WO2014002787A1 - ビスフェノールaの製造方法 - Google Patents
ビスフェノールaの製造方法 Download PDFInfo
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- WO2014002787A1 WO2014002787A1 PCT/JP2013/066390 JP2013066390W WO2014002787A1 WO 2014002787 A1 WO2014002787 A1 WO 2014002787A1 JP 2013066390 W JP2013066390 W JP 2013066390W WO 2014002787 A1 WO2014002787 A1 WO 2014002787A1
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- bisphenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
Definitions
- the present invention relates to a method for producing bisphenol A (2,2-bis (4-hydroxyphenyl) propane), and more particularly to a method for producing bisphenol A from phenol and acetone.
- Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin, or epoxy resin, and in recent years its demand has been increasing. High quality bisphenol A is required as a raw material for producing high quality resin.
- Bisphenol A is usually produced by reacting a stoichiometric excess of phenol and acetone in the presence of an acidic catalyst. Then, bisphenol A is recovered as an adduct of bisphenol A and phenol by crystallization and solid-liquid separation from the solution after the reaction, and as a product by removing phenol contained in the adduct. can get. Then, the mother liquor from which the adduct has been separated after crystallization is circulated to the reaction process and the like and reused in the system.
- Patent Document 1 a part of the mother liquor obtained by separating and dividing the reaction solution after the reaction of phenol and acetone is returned to the reactor, and part of the mother liquor is isomerized and mother liquor concentrated. After obtaining a recovered solution that recovered an adduct of bisphenol A and phenol through a crystallization / solid-liquid separation step, bisphenol A and phenol are obtained from the recovered solution through an alkali decomposition step and a recombination reaction step.
- a manufacturing method having a process of recovering and returning to the reactor is disclosed.
- Patent Document 2 discloses the total amount of the mother liquor without circulating the mother liquor after crystallization separation of the adduct of bisphenol A and phenol from the reaction mixture after the reaction of phenol and acetone. After isomerization, bisphenol A and phenol are recovered from the blown isomerization solution to recycle to the condensation reaction step, concentration step or crystallization / solid-liquid separation step, and to prevent accumulation of impurities in the system.
- a manufacturing method having a process of performing is disclosed.
- the present invention has been made in view of the above problems, and provides a method for producing bisphenol A, which can produce high-quality bisphenol A and can effectively reduce the amount of raw material used to be supplied. For the purpose.
- a method for producing bisphenol A comprising the following steps (A) to (F): Step (A): Step (B) in which a reaction mixture containing bisphenol A is obtained by producing bisphenol A in a reactor in which excess phenol and acetone are subjected to a condensation reaction in the presence of an acid catalyst.
- FIG. 1 is a process diagram of a method for producing bisphenol A described in Example 1.
- FIG. 2 is a process diagram of a method for producing bisphenol A described in Comparative Example 1.
- FIG. 5 is a process diagram of a method for producing bisphenol A described in Comparative Example 2.
- the method for producing bisphenol A of the present invention includes the following steps (A) to (F).
- the production method of bisphenol A of the present invention is a production method in which the mother liquor separated from the reaction mixture after the reaction of phenol and acetone is not returned to the reactor in which the reaction is carried out. Therefore, since the amount of impurities present in the reactor is reduced, high quality bisphenol A can be produced.
- step (D) by isomerizing at least a part of the mother liquor present in the system from the mother liquor from which the solid content has been separated, isomerizable components in the mother liquor are bisphenol as much as possible. A can be converted to A to increase the concentration of bisphenol A. Therefore, when purging a part of the mother liquor out of the system to prevent impurities from accumulating in the system, more bisphenol A can be recovered from the purge mother liquor, and the recovery rate of bisphenol A can be increased. Can be improved.
- the isomerization treatment in the step (D) refers to a treatment for converting a by-product produced in the reaction step into a 4,4′-form. Examples of the by-product include isomers such as 2,4′-form of bisphenol A.
- step (F) bisphenol present in the mother liquor is obtained by subjecting at least a part of the mother liquor present in the system to alkali decomposition treatment among the mother liquor obtained by removing solids from the solution after isomerization treatment.
- Impurities such as A, 2.4′-bisphenol A and trisphenol can be decomposed to recover phenol as a raw material and / or p-isopropenylphenol (IPP) as an intermediate of bisphenol A as an active ingredient.
- IPP p-isopropenylphenol
- the recovered phenol and / or IPP passes through the recombination reactor, phenol and IPP react in the recombination reactor to produce bisphenol A, and the produced bisphenol A is reacted in step (A).
- the recovered phenol and / or IPP is supplied to the reactor of step (A) without going through the recombination reactor.
- the recovered phenol and / or IPP can be mixed with the raw material phenol and supplied to the reactor of the step (A), the amount of raw material phenol and acetone can be reduced, and the same high level as in the past can be achieved. Quality bisphenol A can be obtained.
- Step (A) is a step in which bisphenol A is produced in a reactor in which an excess phenol and acetone are subjected to a condensation reaction in the presence of an acid catalyst to obtain a reaction mixture containing bisphenol A.
- the supplied phenol and acetone undergo a condensation reaction to produce p-isopropenylphenol (IPP), and then the IPP and phenol further undergo a condensation reaction to produce bisphenol A.
- IPP p-isopropenylphenol
- a strongly acidic cation exchange resin is used, but a sulfonic acid type cation exchange resin is preferable from the viewpoint of catalytic activity.
- the sulfone-type cation exchange resin is not particularly limited as long as it is a strongly acidic cation exchange resin having a sulfonic acid group.
- sulfonated styrene-divinylbenzene copolymer, sulfonated crosslinked styrene polymer, phenol formaldehyde-sulfonic acid resin And benzene formaldehyde-sulfonic acid resin You may use these individually or in combination of 2 or more types.
- strong acid cation exchange resins in which a part of the resin is neutralized with mercaptans are preferable.
- mercaptans means a compound having an SH group in the molecule in a free form. Examples of such mercaptans include alkyl mercaptans, alkyl mercaptans having one or more substituents such as a carboxyl group, an amino group, and a hydroxyl group.
