JP2001139604A - Method for cleaning vessel for chemical reaction, apparatus therefor and cleaning material therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove adhesive resins adhered to the surface of a body without fail in a short time. SOLUTION: This cleaning material comprises a solvent which is suitable for dissolving and swelling adhesive resins 9 adhered to the surface 1a to be cleaned as well as a solid substance 4 for bombarding the surface 1a to be cleaned so as to physically peel the resins 9 off the surface. Some part of the adhesive resins 9 is dissolved by the solvent to be removed. The other part which is composed of the adhesive resins 9 and is adhered fast to the inner wall surface 1a is collided with the solid substance 4 to be physically peeled off.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of cleaning technology, in particular, a method and apparatus for cleaning a chemical reaction vessel and a cleaning material capable of removing an adhesive resin adhered to a surface to be cleaned in a short time.

[0002]

2. Description of the Related Art Conventionally, when a surface to which an adhesive resin having low adhesiveness is adhered is washed, a washing method by spraying a solvent in which the adhesive resin is soluble or dipping in a solvent is used. For strongly adhering resin, contact peeling method with release agent, wiping method with paste containing abrasive, sand blasting to remove adhesive resin, jet method with high pressure water, chemical etching with acid or alkali, hydrolysis Method or a manual cutting method is used. These approaches take a long time to clean and involve damage to the surface to be cleaned. Further, since a solvent that has a bad effect on the human body and the environment is used, further cleaning is required after the cleaning to prevent the solvent from remaining. In particular, cleaning of reaction vessels and jigs used when manufacturing products involving chemical reactions consumes a large amount of solvent and requires a long time for cleaning. It is.

For example, a reaction apparatus used for producing paints, inks, adhesives, synthetic resins, and the like by a polycondensation reaction takes a reaction product out of a reaction vessel and then deposits an adhesive resin on the inner surface of the reaction vessel. Cannot be avoided. It is difficult to remove the remaining adhesive resin, but if it is not completely removed, when another type of polymerization reaction is performed in the reaction vessel, the reaction product and the adhesive resin are mixed, resulting in deterioration of product quality. Further, if a large amount of the adhesive resin adheres to a coil or the like for controlling the temperature by the polymerization reaction, the overall heat transfer coefficient decreases, and it becomes difficult to sufficiently control the temperature.

For this reason, the conventional standard washing method uses a solvent which is soluble in the adhesive resin, and performs reflux washing every time the polymerization reaction is completed. The reflux washing is performed by heating the solvent, which is about half filled in the reaction vessel, to a temperature near the boiling point, evaporating and condensing the solvent, wetting the inner wall surface, and dissolving the adhesive resin. The evaporated solvent is liquefied and collected in a condenser connected to the upper part of the reaction vessel, and returned to the reaction vessel. This reflux operation is repeated for 60 to 90 minutes. The next polymerization reaction is performed ignoring the adhesive resin that cannot be removed by the reflux washing. After repeated use in the polymerization reaction, washing with an alkali solution is performed at least once every several times of the polymerization reaction for at least 16 hours according to the accumulated amount of the adhered resin. Further, a worker removes the adhered resin by manual operation.

[0005] The degree of adhesion of the resin differs depending on the polymerization method such as solution polymerization, emulsion polymerization, and the like.
It also differs in adhesiveness, reaction speed, temperature control of heating by a rapid high-temperature heat source, and the like. Improvements have been made by surface treatment of the reaction vessel, handling vessel and jig to prevent the adhesion of the resin, but they are incomplete in terms of temperature controllability and durability.

[0006] The cleaning cost of the standard cleaning method reaches about 5 million yen / year in a 5000 L reaction vessel. This is because it takes a long time for the reflux cleaning, the alkali cleaning, and the stripping operation, and the solvent used for the reflux cleaning cannot be regenerated, and is burned, discarded, and discharged into the atmosphere. This is an essential problem in the chemical industry which causes not only cost but also environmental pollution, waste of resources and impairment of worker's health.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for cleaning a chemical reaction vessel, which reliably removes the adhesive resin adhered to the surface of an object in a short time by a reasonable closed system that does not require human power. An object of the present invention is to provide an apparatus and a cleaning material. It is another object of the present invention to provide a method and an apparatus for cleaning a chemical reaction vessel and a cleaning material for safely and easily removing an adhesive resin.

