The step (a) of cleaning with the cleaning solvent composition and the cleaning solvent composition in which the stain component generated in the step (a) is dissolved are regenerated by using the method for regenerating the cleaning solvent composition of the present invention, which will be described in detail later. It is characterized by including a step (b) and a step (c) of cleaning an object to be cleaned to which a stain component is attached by using the regenerated cleaning solvent composition obtained in the step (b). Then, according to the method for cleaning the object to be cleaned of the present invention, the regenerated cleaning solvent composition obtained in the step (b) is reused to clean the object to be cleaned, so that the cost required for cleaning the object to be cleaned is Can be effectively reduced.

(1-1) Object to be cleaned Here, the object to be cleaned is not particularly limited, and examples thereof include various materials such as metal materials, ceramic materials, and plastics materials, intermediate products, and final products.

(1-2) Dirt component The dirt component is not particularly limited, and is, for example, processing oil (for example, cutting oil, press oil, drawing oil, rolling oil, etc.), lubricating oil, rust preventive oil, wax. Classes, greases, fluxes and the like. Here, the processing oil may be either a water-soluble processing oil or an oil-soluble processing oil, but is preferably an oil-soluble processing oil such as a hydrocarbon-based processing oil.

(1-3) Cleaning solvent composition The cleaning solvent composition used in the present invention contains a fluorine-based solvent and a flammable organic solvent, and optionally azeotropically co-boils with the fluorine-based solvent. It further contains a system antioxidant and the like. In addition, the cleaning solvent composition used in the present invention may optionally further contain an epoxy compound. The cleaning solvent composition preferably does not have flammability.
In the present invention, "not flammable" means that the flash point is measured by the tag sealing method and the Cleveland opening method in accordance with JIS K2265, and the flash point is not recognized by any of the methods. Point.

Here, specific examples of the fluorosolvent contained in the cleaning solvent composition are not particularly limited, and are not particularly limited, and are methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, ethyl perfluorobutyl ether, and ethyl. Hydrofluoroethers such as perfluoroisobutyl ether; Hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane; Hydrofluorochloroolefins such as 1-chloro-3,3,3-trifluoropropene Hydrofluorocyclocarbons such as 1,1,2,2,3,3,4-heptafluorocyclopentane; can be mentioned. Among these, as the fluorocarbon solvent, hydrofluorocarbons and hydrofluorocyclocarbons are preferable, and 1,1,1,3,3-pentafluorobutane and 1,1,2,2,3,3,4- Heptafluorocyclopentane is more preferred.
The above-mentioned fluorine-based solvent may be used alone or in combination of two or more.

Further, specific examples of the flammable organic solvent contained in the cleaning solvent composition are not particularly limited, and are dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol mono. Glycol ethers such as butyl ether and 3-methoxy-3-methylbutanol; Glycol ether acetates such as 3-methoxy-3-methylbutyl acetate; aliphatic alcohols such as butanol, propanol, heptanol, hexanol, decanol and nonanol; Fragrances such as benzyl alcohol, methyl benzyl alcohol, ethyl benzyl alcohol, methoxybenzyl alcohol, ethoxybenzyl alcohol, hydroxybenzyl alcohol, 3-phenylpropanol, cumyl alcohol, furfuryl alcohol, phenethyl alcohol, methoxyphenethyl alcohol, ethoxyphenethyl alcohol, etc. Alcohols; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; esters such as butyl acetate, butyl propionate, methyl caproate, butyl caproate; carbonates such as dimethyl carbonate, diethyl carbonate, propyl carbonate, etc. Classes; lactones such as γ-butyl lactone; can be mentioned. Among these, as the flammable organic solvent, glycol ethers and aromatic alcohols are preferable, and 3-methoxy-3-methylbutanol, benzyl alcohol and phenethyl alcohol are more preferable. Further, the flammable organic solvent preferably has a higher boiling point than the fluorine-based solvent. When the fluorosolvent is 1,1,2,2,3,3,4-heptafluorocyclopentane, the flammable organic solvent is particularly preferably an aromatic alcohol, and benzyl alcohol and / Or more preferably contains phenethyl alcohol.
The above-mentioned flammable organic solvent may be used alone or in combination of two or more.

The alcohols that can be used in the cleaning solvent composition and that azeotrope with the fluorine-based solvent are not particularly limited, and any alcohols such as tert-amyl alcohol can be used. Above all, when the fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane, the cleaning solvent composition is tert-amyl alcohol as alcohols that azeotrope with the fluorine-based solvent. Is preferably included.

Further, the phenolic antioxidant that can be used in the cleaning solvent composition is not particularly limited, and is phenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-. Examples thereof include cresol and butyl hydroxylanisole. Among these, 2,6-di-t-butyl-p-cresol is preferable as the phenolic antioxidant from the viewpoint of high antioxidant effect.
The above-mentioned phenolic antioxidants may be used alone or in admixture of two or more.

Further, the epoxy compound that can be used in the cleaning solvent composition is not particularly limited, but butylene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, cyclopentene oxide, cyclohexene oxide, cyclohexene oxide. , Cyclooctene oxide, glycidol, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether and the like.
The above-mentioned epoxy compounds may be used alone or in admixture of two or more.

The proportions of the fluorine-based solvent and flammable organic solvent contained in the cleaning solvent composition, and the alcohols, phenol-based antioxidants, and epoxy-based compounds that azeotrope with the fluorine-based solvent, which is an optional component, are dirty. It can be appropriately set according to the type of component and the like.

(1-4) Step (a)
In the step (a), the object to be cleaned to which the dirt component is attached is washed with the cleaning solvent composition. In step (a), after cleaning the object to be cleaned with the dirt component attached with the cleaning solvent composition, the object to be cleaned that has been washed with the cleaning solvent composition may be optionally rinsed and steam-cleaned.
Here, "rinse" refers to replacing the cleaning solvent composition and / or the cleaning solvent composition containing a stain component adhering to the object to be cleaned washed with the cleaning solvent composition with a rinsing solution. .. Further, "steam cleaning" is to remove a cleaning solvent composition or the like containing a slight residual stain component on the surface of the rinsed object to be cleaned by using steam containing vapor of a fluorine-based solvent as a main component. Point to that.

