JP2021123664A - Sulfidizing agent and method for producing polyarylene sulfide resin - Google Patents

Abstract

To recover and reduce unreacted sulfidizing agent included in discharged waste water generated by polymerization reaction of polyarylene sulfide resin (PAS resin) followed by washing of the PAS resin with water or hot water, and to provide a method for producing a PAS resin having a higher molecular weight by reusing the recovered unreacted sulfidizing agent as a raw material of the PAS resin.SOLUTION: In a first embodiment, a method for producing a sulfidizing agent is provided, including the steps of: washing a mixture including a PAS resin, an alkali metal halide and an unreacted sulfidizing agent with water thereby obtaining an aqueous solution including an alkali metal halide, a thiophenol derivative and an unreacted sulfidizing agent; adding a metal carbonate and/or a metal hydrogen carbonate and an acid to the obtained aqueous solution, adjusting pH to more than 4.5 and 8 or less, thereby producing hydrogen sulfide; recovering the produced hydrogen sulfide; reacting the recovered hydrogen sulfide with an alkali metal hydroxide. In a second embodiment, a method for producing a PAS resin is provided which is identical to the method in the first embodiment except that the sulfidizing agent is reacted with a polyhalo aromatic compound in the presence of an organic amide solvent.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a sulfidizing agent and a method for producing a polyarylene sulfide resin using the same. More specifically, a method for separating, purifying and producing a sulfidizing agent from waste water discharged in the manufacturing process of a polyarylene sulfide resin, and a method for reusing the obtained sulfidizing agent as a part of a raw material of a polyarylene sulfide resin. Regarding the manufacturing method.

Polyphenylene sulfide resin (PAS resin) represented by polyphenylene sulfide resin (PPS resin) has excellent heat resistance, chemical resistance, etc., and is widely used in electrical and electronic parts, automobile parts, water heater parts, fibers, film applications, etc. Has been done. In particular, in applications such as packings for lithium ion batteries and gasket members, ultra-high molecular weight polyarylene sulfide resins have been widely used in recent years because of their excellent toughness and moldability.

Polyarylene sulfide resin is a polyhaloaromatic compound in an aproton polar solvent such as N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP), alkali metal sulfide and / or alkali metal hydrosulfide. It can be obtained by a polymerization reaction with a substance (hereinafter sometimes referred to as a sulfidizing agent), but together with the polyarylene sulfide resin of the target substance, a solvent, an alkali metal hydrosulfide remaining without a polymerization reaction, or an alkali metal sulfurization. A crude reaction product containing by-products such as a sulfide agent such as a substance, an alkali metal halide typified by sodium chloride, another alkali metal-containing inorganic salt, an oligomer produced by a side reaction and a derivative thereof can be obtained. The crude reaction product after the polymerization reaction is taken out into a suitable container, and the solvent in the crude reaction product is separated by a solvent removal treatment using a suitable solid-liquid separator such as a solvent drying device, a filter, or a centrifuge. It is recovered (this operation is called desolvation).

Further, since the reaction product obtained after the desolvation treatment contains an alkali metal halide, other alkali metal-containing inorganic salts and by-products together with the polyarylene sulfide resin as the target substance, washing with water and filtration are repeated. These are removed. Generally, there are a water washing method performed at a temperature of less than 100 ° C. and a hot water washing method performed at a high temperature and high pressure of 100 ° C. or higher. The polyarylene sulfide obtained after washing with water or hot water is separated by a filter, a centrifugal filter, or the like, then dried, and if necessary, heat-treated to carry out a cross-linking reaction to obtain a product.

On the other hand, the wastewater obtained after washing with water or hot water has been treated as industrial waste and has not been effectively utilized. However, since the wastewater has a high COD load, it has been required to reduce the COD substance in order to reduce the environmental load.

As a treatment method for reducing COD substances in wastewater, for example, a wastewater treatment method is characterized in that an acidic flocculant is added to wastewater to adjust the pH, the COD substances are insolubilized, and the insolubilized COD substances are separated. Etc. are known (see Patent Document 1). However, this method was introduced from an agglutination reaction tank in which wastewater from the purification process was introduced, a mixing function, a pH indicator controller, and a pH adjustment and agglutination treatment were possible, and the agglutination reaction tank. Since the method is to separate the insolubilized COD substance using a continuous centrifugation device, the separated COD substance has a high water content and cannot be reused as a raw material for producing a polyarylene sulfide resin. Moreover, since the COD substance separated by the acidic flocculant was precipitated in a large floc shape, it had to be treated as industrial waste, which was not preferable.

Therefore, when the wastewater discharged by washing with water or hot water after the polymerization reaction was examined in detail, the sulfidizing agent remaining unreacted remained in about 3 to 5 mol% of the charged amount in terms of sulfur atoms. It is clear that the unreacted sulfidizing agent is one of the factors that increase the COD value of wastewater, and that it is also a cause of sulfur atom loss (decrease in raw material basic unit). became.

Therefore, in the wastewater discharged by washing with water or hot water after the polymerization reaction, in addition to the sulfidizing agent remaining without polymerization, by-products such as alkali metal halides, oligomers produced by the side reaction and derivatives thereof. Is contained, the unreacted sulfidizing agent is once gasified by adding an acid, separated and recovered to remove and recover the unreacted sulfidizing agent from the wastewater, thereby removing the unreacted sulfidating agent from the wastewater. It has been proposed that COD can be reduced and that it can be reused as a raw material for producing a polyarylene sulfide resin (see Patent Document 2). However, when the recovered product containing the unreacted sulfidating agent is reused as a raw material for producing the polyarylene sulfide resin, there is still room for improvement in increasing the molecular weight of the obtained polyarylene sulfide resin.

Japanese Unexamined Patent Publication No. 2003-275773 JP-A-2015-218214

Therefore, the problem to be solved by the present invention is to provide a method for recovering the unreacted sulfidizing agent contained in the waste water discharged by washing with water or hot water after the polymerization reaction of the polyarylene sulfide resin, and further, the recovered unreacted sulfidizing agent. An object of the present invention is to provide a method for producing a polyarylene sulfide resin having a higher molecular weight when the reactive sulfidizing agent is reused as a polymerization raw material for the polyarylene sulfide resin.

As a result of various studies, the inventors of the present application recovered the unreacted sulfidizing agent contained in the waste water discharged by washing with water or hot water after the polymerization reaction of the polyarylene sulfide resin. , Thiophenol or a derivative thereof, thereby inhibiting the increase in the amount of polyarylene sulfide resin when the recovered product containing the above-mentioned unreacted sulfidating agent is reused as a raw material for producing the polyarylene sulfide resin. Furthermore, we have found a method that can easily and productively reduce the thiophenol concentration in the recovered product, and have solved the above-mentioned problems.

That is, in the present invention, [1] at least, after contacting water with a mixture (a) containing a polyarylene sulfide resin, an alkali metal halide and a sulfidizing agent, the polyarylene sulfide resin is separated and removed to at least. , A step (1) of obtaining an aqueous solution (b) containing an alkali metal halide, a thiophenol derivative and a sulfidizing agent.
To the obtained aqueous solution (b), at least one selected from the group consisting of a metal carbonate and a metal hydrogen carbonate exhibiting solubility in the aqueous solution (b) at 25 ° C. is added, and at least an alkali is added. Step (2) of adding an acid to an aqueous solution (b) containing a metal halide, a thiophenol derivative and a sulfide agent to adjust the pH in the range of more than 4.5 to 8 or less to generate hydrogen sulfide.
Step (3) to recover the generated hydrogen sulfide, and
Step of reacting the recovered hydrogen sulfide with the alkali metal hydroxide (4),
The present invention relates to a method for producing a sulfidizing agent, which comprises the above.

Further, in the present invention, [2] the ratio of thiophenol recovered in the step (3) is less than 100 mol with respect to 100 mol of the thiophenol derivative contained in the aqueous solution (b) in the step (3). The method for producing a sulfidizing agent according to the above [1], which is in the range of.
Further, in the present invention, [3] at least the mixture (a) containing a polyarylene sulfide resin, an alkali metal halide and a sulfidizing agent is used.
At least a polyarylene sulfide resin, an alkali metal halide, the aprotonic polar solvent, a thiophenol derivative and sulfide obtained after reacting a polyhalo aromatic compound with a sulfide agent in an aprotonic polar solvent. The production method according to the above [1] or [2], which is a crude reaction mixture containing an agent, or a reaction mixture obtained by solid-liquid separation of the aprotic polar solvent from the crude reaction mixture.
Further, in the present invention, [4] the sulfidizing agent used when reacting a polyhalo aromatic compound with a sulfidizing agent in an aprotic polar solvent is a hydrous sulfide at least in the presence of an aprotic polar solvent. The production method according to the above [3], which is obtained through a dehydration step of dehydrating the agent.

