JP4506210B2 - Method for producing bisphenol A - Google Patents

Method for producing bisphenol A Download PDF

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JP4506210B2
JP4506210B2 JP2004062552A JP2004062552A JP4506210B2 JP 4506210 B2 JP4506210 B2 JP 4506210B2 JP 2004062552 A JP2004062552 A JP 2004062552A JP 2004062552 A JP2004062552 A JP 2004062552A JP 4506210 B2 JP4506210 B2 JP 4506210B2
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bisphenol
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phenol
acetone
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竜郎 田中
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三菱化学株式会社
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  The present invention relates to a method for producing bisphenol A, and more particularly to a method for producing bisphenol A that prevents shrinkage of an ion exchange resin catalyst during an operation stop period.

  Bisphenol A is usually produced by reacting phenol and acetone in the presence of an acidic catalyst made of a strongly acidic cation exchange resin. In addition to bisphenol A, the reaction product contains reaction by-products such as unreacted phenol, unreacted acetone, reaction product water, and coloring substances. A typical example of the acidic catalyst is a strong acidic cation exchange resin. Among the reaction by-products, the main one is 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane (hereinafter sometimes referred to as 2,4′-isomer), and other trimethyl Examples include indane, dianin's compound, trisphenol, polyphenol, and coloring substances.

  As one method for separating high-purity bisphenol A from the reaction mixture, unreacted acetone, reaction product water and some unreacted phenol are removed from the reaction product solution by distillation or the like, and then the remaining concentrated mixture There is a method in which bisphenol A is crystallized as an adduct (adduct) with phenol by cooling the liquid, this crystal is separated from the mother liquor containing reaction by-products, and then phenol is removed from the adduct to recover bisphenol A. is there. The mother liquor from which this adduct crystal has been separated contains a large amount of phenol and bisphenol A in addition to reaction by-products such as 2,4′-isomer, trimethylindane, dianine compound, trisphenol, polyphenol and colored substances. Therefore, this mother liquor is circulated in the reaction system (for example, JP-A-5-331088).

In JP-A-2002-255879, in order to prevent deterioration of the cation exchange resin catalyst while the production apparatus for bisphenol A is stopped, after the production apparatus is stopped, the cation exchange resin is washed with phenol, It is described that it is stored in a phenolic solution. The method disclosed in Japanese Patent Application Laid-Open No. 2002-255879 is intended to prevent the cation exchange resin from flowing out by preventing the sulfonic acid from flowing out of the cation exchange resin during the operation stop period.
JP-A-5-331088 JP 2002-255879 A

  When bisphenol A is produced from phenol and acetone over a long period of time in a fixed bed flow reactor using a cation exchange resin or at least partly modified one as a catalyst, the pressure loss of the reactor increases. There was a problem. For this reason, the allowable pressure loss of the reactor is eventually exceeded, and the production load must be reduced, or in the worst case, there is no possibility of destroying the reactor. Such an increase in the pressure loss of the reactor can be a factor that hinders stable and safe production of bisphenol A.

  As a result of various studies, the cation exchange resin in the reactor contracts and the packing density is reduced while the operation of the bisphenol A production facility is temporarily stopped during regular maintenance or various maintenance of the production facility. It was found that the cation exchange resin swells again after restarting operation, thereby increasing the reactor pressure drop.

  That is, when producing bisphenol A by reaction of phenol and acetone, the cation exchange resin of the catalyst or at least a part thereof is slightly swollen by the reaction byproduct water. On the other hand, when the reaction is temporarily stopped, it is necessary to first stop the supply of acetone to the reactor and continue the supply of phenol for a while. This is because bisphenol A produced by the reaction is pushed out from the reactor by the phenol, and crystals of an adduct of bisphenol A and phenol are prevented from being precipitated in the reactor.