The cleaning of the object to be cleaned to which the stain component is attached is not particularly limited, and the cleaning solvent composition is obtained by immersing the object to be cleaned in the cleaning solvent composition or by spraying the cleaning solvent composition onto the object to be cleaned. This can be done by dissolving the dirt component in the solvent. At this time, the temperature of the cleaning solvent composition used can be appropriately set according to the solubility of the dirt component, and the cleaning solvent composition used for cleaning may be boiling.

The rinse of the object to be cleaned, which has been washed with the cleaning solvent composition, is not particularly limited, and the object to be cleaned is immersed in the rinse solution or the rinse solution is sprayed onto the object to be cleaned and adheres to the object to be cleaned. This can be done by replacing the cleaning solvent composition and / or the cleaning solvent composition containing a stain component with a rinsing solution.
From the viewpoint of improving the steam cleaning property during steam cleaning, the temperature of the rinse liquid used is preferably kept as low as possible. For example, the temperature of the rinse liquid is 20 higher than the temperature of the steam used in steam cleaning. It is preferably lower than ° C. Further, when rinsing the object to be cleaned by immersing the object to be cleaned in the rinse liquid, the object to be cleaned may be irradiated with ultrasonic waves, or a physical force such as a jet or a sway may be applied. May be added.

Here, the rinsing solution is not particularly limited, and it is preferable to use the solvent containing the above-mentioned fluorine-based solvent as a main component (that is, a solvent containing 50% by mass or more of the fluorine-based solvent). Here, the solvent containing a fluorine-based solvent as a main component is an alcohol that azeotropes with the above-mentioned flammable organic solvent and / or a fluorine-based solvent in addition to the fluorine-based solvent as long as the rinse property and vapor cleaning property are not impaired. May include the like. Further, the solvent containing a fluorine-based solvent as a main component may further contain the above-mentioned epoxy-based compound as long as it does not impair the rinsability and vapor cleaning property. However, when a component other than the fluorine-based solvent is contained, it is preferable that the solvent containing the fluorine-based solvent as a main component forms an azeotropic composition from the viewpoint of predictability of the flash point.
The fluorine-based solvent contained in the solvent containing the fluorine-based solvent as a main component, the flammable organic solvent as an optional component, the alcohols co-boiling with the fluorine-based solvent, and the epoxy-based compound are covered. It is preferable to use the same one contained in the cleaning solvent composition used for cleaning the cleaning product.

The steam cleaning of the object to be cleaned that has been rinsed with the rinsing solution is not particularly limited, and can be performed by exposing the object to be cleaned to the vapor containing the vapor of the above-mentioned fluorine-based solvent as a main component. In steam cleaning, due to the temperature difference between the steam and the object to be cleaned, the vapor containing the vapor of the fluorine-based solvent as the main component becomes a condensate on the surface of the object to be cleaned, and the cleaning solvent composition containing the dirt component is removed. Will be done. Here, the steam cleaning can be completed 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 steam containing the steam of the fluorine-based solvent as a main component stops.

The steam containing the vapor of the fluorine-based solvent used for steam cleaning as a main component is not particularly limited, and it is preferable to use the vapor of the cleaning solvent composition used for cleaning the object to be cleaned.
Here, when the steam of the cleaning solvent composition is used for steam cleaning, the change in the composition of the cleaning solvent composition used for cleaning the object to be cleaned evaporates the solvent containing a fluorine-based solvent such as a rinsing solution as a main component. It can be suppressed by supplying the cleaning solvent composition in an amount substantially equal to the amount.

Then, the object to be washed, which has been washed with the washing solvent composition and then optionally rinsed and steam-washed, can be dried by using a known drying method without particular limitation.

(1-5) Step (b)
The cleaning solvent composition used in the step (a) is mixed with a stain component by cleaning the object to be cleaned. Since the cleaning solvent composition containing the stain component has a reduced detergency, if the cleaning solvent composition is used as it is for cleaning, the stain component tends to remain in the object to be cleaned. Therefore, in the method for cleaning the object to be cleaned of the present invention, the cleaning solvent composition in which the stain component generated in the step (a) is dissolved is regenerated by using the method for regenerating the cleaning solvent composition of the present invention described later, and the cleaning solvent is used. Allow sufficient cleaning capacity of the composition to be ensured.
The concentration of the stain component in the cleaning solvent composition regenerated in the step (b) can be appropriately set according to the cleaning power required for the cleaning solvent composition. That is, the regenerated cleaning solvent composition may be one in which the ability to remove stain components is completely lost, or may be one having some ability to remove stain components.

(1-6) Step (c)
In the step (c), the object to be cleaned to which the stain component is attached is washed using the regenerated cleaning solvent composition obtained in the step (b). By cleaning the object to be cleaned by reusing the regenerated cleaning solvent composition in this way, even when a plurality of objects to be cleaned are continuously or intermittently cleaned, the object to be cleaned is cleaned. The cost required for the cleaning can be effectively reduced.

Here, the cleaning of the object to be cleaned using the regenerated cleaning solvent composition is not particularly limited, and the cleaning solvent containing the regenerated cleaning solvent composition as the cleaning solvent composition used for cleaning the object to be cleaned is not particularly limited. It can be carried out in the same manner as in the above-mentioned step (a) except that the composition is used. That is, the cleaning of the object to be cleaned in the step (c) may be performed using only the regenerated cleaning solvent composition, or other cleaning solvent composition such as the cleaning solvent composition not subjected to the regeneration in the step (b). A mixture of the cleaning solvent composition and the regenerated cleaning solvent composition may be used.