Further, in the present invention, after the step (4) of reacting the recovered hydrogen sulfide with the alkali metal hydroxide, hydrogen sulfide is added to the unreacted alkali metal hydroxide to obtain the hydrogen sulfide. The production method according to the above [1], which comprises a step (5) of reacting with an unreacted alkali metal hydroxide.

Further, the present invention is characterized by having [6] a step of recovering hydrogen sulfide produced in the dehydration step according to the above [4] and then reacting with an alkali metal hydroxide to obtain a sulfidizing agent. Regarding the method for producing the agent.

Further, in the present invention, after the step of [7] reacting with an alkali metal hydroxide to obtain an alkali metal hydrosulfide and / or an alkali metal sulfide, hydrogen sulfide is added to the unreacted alkali metal hydroxide. The present invention relates to the method for producing a sulfidizing agent according to the above [6], which comprises a step of reacting the hydrogen sulfide with an unreacted alkali metal hydroxide.

Further, in the present invention, [8] a sulfidizing agent obtained by dehydrating a hydrous sulfidizing agent in the presence of an organic amide solvent is reacted with a polyhalo aromatic compound in the presence of an organic amide solvent to obtain a polyarylene sulfide resin. In the method for producing a polyarylene sulfide resin to be produced, the sulfidizing agent obtained by the production method according to any one of the above [1] to [5] and / or the above-mentioned [ 6] or [7] The present invention relates to a method for producing a polyarylene sulfide resin, which comprises a step of adding a sulfidizing agent obtained by the production method.

According to the present invention, it is possible to provide a method for recovering an unreacted sulfide agent contained in waste water discharged by washing with water or hot water after a polymerization reaction of a polyarylene sulfide resin, and further, the recovered unreacted sulfide agent can be used. It is possible to provide a method for producing a polyarylene sulfide resin having a higher molecular weight when the polyarylene sulfide resin is reused as a polymerization raw material.

In the method for producing a sulfidizing agent of the present invention, at least the mixture (a) containing a polyarylene sulfide resin, an alkali metal halide and a sulfidizing agent is brought into contact with water, and then the polyarylene sulfide resin is separated and removed. In the step (1) of obtaining an aqueous solution (b) containing at least an alkali metal halide, a thiophenol derivative and a sulfidizing agent, the obtained aqueous solution (b) was added to the obtained aqueous solution (b) at 25 ° C. with respect to the aqueous solution (b). At least one selected from the group consisting of soluble metal carbonates and metal hydrogen carbonates is added, and an acid is further added to the aqueous solution (b) containing at least an alkali metal halide, a thiophenol derivative and a sulfide agent. The step of adjusting the pH to a range of more than 4.5 to 8 or less to generate hydrogen sulfide (2), the step of recovering the generated hydrogen sulfide (3), and the recovered hydrogen sulfide and alkali metal water. It is characterized by having a step (4) of reacting with an oxide.

In step (1), water is brought into contact with a mixture (a) containing at least a polyarylene sulfide resin, an alkali metal halide, a thiophenol derivative and a sulfidizing agent to form an alkali metal halide, a thiophenol derivative and sulfidation. A step of separating the aqueous solution (b) containing the agent and the polyarylene sulfide resin, and then removing the polyarylene sulfide resin to obtain an aqueous solution (b) containing at least an alkali metal halide, a thiophenol derivative and a sulfidizing agent. Is.

The mixture (a) used in the step (1) is particularly limited as long as it is a mixture containing at least a thiophenol derivative such as a polyarylene sulfide resin, an alkali metal halide, thiophenol or an alkali metal salt thereof, and a sulfidizing agent. However, preferably, a reaction mixture containing at least a polyarylene sulfide resin, an alkali metal halide, the thiophenol derivative and a sulfidizing agent, which is obtained in the method for producing a polyarylene sulfide resin used in the present invention described later. It is preferable to use it.

The mixture (a) is brought into contact with water to remove the polyarylene sulfide resin from the mixture (a) to obtain an aqueous solution (b) containing at least an alkali metal halide, a thiophenol derivative and a sulfidizing agent. The method is not particularly limited as long as the effect of the present invention is not impaired, but it is solid-liquid by contacting with water (hereinafter, may be referred to as "washing with water") and then filtering out the polyarylene sulfide resin. A method of separation can be mentioned.

As a method of solid-liquid separation by contacting the mixture (a) with water and then filtering the polyarylene sulfide resin, for example, aprotonicity is obtained from the crude reaction mixture obtained in the PAS production step described later. A method of adding water to a reaction slurry obtained by solid-liquid separation of a polar solvent, stirring the mixture, and then filtering using a filtration device, a filtration residue containing water obtained by the above-mentioned filtration (hereinafter referred to as "hydrous cake"). A method of adding water again to form a slurry and then filtering the mixture, or a method of adding water again while the hydrous cake is held in the filter and filtering the mixture can be mentioned.

At the time of washing with water, the amount of water added to the mixture (a) is preferably in the range of 2 to 10 times the theoretical yield of the finally obtained polyarylene sulfide, and is preferable from the viewpoint of washing efficiency. The amount of water is preferably divided into 2 to 10 times, preferably 2 to 4 times and subjected to washing with water. The washing with water is carried out under a nitrogen or air atmosphere, preferably at a water temperature of 20 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 70 ° C. or higher, preferably 300 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 90 ° C. Perform within the following range. The washing with water can be repeated once or a plurality of times. When washing with water repeatedly a plurality of times, the atmosphere and temperature conditions may be the same or different.

Since trace amounts of alkali metal halides, thiophenol derivatives, and sulfidizing agents may remain in the filtered polyarylene sulfide resin without being sufficiently washed, the temperature is further 100 ° C to 280 ° C. After contacting with water in the range of (b), solid-liquid separation was performed (hereinafter, may be referred to as "hot water washing"), the polyarylene sulfide resin was separated and removed by filtration or the like, and the obtained filtrate was obtained as the aqueous solution (b). ), Which is preferable from the viewpoint of reducing the COD load and suppressing the loss of sulfur atoms (decrease in raw material basic unit).

The temperature of hot water washing is preferably in the range of 100 ° C. or higher, more preferably 120 ° C. or higher, preferably 280 ° C. or lower, more preferably 275 ° C. or lower, and the alkali metal halide or sulfide remaining in the resin. This is preferable because the extraction efficiency of the agent is good. More specifically, the extraction treatment is carried out with hot water at 140 to 260 ° C. under a pressure of the gas phase in the reactor, more preferably 0.2 to 4.6 MPa (gauge pressure, the same applies hereinafter). Is preferable.

Specific methods for performing such hot water washing include a method in which the polyarylene sulfide resin filtered after the water washing is washed with water in a pressure vessel under predetermined pressure and temperature conditions under stirring. The amount of water during hot water washing is 1.5 to 10 times that of the mass of polyarylene sulfide, because the extraction efficiency of the alkali metal halide, thiophenol derivative, and sulfidizing agent is good. Preferably, this amount of hot water may be washed with hot water in two or more times. For example, when hot water washing is repeated twice, filtration is performed between the first hot water washing and the second hot water washing, and the alkali metal halide, the thiophenol derivative and the sulfidizing agent extracted in the first hot water washing are used. It is preferable to filter out the polyarylene sulfide resin. Further, the above-mentioned water washing may be carried out by performing filtration after performing hot water washing once. This operation can also further promote the separation and removal of the alkali metal halide, the thiophenol derivative and the sulfidizing agent from the polyarylene sulfide resin. The conditions of the first hot water washing step and the second hot water washing step can be arbitrarily selected from the above conditions, but the temperature of the first hot water washing step is, for example, a temperature in the range of 120 ° C. to 200 ° C. After setting, the highly alkaline filtrate is first filtered and removed, and then the temperature of the second hot water washing step is set to a temperature higher than the temperature of the first hot water washing step, for example, a temperature in the range of 150 ° C. to 275 ° C. From the viewpoint of chemical resistance of the apparatus used in the hot water washing, it is preferable to carry out the above.

In the step (1), the pH can be adjusted by adding an acid or a base to the aqueous solution (b), and the pH after washing with hot water is particularly in the range of 11.0 or more and less than 13.0. It is preferable to control to. Examples of the acid used at that time include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid, oxalic acid and the like, and among these, carbonic acid, acetic acid and oxalic acid are preferable. Further, carbon dioxide gas may be introduced and brought into contact under normal pressure or pressure. On the other hand, examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium carbonate, ammonium carbonate, sodium phosphate and the like, and among these, sodium hydroxide is preferable.