- the content of the sulfonic acid group in the strongly acidic cation exchange resin neutralized with mercaptans is preferably 5 to 5 with respect to the total amount of all sulfonic acid groups in the strongly acidic cation exchange resin before neutralization. It is 35 mol%, more preferably 10 to 30 mol%, still more preferably 15 to 25 mol%.
- the supply ratio of phenol and acetone is not particularly limited as long as it is a stoichiometrically excessive ratio of phenol.
- the amount of phenol supplied to 1 mol of acetone is preferably 3 to 30 mol, more preferably 5 to 20 mol.
- the condensation reaction of phenol and acetone in this step may be either a batch type or a continuous type, but a fixed bed continuous reaction method in which raw materials are continuously supplied and reacted is preferable, and an extrusion flow method is used. A fixed bed distribution method is more preferable.
- the reaction tower in the fixed bed continuous reaction system may be one, or may be a fixed bed multistage continuous reaction system in which two or more are arranged in series.
- the liquid hourly space velocity of the raw material supplied to the reactor is preferably 0.1 ⁇ 20 hr -1, more preferably 0.3 ⁇ 15hr -1, more preferably 0.5 ⁇ 10 hr -1 More preferably, it is 0.7 to 6 hr ⁇ 1 .
- the temperature during the reaction between phenol and acetone is preferably 50 to 100 ° C., more preferably 55 to 90 ° C., and still more preferably 60 to 80 ° C. If reaction temperature is 50 degreeC or more, while being able to fully raise reaction rate, the viscosity of a reaction liquid mixture can be made into an appropriate range, and the possibility that a reaction liquid mixture may solidify can be prevented. On the other hand, if reaction temperature is 100 degrees C or less, reaction control is possible and the selectivity of bisphenol A can be made favorable. Moreover, decomposition or deterioration of the catalyst can be prevented.
- the pressure during the reaction between phenol and acetone is preferably normal pressure (0.1 MPa) to 1.5 MPa, more preferably normal pressure (0.1 MPa) to 0.6 MPa.
- Step (B) is a step of concentrating the reaction mixture obtained in step (A) to obtain a concentrated solution.
- low-boiling substances such as unreacted acetone, unreacted phenol, and by-product water are removed from the reaction mixture, and the concentration of the generated bisphenol can be adjusted to an appropriate range.
- the reaction mixture is preferably concentrated by distillation under reduced pressure using a distillation column.
- the concentration in this step is mainly a first concentration step in which unreacted acetone, water, low-boiling substances, etc. are distilled off, and a second concentration step in which mainly unreacted phenol is distilled off to adjust the concentration of the concentrate. It is preferable to divide into two.
- the temperature is preferably 10 to 200 ° C., more preferably 20 to 190 ° C., still more preferably 30 to 180 ° C.
- the pressure is preferably 10 to 90 kPa. More preferably, it is 20 to 80 kPa, and further preferably 25 to 70 kPa.
- the conditions for distillation under reduced pressure in the second concentration step are preferably a temperature of 70 to 170 ° C., more preferably 80 to 140 ° C., still more preferably 85 to 130 ° C., and a pressure of preferably 4 to 70 kPa. More preferably, it is 7 to 50 kPa, and further preferably 10 to 30 kPa. Note that the temperature and pressure in the vacuum distillation in the second concentration step are preferably set lower than those in the first concentration step in consideration of an increase in the boiling point of the component.
- the concentration of bisphenol A in the concentrated liquid obtained through this step is preferably 20 to 60% by mass, more preferably 20 to 40% by mass. If the said density
- step (C) the concentrate obtained in step (B) is crystallized and then solid-liquid separated, and the solid content containing an adduct of bisphenol A and phenol (hereinafter also referred to as “adduct”), mother liquor, It is the process of separating.
- adduct an adduct of bisphenol A and phenol
- the concentrated solution immediately after completion of vacuum distillation before crystallization is cooled to 35 to 60 ° C. (preferably 40 to 55 ° C.) to crystallize the solid content.
- the cooling at this time may be performed by using an external heat exchanger, or by a vacuum cooling crystallization method in which water is added to the concentrate and cooling is performed using the latent heat of vaporization of water under reduced pressure. Also good.
- the slurry containing the solids crystallized in this way is separated into solids and a mother liquor containing reaction by-products by known means such as filtration and centrifugation.
- the equipment used at this time is not particularly limited, and examples thereof include a belt filter, a drum filter, a tray filter, and a centrifuge.
- the solid content after solid-liquid separation after crystallization may be redissolved and re-crystallized, and then the solid-liquid separation may be repeated.
- impurities incorporated in the crystal can be reduced.
- the re-dissolved solution include phenol, water, a water-phenol mixed solution, and the like.
- recovered from the inside of a system may be used for phenol, and the phenol supplied separately from the outside of a system may be used.
- the separated solid content is washed, sent to the adduct decomposition step, and phenol is removed from the adduct contained in the solid content, whereby high-purity bisphenol A can be obtained.
- the cleaning liquid to be used include phenol, water, and a water-phenol mixed liquid.
- recovered from the inside of a system may be used for phenol, and the phenol supplied separately from the outside of a system may be used.
- the amount of the cleaning liquid to be used is preferably 0.1 to 10 times the mass of the separated solid from the viewpoints of cleaning efficiency, loss due to re-dissolution, circulation of the cleaning liquid, recovery, and reuse.
- the adduct (adduct) of bisphenol A and phenol contained in the solid content recovered by the above solid-liquid separation is decomposed into bisphenol A and phenol through an adduct decomposition step, and the phenol is removed. High purity bisphenol A can be obtained.
- the adduct decomposition step it is preferable to first go through a step in which the solid content containing the adduct is heated and melted preferably at 100 to 160 ° C. to decompose the adduct into bisphenol A and phenol to obtain a melt containing these. .
- this molten liquid is sent to an evaporation tower, phenol is removed from this molten liquid by vacuum distillation or the like, and molten bisphenol A is recovered.
- the vacuum distillation is preferably performed under conditions of a temperature of 150 to 190 ° C. and a pressure of 1 to 11 kPa.