  At that time, the reaction by-product water inevitably flows out of the reactor, so that the cation exchange resin or at least part of the catalyst which has been slightly swollen until then shrinks, and the packing density Will increase. After that, when the reaction is restarted, the reaction cation-generated resin or at least partly modified cation exchange resin is swollen again, the voids between the resins are further reduced, and the pressure loss is increased.

  The present invention prevents the contraction of a cation exchange resin of a catalyst or a modified one of the catalyst during the operation stop period of the production apparatus, and produces bisphenol A capable of stably producing bisphenol A after restarting the operation. It aims to provide a method.

The method for producing bisphenol A according to the present invention (Claim 1) is obtained by reacting bisphenol A and phenol with acetone and an excess amount of phenol in the presence of an ion exchange resin or a catalyst made by modifying at least a part thereof. A reactor for obtaining a reaction product containing; a low boiling removal tower for removing a component having a boiling point lower than that of phenol from the reaction product; a mixture obtained in the low boiling removal step is cooled, and bisphenol A and phenol are cooled. A bisphenol A production apparatus comprising: a crystallization means for crystallizing an adduct of bisphenol and a mother liquor for separating a mother liquor; and a mother liquor circulation means for circulating part of the mother liquor separated in the crystallization means to a reactor. A process for producing bisphenol A, the production operation process for producing bisphenol A, and the supply of acetone to the reactor and the liquid being circulated to the reactor. Operation and stopping step of distributing, in the manufacturing method of bisphenol A with, to the water concentration in the liquid circulating flow in the reactor with 0.2 wt% or more and 12 wt% or less during the shutdown process It is a feature.

  The method for producing bisphenol A according to claim 2 is the method according to claim 1, wherein the composition of the liquid circulated during the shutdown step is 5 wt% or less of acetone, 12 wt% or more of bisphenol A, 25 wt% or less, and 70 wt% of phenol. % Or more, 87.8% by weight or less, and water 0.2% by weight or more.

  The method for producing bisphenol A according to claim 3 is characterized in that, in claim 1 or 2, the temperature of the liquid circulated during the operation stop step is 60 ° C. or more and 80 ° C. or less.

  The method for producing bisphenol A according to claim 4 is the method according to any one of claims 1 to 3, wherein the linear velocity of the liquid that is circulated during the shutdown process and the liquid on the basis of an empty column in the reactor, 1.0 m / hr or more and 5 m / hr or less.

  The method for producing bisphenol A according to claim 5 is the method according to any one of claims 1 to 4, wherein when the operation of the production apparatus for bisphenol A is stopped, the supply of raw material acetone is first stopped, and then from the reactor. Before the water concentration in the reaction liquid flowing out becomes lower than 0.2%, the supply of the effluent from the reactor to the low boiling removal tower is stopped and the reactor effluent is circulated to the inflow side of the reactor. It is characterized by making it.

According to the method for producing bisphenol A of the present invention, the water concentration in the liquid circulated through the reactor during the shutdown period of the production apparatus is 0.2 wt% (hereinafter abbreviated as%) to 12 wt%. Therefore, the cation exchange resin catalyst in the reactor is not dehydrated and dehydration shrinkage does not occur. For this reason, there is no increase in packing density in the reactor accompanying shrinkage. Then, the cation exchange resin does not swell again after the operation is restarted, and the packing density of the cation exchange resin after the operation restart is not changed at all or almost before the operation is stopped, and the liquid pressure loss of the reactor after the operation restarts. Is the same as before the shutdown.

The upper limit of the water concentration in the liquid circulated through the reactor during the operation stop period is 12% by weight, and the state during the operation period may be maintained, and water may not be added . Preferably, this upper limit is 5% by weight.

  The composition of the liquid circulating in the reactor during the shutdown period is 5% by weight or less of acetone, 12% by weight or more of bisphenol A, 25% by weight or less, 70% by weight or more of phenol, 87.8% by weight or less, water 0 .2 wt% or more and 12 wt% or less is preferable, and the liquid temperature is preferably 60 to 80 ° C. By setting it as such conditions, it is prevented that the adduct crystal | crystallization consisting of the adduct of bisphenol A and a phenol precipitates in a reactor.