In step (1), it is also possible to use a water washing tank having a stirrer and a centrifuge for solid-liquid separation, but the container has a stirring blade inside and a filter for filtration is arranged at the bottom. It can also be carried out in a container having a mixed function. Further, even in hot water washing exceeding 100 ° C., a water washing tank having a stirrer for hot water washing and a centrifuge after that for filtering at 20 to 100 ° C. can be used, but stirring is performed inside the container. It is also possible to carry out in a container having wings and having a closed type or a closed mixing function in which a filter for filtration is arranged at the bottom. In the present invention, water washing or hot water washing may be continuously performed, or may be performed in a batch manner.

In step (2), at least one selected from the group consisting of a metal carbonate and a metal hydrogen carbonate which are soluble in the aqueous solution (b) at 25 ° C. is added to the obtained aqueous solution (b). Further, an acid is added to an aqueous solution (b) containing at least an alkali metal halide, a thiophenol derivative and a sulfide agent to adjust the pH in the range of more than 4.5 to 8 or less to generate hydrogen sulfide. It is a process.
As at least one selected from the group consisting of metal carbonate and metal hydrogen carbonate exhibiting solubility in the aqueous solution (b) at 25 ° C., for example, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate, carbonate. Examples include potassium hydrogen. The amount to be added at least one selected from the group consisting of the metal carbonate and the metal hydrogen carbonate which are soluble in the aqueous solution (b) at 25 ° C. is not particularly limited, but can be obtained, for example, in the step (1). Per 1 mol of sulfur contained in the aqueous solution (b), preferably 0.05 mol or more, more preferably 0.10 mol or more, still more preferably 0.30 mol or more, preferably 1.00 mol or less, and more. The range is preferably 0.75 mol or less, more preferably 0.50 mol or less.
Another aspect of the step (2) is a step of adding an alkali metal carbonate to the thiophenol derivative contained in the aqueous solution (b) in the step (1) to induce the thiophenol into the alkali metal salt. By producing more alkali metal salts, the alkali metal salts of thiophenols are less likely to evaporate than thiophenols, and the proportion of thiophenols recovered with hydrogen sulfide in step (3). Can be suppressed.

Examples of the acid used in the step (2) include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid and the like, and among these, hydrochloric acid is preferable. The pH range of the aqueous solution (b) is not particularly limited as long as hydrogen sulfide is produced by adding an acid, but more hydrogen sulfide is produced while thiophenol is produced more. Since it is preferable that the conditions are such that the alkali metal salt can be suppressed and easily produced, the condition is more than 4.5, preferably 5.0 or more, more preferably 5.5 or more, preferably 8.0 or less, more preferably 7. The range is 0.0 or less, more preferably 6.0 or less. The acid is preferably added in the range of 0 ° C. or higher, more preferably 10 ° C. or higher, preferably 60 ° C. or lower, more preferably 40 ° C. or lower, and the pressure is also in the range of 0 to 1.0 Pa. Is preferable.

The step (3) is a step of recovering the produced hydrogen sulfide because the hydrogen sulfide produced in the step (2) is evaporated and separated from the aqueous solution (b). The ratio of hydrogen sulfide recovered in the step (3) is preferably in the range of 5 mol or more, more preferably 5 mol or more, with respect to 100 mol of the sulfidizing agent contained in the aqueous solution (b) in the step (2). The range is 20 mol or more, more preferably 50 mol or more, and the upper limit is not particularly limited, but preferably 100 mol or less, more preferably 90 mol or less, still more preferably 80 mol. The range is less than a mole. In addition, thiophenol may also be recovered in the step (3). The ratio of the thiophenol derivative recovered in the step (3) is preferably in the range of less than 100 mol, more preferably to 100 mol of the thiophenol derivative contained in the aqueous solution (b) in the step (2). Is in the range of 90 mol or less, more preferably in the range of 80 mol or less, and further, the lower limit is not particularly limited, but is preferably in the range of 30 mol or more, more preferably in the range of 40 mol or more, still more preferably. The range is 50 mol or more. Within this range, polymerization inhibition can be suppressed when the polyarylene sulfide resin is reused as a polymerization raw material, which is preferable.

Further, the step (4) is a step of reacting the recovered hydrogen sulfide with the alkali metal hydroxide. Steps (3) and (4) can be performed simultaneously or separately.

When the step (3) and the step (4) are performed at the same time, for example, the volatilized hydrogen sulfide (with the thiophenol when the thiophenol is recovered) is discharged to the outside of the reaction system of the step (2). , A method of absorbing and recovering an aqueous solution containing an alkali metal hydroxide and at the same time reacting hydrogen sulfide with an alkali metal hydroxide to produce a sulfidizing agent can be mentioned. In this case, as the alkali metal hydroxide used, the same one used in the PAS polymerization step described above can be used. The amount of alkali metal hydroxide used varies depending on the temperature and pressure at which hydrogen sulfide is absorbed, so it cannot be unconditionally specified, but it must be at least an amount that can sufficiently absorb and react with the total amount of volatilized hydrogen sulfide. Is desirable. Generally, when hydrogen sulfide is absorbed and reacted at normal temperature and pressure, it is preferably 1 mol or more, preferably 1 to 2 mol, with respect to 1 mol of sulfur atoms of volatilized hydrogen sulfide. More preferable. The concentration of alkali metal hydroxide in the aqueous solution also varies depending on the temperature and pressure at which hydrogen sulfide is absorbed and reacted, so it cannot be unconditionally specified, but it is preferably 5 wt% or more, more preferably 10 wt% or more. The range is preferably 49 wt% or less, more preferably 45 wt% or less. Further, since the temperature at which hydrogen sulfide is absorbed and reacted in an aqueous solution containing an alkali metal hydroxide varies depending on the pressure, it cannot be unconditionally defined, but it is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. It is preferably in the range of 200 ° C. or lower, more preferably 150 ° C. or lower. Further, since the pressure at which hydrogen sulfide is absorbed and reacted in an aqueous solution containing an alkali metal hydroxide varies depending on the temperature, it cannot be unconditionally defined, but it is preferably 0 Pa or more, preferably 1.0 Pa or less. More preferably, it is in the range of up to 0.5 Pa.

On the other hand, when the step (3) and the step (4) are performed separately, for example, the volatilized hydrogen sulfide (if the thiophenol is recovered, the thiophenol is discharged) is discharged to the outside of the system to generate hydrogen sulfide. After performing a step of absorbing and recovering a solvent known to absorb hydrogen sulfide, for example, an organic amide solvent, an alkali metal hydroxide is added to the recovered solvent containing hydrogen sulfide to obtain hydrogen sulfide and an alkali metal. Examples thereof include a method of reacting with a hydroxide to form an alkali metal hydrosulfide. In this case, examples of the solvent known to absorb hydrogen sulfide include an organic amide solvent. Further, as the organic amide solvent, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactum, ε- Amides and ureas such as caprolactam, hexamethylphosphoramide, N-dimethylpropylene urea, 1,3-dimethyl-2-imidazolidinone acid, etc. can be mentioned, and among these, N-methyl-2-pyrrolidone, 2- Amides having an aliphatic cyclic structure of pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropylene urea, and 1,3-dimethyl-2-imidazolidinone acid are preferable. N-Methyl-2-pyrrolidone is more preferred.

The amount of the solvent known to absorb hydrogen sulfide varies depending on the temperature and pressure at which hydrogen sulfide is absorbed, so it cannot be unconditionally specified, but it can sufficiently absorb the entire amount of volatilized hydrogen sulfide. It is desirable that it is more than the amount. Generally, when hydrogen sulfide is absorbed at normal temperature and pressure, it is preferably in the range of 1 to 30 kg with respect to 1 mol of sulfur atoms of the volatilized hydrogen sulfide. Although the temperature and pressure at which hydrogen sulfide is absorbed by a solvent known to absorb hydrogen sulfide cannot be unconditionally defined, the absorption temperature is preferably in the range of 0 to 200 ° C, preferably 10 to 150 ° C. The range is more preferable, while the pressure is preferably from 0 Pa or more, preferably 1.0 Pa or less, and more preferably 0.5 Pa or less. Then, an aqueous solution containing an alkali metal hydroxide is added to the recovered solvent containing hydrogen sulfide to react the hydrogen sulfide with the alkali metal hydroxide to produce an alkali metal hydroxide. At that time, it is desirable that the amount of the alkali metal hydroxide added is equal to or greater than the amount capable of sufficiently reacting the total amount of hydrogen sulfide absorbed in the solvent. Generally, when hydrogen sulfide is absorbed at normal temperature and pressure, it is preferably 1 mol or more, preferably 1 to 2 mol, with respect to 1 mol of sulfur atom of hydrogen sulfide absorbed in the solvent. More preferable. The concentration of alkali metal hydroxide in the alkaline aqueous solution added to the solvent also differs depending on the temperature and pressure at which hydrogen sulfide is absorbed, so it cannot be unconditionally specified, but it is preferably 5 wt% or more, more preferably 10 wt% or more. Therefore, it is preferably in the range of 49 wt% or less, more preferably 45 wt% or less. Further, since the temperature at which hydrogen sulfide absorbed in the solvent and the alkali metal hydroxide are reacted varies depending on the pressure, it cannot be unconditionally defined, but the temperature is preferably 0 ° C. or higher, more preferably 0 ° C. or higher. The temperature ranges from 10 ° C. or higher, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. The pressure is also preferably in the range of 0 Pa or more, preferably 1.0 Pa or less, and more preferably 0.5 Pa or less, although it cannot be unconditionally defined.