- the recovered molten bisphenol A preferably further removes the remaining phenol by steam stripping. High purity bisphenol A can be obtained through these steps.
- Step (D) is a step in which at least a part of the mother liquor present in the system is isomerized with the mother liquor obtained in step (C).
- the composition of the mother liquor obtained in the step (C) is usually phenol: 65 to 85% by mass, bisphenol A: 10 to 20% by mass, impurities such as 2,4′-isomer: 5 to 15% by mass, It contains many impurities such as isomers.
- a part of the mother liquor may be discharged out of the system, but at least a part of the mother liquor existing in the system after the discharge is isomerized.
- the proportion of the mother liquor to be isomerized is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, from the viewpoint of improving the recovery rate of bisphenol A. More preferably, it is 80 to 100% by mass, and still more preferably 90 to 100% by mass, and it is particularly preferable to isomerize the whole amount of the mother liquor present in the system.
- a sulfonic acid type cation exchange resin is preferable.
- the sulfonic acid type cation exchange resin include resins used in the above-described step (A).
- the isomerization treatment may be carried out in the presence of the sulfonic acid type cation exchange resin at a reaction temperature of 50 to 100 ° C. (preferably 60 to 90 ° C.) by a fixed bed flow method which is a continuous extrusion flow method. preferable.
- the liquid hourly space velocity of the solution is preferably 0.1 ⁇ 20 hr -1, more preferably 0.3 ⁇ 15hr -1, more preferably 0.5 ⁇ 10 hr -1.
- a plurality of reactors for performing the isomerization treatment may be provided in parallel.
- the mother liquor obtained in the step (C) is sent to an isomerization reactor for recycling the isomerization treatment to the step (B) and a step (E) for treating the solution after the isomerization treatment. It is also possible to divide and install the reactor for the isomerization treatment.
- the solution after the isomerization treatment is sent to the step (E), but a part of the solution is preferably returned to the step (B).
- a part of the solution after the isomerization treatment is preferably returned to the step (B).
- the bisphenol A produced by the isomerization treatment can be recovered and the recovery rate of the bisphenol A can be improved.
- the solution after isomerization treatment contains 65 to 85% by mass of phenol, in order to prepare a concentration of bisphenol A corresponding to the crystallization operation by evaporating a part of the phenol, It is preferable to return to).
- the amount of the solution sent to the step (E) after the isomerization treatment is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 13 to 23% by mass.
- the amount of the solution returned to the step (B) is preferably 95 to 70% by mass, more preferably 90 to 75% by mass, and still more preferably 87 to 77% by mass.
- the step (E) is a step of crystallizing the solution after the isomerization treatment in the step (D), followed by solid-liquid separation to separate the solid and mother liquor.
- a solid content containing an adduct of bisphenol A and phenol is crystallized and separated into a solid content and a mother liquor.
- the solution after isomerization is preferably concentrated by removing a part of phenol before crystallization.
- the concentration is performed at a temperature of 70 to 140 ° C. (preferably 80 to 125 ° C., more preferably 90 to 115 ° C.) and a pressure of 1.5 to 40 kPa (preferably 2.0 to 25 kPa, more preferably 3.0 to 15 kPa). It is preferable to carry out by distillation under reduced pressure under the above conditions.
- the concentration of bisphenol A in the solution after concentration is preferably 20 to 50% by mass.
- the solution immediately after completion of the vacuum distillation is cooled to 35 to 60 ° C. (preferably 40 to 55 ° C.), and the solid content is crystallized to form a slurry. It is preferable.
- the cooling at this time can be performed by the same method as in the above-described step (C).
- the slurry containing solid content can be separated into the crystallized solid content and mother liquor by the same method as in the above-mentioned step (C).
- the solid content crystallized here (hereinafter also referred to as “recovered crystal”) is preferably returned to the above-described step (B) or step (C).
- the recovered crystal contains more impurities than the crystal obtained in the above-mentioned step (C), but the concentration of the impurity in the recovered crystal is the concentration of the impurity in the reaction mixture obtained in the step (A). Lower than. Therefore, by returning the recovered crystals to the step (B) or the step (C), the concentration of impurities in the reaction mixture obtained in the step (A) is lowered, and the purity is higher than when the recovered crystals are not supplied. Can be obtained.
- the composition of the mother liquor obtained in the step (E) is usually phenol: 45 to 70% by mass, bisphenol A: 5 to 15% by mass, impurities such as 2,4′-isomer: 20 to 40% by mass. .
- the mother liquor contains many impurities such as 2,4′-isomer, but often contains more phenol than these impurities.
- the solid content is separated by solid-liquid separation in the step (E). It is preferable to perform a phenol recovery process on the removed mother liquor.
- phenol is recovered from the top of the column by distillation under reduced pressure using a packed distillation column or the like, and a residual liquid containing a large amount of by-products and colored substances after phenol recovery is collected.
- a method obtained from the bottom of the column is preferred.
- the conditions for the distillation under reduced pressure are preferably carried out under conditions of a temperature of 120 to 180 ° C. (preferably 135 to 170 ° C.) and a pressure of 0.5 to 20 kPa (preferably 1.0 to 10 kPa). This vacuum distillation is preferably carried out until the amount of residual phenol in the residual liquid is preferably 20% by mass or less, more preferably 2 to 15% by mass.
- the recovered phenol is, for example, as a solid cleaning solution or re-dissolved solution in the crystallization / solid-liquid separation step of step (C) or (E), or as a reaction raw material used in step (A). Can be used.
- step (F) At least a part of the mother liquor present in the system among the mother liquors obtained in the step (E) is subjected to alkali decomposition treatment to recover phenol and / or p-isopropenylphenol (IPP).
- IPP phenol and / or p-isopropenylphenol
- the recovered phenol and / or IPP is supplied to the reactor in step (A) without going through the recombination reactor.
- the mother liquor obtained by solid separation in step (E) contains a large amount of impurities such as bisphenol A and 2,4′-isomer. Further, in the mother liquor after recovering phenol from the mother liquor, the ratio of impurities such as bisphenol A, 2,4′-isomer increases.