  Further, the linear velocity of the liquid based on the empty column in the reactor of this liquid is preferably 1 to 5 m / hr. Thus, by setting the linear velocity to 1 m / hr or more, the temperature distribution in the reactor can be made uniform. Moreover, the pressure loss does not become excessive by setting the linear velocity to 5 m / hr or less.

  In addition, the produced | generated water is contained in the liquid which flows out from a reactor during bisphenol A manufacturing operation. Therefore, when the operation of the production apparatus is stopped, after the acetone new feed is stopped, the reaction is performed as quickly as possible without delay (at the latest, before the water concentration in the reactor effluent becomes lower than 0.2%). It is preferred to circulate the reactor effluent to the reactor inlet side. As a result, a liquid having a water concentration of 0.2% or more is circulated through the reactor.

  The method for producing bisphenol A of the present invention is carried out using an apparatus having a reactor for reacting phenol with acetone, a low boiling point removal tower, a crystallization means, and a mother liquor circulation means.

  Hereinafter, each process by this manufacturing apparatus and other processes optionally added will be described in detail with reference to the drawings.

  FIG. 1 is a process flow chart suitable for carrying out this bisphenol A production method. New feed acetone and a mother liquor mainly composed of phenol circulated from the line 15 are supplied to the reactor 2 via the line 1, and the reaction product is introduced to the distillation column 4 via the line 3, Distilled.

  In this embodiment, a reaction liquid circulation line 16 for returning the effluent from the reactor 2 to the mother liquor circulation line 13 without sending it to the distillation column 4 is provided. The reaction liquid circulation line 16 is passed only during the production operation stop period, and the valve 16a provided in the reaction liquid circulation line 16 is closed during the production operation of bisphenol A.

  A column top component composed of acetone, water, a small amount of phenol and the like in the distillation column 4 is sent to the separation system 20 by distillation, and the acetone is returned to the line 1 through the line 21. Water is discharged out of the system. Phenol is sent to a phenol storage tank 22.

  The bottom component of the distillation column 4 is sent to the crystallizer 5 to precipitate a crystal adduct formed by adding bisphenol A and phenol. This crystal adduct is solid-liquid separated by the solid-liquid separator 6, then re-dissolved by the re-dissolver 7, re-crystallized by the re-crystallizer 8, and a solid-liquid separation system 9 comprising a centrifugal separator or the like. Solid-liquid separation. In this embodiment, in this solid-liquid separation system 9, the separated crystal adduct is rinsed with clean phenol supplied from the tank 22. The rinse waste liquid is sent to the re-dissolver 7 via the line 10. The crystal adduct after rinsing is heated by the adduct decomposition system 11 to be decomposed into bisphenol A and phenol, and the bisphenol A is purified by the purification system 12 to become the product bisphenol A. The phenol separated by the adduct decomposition system 11 and the purification system 12 is sent to the tank 22.

  The liquid component (mother liquor) separated by the solid-liquid separator 6 is sent to the mother liquor tank 14 via the circulation line 13. The mother liquor in the mother liquor tank 14 is sent to the line 1 via the line 15, mixed with acetone, and introduced into the reactor 2.

  In this embodiment, the supply amount from the line 15 to the line 1 is controlled so that the ratio of acetone and the mother liquor in the mixed liquid of acetone and the mother liquor flowing in the line 1 falls within a predetermined range. The tank 14 is a buffer tank for leveling fluctuations in the circulation amount from the line 13.

  Thus, since the ratio of acetone in the reaction raw material liquid introduced into the reactor 2 via the line 1 and the mother liquor mainly composed of phenol supplied via the line 15 is stabilized, the reactor 2 The reaction in is stabilized, and the quality and yield of the product bisphenol A are stabilized.