Above all, from the viewpoint of continuously and efficiently cleaning the object to be cleaned, in the step (c) of the method for cleaning the object to be cleaned of the present invention, the cleaning solvent composition that was not subjected to regeneration in the step (b) It is preferable to wash the object to be cleaned with a mixture with the regenerated cleaning solvent composition. Further, in the method for cleaning the object to be cleaned of the present invention, after the step (c), a step (b) of regenerating the cleaning solvent composition in which the stain component is dissolved, which is generated in the step (c), in the same manner as in the above step (b). Repeating d) and step (e) of cleaning the object to be cleaned using a mixture of the cleaning solvent composition that was not regenerated in step (d) and the regenerated cleaning solvent composition. Is more preferable. By repeating the steps (d) and (e) after the steps (b) and (c) in this way, the concentration of the stain component in the cleaning solvent composition used for cleaning the object to be cleaned can be increased. The object to be cleaned can be continuously and efficiently washed while keeping the concentration below the desired concentration. As a result, a washed product having excellent cleanliness can be obtained.

(2) Method for Regenerating the Cleaning Solvent Composition The method for regenerating the cleaning solvent composition of the present invention is used when separating and removing the stain component from the cleaning solvent composition in which the stain component is dissolved to regenerate the cleaning solvent composition. The stain component is precipitated from the cleaning solvent composition in which the stain component is dissolved, and the mixture obtained in the step (A) is obtained as a mixture containing the precipitated stain component and the cleaning solvent composition. The step (B) of contacting with the affinity material and the step (C) of removing the stain component from the mixture contacted with the stain component affinity material in the step (B) to obtain a regenerated cleaning solvent composition are included. It is characterized by that.
Then, according to the method for regenerating the cleaning solvent composition of the present invention, the mixture containing the precipitated stain component and the cleaning solvent composition is brought into contact with the stain component-affinity material, so that the stain component is efficiently separated. be able to.

The method for regenerating the cleaning solvent composition of the present invention is particularly preferably used when regenerating the cleaning solvent composition in the steps (b) and (d) of the method for cleaning the object to be cleaned described above. However, the method for regenerating the cleaning solvent composition of the present invention may be used for applications other than the above-mentioned method for cleaning the object to be cleaned of the present invention.

(2-1) Stain component, cleaning solvent composition, and cleaning solvent composition in which the stain component is dissolved Here, the stain component, the cleaning solvent composition, and the cleaning solvent composition in which the stain component is dissolved include the above-mentioned invention. Since the same method as the method for cleaning the object to be cleaned can be used, the description thereof will be omitted.

(2-2) Step (A)
In the step (A), the stain component is precipitated from the cleaning solvent composition in which the stain component is dissolved, and a mixture containing the precipitated stain component and the cleaning solvent composition is obtained. Here, the method for precipitating the stain component is not particularly limited, and examples thereof include cooling, addition of a poor solvent, and a combination thereof. Above all, from the viewpoint that it is not necessary to separate and remove the poor solvent when reusing the regenerated cleaning solvent composition and the stain component can be precipitated by a simple operation, the stain component is precipitated. It is preferably carried out by cooling the dissolved cleaning solvent composition.

The poor solvent is not particularly limited, and the above-mentioned fluorine-based solvent, rinsing solution, or the like can be used. Among them, as the poor solvent, it is preferable to use a fluorine-based solvent or a solvent containing a fluorine-based solvent as a main component, and it is more preferable to use the same fluorine-based solvent as the fluorine-based solvent contained in the cleaning solvent composition. .. Here, when the stain component is precipitated using a poor solvent, the added poor solvent can be recovered from the mixture after removing the stain component in the step (C) by using a known method such as distillation. it can. By recovering the poor solvent from the mixture after removing the dirt component in this way, it is possible to prevent the composition of the regenerated cleaning solvent composition from being changed by the addition of the poor solvent, and to obtain the regenerated cleaning solvent composition. It can be easily reused.

(2-3) Step (B)
In the step (B), the mixture containing the precipitated stain component and the cleaning solvent composition obtained in the step (A) is brought into contact with the stain component affinity material to improve the separability of the precipitated stain component. Specifically, in the step (B), the mixture is brought into contact with the stain component-affinity material to coarsen the stain component, thereby enabling efficient separation of the stain component in the step (C).
In the step (B), it is necessary to bring the mixture in the state where the stain component is precipitated into contact with the stain component affinity material. Therefore, when the stain component is precipitated by cooling in the step (A), the temperature of the mixture in the step (B) is preferably equal to or lower than the temperature at which the stain component is precipitated in the step (A).

Here, examples of the stain component-affinitive material include polyethylene resin, polypropylene resin, nylon resin, polyester resin, phenol resin, ion exchange resin, and the like, although it depends on the type of stain component. Among them, a polyethylene resin and / or an ion exchange resin is preferable as a material having an affinity for a hydrocarbon-based stain component such as a hydrocarbon-based processing oil. The ion exchange resin is not particularly limited, and examples thereof include an ion exchange resin using a copolymer of styrene and divinylbenzene as a base material. Further, as the ion exchange resin, a strongly acidic cation exchange resin or a weakly basic ion exchange resin is preferable, and a strongly acidic ion exchange resin is more preferable.
The above-mentioned stain component affinity material can be used alone or in combination of two or more.

The shape of the stain component-affinity material is not particularly limited, but is preferably particulate, and more preferably spherical. The particle size of the stain component-affinity material is preferably 0.05 mm or more, more preferably 0.1 mm or more, and preferably 2.0 mm or less. When the particle size is equal to or more than the above lower limit, the stain component-affinity material can have a sufficient size as compared with the precipitated stain component, so that the mixture containing the precipitated stain component and the cleaning solvent composition is soiled. It is possible to suppress an increase in pressure loss and clogging when contacting with a component-affinity material. Therefore, the workability and economy when regenerating the cleaning solvent composition can be improved. Further, when the particle size is not more than the above upper limit value, a sufficient contact area with the mixture can be secured.

