JP2008036547A - Method for regenerating ester exchange reaction catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To regenerate the catalytic activity of a used ester exchange reaction catalyst. <P>SOLUTION: A method for regenerating the ester exchange reaction catalyst comprises the steps of: preparing the used ester exchange reaction catalyst containing alkali metal salt; dissolving the prepared used catalyst in water to obtain an aqueous solution; adding metal hydroxide to the obtained aqueous solution to adjust the pH so that the pH of the obtained aqueous solution becomes within ±20% of the pH of another aqueous solution prepared by dissolving an unused catalyst of the same amount as that of the used catalyst in the water of the same amount as that of the water used when the used catalyst is dissolved; and separating the regenerated catalyst as solid content. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for regenerating a used transesterification catalyst.

  Conventionally, a resin having an ester bond has been developed as a lightweight and high-strength material, and has been widely used in bathtubs, small ships, automobiles, railway vehicles, and the like. However, such a resin is often an inorganic composite material, and there has been no good recycling method.

  For example, in order to separate and recover the filler and the cured resin, a method is disclosed in which the silica is recovered by thermally decomposing the resin at a high temperature of, for example, 900 ° C. or higher (see Patent Documents 1 and 2). Further, there is a method of recovering the filler by thermally decomposing the thermosetting resin (see Patent Document 3). However, in these methods, the resin cannot be recovered because the resin is gasified by thermal decomposition at a high temperature. In addition, fillers other than silica may be altered at temperatures of 300 ° C. or higher. Furthermore, a special apparatus is required for thermal decomposition at 300 ° C. or higher, and it is necessary to pay particular attention to safety.

  Further, unsaturated polyester resins can be cited as resins having an ester bond. As a method for chemically decomposing them, a method using a base and a hydrophilic solvent (see Patent Document 4), a base and a monovalent alcohol are used. The method (refer patent document 5), the method using glycol (refer patent document 6), the method using dicarboxylic acid or diamine (refer patent document 7), and the method using diethanolamine (refer patent document 8) are disclosed. However, among these methods, those that use corrosive chemicals require special consideration for the human body and the environment, and those that do not use corrosive chemicals have a significantly slow decomposition rate.

  A solution to these problems is a treatment method using a decomposition treatment solution containing an alkali metal salt and an alcohol (see Patent Document 9). When an unsaturated polyester, which is a resin having an ester bond, is added to this treatment liquid and treated at a temperature of less than 200 ° C. and normal pressure, a transesterification reaction occurs and decomposes to obtain a prepolymer.

However, when the treatment liquid is used for a long time, there is a problem that the catalytic activity of the alkali metal salt is lowered and the decomposition / dissolution rate of the unsaturated polyester is lowered.
Japanese Patent Application No. 5-139715 JP-A-6-87123 JP-A-7-330946 Japanese Patent Application Laid-Open No. 8-113619 JP-A-8-134340 JP-A-8-225635 Japanese Patent Laid-Open No. 9-221565 JP-A-9-316311 Japanese Patent Application 2000-390804

  An object of this invention is to provide the regeneration method of the catalyst used as a transesterification reaction catalyst.

  One aspect of the present invention includes a step of preparing a catalyst containing a used alkali metal salt as a transesterification catalyst, a step of dissolving the catalyst in water to obtain an aqueous solution, and a catalyst containing the used alkali metal salt. The pH is adjusted by adding a metal hydroxide so that the difference between the same amount of unused catalyst and the pH shown when added to the same amount of water as that of the aqueous solution is within 20%. The present invention relates to a method for regenerating a transesterification catalyst comprising a step and a step of separating a catalyst as a solid content.

  One embodiment of the present invention may further include a step of washing the catalyst with an organic solvent after the step of preparing the catalyst and before the step of obtaining the aqueous solution.

  Furthermore, one embodiment of the present invention may include a step of adding an acid to precipitate a solid after the step of preparing the catalyst and before the step of obtaining the aqueous solution. Furthermore, one embodiment of the present invention may include a step of depositing a solid by adding an acid after the step of washing with the organic solvent and before the step of obtaining the aqueous solution.

  Furthermore, in one embodiment of the present invention, the alkali metal salt may be tripotassium phosphate.

Furthermore, one embodiment of the present invention may be one in which a catalyst containing a used alkali metal salt is used for dissolving a fiber-reinforced plastic.