Hereinafter, conditions and the like of each process executed in the above flow will be described in detail.
[1] Reaction Step In the reaction step performed in the reactor 2, the raw material phenol and acetone are reacted in a stoichiometric excess of phenol. The molar ratio of phenol to acetone is in the range of phenol / acetone = 3-30, preferably 5-20. The reaction temperature is usually 50 to 100 ° C., and the reaction pressure is usually atmospheric pressure to 0.6 MPa.

  As the catalyst, a strongly acidic cation exchange resin such as a sulfonic acid type is particularly suitable.

  The catalyst may be a catalyst obtained by modifying a part of the strongly acidic cation exchange resin catalyst with a promoter such as mercaptoalkylamine or mercaptoalkylpyridine. Examples of such a catalyst include 2-mercaptoethylamine, 3-mercaptopropylamine, N, N-dimethyl-3-mercaptopropylamine, N, N-di-n-butyl-4-mercaptobutylamine, 2,2 -The thing by which 5-30 mol% of the sulfonic acid groups were neutralized with dimethyl thiazolidine, 2- (4-pyridyl) ethanethiol, etc. is mentioned.

The condensation reaction between phenol and acetone is preferably carried out in a continuous bed flow system, a fixed bed flow system, or a suspension bed batch system. In the case of a fixed bed flow system, the liquid space velocity of the raw material liquid supplied to the reactor is preferably 0.2 to 50 hr −1 . In addition, when the suspension bed batch method is used, the amount of the resin catalyst is generally in the range of 20 to 100% by weight with respect to the raw material liquid, although it varies depending on the reaction temperature and reaction pressure. About 5 to 5 hours is preferable.

[2] Low-boiling removal step In the low-boiling removal step in the distillation column 4, the low-boiling components such as unreacted acetone and water are removed from the reaction mixture from the reactor 2 by a method such as vacuum distillation. The vacuum distillation is preferably carried out at a temperature of 50 to 150 ° C. and a pressure of 0.0065 to 0.040 MPa. The concentration of bisphenol A after removal of this low boiling point is preferably 20 to 50% by weight. When the concentration of bisphenol A is less than 20% by weight, the yield is low. When the concentration is more than 50% by weight, the apparent viscosity of the concentrated mixed liquid becomes high and transportation becomes difficult.

  Water, acetone, and a small amount of phenol accompanying them as the top components removed in the low boiling removal step are separated into water, acetone, and phenol in the separation system 20, preferably by multistage distillation. Acetone is returned to the reaction step, mixed with New Feed acetone, and supplied to the reaction tower. Phenol is rectified in the purifier 20a together with Newfeed's phenol, then stored in a clean phenol storage tank 22, and used for rinsing an adduct described later.

[3] Crystallization Step The concentrated liquid from which the low boiling point has been removed in the low boiling removal step in the distillation tower 4 is cooled from 70 to 140 ° C. to 35 to 60 ° C. in the crystallization step in the crystallizer 5. The crystal adduct crystallizes into a slurry.

  This slurry liquid is solid-liquid separated by a filter or the like in the first solid-liquid separation step in the solid-liquid separator 6.

  As the crystallizer 5, a crystallizer having a plurality of external coolers capable of switching operation is preferably used. A plurality of the external coolers are provided and switched to prevent freezing of the coolers. At the time of switching the external cooler, the crystallization characteristics in the crystallization tank vary, and as a result, the amount of mother liquor separated by the solid-liquid separator 6 varies. In the present invention, even if the mother liquor production amount fluctuates, a part of the mother liquor is bypassed to the rear stage side of the reactor 2 via the line 17 in order to prevent fluctuation of the mother liquor amount supplied from the line 15 to the line 1. .

[4] Recovery step of bisphenol A After this solid-liquid separation, the recovered crystal adduct is redissolved in phenol by the re-dissolver 7 and recrystallized by the re-crystallizer 8 to increase the purity. Solid-liquid separation is performed in the second solid-liquid separation step performed in the liquid separation system 9 and rinsed with clean phenol. After that, it is sent to the adduct decomposition system 11.