The contact between the mixture and the stain component-affinity material in the step (B) is not particularly limited, and can be performed by using any contact method. Above all, as a contact method, it is preferable to use a method of circulating the mixture in a container filled with a stain component-affinity material such as a filling tower.
From the viewpoint of satisfactorily coarse-graining the dirt component and further improving the separation performance in the step (C), the line of the mixture when the mixture is circulated in a container filled with a dirt component-affinity material such as a filling tower The speed is preferably 5 m / h or more, more preferably 8 m / h or more, preferably 25 m / h or less, and more preferably 15 m / h or less. For the same reasons, the space velocity at the time of distributing the mixture in a container filled with soil components affinity material such as packed tower, it is preferably 10h ^-1 or more, and 16h ^-1 or more More preferably, it is 30h ^-1 or less, and more preferably 26h ^-1 or less.

(2-4) Step (C)
In the step (C), the stain component is removed from the mixture brought into contact with the stain component-affinity material in the step (B) to obtain a regenerated cleaning solvent composition. Here, in the mixture brought into contact with the stain component-affinity material, the precipitated stain component is coarse-grained. Therefore, in the step (C), for example, the stain component can be easily removed from the mixture by utilizing the difference in specific gravity between the precipitated stain component and the cleaning solvent composition. Specifically, in the step (C), when the specific gravity of the stain component is smaller than the specific gravity of the cleaning solvent composition, the stain component floating in the mixture in contact with the stain component compatible material is removed. And / or, by extracting the cleaning solvent composition existing below the surfaced stain component, the stain component precipitated in the step (A) can be removed from the mixture to obtain a regenerated cleaning solvent composition. it can. Further, in the step (C), when the specific gravity of the stain component is larger than the specific gravity of the cleaning solvent composition, by removing the stain component that settles in the mixture in contact with the stain component compatible material, and / Alternatively, by extracting the cleaning solvent composition as the supernatant liquid, the dirt component precipitated in the step (A) can be removed from the mixture to obtain a regenerated cleaning solvent composition.

In the method for regenerating the cleaning solvent composition of the present invention described above, after performing the above-mentioned step (B) in the contact portion having the stain component compatible material, the stain component is relative to the total amount of the mixture flowing out from the contact portion. The cleaning solvent composition may be regenerated by a one-pass method in which the above-mentioned step (C) is performed in the separation portion for removing the above-mentioned steps (B) and (B) while circulating the mixture between the contact portion and the separation portion. It is preferable to regenerate the cleaning solvent composition by the circulation method in which C) is performed. If the cleaning solvent composition is regenerated while circulating the mixture between the contact portion and the separation portion, the precipitated stain component can be separated and removed while being coarse-grained more satisfactorily. It can be separated more efficiently.

(3) Cleaning system for the object to be cleaned and regenerator for cleaning solvent composition The cleaning system for the object to be cleaned of the present invention is used when cleaning the object to be cleaned with a cleaning solvent composition to which stain components are attached, and stains. A cleaning device that cleans the object to be cleaned with the components attached using the cleaning solvent composition, a regenerating device for the cleaning solvent composition of the present invention described in detail later, and a dirt component discharged from the cleaning device have been dissolved. It is characterized by including a recycling line for sending the cleaning solvent composition to the recycling apparatus and a recycling line for sending the recycled cleaning solvent composition discharged from the recycling apparatus to the cleaning apparatus. Then, according to the cleaning system for the object to be cleaned of the present invention, the regenerated cleaning solvent composition discharged from the regenerating device can be sent to the cleaning device for reuse, which is necessary for cleaning the object to be cleaned. The cost can be effectively reduced.

Further, the cleaning solvent composition regenerating device of the present invention is used when separating and removing the stain component from the cleaning solvent composition in which the stain component is dissolved to regenerate the cleaning solvent composition, and cleaning in which the stain component is dissolved. A precipitation part for precipitating a stain component from the solvent composition, a contact part for contacting a mixture of the precipitated stain component and the cleaning solvent composition obtained in the precipitation part with a stain component-affinitive material, and a stain component at the contact part. It is characterized by including a separating portion for removing a dirt component from the mixture brought into contact with the affinity material. Further, according to the regenerator of the cleaning solvent composition of the present invention, since the contact portion is provided, the dirt component can be efficiently separated at the separation portion.
The regenerating device for the cleaning solvent composition of the present invention can be particularly preferably used as the regenerating device for the cleaning system for the object to be cleaned described above. It may be used in a cleaning system other than the cleaning system of the object to be cleaned described above, or may be used alone without being incorporated in the cleaning system.

An example of the cleaning system for the object to be cleaned and the regenerating device for the cleaning solvent composition of the present invention is not particularly limited and has a configuration as shown in FIG. 1, for example.

Here, the cleaning system 100 for the object to be cleaned shown in FIG. 1 is discharged from the cleaning device 10 for cleaning the object to be cleaned to which the dirt component is attached, the regenerating device 20 for the cleaning solvent composition, and the cleaning device 10. A recycling line 18 for sending the cleaning solvent composition in which dirt components are dissolved to the regenerating device 20, and a reusing line 26 for sending the regenerated cleaning solvent composition discharged from the regenerating device 20 to the cleaning device 10 are provided. There is.
As the cleaning solvent composition in which the object to be cleaned, the stain component, the cleaning solvent composition and the stain component are dissolved, the same method as the above-mentioned cleaning method for the object to be cleaned can be used. The explanation is omitted.