The step (3) may be a continuous type or a batch type. Since the absorption rate of hydrogen sulfide of alkali metal hydroxide to aqueous solution or organic amide solvent is fast, general ones such as a filling tower with a circulation pump can be used, and liquid-filled type and bubbling type can be sufficiently used. be. Further, when the step (3) and the step (4) are performed at the same time, the step (4) can be performed in the same device as the step (3), and the step (3) and the step (4) are performed separately. In this case, even if step (4) is performed in the same device as step (3), the hydrogen sulfide recovered in step (3) is transferred to another device, for example, a reaction vessel with a stirring blade, a vessel, a drum, or the like. Later, an aqueous solution containing an alkali metal hydroxide may be added and reacted.

As described above, in steps (3) and (4), the amount of alkali metal hydroxide that is sufficient to absorb and react with the entire amount of recovered hydrogen sulfide is used, so that the excess alkali metal hydroxide is unreacted. It will remain in the system as it is. Therefore, after the step (4), there is a step (5) of adding hydrogen sulfide to the unreacted alkali metal hydroxide to react the unreacted alkali metal hydroxide with the hydrogen sulfide. Is preferable. The amount of hydrogen sulfide added is preferably in the range of 0.5 to 1 mol with respect to 1 mol of the alkali metal hydroxide remaining unreacted. By reacting with hydrogen sulfide in the above range, 0.5 to 1 mol of alkali metal hydrosulfide and / or alkali metal sulfide is produced per 1 mol of residual alkali metal hydroxide.

The ratio of the alkali metal hydrosulfide produced through the step (4) or the step (5) to the alkali metal sulfide is the amount of the alkali metal hydroxide to be reacted with hydrogen sulfide, the reaction time, the temperature, and the pressure. Since it changes according to the above, it cannot be unconditionally specified, and any of alkali metal hydrosulfide and alkali metal sulfide can be re-used as a sulfidizing agent which is a polymerization raw material of polyarylene sulfide resin described later. Since it is available, the alkali metal hydrosulfide and the alkali metal sulfide may be in any ratio in the range of 0/100 to 100/0 on a mass basis.

As the mixture (a) containing at least a polyarylene sulfide resin, an alkali metal halide, a thiophenol derivative and a sulfidizing agent used in the present invention, those obtained by the following method for producing a polyarylene sulfide resin can be used. can. Further, the alkali metal hydrosulfide and / or alkali metal sulfide obtained through the above steps (1) to (4) or steps (1) to (5) can be used as a sulfidizing agent in the following polyarylene. In the method for producing a sulfide resin, it can be used as at least a part of a polymerization raw material. At that time, since the thiophenol to be contained together with the alkali metal hydrosulfide and / or the alkali metal sulfide can be reduced or absent, the polymerization inhibition of the polyarylene sulfide resin can be suppressed. It can be done and is preferable.

The PAS polymerization step, that is, the method for producing the polyarylene sulfide resin used in the present invention, comprises mixing an aprotic polar solvent, a polyhalo aromatic compound, and a sulfide agent, and polyhalo fragrance in the aprotonic polar solvent. A crude reaction mixture containing at least a polyarylene sulfide resin, a sulfide agent remaining without polymerization, an alkali metal halide, and an aprotonic polar solvent is obtained by polymerizing a group compound and a sulfide agent. The PAS polymerization step obtained, a reaction containing at least a polyarylene sulfide resin obtained by solid-liquid separation of an aprotonic polar solvent from the crude reaction mixture, a sulfide agent remaining without polymerization, and an alkali metal halide. Examples thereof include a method of obtaining a mixture through a PAS / solvent solid-liquid separation step. At that time, the crude reaction mixture or the reaction mixture contains a thiophenol derivative as a by-product.

Here, in the present invention, the polyhalo aromatic compound is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to the aromatic ring, and specifically, p-dichlorobenzene, o. -Dichlorobenzene, m-Dichlorobenzene, Trichlorobenzene, Tetrachlorobenzene, Dibrombenzene, Diiodobenzene, Tribrombenzene, Dibromnaphthalene, Triiodobenzene, Dichlordiphenylbenzene, Dibrom diphenylbenzene, Dichlor Includes dihaloaromatic compounds such as benzophenone, dibrom benzophenone, dichlorodiphenyl ether, dibrom diphenyl ether, dichlorodiphenyl sulfide, dibrom diphenyl sulfide, dichlorobiphenyl, dibrombiphenyl and mixtures thereof, and blocks these compounds. It may be copolymerized. Among these, benzene dihalogenates are preferable, and those containing 80 mol% or more of p-dichlorobenzene are particularly preferable. Further, for the purpose of increasing the viscosity of the polyarylene sulfide resin by forming a branched structure, a polyhaloaromatic compound having three or more halogen substituents in one molecule may be used as a branching agent, if desired. Examples of such polyhalo aromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like. Further, polyhaloaromatic compounds having a functional group having an active hydrogen such as an amino group, a thiol group and a hydroxyl group can be mentioned, and specifically, 2,6-dichloroaniline and 2,5-dichloroaniline. , 2,4-Dichloroaniline, 2,3-dichloroaniline and other dihaloanilines; 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,4,6-trichloroaniline, 3, Trihaloanilines such as 4,5-trichloroaniline; dihaloaminodiphenyl ethers such as 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2', 4-dichlorodiphenyl ether And compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof and the like are exemplified. Further, the active hydrogen-containing polyhalo in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is replaced with another inactive group, for example, a hydrocarbon group such as an alkyl group. Aromatic compounds can also be used.

Among these various active hydrogen-containing polyhaloaromatic compounds, an active hydrogen-containing dihaloaromatic compound is preferable, and dichloroaniline is particularly preferable.

Examples of the polyhaloaromatic compound having a nitro group include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether and the like. Dihalonitrodiphenyl ethers; dihalonitrodiphenylsulfones such as 3,3'-dinitro-4,4'-dichlorodiphenylsulfone; 2,5-dichloro-3-nitropyridine, 2-chlor-3,5 -Mono or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalene and the like.

In addition, examples of the sulfidizing agent in the present invention include alkali metal sulfides and / or alkali metal hydrosulfides.

The alkali metal sulfide includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof. Such alkali metal sulfides can be used as hydrates, aqueous mixtures or anhydrides. Alkali metal sulfides can also be derived by the reaction of alkali metal hydrosulfides with alkali metal hydroxides. Normally, a small amount of alkali metal hydroxide may be added in order to react with the alkali metal hydrosulfide and the alkali metal thiosulfate present in a trace amount in the alkali metal sulfide.

The alkali metal hydrosulfide includes lithium hydrosulfide, sodium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture thereof. Such alkali metal hydrosulfides can be used as hydrates, aqueous mixtures or anhydrides.

Further, the alkali metal hydrosulfide is used together with an alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, but these may be used alone or in combination of two or more. May be used. Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable because they are easily available, and sodium hydroxide is particularly preferable.

As described above, the alkali metal hydrosulfide and / or the alkali metal sulfide obtained through the steps (1) to (4) or the steps (1) to (5) is also poly as a sulfidizing agent. It can be reused as a raw material in the polymerization reaction of the arylene sulfide resin.

In the method for producing a polyarylene sulfide resin used in the present invention, a hydrous sulfide agent can also be used as a raw material, and in that case, a step of dehydrating the hydrous sulfide agent at least in the presence of an aprotonic polar solvent is performed. It is preferable to use it for the polymerization reaction of the polyarylene sulfide resin. Further, when the amount of the aprotic polar solvent charged is small, for example, when it is less than 1 mol with respect to 1 mol of the sulfur atom of the sulfidizing agent, in the presence of the polyhalo aromatic compound, the hydrous sulfide agent and the non-hydrophilic sulfidizing agent are used. It is preferable to dehydrate the protic and aprotic polar solvent.

In the dehydration step, at least an aprotonic polar solvent and a hydrous alkali metal sulfide or a hydrous alkaline hydrosulfide and an alkali metal hydroxide as a hydrous sulfide agent are charged into a reaction vessel equipped with a distillation apparatus, and water is coexisted. The temperature removed by boiling, specifically, heating to a range of 300 ° C. or lower, preferably 220 ° C. or lower, more preferably 200 ° C. or lower, preferably 80 ° C. or higher, more preferably 100 ° C. or higher. Then, water is discharged to the outside of the system by distillation. In the dehydration step, the amount of water in the system to be subjected to the polymerization reaction is in the range of 5 mol or less, more preferably 2 mol or less, and preferably 0.01 mol or more with respect to 1 mol of the sulfur atom of the sulfidizing agent. It is preferable to dehydrate until it becomes.