  Note that most of the separated liquid and the rinse waste liquid from the second solid-liquid separation step are used as the adduct redissolving phenol in the remelter 7. A part of the separation liquid from the second solid-liquid separation step is circulated to the tank 14 together with the circulation mother liquor.

  The recovery method employed in the adduct decomposition system 11 is preferably a method in which the adduct is heated and melted at 100 to 160 ° C. to decompose into bisphenol A and phenol, and most of the phenol is distilled off from the melt. is there. In the purification system 12, a method of purifying bisphenol A by removing residual phenol by steam stripping is preferable. This method is known, for example, from JP-A-2-28126 and JP-A-63-132850.

[5] Mother-Liquid Circulation Step The liquid phase portion (mother liquor) separated by the solid-liquid separator 6 is circulated through the lines 13, 15 and 16 to the front side and the rear side of the reaction step as described above. .

  In the present invention, the whole amount of the mother liquor from the solid-liquid separation step is not circulated as it is, but a part of the mother liquor is separated and subjected to an impurity removal treatment to increase purity, and then supplied to the above circulation supply. preferable.

  That is, the composition of the mother liquor obtained in the solid-liquid separation step in the solid-liquid separator 6 is usually from 65 to 85% by weight of phenol, from 10 to 20% by weight of bisphenol A, and from by-products such as 2,4′-isomer. It is 15% by weight and contains a large amount of impurities such as 2,4′-isomer. In order to prevent the accumulation of impurities in the circulation system, it is subjected to impurity decomposition and removal treatment and then supplied to circulation.

  In order to decompose and remove impurities, a part of the mother liquor is separated from the line 13 into the impurity removing system 13a, a decomposition catalyst such as sodium hydroxide is added to the separated mother liquor, and distilled to remove phenol and isoform. It is preferable to recover propenylphenol as a top component and return the recovered portion to the circulation line 13 after contacting the recovered portion with the acidic ion exchange resin. The bottom of the column is discharged out of the system.

  The fraction of mother liquor fractionated from the line 13 to the impurity removal system 13a is preferably about 4 to 15% by weight. By providing this impurity removal system 13a, the composition of the mother liquor circulated from the line 13 to the tank 14 is approximately 50 to 85% by weight of the above-mentioned phenol, 10 to 20% by weight of bisphenol A, and a minor component such as 2,4′-isomer. The organism becomes stable in the range of 5 to 15% by weight.

  The line 13 is preferably provided with means for separating a part of the mother liquor and removing the cation exchange resin residue derived from the reaction step contained in a trace amount, and then returning the liquid to the line again. .

  The mother liquor from the line 13 is supplied to the line 1 via the tank 14 and the line 15 as described above.

A pump for sending mother liquor from the tank 14 to the line 15 so as to have a constant mixing ratio with respect to the total amount of the new feed amount A 1 of acetone to the line 1 and the return amount A 2 of acetone through the line 21 ( (Not shown) is controlled. The preferred ratio of phenol / acetone is as described above.

  Next, the case where the manufacturing operation process of bisphenol A is stopped and the operation is shifted to the operation stopping process will be described.

  In order to stop the production operation, first, the supply of acetone (new feed) is stopped. Thereafter, the valve 3a of the line 3 is immediately closed and the valve 16a of the reaction liquid circulation line 16 is opened, and the liquid flowing out from the reactor 2 is circulated to the reactor 2 through the tank 14, and this state is maintained during the operation stop period. continue. Thus, when the effluent of the reactor 2 is circulated to the reactor 2 immediately after the supply of new feed acetone is stopped, the liquid containing a large amount of water (reaction product water) flowing out of the reactor 2 It will circulate. By continuing this state during the shutdown period, the water concentration in the liquid passed through the reactor 2 is kept at 0.2% or more. As a result, the dehydration and shrinkage of the catalyst ion exchange resin in the reactor 2 is prevented, and the loss of liquid passage pressure in the reactor 2 after the restart of operation becomes equivalent to that before the stop of operation.

