CN1229074A - Method for obtaining bisphenol A - Google Patents
Method for obtaining bisphenol A Download PDFInfo
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- CN1229074A CN1229074A CN 98109430 CN98109430A CN1229074A CN 1229074 A CN1229074 A CN 1229074A CN 98109430 CN98109430 CN 98109430 CN 98109430 A CN98109430 A CN 98109430A CN 1229074 A CN1229074 A CN 1229074A
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Abstract
The method according to the invention solves obtaining bisphenol A of high purity.
Description
Theme of the present invention is that the highly purified known name of preparation is called 2 of dihydroxyphenyl propane (BPA), the method for two (4-hydroxy phenyl) propane of 2-.
Dihydroxyphenyl propane is main half product of preparation polycarbonate and Resins, epoxy, and it is by the condensation reaction preparation of phenol in the presence of acid catalyst and acetone, and modal acid catalyst is a strong acid ion exchange resin.The main by product of this reaction is listed in the table 1.Exist by product being feature to the color of the dihydroxyphenyl propane that obtains and the various interference of other mass parameter.Existed multiple from dihydroxyphenyl propane the method for separating impurity.
In Poland Patent specification sheets № 153396, disclose a kind of method for preparing dihydroxyphenyl propane, wherein be used for the raw mix that reacts and mix by the postreaction mixture that round-robin phenol mother liquor and a part are collected at reactive system and obtain.The starting point concentration of dihydroxyphenyl propane is counted 12-20% by dihydroxyphenyl propane weight in the raw mix that obtains by this way, and the content of its isomer is for being less than 25% in the total amount of by product, and the mol ratio of phenol and acetone is (5-30): 1.Be reflected at temperature 60-95 ℃ and carry out in the presence of catalyzer, catalyzer is that weight ratio is respectively (0.05-0.5): the mixture of 1 macropore and aperture cationite.It is the mixture of 12-24% by product by weight that the reaction of carrying out in this mode produces high final dihydroxyphenyl propane that concentration equals 21-35% by weight and content.Because the phenol mother liquor is circulated to reactive system, the quantity of impurity increases.For avoiding the accumulation of unwanted material in method, by from reactive system, discharging a part of mother liquor logistics and it being carried out suitable processing remove impurity with the dihydroxyphenyl propane that it is carried out purifying and recovery appropriate amount.
European patent № 332877 has described a kind of method of removing dihydroxyphenyl propane impurity, its main points are remove catalyzer from the postreaction mixture after, to wherein adding entry, and from mixture reduction vaporization water and a part of phenol, cause the crystallization of bisphenol a/phenol adducts.Subsequently, before being circulated to crystalline adduct and further handling, isolating water is as contacting with weak-base ion-exchange resin with the mixture of phenol and impurity.The shortcoming of this method is only to have removed the impurity of a small amount of percentage ratio in the postreaction mixture by this way.
Disclose a kind of method that reclaims dihydroxyphenyl propane and remove the impurity of band look from the logistics of at least a portion circulating mother liquor in UK patent № 1565667, it comprises the logistics of described at least a portion circulating mother liquor is contacted with the absorbent bed of Zeo-karb form.This only can remove a part and be present in impurity in the mother liquor.
The also more known method of from the additional crystalline mother solution of at least a portion bisphenol a/phenol adducts separating step or from the by product that among the preparation methods of dihydroxyphenyl propane, obtains, removing impurity and reclaiming dihydroxyphenyl propane of people, distill out the product of formation when comprising the catalytic decomposition by product, and they are circulated to reactions steps.
According to the method described in Poland Patent specification sheets № 113641 and 103054, remove impurity by the following method expeditiously and reclaim dihydroxyphenyl propane, wherein phenol and right-isopropenyl phenol and the reaction of their dipolymer in the presence of cation exchange resin catalyst, described dipolymer obtains by the thermocatalysis decomposition of dihydroxyphenyl propane method by product.According to these inventions, the cationite that is reflected at as catalyzer of the thermocatalysis degradation production of phenol and preparation method of bisphenol A exists down, in independent reactor, be different under the condition of carrying out the reaction of phenol-acetone, preferably in the presence of the water of 5-20% by weight, carry out.
Above-mentioned method of removing impurity from reactive system is not in full force and effect, and a part of unwanted impurity is brought in subsequently the dihydroxyphenyl propane preparation process with adducts.
Described a kind of method that obtains bisphenol A with high purity in patent specification EP0332203, it comprises main method and so-called submethod.In main method, phenol and acetone react, and handle additional reaction mixture to obtain the solution of desired concn dihydroxyphenyl propane; This is so-called concentration control first step, is bisphenol a/phenol adducts crystalline first step then; The first step of isolated adduct and from adducts, remove phenol from mother liquor to obtain the step of bisphenol A with high purity.Submethod comprises reaction second step, wherein right-isopropenyl phenol and phenol reactant, bisphenol A concentration is controlled second step, bisphenol a/phenol adducts crystalline second step, isolated adduct crystallization cut II is to obtain second step to isopropenyl phenol and phenol from second mother liquor, its prerequisite is, first mother liquor that obtains from main method is transported to submethod, and the second adducts crystallization cut that obtains from submethod is transported to main method.