Further, in the dehydration step, alkali metal sulfide and alkali metal hydrosulfide react with water to generate hydrogen sulfide as a gas in an equilibrium manner. Therefore, it is preferable to recover the produced hydrogen sulfide and then react it with an alkali metal hydroxide to obtain an alkali metal hydrosulfide and / or an alkali metal sulfide. Specifically, the generated hydrogen sulfide is discharged to the outside of the reaction system together with water or the co-boiling mixture, and after separating the water or the co-boiling mixture and hydrogen sulfide by a distillation apparatus, the same method as in the above step (3). Further, the recovered hydrogen sulfide is reacted with an alkali metal hydroxide in the same manner as in the above step (4) to produce an alkali metal hydrosulfide and / or an alkali metal sulfide. It is preferable to do so. Further, after the step of producing the alkali metal hydrosulfide and / or the alkali metal sulfide by reacting the hydrogen sulfide recovered in the dehydration step with the alkali metal hydroxide, by the same method as in step (5). It is preferable to have a step of adding hydrogen sulfide to the unreacted alkali metal hydroxide to react the unreacted alkali metal hydroxide with the hydrogen sulfide. The alkali metal hydrosulfide and / or alkali metal sulfide obtained in the dehydration step is also preferably used as a part of the raw material in the method for producing a polyarylene sulfide resin as a sulfidizing agent.

Further, as the aprotonic polar solvent in the present invention, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε Amides such as −caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid, urea and lactams; sulfolanes such as sulfolane, dimethylsulfolane; benzo Nitrives such as nitriles; ketones such as methylphenylketone and mixtures thereof can be mentioned, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, An amide having an aliphatic cyclic structure of hexamethylphosphoramide, N-dimethylpropylene urea, and 1,3-dimethyl-2-imidazolidinone acid is preferable, and N-methyl-2-pyrrolidone is more preferable.

In the polymerization reaction of the polyarylene sulfide resin in the PAS polymerization step, the alkali metal sulfide is reacted with the polyhalo aromatic compound as a sulfidizing agent in the presence of these aprotonic polar solvents. Alternatively, in the polymerization reaction of the polyarylene sulfide resin, the alkali metal hydrosulfide and the alkali metal hydroxide are reacted with the polyhalo aromatic compound as a sulfide agent in the presence of these aprotonic polar solvents. The polymerization conditions should generally be in the range of temperature 200-330 ° C. and the pressure should be in the range of substantially retaining the polyhalo aromatic compound, which is the polymerization solvent and the polymerization monomer, in the liquid phase, generally 0. It is selected from the range of 1 MPa or more, preferably 20 MPa or less, and more preferably 2 MPa or less. The amount of the polyhalo aromatic compound charged is 0.2 mol or more, preferably 0.8 mol or more, more preferably 0.9 mol or more, and 5.0 mol with respect to 1 mol of the sulfur atom of the sulfide agent. Hereinafter, the preparation is preferably made in the range of 1.3 mol or less, more preferably 1.1 mol or less. The amount of the aprotic polar solvent charged is 1.0 mol or more, preferably 2.5 mol or more, and 6.0 mol or less, preferably 4.5 mol, with respect to 1 mol of the sulfur atom of the sulfide agent. Adjust so that the range is up to the mole or less. The polymerization reaction is preferably carried out in the presence of a small amount of water, and the ratio thereof is preferably adjusted appropriately in consideration of the polymerization method, the molecular weight of the obtained polymer and the productivity. Specifically, the dehydration operation is performed so as to be in the range of 2.0 mol or less, preferably 1.6 mol or less with respect to 1 mol of the sulfur atom of the sulfide agent, and further dehydrated in the presence of a polyhalo aromatic compound. In the case of performing the operation (for example, the method of "5)" in the following specific embodiment), 0.9 mol or less, preferably 0.3 mol or less, more preferably 0.02 mol or less, preferably 0.05. The dehydration operation may be carried out so as to be in the range of mol or more, more preferably 0.01 mol or more.

Specific embodiments for polymerizing the sulfidating agent and the polyhaloaromatic compound in the presence of the above-mentioned aprotic polar solvent include, for example,
1) A method using a polymerization aid such as alkali metal carboxylate or lithium halide,
2) Method using a branching agent such as an aromatic polyhalogen compound,
3) A method in which a polymerization reaction is carried out in the presence of a small amount of water, and then water is added to further polymerize.
4) A method of cooling the gas phase portion of the reaction kettle during the reaction of the alkali metal sulfide and the aromatic dihalogen compound to condense a part of the gas phase in the reaction kettle and return it to the liquid phase.
5) In the presence of a polyhalo aromatic compound, an alkali metal sulfide or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide are reacted with an amide, urea or lactam having an aliphatic cyclic structure while dehydrating. A step of producing a slurry containing a solid alkali metal sulfide, a step of producing the slurry, further adding a polar organic solvent such as NMP, distilling off water to perform dehydration, and then a dehydration step. In the resulting slurry, a polyhalo aromatic compound, an alkali metal hydrosulfide, and an alkali metal salt of an amide, urea, or lactam hydrolyzate having the aliphatic cyclic structure are mixed in 1 mol of a polar organic solvent such as NMP. On the other hand, there is a method for producing a polyarylene sulfide resin, which comprises a step of reacting with an existing water content of 0.02 mol or less in the reaction system to carry out polymerization as an essential production step.

Of these, in the case of producing a polyarylene sulfide resin by the polymerization methods of 1) to 5), particularly 1) to 4), for example, an aprotic polar solvent is N-methyl-2-pyrrolidone as a production raw material. , When the polyhaloaromatic compound is p-dichlorobenzene, the following general formula (1) is used as a side reaction product of the polymerization reaction.

（式中、Ｘはアルカリ金属原子または水素原子を表す。）で表されるカルボキシアルキルアミノ基含有化合物が該粗反応混合物に含まれる場合がある。本発明は、ポリアリーレンスルフィド樹脂を製造方法について公知の方法であれば特に限定するものではないため、製造方法によっては該カルボキシアルキルアミノ基含有化合物が生成しない場合もあることから必須の成分ではない。しかし、例えば、１）〜５）、特に１）〜４）の重合方法で、前記カルボキシアルキルアミノ基含有化合物が生成した場合は、当該カルボキシアルキルアミノ基含有化合物は粗反応混合物と非プロトン性極性溶媒のＰＡＳ／溶媒固液分離工程を経て、反応混合物中に含まれ、さらに本発明の工程（１）を経て、前記水溶液（ａ）中に含まれ、さらに本発明の工程（２）を経て、前記水溶液（ｂ）中に含まれ、さらに工程（３）、（４）において硫化水素と分離されることとなる。すなわち、アルカリ金属ハロゲン化物と同様に移行する。このため、アルカリ金属水硫化物を生成する反応には関与せず、必須の成分ではない。

(In the formula, X represents an alkali metal atom or a hydrogen atom.) A carboxyalkylamino group-containing compound represented by (X represents an alkali metal atom or a hydrogen atom) may be contained in the crude reaction mixture. The present invention is not particularly limited as long as the method for producing the polyarylene sulfide resin is known, and the carboxyalkylamino group-containing compound may not be produced depending on the production method, so that the present invention is not an essential component. .. However, for example, when the carboxyalkylamino group-containing compound is produced by the polymerization methods of 1) to 5), particularly 1) to 4), the carboxyalkylamino group-containing compound has an aprotonic polarity with the crude reaction mixture. It is contained in the reaction mixture through the PAS / solvent solid-liquid separation step of the solvent, further contained in the aqueous solution (a) through the step (1) of the present invention, and further through the step (2) of the present invention. , It is contained in the aqueous solution (b) and is further separated from hydrogen sulfide in the steps (3) and (4). That is, it migrates in the same manner as the alkali metal halide. Therefore, it is not involved in the reaction for producing alkali metal hydrosulfide and is not an essential component.

At least a polyarylene sulfide resin obtained through the above PAS polymerization step, alkali metal hydrosulfide and / or alkali metal sulfide remaining as an unreacted sulfidizing agent, alkali metal halide, and aprotonic polarity. The crude reaction mixture containing the solvent can be used as the mixture (a).

Next, in the PAS / solvent solid-liquid separation step, at least the polyarylene sulfide resin obtained through the PAS polymerization step and the alkali metal hydrosulfide and / or alkali metal sulfide remaining as an unreacted sulfide agent are used. The crude reaction mixture containing the alkali metal halide and the aprotonic polar solvent was subsequently subjected to solid-liquid separation of the aprotonic polar solvent from the crude reaction mixture to at least a polyarylene sulfide resin and an alkali metal halogen. This is a step of obtaining a reaction mixture containing a compound and an alkali metal hydrosulfide and / or an alkali metal sulfide. The obtained reaction mixture can also be used as the mixture (a).