[0008]

Means for Solving the Problems The technical idea of the present invention for solving the above problems is as follows: [1] As an alternative to the conventional manual mechanical cutting method, a physical method without damaging the surface to be cleaned is used. Select a solid substance that can attack the adhesive resin, and let it flow to separate the adhesive resin,
[2] A solvent conventionally used is used as a dispersion medium for a solid substance, and is used in combination with reflux cleaning to smoothly dissolve, swell, and peel off. [3] A cleaning method using a cleaning material according to the present invention is industrial. It is easy and safe to implement a closed system.

That is, the method for cleaning a chemical reaction vessel according to the present invention comprises the steps of: 50 to 90 parts by weight of the solvent (3) and a solid substance (4) having a maximum length of 0.1 to 50 mm which is not dissolved in the solvent (3). A step of filling the reaction vessel (1) with a cleaning material consisting of parts by weight, a step of flowing the cleaning material in the reaction vessel (1), and a reaction vessel (1)
The adhesive resin (9) fixed to the inner wall surface (1a) is dissolved, permeated and swelled by the solvent (3), and the solid substance (4) flowing together with the solvent (3) is flowed into the inner wall surface of the reaction vessel (1). 1a), a step of physically peeling the swollen adhesive resin (9), and a step of removing the dissolved and peeled adhesive resin (9) from the reaction vessel (1) together with the cleaning material. including.

The cleaning apparatus for a chemical reaction vessel according to the present invention comprises:
The adhesive resin (9) fixed to the inner wall surface (1a) of the reaction vessel (1) by a chemical reaction is removed from the inner wall surface (1a) by washing. In the present invention, a supply device (23) for supplying a solvent (3) for dissolving and swelling the adhesive resin (9) and a solid substance (4) for physically peeling the adhesive resin (9) to the reaction vessel (1). , 7), and a stirrer (2) for flowing a cleaning material containing a solvent (3) and a solid substance (4) to impinge the solid substance (4) on the swollen adhesive resin (9). A separator (22) that separates the used cleaning material into a solvent (3) and a solid substance (4), and the solvent (3) is purified by removing the adhesive resin (9) from the separated solvent (3). And a storage tank (5, 6) for storing the purified solvent (3) and the separated solid substance (4).

[0011] The cleaning material according to the present invention comprises a surface to be cleaned (1
A good solvent that dissolves and swells the adhesive resin (9) fixed to a) and a solid substance (4) that collides with the surface (1a) to be cleaned and physically peels off the adhesive resin (9). Including. As used herein, the term "good solvent" refers to a solvent that has a high ability to dissolve solutes. The term "poor solvent" refers to a solvent having a low ability to dissolve a solute. Since the adhesive resin (9) is dissolved and removed with a good solvent, the adhesive resin (9) firmly adhered to the surface of the object is swollen, and the solid substance (4) is collided and physically peeled off. The adhesive resin (9) fixed to the surface (1a) can be reliably and automatically removed. Therefore, not only the soluble resin that can be removed with a good solvent but also the resin that is insoluble in a good solvent can be removed without a worker performing a scraping operation.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an embodiment of a method and an apparatus for cleaning a chemical reaction vessel and a cleaning material according to the present invention.
This will be described with reference to FIG.

[0013] The cleaning material according to the present invention comprises a surface (1) to be cleaned.
Solvent that dissolves and swells the adhesive resin (9) fixed to a)
(3) and a solid substance (4) that collides with the surface (1a) to be cleaned and physically peels off the adhesive resin (9). Solvent (3) is a good solvent, ethyl acetate, esters such as butyl acetate, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, trichloroethylene, halides such as carbon tetrachloride, toluene, aromatic hydrocarbons such as xylene, One or more of alcohol such as isopropyl alcohol, alkali such as sodium hydroxide, and water. If necessary, organic amino compounds such as dimethylaminoethanol, diethylaminoethanol, and triethylamine, organic acids such as acetic acid, a surfactant, and ammonia can be used. Further, in order to adjust the viscosity of the solvent (3) and promote the dissolution of the adhesive resin (9), a low molecular weight acrylic resin, polyester resin and vinyl chloride resin may be added to the solvent (3).