The cleaning device 10 is not particularly limited, and is, for example, a two-tank type cleaning device, in which a cleaning solvent composition is stored and a cleaning tank 11 for cleaning an object to be cleaned is stored, and a rinse liquid is stored in the cleaning tank. It is provided with a rinsing tank 12 for rinsing the object to be washed that has been washed in No. 11. Further, the cleaning device 10 includes an overflow pipe 13 for sending 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. Further, a cooling coil 16 is provided above the cleaning tank 11 and the rinsing tank 12 in the cleaning apparatus 10, and more specifically, the cleaning tank 11 and the rinsing tank 12 are provided above the cleaning tank 11 and the rinsing tank 12. A steam phase 15 in which the steam heated by the heater 14 and vaporized stays is formed between the cooling coil 16 and the cooling coil 16. Further, the cleaning device 10 further includes a water separator 17 that removes water from the condensed liquid of steam cooled by the cooling coil 16 and sends the obtained liquid to the rinsing tank 12. Even if the cleaning tank 11 of the cleaning device 10 is provided with a sensor (for example, a thermometer, a hydrometer, a liquid level meter, etc.) for controlling the concentration of the flammable organic solvent in the cleaning solvent composition. Good.

Here, as the rinsing liquid in the rinsing tank 12, the same method as the above-described method for cleaning the object to be cleaned can be used, and thus the description thereof will be omitted below.
The steam obtained by heating the cleaning solvent composition with the heater 14 usually contains the vapor of a fluorine-based solvent as a main component. The vapor condensate contains a fluorine-based solvent as a main component and may contain water.

The regenerating device 20 contacts the precipitation tank 21 as a precipitation part for precipitating the stain component from the cleaning solvent composition in which the stain component is dissolved, and the mixture containing the precipitated stain component and the cleaning solvent composition in contact with the stain component compatible material. It is provided with a filling container 24 as a contact portion to be contacted, and a separation tank 22 as a separation portion for removing the stain component from the mixture in contact with the stain component-affinitive material in the filling container 24. Further, the regenerator 20 is a pump that extracts a mixture containing the precipitated dirt component and the cleaning solvent composition from the lower part of the separation tank 22 and sends it to the filling container 24, and allows the mixture to flow through the filling container 24 in an upward flow. It is provided with a delivery line 27A provided with 23 and a return line 27B for returning the mixture flowing out of the filling container 24 and in contact with the dirt component compatible material to the separation tank 22. Then, in the regenerator 20, the delivery line 27A and the return line 27B form a circulation line for circulating the mixture between the filling container 24 as the contact portion and the separation tank 22 as the separation portion. Further, the regenerator 20 includes a discharge line 25 for discharging the dirt components separated in the separation tank 22.

Here, the precipitation tank 21 of the regeneration device 20 is connected to the lower part of the cleaning tank 11 of the cleaning device 10 via the regeneration line 18. Further, the precipitation tank 21 is provided with a cooler (not shown). Then, in the precipitation tank 21, the cleaning solvent composition in which the dirt component flowing from the cleaning tank 11 is dissolved is stored via the regeneration line 18, and the cleaning solvent composition is cooled by the cooler and dissolved. Ingredients precipitate.

The separation tank 22 is provided with at least two partition plates (two of the first partition plate 22A and the second partition plate 22B in the illustrated example) in the tank. Then, in the first region of the separation tank 22 located on the side opposite to the second partition plate 22B side (left side in the illustrated example) with respect to the first partition plate 22A, the precipitated dirt component and the cleaning solvent composition are formed. The mixture containing the above-mentioned material flows in from the precipitation tank 21, and the mixture in contact with the dirt component-affinitive material flows in through the return line 27B. Further, a discharge line 25 for discharging the separated dirt component is connected to the first region. Further, a delivery line 27A is connected to the lower part of the second region located between the first partition plate 22A and the second partition plate 22B in the separation tank 22. Further, in the third region of the separation tank 22 located on the side opposite to the first partition plate 22A side (right side in the illustrated example) with respect to the second partition plate 22B, the separation tank 22 of the recycling device 20 and the cleaning device A reuse line 26 connecting the lower part of the washing tank 11 of 10 is connected.

The filling container 24 is filled with a dirt component-affinity material. Here, the filling container 24 is not particularly limited, and for example, a filling tower or the like can be used. The filling of the stain component-affinitive material is not particularly limited, and for example, the stain component-friendly material is filled in the container 24 using a mesh-shaped support member that allows the mixture to pass through but not the stain component-affinity material. It can be done by holding it inside.
As the stain component-affinity material, the same material as the above-mentioned method for regenerating the cleaning solvent composition of the present invention can be used, and thus the description thereof will be omitted below.

Then, in the above-mentioned cleaning system 100, the cleaning of the object to be cleaned, the regeneration of the cleaning solvent composition, and the reuse of the regenerated cleaning solvent composition can be performed as follows.

The object to be cleaned to which the stain component is attached can be cleaned by immersing it in the cleaning solvent composition in the cleaning tank 11 and dissolving the stain component in the cleaning solvent composition. At this time, the temperature of the cleaning solvent composition in the cleaning tank 11 can be appropriately set according to the solubility of the dirt component, and the cleaning solvent composition used for cleaning may be boiling. .. Then, the object to be cleaned washed in the cleaning tank 11 is immersed in the rinsing solution of the rinsing tank 12 in order to rinse the cleaning solvent composition and / or the cleaning solvent composition containing the stain component adhering to the object to be cleaned. Will be done. At this time, in the rinse tank 12, the object to be cleaned may be irradiated with ultrasonic waves, or a physical force such as a jet or a sway may be applied. The temperature of the rinsing liquid in the rinsing tank 12 is not particularly limited, but is preferably kept as low as possible in order to improve the steam cleaning property, and is preferably 20 ° C. or more lower than the temperature of the steam of the steam phase 15. .. After that, the object to be cleaned is pulled up from the rinsing tank 12 to the steam phase 15 and steam-cleaned. Then, the object to be cleaned, which has been steam-cleaned, is pulled up further above the steam phase 15 and dried.

In the above-mentioned cleaning process of the object to be cleaned, the composition and amount of the cleaning solvent composition and the rinsing solution are such that the steam containing the vapor of the fluorine-based solvent generated by heating by the heater 14 as the main component is used by the cooling coil 16. It is cooled to become a condensate, and after the water is removed by the water separator 17, it is returned to the rinse tank 12, so that the rinse liquid containing a fluorosolvent as a main component in an amount substantially equal to the amount of evaporation overflows the pipe 4. By flowing into the washing tank 11 via the solvent, the cleaning tank 11 is kept substantially uniform.