The solid-liquid separation is roughly divided into two types, a flash method and a Quench method, which will be described later. The flash method is a method of evaporating a solvent to recover the solvent and at the same time recovering a solid substance, and is generally carried out by heating under reduced pressure to distill off the solvent.

On the other hand, the Quench method is a method in which the polymerization reaction product is cooled to recover the particulate polyarylene sulfide resin. Generally, the reaction slurry is cooled in the reaction vessel and then the polyarylene sulfide resin is crystallized. Examples thereof include a method of solid-liquid separation after sulphating. The solid-liquid separation in the Quench method can be obtained by a method of separating by filtration or using a centrifuge such as a screw decanter, then directly adding water to the obtained filtration residue to form a slurry, and then repeating solid-liquid separation. Examples thereof include a method of removing the residual solvent by heating the filtered residue in a non-oxidizing atmosphere. The flash method is preferable because the solid matter can be recovered relatively easily, and the Quench method is preferable because it is easy to control the particle size of the polyarylene sulfide resin and the polymer particles are charged with an alkali metal halide or a sulfidizing agent during crystallization. It is preferable in that a high-purity polymer can be obtained because it becomes difficult to take in impurities such as.

Subsequently, the reaction mixture is separated into a polyarylene sulfide resin and an aqueous solution containing at least an alkali metal halide and a sulfidizing agent through a purification step by washing with water or hot water of the present invention. The purification step can be carried out in the same manner as in the step (1), and in the case of producing a polyarylene sulfide resin, the polyarylene sulfide resin separated by filtration may be recovered.

The polyarylene sulfide resin separated by filtration may be recovered and then dried as it is and used as a polyarylene sulfide resin powder, or after further washing treatment, solid-liquid separation and drying are performed to form a powder or granules. It can also be prepared as a polyarylene sulfide resin of.

As described above, the polyarylene sulfide resin polymerized by reusing the sulfide agent obtained through the steps (1) to (4) of the present invention as at least a part of the raw material impairs the effect of the present invention. Additives such as mold release agents, colorants, heat-resistant stabilizers, ultraviolet stabilizers, foaming agents, rust preventives, flame retardants, lubricants, coupling agents, and fillers can be contained within the range. Further, similarly, the following synthetic resin and elastomer can be mixed and used. Examples of these synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulphon, polyethersulphon, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluorinated ethylene, and the like. Examples thereof include polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer and the like, and examples of the elastomer include polyolefin rubber, fluororubber, silicone rubber and the like.

Further, the polyarylene sulfide resin polymerized by reusing the sulfide agent obtained through the steps (1) to (4) as at least a part of the raw material can be used for injection molding, extrusion molding, compression molding, or blow molding. By various melt processing methods such as, it is possible to produce a molded product having excellent heat resistance, molding processability, dimensional stability and the like, and particularly excellent adhesion to an epoxy resin. For this reason, for example, electrical / electronic parts such as connectors, printed circuit boards, and sealed molded products, automobile parts such as lamp reflectors and various electrical components, interior materials such as various buildings, aircraft, and automobiles, or OA equipment parts. It can be widely used as injection-molded / compression-molded products for precision parts such as camera parts and watch parts, or extrusion-molded / draw-molded products for fibers, films, sheets, pipes, etc.

INDUSTRIAL APPLICABILITY According to the present invention, an alkali metal hydrosulfide remaining as an unreacted sulfide agent in a reusable state is separated and recovered from wastewater obtained after washing with water or hot water in the process of producing a polyarylene sulfide resin. It is possible to reduce the COD value of wastewater, reduce the environmental load by reducing industrial waste, suppress the loss of sulfur atoms (decrease in raw material basic unit), and improve the productivity of polyarylene sulfide resin. Further, when the recovered unreacted sulfidizing agent is reused as a polymerization raw material for the polyarylene sulfide resin, a polyarylene sulfide resin having a higher molecular weight can be produced.

Hereinafter, the present invention will be specifically described with reference to examples. These examples are exemplary and not limiting.

(Measurement method 1 Measurement method of melt viscosity)
The polyphenylene sulfide resin used was a flow tester manufactured by Shimadzu Corporation, CFT-500D, and was held at 300 ° C., a load of 1.96 × 10 ⁶ Pa, L / D = 10 (mm) / 1 (mm) for 6 minutes. It was measured.

(Measurement method 2 Measurement method of scattered hydrogen sulfide (scattered S) and sulfur in unreacted sulfidizing agent)
0.5 g of the sample was precisely weighed in a beaker, then 70 ml of pure water and 4 ml of a 1 wt% sodium hydroxide aqueous solution were added, and the mixture was titrated with a 0.02 mol / L silver nitrate aqueous solution using an automatic potential difference titrator while stirring.

(Measurement method 3 Measurement method of the first neutralization point (sodium sulfide + sodium carbonate))
10 g of the sample was precisely weighed in a beaker, then 70 ml of pure water was added, and the mixture was titrated with 0.1 mol / L hydrochloric acid using an automatic potential difference titrator while stirring.

(Measurement method 4 Measurement method of pH in wastewater)
Uses "Personal pH Meter PH72" manufactured by Yokogawa Electric Corporation. After pH calibration with pH 4 and pH 7 standard solutions, the pH was measured by immersing the attached electrode "PH72" in wastewater.

(Measurement method 5 Measurement method of sodium sulfide concentration and sodium sulfide concentration in the recovered liquid)
90 g of a 110-fold diluted aqueous solution of the sample is precisely weighed, and while stirring, neutralization titration is performed with 0.5 mol / L hydrochloric acid using an automatic potential difference titrator, and the sodium sulfide concentration is calculated from the titration at the first equivalence point. Then, the sodium hydrosulfide concentration was calculated from the difference between the titration at the second equivalence point and the titration at the first equivalence point. The recovery rate (%) of sodium sulfide and / or sodium sulfide (sulfidating agent) is (molar part of hydrogen sulfide scattered during dehydration and molar part of sulfide agent transferred to the sodium sulfide recovery liquid) ÷ (waste water). It was calculated as (molar part of the sulfidizing agent) × 100.

(Measurement method 6 Measurement method of thiophenol concentration)
0.5 g of the sample and 2.5 g of methyl isobutyl ketone are precisely weighed in a vial with a lid, and then 1.5 g of 5M hydrochloric acid is slowly added dropwise under an ice bath. Add 0.1 g of monochlorobenzene and 8 g of acetone into the vial, cover the vial, and stir the contents sufficiently. The thiophenol concentration of the supernatant of the obtained slurry was measured using a gas chromatograph device manufactured by Shimadzu Corporation. The thiophenol recovery rate (%) was calculated as (molar portion of thiophenol transferred to the sodium sulfide recovery liquid) ÷ (molar portion of thiophenol derivative in waste water) × 100.

Example 1
<Example (1-1)> PPS polymerization and production of waste water A condenser, a pressure gauge, a thermometer, a decanter, and a rectification tower connected to a gas absorption bottle in which 3.30 kg of a 15 wt% sodium hydroxide aqueous solution was previously charged were connected. 33.20 kg (226 mol) of p-dichlorobenzene (hereinafter abbreviated as p-DCB), 2.28 kg (23.00 mol) of NMP, 27.30 kg of 47.23 mass% NaOH aqueous solution (sulfur atom 230) in an autoclave with a stirring blade. Mol, "sodium sulfide (liquid) 45% product" manufactured by Nagao Co., Ltd.) and 18.34 kg (228 mol) of 49.21 mass% NaOH aqueous solution were charged, and it took 5 hours to 173 ° C under a nitrogen atmosphere while stirring. The temperature was raised to distill off 27.21 kg of water. Hydrogen sulfide scattered during dehydration was absorbed by a sodium hydroxide aqueous solution by a gas absorbing bottle to obtain a sodium hydroxide aqueous solution (1) in which hydrogen sulfide was absorbed. The aqueous sodium hydroxide solution (A) that had absorbed hydrogen sulfide was titrated with silver nitrate (measurement method 2). The results are shown in Table 1.

After that, the kettle was sealed, and the DCB distilled by azeotropic boiling during dehydration was separated by a decanter and returned to the kettle at any time. After the dehydration was completed, the inside of the kettle was in a state in which the anhydrous sodium sulfide composition in the form of fine particles was dispersed in the DCB. After completion of the dehydration step, the internal temperature was cooled to 160 ° C., 47.49 kg (479 mol) of NMP was charged, and the temperature was raised to 185 ° C. When the pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of DCB and water was condensed by a condenser, separated by a decanter, and the DCB was returned to the kettle. The amount of distilled water was 414 g. The temperature was raised from 200 ° C. to 230 ° C. over 3 hours and stirred for 2 hours, then raised to 250 ° C. and stirred for 1 hour. The final pressure was 0.48 MPa.