The solid substance (4) is a solid resin having a cylindrical shape, a spherical shape, a polyhedral shape, a confetti type or a tetrapod type, and has a maximum length of 0.1 to 50 mm. The maximum length of the solid substance (4) is 0.
When it is less than 1 mm, the solid substance (4) and the adhesive resin (9) are completely separated when the adhesive resin (9) which has been peeled off to reuse the solvent (3) and the solid substance (4) is separated. This makes it difficult to separate them. When the maximum length of the solid substance (4) exceeds 50 mm, the reaction vessel (1), which is the surface to be cleaned (1a), and the inner wall of the pipe
The number of collisions between (1a) and the solid substance (4) is reduced, and the releasability of the adhesive resin (9) fixed to the inner wall surface (1a) is reduced. Also, 5
If it exceeds 0 mm, the uneven portion in the reaction vessel (1), for example,
The solid substance (4) does not enter the gap between the uneven portions (not shown) at the connection point between the shaft (2a) and the stirring blade (2b) of the stirrer (2), and the dead space that cannot collide increases.

The solid substance (4) is insoluble in the solvent (3) and
Any material that is softer than that of a) may be used, and a material having an impact strength of 20 to 220 J / m, which can give an appropriate impact to the adhesive resin (9) fixed to the inner wall surface (1a), is preferable. . Polyolefin resin, polyester resin, phenol resin, melamine resin, urea resin, epoxy resin, silicone resin or fluororesin can be used.
Pellets such as polyethylene, polypropylene, polyethylene terephthalate or polytetrafluoroethylene having high heat resistance and high mechanical strength are preferred. The density of the solid substance (4) alone is 0.92 ×
10 ^{3 to} 0.96 × 10 ³ kg / m ³ , 0.85 × 10 ^{3 to} 0.92 × 10 ³ kg / m ³ for polypropylene, 1.37 × 10 ^{3 to} 1.38 × for polyethylene terephthalate 10 ³
kg / m ³ and polytetrafluoroethylene 2.1
2.3 g / cm ³ , good dispersibility in the solvent (3), and effective repetitive soft attack by flowing. The solid substance (4) can be an organic material, an inorganic material, a metal or a composite thereof as long as the material is inexpensive and has appropriate hardness, specific gravity, thermal stability and abrasion resistance in addition to the resin. Those having a specific gravity that can be dispersed in (3) are preferable.

The relationship between the solvent (3) and the solid substance (4) is 50 to 50.
90 parts by weight of solvent (3) and 10 to 50 parts by weight of solid substance (4)
May be selected according to the properties of the adhesive resin (9).
The ratio of the density of the solvent (3) to the solid substance (4) alone is 1: 0.9 to
1.4. When the ratio of the density of the solid substance (4) alone to the solvent (3) is less than 0.9, the solid substance (4) becomes the solvent (3).
The inner wall (1a) at the lower part of the reaction vessel (1) cannot be sufficiently washed. When the ratio of the density of the solid substance (4) alone to the solvent (3) exceeds 1.4, the solid substance (4) settles in the solvent (3), and the solid substance (4) precipitates in the upper part of the reaction vessel (1). The wall (1a) cannot be sufficiently cleaned. In addition, the flow speed of the solid substance (4) is reduced, and the impact force and the number of collisions on the adhesive resin (9) are reduced. The density ratio between the mixed solvent (3) and the solid substance (4) described below is also 1: 0.9 to 1.4 for the same reason.

Adhesive resin removed by the cleaning material according to the present invention
Since (9) is physically separated by the solid substance (4), the type of the adhesive resin (9) is not particularly limited. The effective effect is achieved by the production of acrylic resin, polyester resin, urethane resin, vinyl chloride resin, polystyrene or ABS resin widely used industrially or the production of a modified resin by a combination of these resins in a reaction vessel ( 1) and resin adhered in the piping.