- alkali is added to these mother liquors containing a large amount of impurities, and the mother liquor is supplied to the reaction tank of the alkali decomposition reaction tower. By operating under high temperature and reduced pressure, impurities such as bisphenol A and 2.4′-isomer are decomposed into phenol and IPP. The phenol and IPP can be recovered from the top of the reaction tower.
- Impurities such as chromane compounds are converted into heavy impurities (high-boiling substances), and tar (from the bottom of the reaction tower (reaction tank)) Take out as residue).
- both the said phenol and IPP may collect
- the alkali decomposition treatment can be performed either continuously or batchwise.
- a part of the mother liquor obtained in the step (E) may be discharged out of the system, but at least a part of the mother liquid present in the system after discharge is subjected to an alkali decomposition treatment.
- an alkali decomposition treatment As described above, by subjecting at least a part of the mother liquor present in the system to alkali decomposition treatment, bisphenol A, 2.4′-bisphenol A, trisphenol, etc. present in the mother liquor are decomposed, and phenol and / or Alternatively, IPP can be recovered. Since IPP is a product of phenol and acetone and is an intermediate of bisphenol A, it is necessary to newly supply the system by returning the phenol and / or IPP obtained here to step (A). The supply amount of phenol and acetone as raw materials can be reduced.
- the total amount of the mother liquor obtained in the step (E) is subjected to an alkali decomposition treatment. It is preferable to do.
- alkali used in the alkali decomposition treatment examples include sodium hydroxide and potassium hydroxide, and these may be added in the form of an aqueous solution.
- the amount of alkali to be added is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 2.0% by mass, based on the supply amount excluding phenol supplied to the reaction vessel.
- the temperature of the reaction vessel and distillation column is preferably 180 to 350 ° C., more preferably 190 to 300 ° C., and further preferably 200 to 280 ° C.
- the pressure in the reaction tank and distillation column is preferably 0.5 to 50 kPa, more preferably 1.5 to 20 kPa, and even more preferably 3.0 to 10 kPa.
- the phenol and / or IPP recovered from the top of the column is condensed and liquefied, mixed with the feedstock phenol and acetone, and then supplied to the reactor in step (A).
- the recovered phenol and / or IPP when the recovered phenol and / or IPP is supplied to the reactor of step (A) via the recombination reactor, the phenol and IPP react in the recombination reactor as described above. Bisphenol A is produced.
- this produced bisphenol A is sent into the reactor of step (A), it further reacts with the highly reactive intermediate IPP to produce a by-product, and the quality of the produced bisphenol A is improved. causess a drop. Therefore, in this invention, the collect
- the recovered phenol and IPP are supplied to the reactor of step (A) via other processes / reactors as long as the effects of the present invention are not impaired unless they pass through the recombination reactor. Although it may be carried out, it is preferred that it is fed directly to the reactor in step (A).
- the hue (APHA) measured by the colorimetric method based on JIS K 4101 of bisphenol A obtained by the production method of the present invention is preferably 15 or less, more preferably 12 or less, and still more preferably 10 or less.
- FIG. 2 is a process diagram of the method for producing bisphenol A of Example 1.
- a method for producing bisphenol A performed in Example 1 will be described.
- a catalyst a product obtained by partially neutralizing 20 mol% of a sulfonic acid group with 2-mercaptoethylamine to a sulfonic acid type ion exchange resin (product name “Diaion-104H” manufactured by Mitsubishi Chemical Corporation)
- a packed bed reactor was charged with a mixture of an initial feed amount of phenol 51.9 t / h and acetone 4.5 t / h under an environment of normal pressure (0.1 MPa) while maintaining the temperature of the catalyst layer at 80 ° C.
- the liquid was continuously supplied at a liquid space velocity of 1.0 hr ⁇ 1 (the amount of phenol supplied was 7.1 mol per 1 mol of acetone). And bisphenol A was produced
- unreacted acetone, reaction product water and low-boiling substances were distilled off mainly under conditions of a temperature of 150 ° C. and a pressure of 40 kPa, and then mainly phenol under a condition of a temperature of 90 ° C. and a pressure of 10 kPa.
- the concentrated liquid is cooled from 90 ° C.
- step (C) a solid content containing an adduct of bisphenol A and phenol is crystallized, and then separated by a centrifuge, Separated into 11.2 t / h mother liquor (step (C)).
- the solid matter was washed, melted and adduct decomposed, and then sent to a distillation column operated under conditions of a temperature of 170 ° C. and a pressure of 2 kPa, and phenol was removed by distillation. Then, a solution containing bisphenol A was extracted from the bottom of the distillation column, and the residual phenol was completely removed from the solution by steam stripping to obtain 6.3 t / h bisphenol A.
- the total amount of the 11.2 t / h mother liquor separated by the centrifugal separator was sulfonated cation exchange resin (manufactured by Mitsubishi Chemical Corporation) under the conditions of a temperature of 70 ° C. and a liquid space velocity of 1 hr ⁇ 1.
- No. “Diaion-104H”) was subjected to isomerization treatment (step (D)).
- the 8.8 t / h solution is returned to the concentration step of step (B), and the remaining 2.4 t / h solution is subjected to the conditions of a temperature of 100 ° C. and a pressure of 5 kPa.
- step (E) After concentrating with, and partially distilling off phenol, the mixture was cooled to 50 ° C., and a solid content containing an adduct of bisphenol A and phenol was crystallized, then separated by a centrifuge and solid. The minutes were washed to obtain a 0.7 t / h solid and a 1.7 t / h mother liquor (step (E)). After this solid matter was melted, it was returned to the concentration step of step (B). On the other hand, the mother liquor from which the solid content has been removed in the above step (E) evaporates phenol under the conditions of a temperature of 160 ° C. and a pressure of 2 kPa to recover 1.3 t / h of phenol and 0.4 t / h. A residual liquid (residual mother liquor) was obtained.
- the cycle consisting of the above steps is repeated, the feed phenol and acetone are adjusted, and after a certain time has elapsed so that the production amount of bisphenol A is constant at 6.3 t / h, the feed phenol amount becomes 5.40 t / h, The amount of acetone supplied was 1.70 t / h.