  According to one aspect of the present invention, it is possible to regenerate the catalytic activity of a used transesterification catalyst. Moreover, according to one aspect of the present invention, the regenerated transesterification catalyst has a catalytic activity equal to or higher than that of an unused transesterification catalyst. Furthermore, according to one embodiment of the present invention, since the catalytic activity of the used transesterification reaction catalyst can be regenerated repeatedly, it is excellent in economic effect without producing waste.

  The transesterification catalyst refers to a catalyst that promotes transesterification of a resin having an ester bond, and specifically an alkali metal salt. The alkali metal salt is preferably one that dissolves in water in the form of an alkali metal salt (normal salt) and has low solubility in water in the form of a hydrogen salt of the alkali metal salt when dissociated in water in two or more stages. Examples of the alkali metal salt include an alkali metal phosphate, an alkali metal carbonate, and an alkali oxalate. Examples of the alkali metal phosphate include sodium phosphate, potassium phosphate, rubidium phosphate, and cesium phosphate. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. Examples of the alkali metal oxalate include sodium oxalate, potassium oxalate, rubidium oxalate, and cesium oxalate. Among them, a preferable alkali metal salt is potassium phosphate, particularly tripotassium phosphate.

  The resin decomposed by the transesterification reaction catalyst is a resin having an ester bond. Examples of the resin having an ester bond include an epoxy resin, a saturated polyester, and an unsaturated polyester. The unsaturated polyester may be, for example, a plastic (FRP) whose strength is increased by molding in combination with a fibrous reinforcing agent.

  First, according to one embodiment of the present invention, the method includes a step of preparing a catalyst containing a used alkali metal salt as a transesterification catalyst. For example, a resin treatment solution having an ester bond and a transesterification catalyst are placed in a treatment tank, and the ester exchange reaction catalyst is recovered after the resin having the ester bond is dissolved in the treatment tank while stirring with nitrogen gas. And used in this reproduction method.

  Next, if necessary, a step of washing the catalyst with an organic solvent may be provided. When a resin having an ester bond is dissolved, the dissolved resin or its decomposition product may adhere to the catalyst. If the resin or its decomposition product is attached, the surface area of the catalyst will decrease and the catalyst activity will decrease. It becomes one of. In order to prevent this, the adhered resin or a decomposition product thereof is removed by washing with an organic solvent. The organic solvent is preferably an organic solvent capable of dissolving a resin having an ester bond or a decomposition product thereof, and may be the same organic solvent as that used for dissolving the resin having an ester bond or a decomposition product thereof. Examples of the organic solvent capable of dissolving the resin having an ester bond or a decomposition product thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phorone, isophorone, acetylacetone, acetophenone, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole , Phenetole, dioxane, tetrahydrofuran, acetal, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, die Lenglycol diethyl ether, methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, 3-methoxy Butyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl butyrate , Ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isopentyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyro Kuton, diethyl oxalate, dibutyl oxalate, diethyl malonate, methyl salicylate, ethylene glycol diacetate, tributyl borate, trimethyl phosphate, triethyl phosphate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol 2-butanol, iso-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, iso-pentyl alcohol, tert-pentyl alcohol, 3-methyl- 2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexa 3-methylcyclohexanol, 4-methylcyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol, polyethylene glycol (molecular weight 200-400), 1,2-propanediol, 1,3 -Propanediol, 1,2-butanedio 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, glycerin, dipropylene glycol, benzyl alcohol, pentane, hexane, cyclohexane, methylpentane, heptane , Octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, styrene, methylcyclohexane, petroleum ether. For washing, for example, 100 parts by weight of the catalyst may be added to 50 to 1000 parts by weight of the organic solvent and stirred for 1 to 60 minutes to disperse the catalyst, and then the organic solvent is filtered to recover the solid content on the filter paper. . In this step, an ultrasonic cleaner may be used.