In the embodiment of the present invention, a poor solvent for curing the adhesive resin (9) swollen by permeation is included. Use of the mixed solvent (3) containing a good solvent and a poor solvent further enhances the detergency. That is, when the adhesive resin (9) is composed of a gel component and a sol component having a small molecular weight, the sol component dissolves well in the good solvent, but the gel component absorbs a large amount of the good solvent and swells. The gel that has swollen by absorbing a large amount of good solvent does not elute from the good solvent and remains attached to the inner wall surface (1a) to increase flexibility. It is difficult to reduce the mechanical impact and scrape the adhesive resin (9) from the inner wall surface (1a). On the other hand, a poor solvent having a low ability to dissolve a solute limits the amount of good solvent absorbed by the gel and hardens the swollen gel. Thereby, the sol content is dissolved in a good solvent and the gel content is swollen, and the swollen gel content is cured with a poor solvent, and then physically separated with the solid substance (4). 9) can be completely removed from the inner wall surface (1a). When the mixed solvent (3) is stirred by the stirrer (2) as shown in FIG. 1, the solid substance (4) collides with the adhesive resin (9) as shown in FIG. Can be completely separated from the inner wall surface (1a) of the reaction vessel (1). Poor solvents are alcohols,
One or more of petroleum ethers, aliphatic hydrocarbons and water.

The combination of the good solvent and the poor solvent as the mixed solvent (3) is determined by the adhesive resin (9). Adhesive resin (9) is a monomer having an ethylenically unsaturated double bond capable of emulsion polymerization, suspension polymerization and solution polymerization, for example, vinyl chloride, vinyl acetate, styrene, methyl methacrylate,
When attached to the inner wall surface (1a) by polymerization reaction of butyl acrylate, isooctyl acrylate or acrylonitrile, one or more good solvents of ester, ketone, alkyl halide and aromatic hydrocarbon, alcohol, petroleum ether And one or more poor solvents of aliphatic hydrocarbons. Adhesive resin (9) is a polymerization reaction of a monomer having an ethylenically unsaturated double bond having a functional group as a main component, for example, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, acrylamide or N-methylolacrylamide When attached to the inner wall surface (1a), one or more good solvents of ester, ketone, alkyl halide, aromatic hydrocarbon, alcohol and water, and one or more of petroleum ether and aliphatic hydrocarbon or 2
More than one poor solvent is used. As described above, the good solvent and the poor solvent are determined by the chemical components of the adhesive resin (9), and there are solvents such as alcohol which can be either a good solvent or a poor solvent.

The combination of the good solvent, the poor solvent and the solid substance (4) is, for example, 20 to 70% by weight of an ester having a molecular weight of 100 or less as a good solvent and 30 to 80% by weight of an alcohol having 1 to 6 carbon atoms as a poor solvent. % Of the mixed solvent (3) and a solid substance having a maximum length of 0.1 to 50 mm (4) 10 to 30
Parts by weight. When the ester having a molecular weight of 100 or less, which is a good solvent, is less than 20% by weight, the sol content contained in the adhesive resin (9) is insufficiently dissolved, and the solubility does not change even when it exceeds 70% by weight. Further, if the alcohol content of the poor solvent is less than 30% by weight of alcohol having 1 to 6 carbon atoms, the gel portion swollen by the good solvent cannot be completely cured, and the flexibility is maintained. Makes physical separation difficult. Even if it exceeds 80% by weight, it will not cure any more. 0.1 to 100 parts by weight of the mixed solvent (3)
When the solid substance (4) of 50 mm is less than 10 parts by weight, the content of the solid substance (4) contained in the reaction vessel (1) is small, and the solid substance (4) and the inner wall surface of the reaction vessel (1) ( The number of collisions with 1a) is reduced, and the releasability of the adhesive resin (9) is reduced. If it exceeds 30 parts by weight, the solid substance (4) content contained in the reaction vessel (1) is large and heavy, the flow rate of the solid substance (4) is slow, and the solid substance (4) is violently exposed to the inner wall surface (1a). Since it does not collide with, the releasability is reduced.

As shown in FIG. 3, the cleaning apparatus for cleaning the reaction vessel (1) using the cleaning material includes a solvent (3) for dissolving and swelling the adhesive resin (9) and an adhesive resin (9). As shown in FIG. 1, a supply device (23, 7) for supplying a solid substance (4) for physically exfoliating to the reaction vessel (1) and a cleaning material containing the solvent (3) and the solid substance (4) are provided as shown in FIG. Flowable, swollen adhesive resin
A stirrer (2) for colliding the solid substance (4) with (9), and a separator (22) for separating the cleaning material used for cleaning into the solvent (3) and the solid substance (4), were separated. Solvent (3) to adhesive resin (9)
A filter (20) for purifying the solvent (3) by removing water, and storage tanks (5, 6) for storing the purified solvent (3) and the separated solid substance (4).