- the produced bisphenol A had a hue (APHA) of 10.
- FIG. 3 is a process diagram of the method for producing bisphenol A of Comparative Example 1.
- Bisphenol A was produced according to the process shown in FIG. That is, the 0.4 t / h residual liquid (residual mother liquor) remaining after recovering phenol from the mother liquor from which the solid content was removed in the process (E) of Example 1 was discarded without passing through the process (F). Except for the above, it was adjusted by the same production method as in Example 1 so that 6.3 t / h bisphenol A was produced.
- the amount of phenol supplied was 5.55 t / h, and the amount of acetone supplied was 1.75 t / h.
- the produced bisphenol A had a hue (APHA) of 10.
- the produced bisphenol A was of high quality as in Example 1.
- the amount of supplied phenol was 0.15 t / h, the amount of supplied acetone was 0.05 t / h, and Example 1 was used. It was necessary to supply more than that of the manufacturing method. That is, the production method of Comparative Example 1 requires more raw materials than the Example 1 by the amount of feed phenol 1,200 t and feed acetone 400 t per year.
- FIG. 4 is a process diagram of the method for producing bisphenol A of Comparative Example 2.
- Bisphenol A was produced according to the process diagram shown in FIG. That is, in step (F) of Example 1, phenol and IPP obtained from the top of the evaporation tower are mixed with phenol recovered in another step, and phenol and IPP are mixed in a recombination reactor.
- step (F) of Example 1 phenol and IPP obtained from the top of the evaporation tower are mixed with phenol recovered in another step, and phenol and IPP are mixed in a recombination reactor.
- step (F) of Example 1 phenol and IPP obtained from the top of the evaporation tower are mixed with phenol recovered in another step, and phenol and IPP are mixed in a recombination reactor.
- step (F) of Example 1 phenol and IPP obtained from the top of the evaporation tower are mixed with phenol recovered in another step, and phenol and IPP are mixed in a recombination reactor.
- the amount of phenol supplied was 5.40 t / h, and the amount of acetone supplied was 1.70 t / h, which was the same as in Example 1.
- the hue (APHA) of the produced bisphenol A was 20, and the quality was inferior to that of the bisphenol A produced in Example 1. This is because, for example, by-product obtained by further reacting IPP and bisphenol A existing in the reactor remains as bisphenol A produced in the recombination reactor is supplied to the reactor. The cause is thought to be.
- the method for producing bisphenol A of the present invention high-quality bisphenol A can be produced, and the amount of raw material used can be effectively reduced.
- the obtained bisphenol A can be used as a raw material for engineering plastics such as polycarbonate resins and polyarylate resins.
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Abstract
Description