  When the step of washing with the organic solvent described above is performed, a step of washing the solid (catalyst) with an organic solvent having compatibility with water is provided as necessary. In order to dissolve the catalyst in the aqueous solution in a later step, the organic solvent adhering to the catalyst is removed using an organic solvent having high compatibility with water. Examples of the organic solvent having compatibility with water include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, acetylacetone, dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Monobutyl ether, triethylene glycol, 1,2-propanediol Examples include 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, glycerin, and dipropylene glycol. . The washing may be carried out, for example, by adding 100 parts by weight of the catalyst to 50 to 1000 parts by weight of an organic solvent having compatibility with water and stirring for 1 to 60 minutes, and thereafter, the organic solvent having compatibility with water. The solid content on the filter paper is recovered. In this step, an ultrasonic cleaner may be used.

  Next, if necessary, a step of washing the catalyst with an aqueous solution may be provided. In order to obtain a catalyst with less impurities, washing is performed using an aqueous solution. Specifically, first, 100 parts by weight of the solid content obtained in the previous step is added to 50 to 500 parts by weight of water, and stirred for 1 to 60 minutes to dissolve the catalyst in water. At this time, a cleaning agent may be added to the aqueous solution to improve the cleaning effect on the catalyst. As the cleaning agent, those having high compatibility with water and high cleaning effect are preferable. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, acetylacetone, Dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, Examples include glycerin and dipropylene glycol.

  Next, you may provide the process of adding an acid and depositing a solid substance. That is, an acid is added to this aqueous solution to precipitate the dissolved alkali metal salt as a hydrogen salt of the alkali metal salt. The acid content is preferably within 20% of the pH when the same amount of pure alkali metal salt hydrogen salt as the used catalyst is added to the same amount of water as that added in the previous step, more preferably Is within 10%. For example, when 20 g of solid content (for example, tripotassium phosphate) is dissolved in 40 g of water, the amount of acid (for example, phosphoric acid) added is 20 g of pure potassium dihydrogen phosphate dissolved in 40 g of water. The pH (3.14 to 4.70) is within 20% above and below the pH (3.92). Moreover, when it shall be 10% or less, it is pH (3.53-4.31).

  As the acid, an acid containing an anion of a salt used as a catalyst is preferable. For example, phosphoric acid is used when the catalyst is a phosphate, and carbonic acid and oxalate are used when the catalyst is a carbonate.

  Next, this aqueous solution is filtered and solid content (crystals) on the filter paper is recovered. Next, the crystal may be washed with a washing solvent to remove impurities attached to the surface. The washing solvent for washing the crystals may be any solvent as long as it does not dissolve the crystals, but a solvent having a relatively low boiling point is preferable in view of ease of drying. For example, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, dipropyl ether, diisopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate , Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol, ethylene glycol, Ethylene glycol monomethyl ether, benzyl alcohol, pentane, hexane, cyclohexane, methyl pentane, heptane, octane, isooctane, benzene, toluene, xylene, ethyl Examples include rubenzene, tetralin and methylcyclohexane. Next, this is filtered and solid content on the filter paper is recovered.

  Next, a step of dissolving the obtained solid content (a catalyst in the case of washing with an organic solvent and a step of washing with an aqueous solution in the case of not performing the catalyst) in water to obtain an aqueous solution is provided. The blending ratio of the solid content and water is not particularly limited, but it is preferable to blend so that the water content is 50 to 500 parts by weight with respect to 100 parts by weight of the solid content.

  Next, the process of adjusting pH is provided. The difference from the pH shown when an unused catalyst in the same amount as the catalyst containing the used alkali metal salt is added to the same amount of water as that added to the aqueous solution used in the previous step is within 20%, preferably 10 The metal hydroxide is added to the aqueous solution obtained in the previous step so that it is within%. As the metal hydroxide, a strong base is preferable, and an alkali metal hydroxide is more preferable. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, the hydroxide containing the metal ion of the salt used for the catalyst is more preferable. For example, when 20 g of a catalyst (for example, tripotassium phosphate) was dissolved in 40 g of water in the previous step, 20 g of unused tripotassium phosphate was dissolved in 40 g of water. So that the pH (10.82 to 14.00) is within 20% above and below the pH (13.53) shown in the figure, and more preferably within 10% (12.18 to 14.00) above and below. In the process, a metal hydroxide (eg, potassium hydroxide) is added.

  Next, a step of separating the catalyst as a solid content is provided. For example, it may be concentrated using an evaporator, and heated and dried using a dryer, vacuum dryer, or desiccator.

  Hereinafter, the method for regenerating the transesterification catalyst of the present invention will be described in more detail, but the present invention is not limited to the following examples.