Further, a part of the cleaning solvent composition mixed with the stain component by cleaning the object to be cleaned is sent from the cleaning tank 11 to the regenerating device 20 and regenerated as follows. Specifically, the cleaning solvent composition in the cleaning tank 11 is sent to the precipitation tank 21 via the regeneration line 18 and cooled to a temperature or lower at which the dirt component is precipitated in the precipitation tank 21. Next, the mixture containing the precipitated stain component and the cleaning solvent composition is sent to the separation tank 22, and then sent from the separation tank 22 to the filling container 24 via the pump 23 and the delivery line 27A, and the stain component is sent. Contact with affinity material. Further, the mixture flowing out of the filling container 24 is returned to the separation tank 22 and circulates and flows between the separation tank 22 and the filling container 24. Then, the dirt components that have been finely dispersed in the mixture are coarse-grained by contact with the dirt component-affinity material, and are easily separated due to the difference in specific gravity from the cleaning solvent composition. As a result, the precipitated dirt components float and accumulate in the first region and the second region of the separation tank 22, and are discharged from the discharge line 25 to an arbitrary treatment facility such as a waste liquid tank for disposal. .. Further, the cleaning solvent composition (recycled cleaning solvent composition) in which the dirt components are separated and removed and the cleaning power is restored is transferred from the third region of the separation tank 22 to the cleaning tank 11 via the reuse line 26. It is sent and reused for cleaning the object to be cleaned.
Although the case where the specific gravity of the dirt component is smaller than the specific gravity of the cleaning solvent composition and the dirt component floats in the separation tank 22 is described here, the specific gravity of the dirt component is higher than the specific gravity of the cleaning solvent composition. If it is large, the dirt component settled in the separation tank 22 may be pulled out from the lower part of the separation tank 22.

In this way, a plurality of cleaning solvent compositions are extracted from the cleaning tank 11 and regenerated and reused in an amount determined by the amount of the stain component to be removed and the solubility of the stain component and the cleaning solvent composition. Even when the washed object is continuously washed, the concentration of the stain component in the cleaning solvent composition can be kept below a certain level, and the cleaning ability of the cleaning solvent composition can be sufficiently ensured. As a result, efficient cleaning of the object to be cleaned can be realized.

The cleaning system for the object to be cleaned and the regenerating device for the cleaning solvent composition of the present invention have been described above using an example. However, the cleaning system for the object to be cleaned and the regenerating device for the cleaning solvent composition of the present invention of the present invention are described above. It is not limited to the above-mentioned example.

Specifically, in the cleaning system for the object to be cleaned of the present invention, the number of cleaning tanks and rinsing tanks may be two or more, if necessary. Further, the return destination of the regenerated cleaning solvent composition is not limited to the cleaning tank 11, and the regenerated cleaning solvent composition may be used for cleaning the object to be cleaned in a separately prepared cleaning tank. Good.
Further, in the regenerating apparatus for the cleaning solvent composition of the present invention, a stain component may be precipitated by adding a poor solvent. In this case, for example, the precipitation tank 21 may be provided with a poor solvent addition mechanism, and the reuse line 26 may be provided with a device for recovering the poor solvent, such as a distillation device. Further, in the cleaning solvent composition regenerating apparatus of the present invention, the cleaning solvent composition may be cooled in the separation tank 22 to precipitate the stain component without providing the precipitation tank 21. Further, the separation tank 22 may be provided with an inclined plate for accelerating the separation of dirt components. Further, in the washing solvent composition regenerating apparatus of the present invention, the sending line 27A and the returning line 27B may not be provided, and the precipitation tank 21 and the filling container 24 may be directly connected.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following, the concentration of the stain component was measured as follows.

<Measurement of concentration of dirt components>
The concentration of the stain component was determined by using the calibration curve method.
Specifically, first, 25 ml of a cleaning solvent composition in which a stain component having a known concentration is dissolved is prepared, and the mass at 25 ° C. is measured to determine the density. Further, 25 ml of a cleaning solvent composition containing no stain component is prepared, and the mass at 25 ° C. is measured to determine the density. Then, a calibration curve is prepared using the density of the cleaning solvent composition containing no stain component and the density of the cleaning solvent composition in which the stain component is dissolved.
Next, the mass of 25 ml of the cleaning solvent composition to be measured at 25 ° C. is measured to determine the density. Then, the concentration of the stain component in the cleaning solvent composition to be measured is obtained from the calculated density using a calibration curve.

(Evaluation of affinity between dirt components and fillers)
First, the affinity of the filler for the stain component was evaluated.
Specifically, a cleaning solvent composition having the composition shown in Table 1, a stain component (hydrocarbon-based processing oil) shown in Table 2, and a filler shown in Table 3 were prepared. Next, the stain components shown in Table 4 were dissolved in the cleaning solvent composition shown in Table 4 so as to have a concentration of 6% by mass, and a cleaning solvent composition in which the stain components were dissolved was prepared. Then, 50 ml of the cleaning solvent composition in which the stain component is dissolved is cooled until the turbidity value measured by a turbidity meter (2100N TURBIDIMETER manufactured by HACH) rises by 5 or more, and the cleaning solvent composition in which the stain component is precipitated. After obtaining 50 ml of the product, 25 ml of the filler shown in Table 4 was added while maintaining the temperature, mixed at a stirring speed of 300 rpm, and then the reduction rate of the concentration of the stain component when immersed for 30 minutes was measured. Affinity was evaluated according to the criteria. The results are shown in Table 4. If the reduction rate of the concentration of the stain component is 10% or more, the filler corresponds to the stain component affinity material.
A: The reduction rate of the dirt component concentration is 30% or more B: The reduction rate of the dirt component concentration is 10% or more and less than 30% C: The reduction rate of the dirt component concentration is less than 10%