A solvent pump (23) which is a supply device for the solvent (3)
Is connected between a solvent tank (5), which is a storage tank for the solvent (3), and the reaction vessel (1), and supplies the solvent (3) to the reaction vessel (1) when washing is started. The feeder (7), which is a supply device of the solid substance (4), is connected between the bucket tank (6), which is a storage tank for the solid substance (4), and the reaction vessel (1). The substance (4) is supplied to the reaction vessel (1). As shown in FIG. 1, a stirrer (2) includes a shaft (2a) that is given a rotational motion from a motor (2c), and a stirring blade (2) connected to the shaft (2a).
b) to flow the solvent (3) and the solid substance (4). The cleaning material after cleaning is stored in a bucket tank (6), and the solvent (3) and the solid substance are separated by a flat separator (22) formed between the bucket tank (6) and the diatomaceous earth charging tank (10). (4). The separator (22) is formed of a perforated metal or a wire mesh having an opening on the entire surface so that the solid substance (4) cannot pass through. The filter (20) has a plurality of filter plates (20a) formed therein, on which the filter paper is disposed on the outer surface or the inner surface, and diatomaceous earth having a particle diameter of 3 to 5 μm is about 0.1% by weight of the solvent (3). , Pre-coated as a filter aid. Also filter
A circulation pump that returns the solvent (3) purified in (20) into the reaction vessel (1) and circulates between the filter (20) and the reaction vessel (1).
(24). Furthermore, in order to prevent the filtration speed of the filter (20) from being lowered early, as a pretreatment of the filter (20), a strainer (21) having a higher separation accuracy than the separator (22) and a lower filtration accuracy than the filter (20). Can be arranged.

The method for cleaning the reaction vessel (1) according to the present invention using the above-mentioned cleaning material and the cleaning apparatus is as follows: 50 to 90 parts by weight of the solvent (3) and a maximum length of 0.1 to 1.0 which is not dissolved in the solvent (3) A cleaning material consisting of 10 to 50 parts by weight of a 50 mm solid substance (4)
Fill in (1). When the solid substance (4) is less than 10 parts by weight, the number of collisions between the solid substance (4) and the inner wall surface (1a) of the reaction vessel (1) decreases, and the releasability of the adhesive resin (9) decreases. . When the amount of the solid substance (4) exceeds 50 parts by weight, the flow rate of the solid substance (4) becomes slow and the solid substance (4) does not violently collide with the inner wall surface (1a). As the solvent (3), a mixed solution of an organic solvent, particularly a mixed solvent (3) containing a poor solvent such as methanol for enhancing the detergency may be used.

Next, the cleaning material filled in the reaction vessel (1) is stirred and fluidized by a stirrer (2) as shown in FIG. Thereby, the adhesive resin (9) fixed to the inner wall surface (1a) of the reaction vessel (1) is dissolved, permeated and swelled by the solvent (3), and the solvent is removed.
(3) The solid material (4) flowing together with the inner wall (1a) of the reaction vessel
The swollen adhesive resin (9) is physically peeled off. After completion of the stirring, the dissolved and peeled adhesive resin (9) is removed from the reaction vessel (1) together with the cleaning material.

In the present invention, a step of recovering the cleaning material used for cleaning from the reaction vessel (1), a step of separating the solid substance (4) from the collected cleaning material, and a step of recovering the separated solid substance (4) )
And supplying the solvent (3) to the reaction vessel (1);
(1) flowing the cleaning material. In addition, the cleaning material used for cleaning is filtered and the adhesive resin (9)
May be included, a step of mixing the solvent (3) and the solid substance (4) to prepare and regenerate the cleaning material, and a step of reusing the regenerated cleaning material.

[0026]

EXAMPLE An example of a cleaning method using a cleaning material and a cleaning apparatus according to the present invention applied to cleaning of a solvent type acrylic resin polymerization reaction vessel will be described.

After the acrylic resin polymerized in the reaction vessel (1) shown in FIG. 3 is taken out of the reaction vessel (1), the reaction vessel (1)
In order to remove the acrylic resin (9) adhered to the inner wall surface (1a) of the above, reflux washing was performed as a previous step with toluene which is a good solvent. The reflux washing method is as described above. After that, the reaction vessel (1) was washed using a washing material containing the mixed solvent (3) and the solid substance (4), and the composition of the mixed solvent (3) 5100 kg was ethyl acetate 50% by weight, 25% by weight of isopropyl alcohol and 25% by weight of methanol, a cylindrical (3 mm diameter x 2 mm height) polyethylene resin solid material (4)
Used 900 kg.