  When the supply of acetone is stopped, the synthesis reaction of bisphenol A in the reactor 2 will eventually stop and water will not be produced, but bisphenol will still remain in the reactor 2 immediately after the acetone stop. Since the production reaction of A proceeds and water is produced, the effluent of the reactor 2 contains 0.2% or more of water.

  And the liquid which contains 0.2% or more of this water circulates through the reactor 2 and the reaction liquid circulation line 16 during the operation stop period. When the effluent from the reactor 2 is circulated through the reactor 2 immediately after the supply of acetone is stopped, the composition of the liquid circulated through the reactor 2 during the operation stop period is usually 5% by weight or less of acetone. Bisphenol A is 12% by weight or more and 25% by weight or less, phenol is 70% by weight or more and 87.8% by weight or less, and water is 0.2% by weight or more and 5% by weight or less.

  Although not shown, a heat exchanger is provided on the inlet side of the reactor 2 for heating the liquid that is circulated and introduced into the reactor 2. It is desirable to prevent precipitation of adduct crystals in the reactor 2 by heating the liquid introduced into the reactor 2 to 60 to 80 ° C. with this heat exchanger. At this time, the linear velocity of the empty standard in the reactor 2 is set to 1 m / hr or more, the heated liquid is circulated in the region in the reactor 2, and the temperature distribution in the reactor 2 is reduced. However, it is preferable to eliminate the local temperature drop. However, if the linear velocity of the liquid is excessive, the pressure loss increases and the liquid passing power cost increases. Therefore, it is desirable that the linear velocity of the liquid based on the empty column is 5 m / hr or less.

  Hereinafter, the method of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[Example 1]
A pilot plant having the flow shown in FIG. 1 was operated to continuously produce bisphenol A. As a catalyst in the reactor 2, Amberlyst-31 (manufactured by Rohm and Haas), which is a sulfonic acid type cation exchange resin, was partially mixed with 2-mercaptoethylamine in 20 mol% of sulfonic acid groups. The sum was filled with 2.0 m 3 .

  The new feed amount of acetone was 58.0 kg / h.

  The temperature of the distillation column 4 was 137 ° C., and the pressure was 0.02 MPa. As the crystallizer 5, a crystallization tank having three external coolers was used, and crystallization was performed while sequentially stopping one of the three external coolers. The temperature of the crystallization tank fluctuated in the range of 49 ° C to 51 ° C.

  Table 1 shows the differential pressure in the reactor on the 250th day after the start of operation. (Example 1- (1))

Next, the new feed of acetone was stopped, and after 300 seconds, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 40 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.01%
Bisphenol A: 22.8%
Phenol: 71.8%
Water: 1.05%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Example 1- (1))

  Table 1 shows the differential pressure of the reactor on the 340th day after the start of operation. (Example 1- (2))

Next, the new feed of acetone was stopped, and after 300 seconds, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 5 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.05%
Bisphenol A: 21.0%
Phenol: 70.5%
Water: 1.03%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Example 1- (2))

  The operation was continued, and the pressure difference in the reactor on day 430 after the start of operation is as shown in Table 1. (Example 1- (3))

Next, the new feed of acetone was stopped, and after 300 seconds, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.06%
Bisphenol A: 22.5%
Phenol: 72.3%
Water: 1.06%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Example 1- (3))

[Example 2]
A pilot plant having the flow shown in FIG. 1 was operated to continuously produce bisphenol A. As a catalyst in the reactor 2, Amberlyst-31 (manufactured by Rohm and Haas), which is a sulfonic acid type cation exchange resin, was partially mixed with 2-mercaptoethylamine in 20 mol% of sulfonic acid groups. The sum was filled with 2.0 m 3 .

  The new feed amount of acetone was 42.0 kg / h.