(Example 1)
A regeneration test of the cleaning solvent composition was carried out using the combination (1) shown in Table 4 as the stain component, the cleaning solvent composition and the filler.
Specifically, first, 6% by mass of Relior Cut DS-10 as a stain component was added to 1 L of the cleaning solvent composition (1), and after boiling, the test solution (cleaning in which the stain component was dissolved) was cooled to room temperature. Solution composition) was obtained.
Further, after filling the filling tower (inner diameter 30 mm, length 600 mm) having an outer cylinder with 400 ml of a strong acid cation exchange resin (manufactured by Purolite Co., Ltd., OL100) as a filler corresponding to a stain component compatible material, The inside of the filling tower was cooled to 2 ° C. by passing a coolant through the outer cylinder.
Then, 1 L of the test solution cooled to 2 ° C. in the glass bottle to precipitate the dirt component is supplied from the lower part of the filling tower under the conditions shown in Table 5, and the test solution flowing out from the upper part of the filling tower is made into the glass bottle. The test solution was circulated for a predetermined time by returning it to the inside. The test solution was extracted from the glass bottle from the bottom of the bottle using a circulation pump, and the test solution flowing out from the top of the filling tower was returned to the middle part of the bottle.
Every time a predetermined time elapses, the cleaning solvent composition is collected from the bottom of the bottle so that the dirt components floating in the bottle are not mixed, the concentration of the dirt components is measured, and the removal rate of the dirt components ( = {(Initial concentration-Concentration of collected test solution) / Initial concentration} x 100%) was calculated. Then, the removal efficiency of the dirt component was evaluated according to the following criteria. The results are shown in Table 5.
A: Removal rate is 30% or more B: Removal rate is 10% or more and less than 30% C: Removal rate is less than 10%

From Table 5, it can be seen that the stain component floated on the upper part of the test solution and was separated in the circulation time of 5 minutes, and the concentration of the stain component contained in the cleaning solvent composition decreased.

(Example 2)
A regeneration test of the cleaning solvent composition was carried out in the same manner as in Example 1 except that the temperature in the test solution and the filling column was changed to 4 ° C. and the circulation conditions were changed as shown in Table 6. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

From Table 6, it can be seen that under any of the circulation conditions, the stain component floated on the upper part of the test solution and was separated, and the concentration of the stain component contained in the cleaning solvent composition decreased.

(Example 3)
Using the combination (2) shown in Table 4 as the stain component, the cleaning solvent composition and the filler, 10% by mass of Cut Arbus KZ216 as the stain component was added to 1 L of the cleaning solvent composition (1) to prepare a test solution. Then, a regeneration test of the cleaning solvent composition was carried out in the same manner as in Example 1 except that the circulation conditions were further changed as shown in Table 7. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 7.

From Table 7, it can be seen that the stain component floated on the upper part of the test solution and was separated, and the concentration of the stain component contained in the cleaning solvent composition was reduced.

(Example 4)
The cleaning solvent composition was used in the same manner as in Example 1 except that the combination (3) shown in Table 4 was used as the stain component, the cleaning solvent composition and the filler, and the circulation conditions were changed as shown in Table 8. A regeneration test was performed. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 8.

From Table 8, it can be seen that the stain component floated on the upper part of the test solution and was separated, and the concentration of the stain component contained in the cleaning solvent composition was reduced.

(Example 5)
Using the combination (4) shown in Table 4 as the stain component, the cleaning solvent composition and the filler, 10% by mass of Cut Arbus KZ216 as the stain component was added to 1 L of the cleaning solvent composition (2) to prepare a test solution. Then, a regeneration test of the cleaning solvent composition was carried out in the same manner as in Example 1 except that the temperature in the test solution and the filling column was changed to 5 ° C. and the circulation conditions were further changed as shown in Table 9. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 9.

From Table 9, it can be seen that the stain component floated on the upper part of the test solution and was separated, and the concentration of the stain component contained in the cleaning solvent composition was reduced.

(Example 6)
In the test apparatus 30 shown in FIG. 2, a continuous regeneration test of the cleaning solvent composition was carried out using the combination (1) shown in Table 4 as the stain component, the cleaning solvent composition and the filler.
Specifically, first, 6% by mass of Reliar Cut DS-10 as a stain component is added to the cleaning solvent composition (1), and after boiling, the test solution (cleaning solution in which the stain component is dissolved) is cooled to room temperature. Composition) was obtained.
Next, the test solution was put into the container 34 (volume: 3.2 L, partition plate 36 and inclined plate 37 installed) of the test apparatus 30 shown in FIG. 2 from the test solution supply port 31 and cooled to 5 ° C. Further, the filling tower 38 (inner diameter 30 mm, length 600 mm) having an outer cylinder is filled with 400 ml of a strong acid cation exchange resin (manufactured by Purolite Co., Ltd., OL100) as a filler corresponding to a stain component compatible material. It was cooled to 5 ° C.
Then, a continuous reproduction test was conducted according to the following procedure.
(1) The cleaning solvent composition in the container 34 is subjected to a linear velocity of 10.2 m / h in the filling tower 38 in the order of the circulating fluid intake port 35, the filling tower 38, and the circulating fluid discharge port 33, and the space velocity is increased. It was circulated so as to be 18h ^-1, and circulated for 50 minutes.
(2) Next, the test solution cooled to 5 ° C. was continuously supplied from the test solution supply port 31 to the container 34 at a flow rate of 1.8 L / h while continuing the circulation. Then, the concentration of the stain component in the cleaning solvent composition flowing out from the sampling port 32 was measured, the removal rate of the stain component was calculated and the removal efficiency of the stain component was evaluated in the same manner as in Example 1. The results are shown in Table 10.

From Table 10, it can be seen that the stain components floated and separated, and the concentration of the stain components in the cleaning solvent composition decreased.