特許文献1には、フェノールとアセトンとの反応後の反応溶液を、分離・分割して得た母液の一部を反応器に戻しつつ、当該母液の一部を、異性化工程、母液濃縮工程、晶析・固液分離工程を経て、ビスフェノールAとフェノールとの付加物を回収した回収溶液を得た後、当該回収溶液から、アルカリ分解工程、再結合反応工程を経て、ビスフェノールA及びフェノールを回収して反応器に戻すというプロセスを有する製造方法が開示されている。
異性化処理液からビスフェノールA及びフェノールを回収後、残りの溶液は廃棄している。当該溶液には、アルカリ分解により、フェノールやビスフェノールAの中間体であるp-イソプロペニルフェノールとなり得る有効成分が含まれている。
ビスフェノールAの製造方法において、従来は廃棄していた当該溶液を有効利用し、供給する原料使用量の低減が望まれている。
すなわち、本発明は、下記〔1〕~〔7〕を提供するものである。
〔1〕下記工程(A)~(F)を有する、ビスフェノールAの製造方法。
工程(A):酸触媒の存在下、過剰のフェノールとアセトンとを縮合反応させる反応器において、ビスフェノールAを生成し、ビスフェノールAを含む反応混合液を得る工程
工程(B):工程(A)で得た反応混合液を濃縮し、濃縮液を得る工程
工程(C):工程(B)で得た濃縮液を晶析した後固液分離し、ビスフェノールAとフェノールとの付加物を含む固形分と、母液とに分離する工程
工程(D):工程(C)で得た母液のうち、系内に存在する当該母液の少なくとも一部を異性化処理する工程
工程(E):工程(D)の異性化処理後の溶液を晶析した後固液分離し、固形分と、母液とに分離する工程
工程(F):工程(E)で得た母液のうち、系内に存在する当該母液の少なくとも一部をアルカリ分解処理し、フェノール及び/又はp-イソプロペニルフェノールを回収して、回収した当該フェノール及び/又はp-イソプロペニルフェノールを、再結合反応器を経由することなく、工程(A)の前記反応器に供給する工程
〔2〕工程(D)において、工程(C)で得た母液のうち、系内に存在する当該母液の全量を異性化処理する、上記〔1〕に記載のビスフェノールAの製造方法。
〔3〕工程(D)の異性化処理後の溶液の5~30質量%を工程(E)に送り、当該溶液の95~70質量%を工程(B)へ戻す、上記〔1〕又は〔2〕に記載のビスフェノールAの製造方法。
〔4〕工程(F)において、回収したフェノール及び/又はp-イソプロペニルフェノールを、直接工程(A)の前記反応器に供給する、上記〔1〕~〔3〕のいずれかに記載のビスフェノールAの製造方法。
〔5〕工程(E)で固液分離して固形分を除去した母液に対しフェノール回収処理を行い、フェノール回収処理後の母液を工程(F)に送る、上記〔1〕~〔4〕のいずれかに記載のビスフェノールAの製造方法。
〔6〕製造されるビスフェノールAのJIS K 4101の基づく比色法にて測定される色相(APHA)が15以下である、上記〔1〕~〔5〕のいずれかに記載のビスフェノールAの製造方法。
工程(A):酸触媒の存在下、過剰のフェノールとアセトンとを縮合反応させる反応器において、ビスフェノールAを生成し、ビスフェノールAを含む反応混合液を得る工程
工程(B):工程(A)で得た反応混合液を濃縮し、濃縮液を得る工程
工程(C):工程(B)で得た濃縮液を晶析した後固液分離し、ビスフェノールAとフェノールとの付加物を含む固形分と、母液とに分離する工程
工程(D):工程(C)で得た母液のうち、系内に存在する当該母液の少なくとも一部を異性化処理する工程
工程(E):工程(D)の異性化処理後の溶液を晶析した後固液分離し、固形分と、母液とに分離する工程
工程(F):工程(E)で得た母液のうち、系内に存在する当該母液の少なくとも一部をアルカリ分解処理し、フェノール及び/又はp-イソプロペニルフェノールを回収して、回収した当該フェノール及び/又はp-イソプロペニルフェノールを、再結合反応器を経由することなく、工程(A)の前記反応器に供給する工程
なお、工程(D)における異性化処理とは、反応工程で生成する副生成物を4,4’-体へ転化させる処理を指す。当該副生成物としては、ビスフェノールAの2,4’-体等の異性体が挙げられる。
そこで、本発明では、この回収したフェノール及び/又はIPPは、再結合反応器を経由することなく、工程(A)の反応器に供給される。
また、回収したフェノール及び/又はIPPは、原料フェノールと混合し、工程(A)の反応器に供給することができるので、原料のフェノールやアセトンの供給量を低減できると共に、従来と変わらない高品質のビスフェノールAを得ることができる。
工程(A)は、酸触媒の存在下、過剰のフェノールとアセトンとを縮合反応される反応器において、ビスフェノールAを生成し、ビスフェノールAを含む反応混合液を得る工程である。
本工程では、供給されるフェノールとアセトンとが縮合反応して、p-イソプロペニルフェノール(IPP)を生成した後、当該IPPとフェノールとが更に縮合反応して、ビスフェノールAを生成する。
スルホン形陽イオン交換樹脂としては、スルホン酸基を有する強酸性陽イオン交換樹脂であれば特に制限されず、例えば、スルホン化スチレン-ジビニルベンゼンコポリマー、スルホン化架橋スチレンポリマー、フェノールホルムアルデヒド-スルホン酸樹脂、ベンゼンホルムアルデヒド-スルホン酸樹脂等が挙げられる。これらは、単独で又は2種以上を組み合わせて用いてもよい。
本発明において、メルカプタン類とは、分子内にSH基を遊離の形で有する化合物を意味する。このようなメルカプタン類としては、例えば、アルキルメルカプタン、カルボキシル基、アミノ基、ヒドロキシル基等の置換基一種以上を有するアルキルメルカプタン類等が挙げられる。これらの中でも、2-メルカプトエチルアミン、3-メルカプトプロピルアミン、N,N-ジメチル-3-メルカプトプロピルアミン、N,N-ジ-n-ブチル-4-メルカプトブチルアミン、2,2-ジメチルチアゾリジン等のメルカプトアルキルアミンが好ましい。
メルカプタン類により中和された強酸性陽イオン交換樹脂中のスルホン酸基の含有量としては、中和前の強酸性陽イオン交換樹脂中の全スルホン酸基の総量に対して、好ましくは5~35モル%、より好ましくは10~30モル%、更に好ましくは15~25モル%である。
ただし、生成するビスフェノールAの精製の容易さや経済性等の観点から、アセトン1モルに対するフェノールの供給量が、好ましくは3~30モル、より好ましくは5~20モルである。
固定床連続反応方式における反応塔は、1基でもよく、2基以上を直列に配置した固定床多段連続反応方式としてもよい。
また、フェノールとアセトンとの反応の際の圧力は、好ましくは常圧(0.1MPa)~1.5MPa、より好ましくは常圧(0.1MPa)~0.6MPaである。
工程(B)は、工程(A)で得た反応混合液を濃縮し、濃縮液を得る工程である。本工程により、反応混合液から、未反応アセトン、未反応フェノール、副生成物である水等の低沸点物質等が除去されると共に、生成したビスフェノールの濃度を適度な範囲に調製することができる。
本工程は、蒸留塔を用いた減圧蒸留により、反応混合液を濃縮することが好ましい。
また、本工程の濃縮は、主として未反応アセトン、水、低沸点物質等を留去する第一濃縮工程と、主として未反応フェノール等を留去し、濃縮液の濃度を調整する第二濃縮工程とに分けて行うことが好ましい。