(Reproduction example 1)
An alkali metal salt catalyst (hereinafter referred to as a used catalyst) used for dissolving a resin having an ester bond is prepared. Next, the spent catalyst is dissolved in water to obtain an aqueous solution. Further, a metal hydroxide is added to this aqueous solution. The amount of metal hydroxide added is such that the same amount of unused catalyst as used catalyst is dissolved in the same amount of water as that added to the aqueous solution, and the pH is within 20% of the pH. To do. Next, the catalyst is separated as a solid content to obtain a regenerated catalyst.

(Reproduction example 2)
Prepare the spent catalyst. Next, the spent catalyst is dispersed in an organic solvent, washed and filtered, and the solid content remaining on the filter paper is recovered. Next, this solid content is added to an organic solvent having compatibility with water and washed and filtered to obtain a solid content remaining on the filter paper. Next, this solid content is dissolved in water and a metal hydroxide is added. The amount of metal hydroxide added is such that the same amount of unused catalyst as used catalyst is dissolved in the same amount of water as that added to the aqueous solution, and the pH is within 20% of the pH. To do. Next, the catalyst is separated as a solid content to obtain a regenerated catalyst.

(Reproduction example 3)
Prepare the spent catalyst. Next, this catalyst is dispersed in an organic solvent, washed and filtered, and the solid content remaining on the filter paper is recovered. Next, this solid content is added to an organic solvent having compatibility with water, washed and filtered, and the solid content remaining on the filter paper is recovered. Next, this solid content is dissolved in water to form an aqueous solution, and an acid is added to precipitate an alkali metal hydride salt, followed by filtration to recover the solid content on the filter paper. The amount of acid added should be within 20% of the pH when the same amount of pure alkali metal hydride as the spent catalyst is dissolved in the same amount of water. The obtained solid content is washed with a cleaning agent and filtered to collect the solid content on the filter paper. Next, this solid content is added to water to form an aqueous solution, and further a metal hydroxide is added. The addition amount of the metal hydroxide is set to a pH within 20% of the pH when an unused catalyst in the same amount as the used catalyst is dissolved in the same amount of water as the aqueous solution. Next, the catalyst is separated as a solid content to obtain a regenerated catalyst.

  Hereinafter, the method for regenerating the transesterification catalyst of the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following examples.

  The spent potassium phosphate catalyst was regenerated according to Examples 1-9. Furthermore, the solubility of the resin having an ester bond was evaluated using the regenerated catalyst.

(Standard pH A1)
20 g of potassium dihydrogen phosphate dried at 300 ° C. for 1 hour was weighed and dissolved in 40 g of water, and the pH was measured. The average value of the pH measured three times every 10 minutes was 3.92, which was designated as standard pH A1.

(Standard pH A2)
When the pH was measured in the same manner as the standard pH A1 except that 40 g of water was changed to 60 g of water, an average value of 3.95 was obtained, which was designated as the standard pH A2.

(Standard pH A3)
When the pH was measured in the same manner as the standard pH A1 except that 40 g of water was changed to 80 g of water, an average value of 4.00 was obtained, which was designated as standard pH A3.

(Standard pH A4)
When the pH was measured in the same manner as the standard pH A1 except that 40 g of water was changed to 100 g of water, an average value of 4.01 was obtained, which was designated as the standard pH A4.

(Standard pH B1)
20 g of tripotassium phosphate dried at 300 ° C. for 1 hour was weighed and dissolved in 40 g of water, and the pH was measured. The average value of pH measured three times every 10 minutes was 13.53, which was designated as standard pH B1.

(Standard pH B2)
When the pH was measured in the same manner as the standard pH B1 except that 40 g of water was changed to 60 g of water, an average value of 13.17 was obtained, which was designated as the standard pH B2.

(Standard pH B3)
When the pH was measured in the same manner as the standard pH B1 except that 40 g of water was changed to 80 g of water, an average value of 12.93 was obtained, which was designated as the standard pH B3.

(Standard pH B4)
When the pH was measured in the same manner as the standard pH B1 except that 40 g of water was changed to 100 g of water, an average value of 12.80 was obtained, which was designated as the standard pH B4.