(Comparative Example 1)
Test using the combination (5) shown in Table 4 as the stain component, cleaning solvent composition and filler, and adding 5.5% by mass of Reliar Cut DS-10 as the stain component to 1 L of the cleaning solvent composition (1). A regeneration test of the cleaning solvent composition was carried out in the same manner as in Example 1 except that the liquid was prepared, the temperature inside the test liquid and the filling column was changed to 4 ° C., and the linear velocity was further changed to 11.3 m / h. Circulation time: 30 minutes) was performed.
However, no floating of the stain component (Reliar Cut DS-10) was observed on the upper part of the test solution, and the concentration of the stain component in the cleaning solvent composition was 5.5% by mass, which was unchanged.

(Comparative Example 2)
The test solution prepared in Example 1 was cooled to 5 ° C. to make it opaque, and allowed to stand for 30 minutes. As a result, the test solution remained opaque, and the dirt components did not float and separate.

According to the cleaning solvent composition regeneration method and the recycling apparatus of the present invention, the stain component can be efficiently separated from the cleaning solvent composition in which the stain component is dissolved, and the cleaning solvent composition can be efficiently regenerated.
Further, according to the cleaning method and cleaning system of the object to be cleaned of the present invention, the object to be cleaned is efficiently cleaned by using the regenerated cleaning solvent composition obtained by efficiently separating the stain components. Can be done.

10 Cleaning device 11 Cleaning tank 12 Rinse tank 13 Overflow pipe 14 Heater 15 Steam phase 16 Cooling coil 17 Water separator 18 Regeneration line 20 Regeneration device 21 Precipitation tank 22 Separation tank 22A First partition plate 22B Second partition plate 23 Pump 24 Filling Container 25 Discharge line 26 Reuse line 27A Delivery line 27B Return line 30 Test equipment 31 Test liquid supply port 32 Sampling port 33 Circulating fluid discharge port 34 Container 35 Circulating fluid intake port 36 Partition plate 37 Inclined plate 38 Filling tower 100 Cleaning system

Claims (14)

A method for regenerating a cleaning solvent composition in which a stain component is dissolved.
The cleaning solvent composition contains a fluorine-based solvent and a flammable organic solvent.
The step (A) of precipitating the stain component from the cleaning solvent composition in which the stain component is dissolved to obtain a mixture containing the precipitated stain component and the cleaning solvent composition.
In the step (B) of bringing the mixture into contact with the stain component-affinity material,
A step (C) of removing a stain component from the mixture in contact with the stain component-affinity material to obtain a regenerated cleaning solvent composition.
A method for regenerating a cleaning solvent composition, which comprises. The first aspect of the present invention, wherein the steps (B) and (C) are performed while circulating the mixture between a contact portion having the stain component compatible material and a separation portion for removing the stain component from the mixture. The method for regenerating a cleaning solvent composition according to the above. The method for regenerating a cleaning solvent composition according to claim 1 or 2, wherein the stain component-affinity material contains at least one of an ion exchange resin and a polyethylene resin. The cleaning solvent according to any one of claims 1 to 3, wherein the fluorocarbon solvent contains one or more solvents selected from hydrofluoroethers, hydrofluorocarbons, hydrofluorochloroolefins, and hydrofluorocyclocarbons. How to regenerate the composition. The flammable organic solvent contains at least one selected from the group consisting of glycol ethers, glycol ether acetates, aliphatic alcohols, aromatic alcohols, ketones, carbonic acid esters, esters, and lactones. The method for regenerating a cleaning solvent composition according to any one of claims 1 to 4. The fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane.
The method for regenerating a cleaning solvent composition according to any one of claims 1 to 5, wherein the flammable organic solvent is an aromatic alcohol. The method for regenerating a cleaning solvent composition according to any one of claims 1 to 6, wherein the flammable organic solvent contains at least one of benzyl alcohol and phenethyl alcohol. The method for regenerating a cleaning solvent composition according to any one of claims 1 to 7, wherein the cleaning solvent composition further contains alcohols that azeotrope with the fluorine-based solvent. The fluorine-based solvent is 1,1,2,2,3,3,4-heptafluorocyclopentane.
The method for regenerating a cleaning solvent composition according to claim 8, wherein the alcohols are tert-amyl alcohol. The method for regenerating a cleaning solvent composition according to any one of claims 1 to 9, wherein the cleaning solvent composition further contains a phenolic antioxidant. A step (a) of cleaning an object to be cleaned with a stain component attached using a cleaning solvent composition containing a fluorine-based solvent and a flammable organic solvent.
The step (b) of regenerating the cleaning solvent composition in which the stain component generated in the step (a) is dissolved by using the method for regenerating the cleaning solvent composition according to any one of claims 1 to 10.
The step (c) of cleaning the object to be cleaned to which the stain component is attached using the regenerated cleaning solvent composition obtained in the step (b).
A method of cleaning an object to be cleaned, including. A regenerator that regenerates a cleaning solvent composition in which dirt components are dissolved.
The cleaning solvent composition contains a fluorine-based solvent and a flammable organic solvent.
A precipitation portion for precipitating the stain component from the cleaning solvent composition in which the stain component is dissolved,
A contact portion obtained in the precipitation portion, which brings the mixture containing the precipitated stain component and the cleaning solvent composition into contact with the stain component affinity material, and the contact portion.
A separation part for removing the dirt component from the mixture brought into contact with the dirt component-affinity material at the contact part,
A device for regenerating a cleaning solvent composition. The regenerating apparatus for a cleaning solvent composition according to claim 12, further comprising a circulation line for circulating the mixture between the contact portion and the separation portion. A cleaning device that cleans the object to be cleaned with a stain component using a cleaning solvent composition containing a fluorine-based solvent and a flammable organic solvent.
The regenerating device for the cleaning solvent composition according to claim 12 or 13.
A regeneration line that sends a cleaning solvent composition in which dirt components are dissolved, which is discharged from the cleaning apparatus, to the regeneration apparatus.
A reuse line that sends the regenerated cleaning solvent composition discharged from the regenerating device to the regenerating device, and
A cleaning system for objects to be cleaned.

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