In the mixed solvent (3), ethyl acetate is a good solvent, and isopropyl alcohol and methanol are poor solvents. The cylindrical solid material can be used only by cutting a long rod-shaped injection-molded polyethylene resin into an appropriate size, and it can scrape off the acrylic resin (9) attached to the inner wall surface (1a). Is good. The frequency of cleaning the reaction vessel (1) with the cleaning material according to the present invention varies depending on the amount of the acrylic resin (9) attached, but in this example, the reaction was performed once every 30 polymerization reactions.

At the time of washing, 5100 kg of the mixed solvent (3) was supplied from the solvent tank (5) to the 6000 L reaction vessel (1) shown in FIG.
(4) was supplied from the bucket tank (6) to the reaction vessel (1) by the feeder (7). The mixed solvent (3) is placed in the upper ring in the reaction vessel (1).
The reaction vessel is sprayed in the form of a shower from the nozzle (8a) of (8).
Filled in (1). Next, the temperature of the filled cleaning material was maintained at 50 ° C., and the cleaning material was stirred with a stirrer (2) as shown in FIG.
And stirred. As a result, the acrylic resin (9) adhering to the inner wall surface (1a) is dissolved and removed with the solvent (3), and at the same time, the acrylic resin (9) remaining without being removed by the dissolution is impinged by the collision of the solid substance (4). Peeled off the wall (1a). The stirring is 20 to
The operation was performed at a speed of 80 rpm for 5 to 8 hours, and half of the time was reversely rotated so that the solid substance (4) efficiently collided with the inner wall surface (1a). Before the completion of the stirring, the temperature was set to 30 ° C. and the stirring speed was set to 20 rpm, and the stirring was terminated.

After completion of the stirring, the valve (11) is opened and the solid substance (4)
And the mixed solvent (3) containing the separated acrylic resin (9) is withdrawn from the reaction vessel (1) into the bucket tank (6), and the mixed solvent (3)
Passes through the opening of the separator (22) to form the bucket tank (6).
At the same time, it was stored in the diatomaceous earth input tank (10). Diatomaceous earth input tank (1
The mixed solvent (3) of (0) was returned to the reaction vessel (1) by the circulation pump (24) with the valves (15) and (13) open. This circulation is performed for 30 to 40 minutes, and when the solid substance (4) in the reaction vessel (1) is almost completely removed, the diatomaceous earth 2 is introduced into the diatomaceous earth charging tank (10).
kg. At the same time, close valves (11) and (13),
Open valve (14) and filter diatomaceous earth with circulation pump (24) (20)
Was pre-coated. When the mixed solvent (3) containing diatomaceous earth is almost exhausted in the diatomaceous earth charging tank (10), 4 kg of diatomaceous earth is further charged into the reaction vessel (1) from an input port (not shown), and the valve (12)
Was opened, the valve (15) was closed, and the filter (20) was precoated. Thereby, the mixed solvent (3) was circulated again through the route of the reaction vessel (1), the strainer (21), the circulation pump (24), the filter (20), and the reaction vessel (1). At this time, the acrylic resin (9) having a large particle size contained in the mixed solvent (3) is replaced with the strainer (2).
Since the acrylic resin (9) separated in 1) and having a small particle size is filtered by the filter (20), the circulated mixed solvent (3) can always be supplied to the reaction vessel (1) in a purified state. . After circulating with the mixed solvent (3) for 90 minutes, the valve (16) was closed, the valve (17) was opened, and the mixed solvent (3) was returned to the solvent tank (5). Since the mixed solvent (3) is subjected to high-precision filtration by a filter (20) pre-coated with diatomaceous earth, the performance as a solvent does not deteriorate, and once every four to five years except for replenishment of the shortage. I just need to replace it. Also, the solid substance (4) can be reused, and a replenishment amount of about 5% is sufficient for one year. Finally, the inside of the reaction vessel (1) was rinsed with toluene to complete the washing of the reaction vessel (1).