(Example 1)
20 g of used potassium phosphate catalyst (K ₃ PO ₄ ) was dispersed in 20 g of benzyl alcohol (hereinafter referred to as BZA), washed and filtered, and the solid content on the filter paper was recovered. Next, the solid content was dispersed in 20 g of isopropyl alcohol (hereinafter referred to as IPA), washed and filtered to obtain a solid content on the filter paper. Next, the solid content was dissolved in 100 g of water, and 100 g of ethylene glycol (hereinafter referred to as EG) was added. Next, phosphoric acid was added to pH 4.06 (pH within 20% of the above standard pH A4), potassium dihydrogen phosphate was precipitated, filtered, and crystals of potassium dihydrogen phosphate were collected. Next, the crystals were washed with 40 g of IPA and filtered to recover the solid content on the filter paper. Next, the crystals were dissolved in 100 g of water and adjusted to pH 13.36 by adding potassium hydroxide (pH within 20% of the above standard pH B4). Next, it concentrated using the evaporator, and it heated and dried at 110 degreeC for 0.5 hour and 300 degreeC for 1 hour, and obtained the reproduction | regeneration catalyst. (Example 2)
In Example 1, the obtained solid content dissolved in 100 g of water was dissolved in 80 g of water, and when EG 100 g was added, EG 80 g was added, and phosphoric acid was added to pH 4.06 (the above standard pH A3 Other than the above, the crystal dissolved in 100 g of water was dissolved in 80 g of water and adjusted to pH 13.36 by adding potassium hydroxide (pH within 20% of the above standard pH B3). Obtained a regenerated catalyst as in Example 1.

(Example 3)
In Example 1, the obtained solid content dissolved in 100 g of water was dissolved in 60 g of water, and EG 60 g was added to the place where EG 100 g was added, and phosphoric acid was added to obtain pH 4.06 (the above standard pH A2). Other than the above, the crystal dissolved in 100 g of water was dissolved in 60 g of water and adjusted to pH 13.36 by adding potassium hydroxide (pH within 20% of the above standard pH B2). Obtained a regenerated catalyst as in Example 1.

Example 4
In Example 1, the obtained solid content dissolved in 100 g of water was dissolved in 40 g of water, and when EG 100 g was added, EG 40 g was added, and phosphoric acid was added to obtain pH 4.06 (the above standard pH A1). Other than the above, the crystal dissolved in 100 g of water was dissolved in 40 g of water, and adjusted to pH 13.36 by adding potassium hydroxide (pH within 20% of the above standard pH B1). Obtained a regenerated catalyst as in Example 1.

(Example 5)
In Example 1, the obtained solid content dissolved in 100 g of water was dissolved in 60 g of water, and where 100 g of EG was added, 60 g of acetone (hereinafter referred to as ACT) was added, and phosphoric acid was added to adjust the pH to 4 0.06 (pH within 20% of the above standard pH A2), the crystal dissolved in 100 g of water was dissolved in 60 g of water, and potassium hydroxide was added to adjust to pH 13.36 (the above standard pH). A regenerated catalyst was obtained in the same manner as in Example 1 except that the pH was within 20% of B2.

(Example 6)
In Example 5, a catalyst regenerated in the same manner as in Example 5 was obtained except that 60 g of ACT was added and 60 g of ethanol (hereinafter referred to as EtOH) was added.

(Example 7)
In Example 5, a catalyst regenerated in the same manner as in Example 5 was obtained except that 60 g of ACT was added and 60 g of isopropyl alcohol (hereinafter referred to as IPA) was added.

(Example 8)
In Example 5, a regenerated catalyst was obtained in the same manner as in Example 5 except that 60 g of ACT was not added.

Example 9
In Example 5, a catalyst was obtained in the same manner as in Example 5 except that the process from adding 60 g of ACT to the process of dissolving crystals in 60 g of water was not performed.

(Evaluation of solubility of resin having ester bond)
First, BZA was added to the treatment tank as a treatment solvent, and the regenerated catalysts of Examples 1 to 9 were added so as to be 0.33 mol / l. Further, a glass fiber reinforced unsaturated polyester (hereinafter referred to as FRP) is added as a resin having an ester bond, and the mixture is stirred with nitrogen gas at 190 ° C. for 4 hours to dissolve the FRP. Heated and dried at 210 degrees for hours. This was repeated three times. The mass of the resin was measured before and after each dissolution.

  The resin dissolution rate (%) was calculated from the following formula.