The slurry obtained after the reaction was cooled to room temperature and then dried under reduced pressure at 150 ° C. for 3 hours using a vacuum dryer to distill off N-methyl-2-pyrrolidone. Next, 142 kg of hot water at 70 ° C. was added and stirred, and then filtered. Further, 81 kg of hot water at 70 ° C. was added and filtered to collect the filtrate to obtain 209 kg of wastewater (1). Waste water (1) is titrated with silver nitrate (measurement method 2), and the amount of sulfidating agent (soda sulfide and sodium hydrosulfide) (mol) is calculated from the sodium sulfide concentration and sodium hydrosulfide concentration, and the amount of thiophenol (mol) is calculated from the thiophenol concentration. ) Was asked. The results are shown in Table 1.

<Example (1-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery liquid)
An aqueous sodium hydroxide solution in which hydrogen sulfide obtained in Example (1-1) was absorbed in a closed container equipped with a stirrer, a pH meter, a gas introduction pipe, a gas discharge pipe, and a dropping funnel via a gas discharge pipe. The gas absorption bottle containing (1) was connected. 209 kg of wastewater (1) and 0.31 kg of sodium carbonate (0.25 mol / mol of sulfur content) were charged into the closed container and stirred.
Next, hydrochloric acid dropwise to stirred while introducing _{N 2} gas (50 ml / min), the first neutralization point in wastewater (1) (measurement 3) + corresponds to a sulfur content of 1 mol per 1.20 mol Then, the pH (measurement method 4) was adjusted to 5.0, and the mixture was stirred for 60 minutes to generate hydrogen sulfide gas. The generated hydrogen sulfide gas was absorbed in an aqueous sodium hydroxide solution (1) to obtain a sodium hydroxide recovery liquid (1). The obtained sodium sulfide recovery solution (1) was measured, and the amount (mol) of the sulfidizing agent was determined from the sodium sulfide concentration and the sodium sulfide concentration (measurements 5 and 6). The results are shown in Table 2.

<Example (1-3)> Production of PPS using the sulfide agent obtained in Example (1-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(1) 14.85g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount was 3.94 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution were charged, and the mixture was raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.37 g of water was distilled off.

After that, the kettle was sealed, and the DCB distilled by azeotropic boiling during dehydration was separated by a decanter and returned to the kettle at any time. After the dehydration was completed, the inside of the kettle was in a state in which the anhydrous sodium sulfide composition in the form of fine particles was dispersed in the DCB. After completion of the dehydration step, the internal temperature was cooled to 160 ° C., NMP309.73 g (3.13 mol) was charged, and the temperature was raised to 185 ° C. When the pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of DCB and water was condensed by a condenser, separated by a decanter, and the DCB was returned to the kettle. The amount of distilled water was 2.70 g. The temperature was raised from 200 ° C. to 230 ° C. over 3 hours and stirred for 2 hours, then raised to 250 ° C. and stirred for 1 hour. The final pressure was 0.48 MPa.

The slurry obtained after the reaction was cooled to room temperature and then dried under reduced pressure at 150 ° C. for 3 hours using a vacuum dryer to distill off N-methyl-2-pyrrolidone. Next, 920 g of hot water at 70 ° C. was added and stirred, and then filtered. Further, 1200 g of hot water at 70 ° C. was added and stirred for 10 minutes and then filtered. 1200 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. .. The obtained hydrous cake and 460 g of ion-exchanged water were charged into a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes. After cooling to room temperature, the cake was filtered, and 1200 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. The obtained hydrous cake and 460 g of ion-exchanged water were charged into a 0.5 liter autoclave, and the mixture was stirred at 220 ° C. for 30 minutes. The slurry was cooled to room temperature, filtered, and 1200 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. Then, it was dried at 120 degreeC for 4 hours to obtain a PPS resin having a melt viscosity of 49 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 2
<Example (2-1)> PPS polymerization and wastewater production The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Example (2-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (2) that has absorbed hydrogen sulfide. The wastewater obtained in Example (2-1) is referred to as wastewater (2). The results are shown in Table 1.

<Example (2-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
To the waste water (2) obtained in Example (2-1), 0.43 kg of sodium carbonate (0.35 mol per mol of sulfur content) was charged, and the first neutralization point (measurement method) in the waste water (2) was added. 3) The same operation as in Example (1-2) was performed except that the pH (measurement method 4) was adjusted to 5.7 by dropping hydrochloric acid corresponding to 1.20 mol / mol of + sulfur content. rice field. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (2).
The sodium sulfide recovery liquid (2) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (2-3)> Production of PPS using the sulfide agent obtained in Example (2-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(2) 14.99g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount is 2.11 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution are charged, and the mixture is raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.49 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 63 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 3
<Example (3-1)> PPS polymerization and wastewater production The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Example (3-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (3) that has absorbed hydrogen sulfide. The wastewater obtained in Example (3-1) is referred to as wastewater (3). The results are shown in Table 1.

<Example (3-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
The same operation as in Example (2-2) was performed. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (3).
The sodium sulfide recovery liquid (3) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (3-3)> Production of PPS using the sulfide agent obtained in Example (3-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 169.14 g (1.43 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(3) 24.98g (7.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 5.0 mol%, thiophenol The amount is 3.51 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution are charged, and the mixture is raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 192.53 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 52 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 4
<Example (4-1)> PPS polymerization and production of wastewater Example (1) except that the amount of 15 wt% sodium hydroxide aqueous solution charged in advance in the gas absorption bottle was changed from 3.30 kg to 3.00 kg. The same operation as in -1) was performed. The sodium hydroxide aqueous solution obtained in Example (4-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (4) that has absorbed hydrogen sulfide. The wastewater obtained in Example (4-1) is referred to as wastewater (4). The results are shown in Table 1.

<Example (4-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
To the waste water (4) obtained in Example (4-1), 0.43 kg of sodium carbonate (0.35 mol per mol of sulfur content) was charged, and the first neutralization point (measurement method) in the waste water (4) was added. 3) The same operation as in Example (2-2) was performed except that the pH (measurement method 4) was adjusted to 6.0 by dropping hydrochloric acid corresponding to 1.00 mol / mol of + sulfur content. rice field. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (4).
The sodium sulfide recovery liquid (4) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (4-3)> Production of PPS using the sulfide agent obtained in Example (4-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(4) 15.03g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount is 2.01 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution are charged and raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.52 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 64 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 5
<Example (5-1)> PPS polymerization and production of wastewater Example (1) except that the amount of 15 wt% sodium hydroxide aqueous solution charged in advance in the gas absorption bottle was changed from 3.30 kg to 0.750 kg. The same operation as in -1) was performed. The sodium hydroxide aqueous solution obtained in Example (5-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (5) that has absorbed hydrogen sulfide. The wastewater obtained in Example (5-1) is referred to as wastewater (5). The results are shown in Table 1.

<Example (5-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
To the waste water (5) obtained in Example (5-1), 0.43 kg of sodium carbonate (0.35 mol per mol of sulfur content) was charged, and the first neutralization point (measurement method) in the waste water (5) was added. 3) The same operation as in Example (2-2) was performed except that the pH (measurement method 4) was adjusted to 7.2 by dropping hydrochloric acid corresponding to 0.30 mol / mol of + sulfur content. rice field. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (5).
The sodium sulfide recovery liquid (5) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (5-3)> Production of PPS using the sulfide agent obtained in Example (5-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 151.34 g (1.28 mol), in an autoclave with a stirring blade connected to a rectification tower. ^{74.38 g (2.25 × 10 -1} mol) of the obtained caustic soda recovery liquid (5), the ratio of recovered caustic soda to the charged mol of total caustic soda was 15.0 mol%, thiophenol. The amount is 2.04 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution are charged, and the mixture is raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 222.45 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 64 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 6
<Example (6-1)> PPS polymerization and wastewater production The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Example (6-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (6) that has absorbed hydrogen sulfide. The wastewater obtained in Example (6-1) is referred to as wastewater (6). The results are shown in Table 1.

<Example (6-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
To the waste water (6) obtained in Example (6-1), 0.34 kg of sodium hydrogen carbonate (0.35 mol per mol of sulfur content) was charged, and the first neutralization point (measurement) in the waste water (6) was added. Method 3) + The same operation as in Example (2-2) except that the pH (measurement method 4) was adjusted to 5.6 by dropping hydrochloric acid corresponding to 1.20 mol per mol of sulfur content. went. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (6).
The sodium sulfide recovery liquid (6) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (6-3)> Production of PPS using the sulfide agent obtained in Example (6-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(6) 15.13g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount is 2.13 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution are charged, and the mixture is raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.59 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 63 Pa · s (measurement method 1). The results are summarized in Table 3.