なお、第二濃縮工程での減圧蒸留における温度及び圧力は、成分の沸点の上昇を考慮して、第一濃縮工程よりも、低く設定することが好ましい。
工程(C)は、工程(B)で得た濃縮液を晶析した後固液分離し、ビスフェノールAとフェノールとの付加物(以下、「アダクト」ともいう)を含む固形分と、母液とに分離する工程である。
濃縮後の溶液から固形分の晶析方法としては、晶析前の減圧蒸留終了直後の濃縮液を、35~60℃(好ましくは40~55℃)まで冷却して、上記固形分を晶析してスラリーとすることが好ましい。
この際の冷却は、外部熱交換器を用いて行なってもよく、また、濃縮液に水を加えて、減圧下での水の蒸発潜熱を利用して冷却する真空冷却晶析法により行なってもよい。
この際、使用する洗浄液としては、例えば、フェノール、水、水-フェノール混合液等が挙げられる。なお、フェノールは、系内から回収したフェノールを用いてもよく、系外から別途供給したフェノールを用いてもよい。
使用する洗浄液の量は、洗浄効率、及び再溶解のための損失、洗浄液の循環、回収、再使用の観点から、分離した固形分の質量に対して、0.1~10倍が好ましい。
上記の固液分離により回収された固形分に含まれる、ビスフェノールAとフェノールとの付加物(アダクト)は、アダクト分解工程を経ることで、ビスフェノールAとフェノールに分解され、フェノールを除去することで、高純度のビスフェノールAを得ることができる。
アダクト分解工程では、はじめに、アダクトを含む固形分を、好ましくは100~160℃で加熱溶融して、アダクトをビスフェノールAとフェノールとに分解し、これらを含む溶融液を得る工程を経ることが好ましい。
次いで、この溶融液を蒸発塔に送り、減圧蒸留等により、この溶融液からフェノールを除去し、溶融状態のビスフェノールAを回収する。当該減圧蒸留は、温度150~190℃で、圧力1~11kPaの条件下で行うことが好ましい。
また、回収した溶融状態のビスフェノールAは、更にスチームストリッピングにより残存するフェノールを除去することが好ましい。
このような工程を経て、高純度のビスフェノールAを得ることができる。
工程(D)は、工程(C)で得た母液で、系内に存在する当該母液の少なくとも一部を異性化処理する工程である。
工程(C)で得た母液の組成は、通常、フェノール:65~85質量%、ビスフェノールA:10~20質量%、2,4’-異性体等の不純物:5~15質量%であり、異性体等の不純物が多く含まれている。
本発明において、工程(C)で得た母液のうち、当該母液の一部系外に排出してもよいが、少なくとも排出後に系内に存在する母液の少なくとも一部を異性化処理する。
上述のとおり、系内に存在する母液の少なくとも一部を異性化処理することで、母液中の不純物をできる限りビスフェノールAに転化して、ビスフェノールAの濃度を上げることができる。そのため、系内に不純物が蓄積することを防止するために母液の一部を系外へパージする際に、パージ母液中から、ビスフェノールAをより多く回収することができ、ビスフェノールAの回収率を向上させることができる。
本工程で系内に存在する母液のうち、異性化処理を行う母液の割合は、ビスフェノールAの回収率を向上させる観点から、好ましくは50~100質量%、より好ましくは70~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%であり、系内に存在する当該母液の全量を異性化処理することが特に好ましい。
異性化処理は、上記スルホン酸型陽イオン交換樹脂の存在下、反応温度50~100℃(好ましくは60~90℃)で、連続式で押し出し流れ方式である固定床流通方式で行われることが好ましい。
この固定床流通方式の場合、溶液の液空間速度は、好ましくは0.1~20hr-1、より好ましくは0.3~15hr-1、更に好ましくは0.5~10hr-1である。
上記観点から、異性化処理後の溶液のうち、工程(E)へ送る溶液量としては、好ましくは5~30質量%、より好ましくは10~25質量%、更に好ましくは13~23質量%であり、工程(B)へ戻す溶液量としては、好ましくは95~70質量%、より好ましくは90~75質量%、更に好ましくは87~77質量%である。
工程(E)は、工程(D)の異性化処理後の溶液を晶析した後固液分離し、固形分と、母液とに分離する工程である。本工程により、ビスフェノールAとフェノールとの付加物(アダクト)を含む固形分を晶析させ、固形分と母液とに分離する。
また、固形分を含むスラリーは、上述の工程(C)と同様の方法により、晶析した固形分と母液とに分離することができる。
工程(E)で得た当該母液の組成は、通常、フェノール:45~70質量%、ビスフェノールA:5~15質量%、2,4’-異性体等の不純物:20~40質量%である。当該母液には、2,4’-異性体等の不純物を多く含んでいるが、これら不純物よりも多くのフェノールが含んでいる場合が多い。そのため、フェノール回収の効率性の観点から、当該母液を工程(F)に送る前に、当該母液中に含まれる多くのフェノールを回収するため、工程(E)で固液分離して固形分を除去した母液に対してフェノール回収処理を行うことが好ましい。
当該減圧蒸留の条件としては、温度120~180℃(好ましくは135~170℃)、圧力0.5~20kPa(好ましくは1.0~10kPa)の条件下で行うことが好ましい。なお、この減圧蒸留は、残留液中の残存フェノール量が、好ましくは20質量%以下、より好ましくは2~15質量%になるまで行うことが好ましい。
工程(F)は、工程(E)で得た母液のうち、系内に存在する当該母液の少なくとも一部をアルカリ分解処理し、フェノール及び/又はp-イソプロペニルフェノール(IPP)を回収して、回収した当該フェノール及び/又はIPPを、再結合反応器を経由することなく、工程(A)の前記反応器に供給する工程である。
なお、本工程において、工程(E)で得た母液のうち、系内に存在する当該母液の全量に対してアルカリ分解処理を行ってもよい。ただし、工程(E)で固液分離して固形分を除去した母液にフェノール回収処理を行い、フェノールを回収後の残りの母液に対してアルカリ分解処理を行うことが好ましい。
当該フェノールとIPPは、反応塔の塔頂より回収することができ、クロマン化合物等の不純物は重質の不純物(高沸点物)に変換され、反応塔の塔底(反応槽)より、タール(残渣)として取り出す。
なお、当該フェノールとIPPは、双方とも回収してもよく、一方のみを回収してもよい。
なお、アルカリ分解処理は、連続式又は回分式のいずれでも行うこともできる。
上述のとおり、系内に存在する当該母液の少なくとも一部をアルカリ分解処理することで、当該母液中に存在するビスフェノールA、2.4’-ビスフェノールA、トリスフェノール等が分解し、フェノール及び/又はIPPを回収することができる。IPPは、フェノールとアセトンからの生成物であり、ビスフェノールAの中間体であるため、ここで得たフェノール及び/又はIPPを、工程(A)に戻すことで、系内に新たに供給を必要とする原料のフェノール及びアセトンの供給量の低減することができる。