After completion of the washing, the inside of the reaction vessel (1) was observed and compared with the state before the washing according to the present invention. The state of the inner wall surface (1a) by the naked eye and the finger before cleaning is such that the adhesive resin (9) is fixed to the entire surface with a thickness of 0.1 to 1.0 mm, there is a rough feeling, and the luminous luster state is Despite the matte condition, the condition of the inner wall surface (1a) after washing with the naked eye and finger touch is that there is no sticking of the adhesive resin (9) on the entire surface, there is a smooth feeling, and the luminous gloss state is metal mirror gloss was there. Since the inner wall surface (1a) after the cleaning according to the present invention has no adhesive resin (9) on the entire surface and is washed to a glossy state, the cleaning vessel according to the present invention is used to clean the reaction vessel (1). It was confirmed that the adhesive resin (9) could be completely removed by washing the inner wall surface (1a).

In this embodiment, the following effects can be obtained. [1] dissolution in a mixed solvent (3) of a good solvent and a poor solvent,
The adhesive resin (9) in the reaction vessel (1) can be almost completely removed by a synergistic effect of permeation and swelling and peeling by the solid substance (4). [2] After removing the adhesive resin (9), the inner wall (1
Since no impurities are attached to a), the reaction yield and quality of the next reaction product can be improved. [3] Since the worker does not need to perform the stripping work in the reaction vessel (1), the working environment is improved. [4] Conventionally, the cleaning operation for two days can be reduced to about 12 hours, and the cleaning time for the reaction vessel (1) can be reduced.
The operation rate can be improved. [5] Since the solvent cost and labor cost can be saved, the cleaning cost can be significantly reduced.

[0033]

As described above, according to the present invention, the adhesive resin can be reliably removed in a short time, thereby improving the cleaning efficiency and the quality of the product and reducing the cleaning cost.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a state in which the inside of a reaction vessel is cleaned with a cleaning material according to the present invention.

FIG. 2 is an enlarged view of the inner wall surface of the reaction vessel shown in FIG.

FIG. 3 is a flowchart for cleaning the inside of a reaction vessel with the cleaning material according to the present invention.

[Explanation of symbols]

(1) ・ ・ Reaction vessel, (1a) ・ ・ Surface (inner wall), (2) ・ ・
Stirrer, (2a) shaft, (2b) stirrer, (2
C) motor, (3) solvent (mixed solvent), (4) solid material, (5) storage tank (solvent tank), (6) storage tank (bucket tank), ( 7) Feeder, (8) Upper ring, (8a) Nozzle, (9) Adhesive resin (acrylic resin), (10) Diatomaceous earth charging tank, (11) to (17)・ ・
Valve, (20) filter, (20a) filter plate, (21)
Strainer, (22) separator, (23) solvent pump, (24) circulation pump,

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 4J011 C11D 7/06 C11D 7/06 7/22 7/22 7/24 7 / 24 7/26 7/26 7/28 7/28 7/32 7/32 7/50 7/50 17/00 17/00 F term (reference) 3B116 AA32 AB53 BA06 BB23 BB33 BB82 BB87 CC05 CD22 3B201 AA32 AB53 BA06 BB23 BB33 BB82 BB87 BB95 CB22 CC21 CD22 4G075 AA57 BD16 DA02 EA01 EB01 ED01 ED02 ED08 FC20 4H003 DA12 DB03 DC04 EA21 EB28 EB37 EB38 ED02 ED03 ED04 ED05 ED28 CC31 EB1 CB1 CB013 EC037 EE037 EH037 GT00 HA06 4J011 EC09

Claims (21)