Example 7
<Example (7-1)> PPS polymerization and wastewater production The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Example (7-1) that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (7) that has absorbed hydrogen sulfide. The wastewater obtained in Example (7-1) is referred to as wastewater (7). The results are shown in Table 1.

<Example (7-2)> Method for producing sulfidating agent (preparation of sodium sulfide recovery solution)
0.55 kg of sodium carbonate (0.45 mol per mol of sulfur content) was charged into the waste water (7) obtained in Example (7-1), and the first neutralization point (measurement method) in the waste water (7) was added. 3) The same operation as in Example (1-2) was performed except that the pH (measurement method 4) was adjusted to 6.1 by dropping hydrochloric acid corresponding to 1.20 mol / mol of + sulfur content. rice field. The obtained sodium hydrogen sulfide recovery liquid was referred to as the sodium water sulfide recovery liquid (7), and the sodium water sulfide recovery liquid (7) was measured (measurement methods 5 and 6). The results are shown in Table 2.

<Example (7-3)> Production of PPS using the sulfide agent obtained in Example (7-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 169.14 g (1.43 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(7) 25.46g (7.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 5.0 mol%, thiophenol The amount was 2.79 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution were charged, and the mixture was raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 192.86 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 58 Pa · s (measurement method 1). The results are summarized in Table 3.

Comparative Example 1
<Comparative Example (1-1)> PPS polymerization and production of wastewater The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Comparative Example 1-1 that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (C1) that has absorbed hydrogen sulfide. The wastewater obtained in Comparative Example (1-1) is referred to as wastewater (C1). The results are shown in Table 4.

<Comparative Example (1-2)> Method for Producing Sulfide Agent (Preparation of Sodium Hydrosulfide Recovery Solution)
Sodium carbonate was not added to the wastewater (C1) obtained in Comparative Example (1-1), but the first neutralization point (measurement method 3) in the wastewater (C1) + 1.20 mol per mol of sulfur content. The same operation as in Example (1-1) was carried out except that the corresponding hydrochloric acid was added dropwise to adjust the pH (measurement method 4) to 3.2. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (C1).
The obtained sodium sulfide recovery liquid (C1) was measured (measurement methods 5 and 6). The results are shown in Table 5.

<Comparative Example (1-3)> Production of PPS using the sulfide agent obtained in Comparative Example (1-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(C1) 14.85g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount was 4.63 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution were charged, and the mixture was raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.36 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 43 Pa · s (measurement method 1). The results are shown in Table 6.

Comparative Example 2
<Comparative Example (2-1)> PPS polymerization and production of wastewater The same operation as in Example (1-1) was performed. The sodium hydroxide aqueous solution obtained in Comparative Example 2-1 that has absorbed hydrogen sulfide is referred to as a sodium hydroxide aqueous solution (C2) that has absorbed hydrogen sulfide. The wastewater obtained in Comparative Example (2-1) is referred to as wastewater (C2). The results are shown in Table 4.

<Comparative Example (2-2)> Method for Producing Sulfide Agent (Preparation of Sodium Hydrosulfide Recovery Solution)
To the waste water (C2) obtained in Comparative Example (2-1), 0.31 kg of sodium carbonate (0.25 mol per 1 mol of sulfur content) was charged, and the first neutralization point (measurement method) in the waste water (C2) was added. 3) The same operation as in Example (1-2) was performed except that the pH (measurement method 4) was adjusted to 4.4 by dropping hydrochloric acid corresponding to 1.30 mol / mol of + sulfur content. rice field. The obtained sodium sulfide recovery liquid is referred to as a sodium sulfide recovery liquid (C2).
The obtained sodium sulfide recovery liquid (C2) was measured (measurement methods 5 and 6). The results are shown in Table 5.

<Comparative Example (2-3)> Production of PPS using the sulfide agent obtained in Comparative Example (2-2) A condenser, a pressure gauge, a thermometer, a decanter, to which a gas absorption bottle containing an aqueous solution of sodium hydroxide is connected. P-DCB 216.53 g (1.47 mol), NMP 14.87 g (0.15 mol), 47.23 mass% NaSH aqueous solution 172.70 g (1.46 mol), in an autoclave with a stirring blade connected to a rectification tower. the resulting sodium hydrosulfide recovered liquid ^{(C2) 14.99g (4.50 × 10} -2 mol, recovered water sodium sulfide proportion of the charged mole of total sodium hydrosulfide is, 3.0 mol%, thiophenol The amount was 4.63 × 10 ^-4 mol per 1 mol of NaOH) and 119.10 g (1.47 mol) of 49.21 mass% NaOH aqueous solution were charged, and the mixture was raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring. After warming, 186.45 g of water was distilled off.
After that, the same operation as in Example (1-3) was performed. The melt viscosity of the obtained PPS resin was 43 Pa · s (measurement method 1). The results are summarized in Table 6.

※「←」印は左記に同様。

* The "←" mark is the same as on the left.

From the above results, in Examples 1 to 5, compared with Comparative Examples 1 and 2, the thiophenol was reduced from the sulfidizing agent used as a raw material for producing the polyphenylene sulfide resin, and remained unreacted. It has been clarified that it can be recovered as a recovery liquid containing a large amount of a sulfidizing agent, and that a higher molecular weight PPS resin can be produced even if it is reused as a raw material for PPS polymerization.

Claims (8)

After contacting water with a mixture (a) containing at least a polyarylene sulfide resin, an alkali metal halide and a sulfidizing agent, the polyarylene sulfide resin is separated and removed to at least an alkali metal halide and a thiophenol. Step (1) to obtain an aqueous solution (b) containing a derivative and a sulfidizing agent,
To the obtained aqueous solution (b), at least one selected from the group consisting of a metal carbonate and a metal hydrogen carbonate exhibiting solubility in the aqueous solution (b) at 25 ° C. is added, and at least an alkali is added. Step (2) of adding an acid to an aqueous solution (b) containing a metal halide, a thiophenol derivative and a sulfide agent to adjust the pH in the range of more than 4.5 to 8 or less to generate hydrogen sulfide.
Step (3) to recover the generated hydrogen sulfide, and
Step of reacting the recovered hydrogen sulfide with the alkali metal hydroxide (4),
A method for producing a sulfidizing agent, which comprises. Claim 1 in which the ratio of thiophenol recovered in the step (3) is less than 100 mol with respect to 100 mol of the thiophenol derivative contained in the aqueous solution (b) in the step (2). The method for producing a sulfide agent according to the above. At least, the mixture (a) containing a polyarylene sulfide resin, an alkali metal halide and a sulfidizing agent is
At least a polyarylene sulfide resin, an alkali metal halide, the aprotonic polar solvent, a thiophenol derivative and sulfide obtained after reacting a polyhalo aromatic compound with a sulfide agent in an aprotonic polar solvent. The production method according to claim 1 or 2, which is a crude reaction mixture containing an agent, or a reaction mixture obtained by solid-liquid separation of the aprotic polar solvent from the crude reaction mixture. The sulfidizing agent used when reacting a polyhalo aromatic compound with a sulfidizing agent in an aprotic polar solvent is a dehydration step of dehydrating a hydrous sulfidating agent in the presence of at least an aprotic polar solvent. The production method according to claim 3, which is obtained through the above. After the step (4) of reacting the recovered hydrogen sulfide with the alkali metal hydroxide, hydrogen sulfide is added to the unreacted alkali metal hydroxide, and the hydrogen sulfide and the unreacted alkali metal hydroxide are added. The production method according to claim 1, further comprising a step (5) of reacting with an object. A method for producing a sulfidizing agent, which comprises a step of recovering hydrogen sulfide produced in the dehydration step according to claim 4 and then reacting with an alkali metal hydroxide to obtain a sulfidizing agent. After the step of reacting with an alkali metal hydroxide to obtain an alkali metal hydrosulfide and / or an alkali metal sulfide, hydrogen sulfide is added to the unreacted alkali metal hydroxide to obtain the hydrogen sulfide and not yet. The method for producing a sulfidizing agent according to claim 6, further comprising a step of reacting with the alkali metal hydroxide of the reaction. A polyarylene sulfide resin produced by reacting a sulfidizing agent obtained by dehydrating a hydrous sulfide agent in the presence of an organic amide solvent with a polyhalo aromatic compound in the presence of an organic amide solvent to produce a polyarylene sulfide resin. The sulfidizing agent obtained by the manufacturing method according to any one of claims 1 to 5 and / or the above-mentioned claim 6 or 7 as at least a part of the hydrous sulfide agent or the sulfide agent. A method for producing a polyarylene sulfide resin, which comprises a step of adding a sulfidizing agent obtained by the production method.