添加するアルカリの量は、反応槽に供給されるフェノールを除いた供給量に対して、好ましくは0.01~3.0質量%、より好ましくは0.05~2.0質量%である。
また、反応槽及び蒸留塔の圧力は、好ましくは0.5~50kPa、より好ましくは1.5~20kPa、更に好ましくは3.0~10kPaである。
そのため、本発明においては、回収したフェノール及び/又はIPPは、再結合反応器を経由することなく、工程(A)の反応器に供給される。
本発明の製造方法により得られたビスフェノールAのJIS K 4101の基づく比色法にて測定される色相(APHA)は、好ましくは15以下、より好ましくは12以下、更に好ましくは10以下である。
なお、以下の実施例及び比較例において、製造工程中に生成されたフェノール及びビスフェノールA等は、HPLC分析によって定量した。
また、製造したビスフェノールAの色相(APHA)は、20gのビスフェノールAを、エタノール20mlに溶解し、分光光度計(日立製作所社製、製品名「U-3410型自記分光光度計」)を用いて、JIS K 4101に基づく比色法にて測定した。
図2は、本実施例1のビスフェノールAの製造方法の工程図である。以下、図2に示した工程図に従って、実施例1で行ったビスフェノールAを製造方法について説明する。
触媒として、スルホン酸型イオン交換樹脂(三菱化学(株)製、製品名「ダイヤイオン-104H」)に対して、2-メルカプトエチルアミンにてスルホン酸基の20モル%を部分中和したものを充填した固定床反応器に、初期供給量フェノール51.9t/hとアセトン4.5t/hとの混合物を、触媒層の温度を80℃に保ちながら、常圧(0.1MPa)の環境下、液空間速度1.0hr-1にて連続的に供給した(アセトン1モルに対するフェノールの供給量は7.1モル)。そして、ビスフェノールAを生成して、該ビスフェノールAを含む反応混合液を得た(工程(A))。
得られた反応混合液から、温度150℃、圧力40kPaの条件下で、主として未反応アセトン、反応生成水、低沸点物質を留去し、次いで温度90℃、圧力10kPaの条件下で、主としてフェノールを留去し、濃縮して、濃縮液を得た(工程(B))。
この濃縮液を、90℃から45℃まで冷却して、ビスフェノールAとフェノールとの付加物(アダクト)を含む固形分を晶析させた後、遠心分離機により分離して、当該固形物と、11.2t/hの母液とに分離した(工程(C))。なお、固形物については、洗浄し、溶融して、アダクト分解した後、温度170℃、圧力2kPaの条件下に操作された蒸留塔に送り、フェノールを留去回収した。そして、蒸留塔の塔底からビスフェノールAを含む溶液を抜き出し、更にスチームストリッピングにより当該溶液から残存フェノールを完全に除去して、6.3t/hのビスフェノールAを得た。
そして、異性化処理後の溶液のうち、8.8t/hの溶液は、工程(B)の濃縮工程に戻し、残りの2.4t/hの溶液を、温度100℃、圧力5kPaの条件下で濃縮して一部フェノールを留去した後、50℃まで冷却して、ビスフェノールAとフェノールとの付加物(アダクト)を含む固形分を晶析させた後、遠心分離機で分離し、固形分を洗浄して、0.7t/hの固形物と、1.7t/hの母液を得た(工程(E))。この固形物は、溶融した後、工程(B)の濃縮工程に戻した。
一方、上記の工程(E)で固形分を除去した母液は、温度160℃、圧力2kPaの条件下で、フェノールを蒸発させ、1.3t/hのフェノールを回収すると共に、0.4t/hの残留液(残留母液)を得た。
図3は、本比較例1のビスフェノールAの製造方法の工程図である。図3に示した工程に従ってビスフェノールAを製造した。
つまり、実施例1の工程(E)で固形分を除去した母液からフェノールを回収した後に残った0.4t/hの残留液(残留母液)を、上記工程(F)を経ずに廃棄した以外は、実施例1と同様の製造方法により、6.3t/hのビスフェノールAが製造されるように調整した。
製造されたビスフェノールAは、実施例1同様に高品質であったが、比較例1の製造方法では、供給フェノール量を0.15t/h、供給アセトン量を0.05t/h、実施例1の製造方法に比べて、多く供給する必要があった。
つまり、比較例1の製造方法は、実施例1に比べて、年間で供給フェノール1,200t、供給アセトン400tだけ多くの原料を必要とする。
図4は、本比較例2のビスフェノールAの製造方法の工程図である。図4に示した工程図に従ってビスフェノールAを製造した。
つまり、実施例1の工程(F)において、蒸発塔の塔頂から得たフェノール及びIPPを、他の工程にて回収したフェノールと混合して、再結合反応器にて、フェノールとIPPとを反応させてビスフェノールAを生成し、再結合反応器で生成したビスフェノールAを含む反応物を工程(A)の固定床反応器に供給した以外は、実施例1と同様の製造方法により、6.3t/hのビスフェノールAが製造されるように調整した。
Claims (6)
- 下記工程(A)~(F)を有する、ビスフェノールAの製造方法。
工程(A):酸触媒の存在下、過剰のフェノールとアセトンとを縮合反応させる反応器において、ビスフェノールAを生成し、ビスフェノールAを含む反応混合液を得る工程
工程(B):工程(A)で得た反応混合液を濃縮し、濃縮液を得る工程
工程(C):工程(B)で得た濃縮液を晶析した後固液分離し、ビスフェノールAとフェノールとの付加物を含む固形分と、母液とに分離する工程
工程(D):工程(C)で得た母液のうち、系内に存在する当該母液の少なくとも一部を異性化処理する工程
工程(E):工程(D)の異性化処理後の溶液を晶析した後固液分離し、固形分と、母液とに分離する工程
工程(F):工程(E)で得た母液のうち、系内に存在する当該母液の少なくとも一部をアルカリ分解処理し、フェノール及び/又はp-イソプロペニルフェノールを回収して、回収した当該フェノール及び/又はp-イソプロペニルフェノールを、再結合反応器を経由することなく、工程(A)の前記反応器に供給する工程 - 工程(D)において、工程(C)で得た母液のうち、系内に存在する当該母液の全量を異性化処理する、請求項1に記載のビスフェノールAの製造方法。
- 工程(D)の異性化処理後の溶液の5~30質量%を工程(E)に送り、当該溶液の95~70質量%を工程(B)へ戻す、請求項1又は2に記載のビスフェノールAの製造方法。
- 工程(F)において、回収したフェノール及び/又はp-イソプロペニルフェノールを、直接工程(A)の前記反応器に供給する、請求項1~3のいずれかに記載のビスフェノールAの製造方法。
- 工程(E)で固液分離して固形分を除去した母液に対しフェノール回収処理を行い、フェノール回収処理後の母液を工程(F)に送る、請求項1~4のいずれかに記載のビスフェノールAの製造方法。
- 製造されるビスフェノールAのJIS K 4101の基づく比色法にて測定される色相(APHA)が15以下である、請求項1~5のいずれかに記載のビスフェノールAの製造方法。
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