  The temperature of the distillation column 4 was 137 ° C., and the pressure was 0.02 MPa. As the crystallizer 5, a crystallization tank having three external coolers was used, and crystallization was performed while sequentially stopping one of the three external coolers. The temperature of the crystallization tank fluctuated in the range of 49 ° C to 51 ° C.

  Table 1 shows the differential pressure in the reactor 100 days after the start of operation.

Next, the new feed of acetone was stopped, and after 1 hour, the opening and closing of the valves 3a and 16a were switched, the effluent of the reactor 2 was heated to 66 ° C., and the liquid flow rate was 2.5 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.03%
Bisphenol A: 16.0%
Phenol: 76.6%
Water: 0.43%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart.

[Example 3]
A pilot plant having the flow shown in FIG. 1 was operated to continuously produce bisphenol A. As a catalyst in the reactor 2, sulfonic acid type cation exchange resin Amberlyst-31 (manufactured by Rohm and Haas Co., Ltd.) was treated with 2- (4-pyridyl) ethanethiol and 20 of sulfonic acid group. A product obtained by partially neutralizing mol% was charged with 1.0 m 3 .

  The new feed amount of acetone was 58.0 kg / h.

  The temperature of the distillation column 4 was 137 ° C., and the pressure was 0.02 MPa. As the crystallizer 5, a crystallization tank having three external coolers was used, and crystallization was performed while sequentially stopping one of the three external coolers. The temperature of the crystallization tank fluctuated in the range of 49 ° C to 51 ° C.

  Table 1 shows the differential pressure in the reactor on the 14th day after the start of operation.

Next, the new feed of acetone was stopped, and after 300 seconds, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. Thereafter, pure water was supplied to the circulation line to obtain the following composition. Further, the effluent of the reactor 2 was set to 52 ° C., and the circulation flow was continued in the reactor 2 at a flow rate of 1.25 m / hr, and this state was continued for 560 days.
Acetone: 0.00%
Bisphenol A: 20.0%
Phenol: 63.0%
Water: 11.5%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart.

[Comparative Example 1]
A pilot plant having the flow shown in FIG. 1 was operated to continuously produce bisphenol A. As a catalyst in the reactor 2, Amberlyst-31 (manufactured by Rohm and Haas), which is a sulfonic acid type cation exchange resin, was partially mixed with 2-mercaptoethylamine in 20 mol% of sulfonic acid groups. The sum was filled with 2.0 m 3 .

  The new feed amount of acetone was 58.0 kg / h.

  The temperature of the distillation column 4 was 137 ° C., and the pressure was 0.02 MPa. As the crystallizer 5, a crystallization tank having three external coolers was used, and crystallization was performed while sequentially stopping one of the three external coolers. The temperature of the crystallization tank fluctuated in the range of 49 ° C to 51 ° C.

  The pressure difference in the reactor on the 140th day after the start of operation is as shown in Table 1. (Comparative Example 1- (1))

Next, the new feed of acetone was stopped, and after 3 hours, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.00%
Bisphenol A: 9.7%
Phenol: 83.0%
Water: 0.11%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Comparative Example 1- (1))

  Table 1 shows the differential pressure in the reactor 200 days after the start of operation. (Comparative Example 1- (2))

Next, the new feed of acetone was stopped, and after 3 hours, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.00%
Bisphenol A: 10.5%
Phenol: 81.5%
Water: 0.11%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Comparative Example 1- (2))

  Table 1 shows the differential pressure in the reactor 230 days after the start of operation. (Comparative Example 1- (3))

Next, the new feed of acetone was stopped, and after 3 hours, the valves 3a and 16a were switched between open and closed, the effluent of the reactor 2 was heated to 75 ° C., and the liquid flow rate was 1.25 m / hr. This was circulated through the reactor 2 and this state was continued for 4 days. The composition of the circulating fluid during this period was as follows on average.
Acetone: 0.02%
Bisphenol A: 10.0%
Phenol: 84.0%
Water: 0.08%

  Thereafter, the production operation of bisphenol A was resumed. Table 1 shows the pressure loss of the reactor 2 at the time when two weeks passed after the restart. (Comparative Example 1- (3))

  Table 1 also shows data of acetone conversion by reaction and bisphenol A selectivity before operation stop and after operation restart.