[Claims] 1. A step of filling a reaction vessel with a cleaning material comprising 50 to 90 parts by weight of a solvent and 10 to 50 parts by weight of a solid substance having a maximum length of 0.1 to 50 mm which is not dissolved in the solvent; A step of flowing in the reaction vessel, dissolving, permeating and swelling the adhesive resin adhered to the inner wall surface of the reaction vessel with a solvent, and colliding a solid substance flowing together with the solvent with the inner wall face of the reaction vessel to cause the swollen adhesion A method for cleaning a chemical reaction vessel, comprising: a step of physically peeling a conductive resin; and a step of removing a dissolved and peeled adhesive resin from a reaction vessel together with a cleaning material. 2. A step of collecting a cleaning material used for cleaning from a reaction container, a step of separating a solid substance from the collected cleaning material, and a step of supplying the separated solid substance and a solvent to the reaction container. The method for cleaning a chemical reaction container according to claim 1, further comprising: flowing a cleaning material in the reaction container. 3. A step of filtering the cleaning material used for cleaning to remove the adhesive resin, a step of adjusting and regenerating the cleaning material by mixing a solvent and a solid substance, and a step of reusing the regenerated cleaning material. The method for cleaning a chemical reaction vessel according to claim 1, comprising a step of using. 4. The method for cleaning a chemical reaction vessel according to claim 1, wherein the adhesive resin is a resinous substance attached to an inner wall surface of the reaction vessel. 5. The method according to claim 1, wherein the solvent is a mixture of organic solvents.
5. The method for cleaning a chemical reaction vessel according to any one of items 4 to 4. 6. The method for cleaning a chemical reaction vessel according to claim 1, wherein the solvent is an organic solvent containing methanol. 7. The method for cleaning a chemical reaction vessel according to claim 1, wherein the solid substance is formed in a columnar shape, a spherical shape, a polyhedral shape, a confetti shape or a tetrapod shape. 8. The chemical reaction vessel according to claim 1, wherein the solid substance is a polyolefin resin, a polyester resin, a phenol resin, a melamine resin, a urea resin, an epoxy resin, a silicone resin or a fluororesin. Cleaning method. 9. The method according to claim 8, wherein the solid substance is polyethylene, polypropylene, polyethylene terephthalate or polytetrafluoroethylene. 10. A cleaning apparatus for a chemical reaction vessel for washing and removing an adhesive resin adhered to an inner wall surface of a reaction container from an inner wall surface by a chemical reaction, wherein a solvent for dissolving and swelling the adhesive resin and a solvent for the adhesive resin are physically removed. A supply device for supplying a solid substance to be peeled off to the reaction vessel, a stirrer for flowing a cleaning material containing a solvent and a solid material to impinge the solid material on the swollen adhesive resin, and a cleaning material used for cleaning A separator that separates the solvent into a solid and a solid substance; a filter that removes the adhesive resin from the separated solvent to purify the solvent; and a storage tank that stores the purified solvent and the separated solid substance. A cleaning device for a chemical reaction vessel, characterized by the following. 11. The cleaning apparatus for a chemical reaction vessel according to claim 10, further comprising a circulation pump for returning the solvent purified by the filter into the reaction vessel and circulating the solvent between the filter and the reaction vessel. 12. A good solvent for dissolving and swelling the adhesive resin adhered to the surface to be cleaned, and a solid substance that collides with the surface to be cleaned and physically peels off the adhesive resin. Cleaning material. 13. The cleaning material according to claim 12, further comprising a poor solvent for curing the swollen adhesive resin. 14. The poor solvent is alcohol, petroleum ether,
14. The cleaning material according to claim 13, wherein the cleaning material is one or more of an aliphatic hydrocarbon and water. 15. The method according to claim 12, wherein the good solvent is one or more of an ester, a ketone, a halide, an aromatic hydrocarbon, an alcohol, an alkali and water.
The cleaning material according to the item. 16. The solid material may be cylindrical, spherical, polyhedral,
The confectionary sugar form or the tetrapod form is formed.
16. The cleaning material according to any one of the above items 15. 17. The cleaning material according to claim 12, wherein the solid substance is a polyolefin resin, a polyester resin, a phenol resin, a melamine resin, a urea resin, an epoxy resin, a silicone resin, or a fluororesin. 18. The cleaning material according to claim 17, wherein the solid substance is polyethylene, polypropylene, polyethylene terephthalate or polytetrafluoroethylene. 19. The cleaning material according to claim 12, wherein the adhesive resin is a resin adhered to the surface of the inside of the reaction vessel and the inside of the pipe. 20.100 parts by weight of a mixed solvent containing 20 to 70% by weight of an ester having a molecular weight of 100 or less as a good solvent and 30 to 80% by weight of an alcohol having 1 to 6 carbons as a poor solvent, and a maximum length of 0.1%. The cleaning material according to any one of claims 13 to 19, comprising 10 to 30 parts by weight of a solid substance of 1 to 50 mm. 21. The cleaning material according to claim 12, wherein the ratio of the density of the solvent or the mixed solvent to the solid substance alone is 1: 0.9 to 1.4.