Dissolution rate (%) = {(resin weight before treatment) − (resin weight after treatment)} ÷ (resin weight before treatment) × 100
For comparison with the regenerated catalyst (Examples 1 to 9), an FRP was prepared using an unused potassium phosphate catalyst (Reference Example 1) and a used but not regenerated potassium phosphate catalyst (Reference Example 2). The dissolution rate of was determined.

According to Table 1, when the resin was dissolved using the regenerated catalyst of Examples 1 to 9, the dissolution rate was equal to or higher than that when the resin was dissolved using an unused catalyst.

  Furthermore, the potassium phosphate catalyst was regenerated according to Examples 10 to 13, and the solubility of FRP was evaluated using the regenerated catalyst.

(Example 10)
20 g of the used potassium phosphate catalyst was dissolved in 40 g of water. Next, potassium hydroxide was added to adjust the pH to 13.36 (pH within 20% of the standard pH B1). Next, it was concentrated using an evaporator and heated and dried at 110 ° C. for 0.5 hour and 300 ° C. for 1 hour to obtain a regenerated catalyst.

(Example 11)
20 g of used potassium phosphate catalyst was dispersed in 20 g of benzyl alcohol (hereinafter referred to as BZA), washed and filtered, and the solid content on the filter paper was recovered. Next, the solid content was dispersed in 20 g of IPA, washed and filtered, and the solid content on the filter paper was recovered. Next, the solid content was dissolved in 40 g of water. Further, potassium hydroxide was added to adjust the pH to 13.36 (pH within 20% of the standard pH B1). Next, it was concentrated using an evaporator and heated and dried at 110 ° C. for 0.5 hour and 300 ° C. for 1 hour to obtain a regenerated catalyst.

Example 12
In Example 11, after the solid content was dissolved in 40 g of water, 60 g of ACT was added, and phosphoric acid was added to adjust the pH to 4.06 (pH within 20% of the standard pH A1). Crystals of potassium dihydrogen acid are collected, dispersed in 40 g of IPA, washed and filtered. Crystals on the filter paper are collected and dissolved in 40 g of water, and then potassium hydroxide is added to adjust the pH to 13.36. A regenerated catalyst was obtained in the same manner as in Example 11 except that it was adjusted (pH within 20% of the standard pH B1).

(Example 13)
In Example 12, a regenerated catalyst was obtained in the same manner as in Example 12 except that 40 g of EG was added instead of 60 g of ACT.

(Evaluation of solubility of resin having ester bond)
Similarly to Examples 1-9, the FRP dissolution rate when the regenerated catalyst of Examples 10-13 was used was determined. For comparison with the regenerated catalyst (Examples 10 to 13), an unused potassium phosphate catalyst (Reference Example 3) and a used and unregenerated potassium phosphate catalyst (Reference Example 4) were used. The dissolution rate of FRP was determined.

  According to Table 2, when the resin was dissolved using the regenerated catalyst of Examples 10 to 13, the dissolution rate was equal to or higher than that when the resin was dissolved using the unused catalyst (Reference Example 3). .

Claims (6)

Preparing a catalyst containing a used alkali metal salt as a transesterification catalyst;
Dissolving the catalyst in water to obtain an aqueous solution;
Metal is used so that the difference from the pH shown when an unused catalyst in the same amount as the catalyst containing the used alkali metal salt is added to the same amount of water as that added to the aqueous solution is within 20%. Adding hydroxide to adjust pH;
A method for regenerating a transesterification reaction catalyst comprising a step of separating the catalyst as a solid content.   The regeneration method according to claim 1, further comprising a step of washing the catalyst with an organic solvent after the step of preparing the catalyst and before the step of obtaining the aqueous solution.   The regeneration method according to claim 1, further comprising a step of adding an acid to precipitate a solid after the step of preparing the catalyst and before the step of obtaining the aqueous solution.   The regeneration method according to claim 2, further comprising a step of adding an acid to precipitate a solid after the step of washing with the organic solvent and before the step of obtaining the aqueous solution.   The regeneration method according to any one of claims 1 to 4, wherein the alkali metal salt is tripotassium phosphate.   The regeneration method according to any one of claims 1 to 5, wherein a catalyst containing a used alkali metal salt is used for dissolving a fiber-reinforced plastic.