  As shown in Table 1, according to Examples 1 to 3, no increase in the differential pressure was observed before and after the operation was resumed, whereas according to Comparative Example 1, the differential pressure after the operation was resumed compared with that before the operation was stopped. Both are expensive.

It is a flowchart of the manufacturing method of bisphenol A which concerns on embodiment.

Explanation of symbols

2 Reactor 4 Distillation tower 5 Crystallizer 13 Mother liquor circulation line 16 Reaction liquid circulation line at the time of production stop 22 Phenol storage tank

Claims (5)

  1. A reactor in which acetone and an excess amount of phenol are reacted in the presence of a catalyst comprising an ion exchange resin or a modification of at least a part thereof to obtain a reaction product containing bisphenol A and phenol;
    A low boiling removal tower for removing a component having a boiling point lower than that of phenol from the reaction product;
    Cooling the mixed liquid obtained in the low boiling removal step to crystallize an adduct of bisphenol A and phenol, and to separate the mother liquor; and crystallization means for separating the mother liquor; A mother liquor circulation means for circulating the part to the reactor
    A process for producing bisphenol A by means of a bisphenol A production apparatus comprising:
    A production operation process for producing bisphenol A;
    An operation stop step of stopping the supply of acetone and circulating the liquid to the reactor;
    In the method for producing bisphenol A having
    A process for producing bisphenol A, characterized in that the water concentration in the liquid circulated through the reactor during the shutdown process is 0.2 wt% or more and 12 wt% or less .
  2.   The composition of the liquid circulated during the shutdown process according to claim 1 is acetone 5 wt% or less, bisphenol A 12 wt% or more, 25 wt% or less, phenol 70 wt% or more, 87.8 wt% or less, water The manufacturing method of bisphenol A characterized by being 0.2 weight% or more.
  3.   3. The method for producing bisphenol A according to claim 1, wherein the temperature of the liquid circulated during the shutdown process is 60 ° C. or more and 80 ° C. or less.
  4.   4. The linear velocity of the liquid that is circulated during the operation stop step in the reactor according to any one of claims 1 to 3 is 1.0 m / hr or more and 5 m / hr or less. The manufacturing method of bisphenol A characterized by these.
  5. In stopping the operation of the bisphenol A production apparatus according to any one of claims 1 to 4,
    First, stop the supply of raw material acetone,
    Next, the supply of the effluent from the reactor to the low-boiling removal tower is stopped before the water concentration in the reaction solution flowing out from the reactor becomes lower than 0.2%, and the reactor effluent is removed from the reactor. A method for producing bisphenol A, characterized by circulating to the inflow side.
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
JP2007186501A (en) * 2005-12-12 2007-07-26 Mitsubishi Chemicals Corp Method for producing bisphenol a
WO2007069561A1 (en) * 2005-12-12 2007-06-21 Mitsubishi Chemical Corporation Process for production of bisphenol-a

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5146007A (en) * 1991-06-17 1992-09-08 General Electric Company Process for preparing bisphenol-A
JPH09173858A (en) * 1995-08-31 1997-07-08 General Electric Co <Ge> Improved production of ion exchange resin used as bisphenol synthesizing catalyst
JP2002255879A (en) * 2001-02-28 2002-09-11 Idemitsu Petrochem Co Ltd Method for bisphenol a production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5146007A (en) * 1991-06-17 1992-09-08 General Electric Company Process for preparing bisphenol-A
JPH09173858A (en) * 1995-08-31 1997-07-08 General Electric Co <Ge> Improved production of ion exchange resin used as bisphenol synthesizing catalyst
JP2002255879A (en) * 2001-02-28 2002-09-11 Idemitsu Petrochem Co Ltd Method for bisphenol a production

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