Obtain the method for bisphenol A with high purity according to the also claimed another kind of method of invention EP № 0332203.Main method comprises the first step of reaction, and catalyzer is removed in wherein phenol and acetone reaction, and crystallisation step wherein reclaims the bisphenol a/phenol adducts, the step of fractional crystallization adducts and the step of removing phenol from crystalline adduct from mother liquor.Submethod comprises, and right-isopropenyl phenol and phenol react in the presence of acid catalyst, remove catalyzer to obtain second phenol solution; From second phenol solution, remove phenol and obtain crude bisphenol; Obtain the distillatory dihydroxyphenyl propane by distillation separation from crude bisphenol is low with high boiling substance; Obtain right-isopropenyl phenol and phenol with handling to hang down with high boiling substance; The mother liquor that obtains from main method is transported to submethod, and second cut of submethod is transported to main method.
Add as starting material by the adducts that will reclaim in the submethod or dihydroxyphenyl propane and to become owner of in the method, and make impurity be obtained highly purified dihydroxyphenyl propane by " dilution ".The main drawback of the method for patent EP0332203 is a complicacy of introducing the bisphenol A with high purity preparation method of submethod, compares with main method, and it contains the step of many complexity.This causes the investment of employed bisphenol A device in this method and process cost significantly to increase.
Method according to Polish patent of invention № 164289, in reactive system, the first step of formation method, carry out the reaction of the dipolymer that the heat-catalytic decomposition of the by product that passes through method of phenol and acetone and phenol and right-isopropenyl phenol and it obtains simultaneously and in the presence of micropore and macroporous cation exchange mixture by product to the isomerization rearrangement reaction of dihydroxyphenyl propane.
In the step of this method, go out the adducts of dihydroxyphenyl propane and phenol from the postreaction mixture separation, carry out purifying by crystallization, wash isolating crystallization cut, in film evaporator, from adducts, remove phenol and obtain highly purified dihydroxyphenyl propane subsequently by distillation.
From a part of mother liquor that obtains by the postreaction mixture of isolating behind the adducts, distill out acetone and reaction water, and rest part carries out catalytic decomposition, obtain containing the distillment of phenol, right-isopropenyl phenol and their dipolymer, it is circulated to the first step of this method.According to described method, in method, need the BPA synthesising by-product that circulates very a large amount of, this causes the obvious decline of the reaction yield of unit catalyst volume.In addition, that uses severe corrosive contains right-isopropenyl phenol and its dipolymer, owing to poison rapidly, can not use the cationite that contains the promotor that increases catalyst efficiency in method.
The objective of the invention is to improve a kind of method,, and do not have the shortcoming of currently known methods and method efficient preferably is provided with the preparation bisphenol A with high purity.
According to the present invention, phenol and the byproduct of reaction of condensation reaction in reaction mixture of acetone have in two reactive systems in parallel of different concns and carry out.In the first reaction condensation system, use the cationite that has added promotor as catalyzer, the concentration of by product is by weight at the most 5% in reaction mixture, preferably by weight 1% to by weight 3%.Advantageously, in first system of condensation reaction, be reflected at 0.5-3% p-tert-butylphenol by weight and carrying out in the presence of the australol of 0.5-2.5% by weight.In second condensation reaction system, the concentration of by product is by weight at the most 20% in reaction mixture, preferably by weight 6% to by weight 12%.To carry out crystallization from the postreaction mixture of second reactive system and isolate crystalline bisphenol a/phenol adducts.Adducts is used in the phenol solution washing in first crystal system subsequently, the adducts that obtains by this way adds in the postreaction mixture of first condensation reaction system, it is carried out crystallization, separate the crystallization of bisphenol a/phenol adducts, be used in the wash phenol in second crystal system.By can easily separating dihydroxyphenyl propane by distilling out phenol in the adducts that obtains by this way, its prerequisite is, to wash the phenol mother liquor that obtains in bisphenol a/phenol adducts Crystallization Separation with in first crystal system and carry out evaporate to dryness, obtain regenerated phenol and acetone, be circulated to condensation reaction, from process, remove the water of phenol.The thermocatalysis that exsiccant phenol Recycling Mother Solution to the second condensation reaction system of major portion, rest part are delivered to by product decomposes and rearrangement process.Should note from Production of Disphenol A, removing the heavy distillation residue as refuse.Reaction and by product rearrangement reaction the regenerate dihydroxyphenyl propane of the distillment that in the thermocatalysis of phenol mother liquor decomposes, obtains by carrying out phenol and right-isopropenyl phenol in the presence of as catalyzer at the macroporous strong-acid cation exchanger, be circulated to second condensation reaction system and/or first crystal system subsequently, be circulated to two condensation reaction systems with fresh phenol by the dry regenerated acetone of phenol mother liquor.The regeneration phenol that is obtained by phenol mother liquor drying is circulated to first condensation reaction system with the phenol that washing bisphenol a/phenol adducts crystallization in second crystal system obtains.
As the catalyzer in the phenol condensation with acetone reaction, use contains the cationite of the gel structure of reaction promotor, and promotor is 2,2-dimethylthiazole alkane or cysteamine, with cationite be less than 40%, preferred 15-25% sulfo group is added by promotor neutral mode.Before being delivered to first reactive system, reaction mixture contacts with ion exchange resin, and the sulfo group of its 25%-90% is neutralized by mercapto-amine.The condensation reaction of phenol and acetone is under 50-80 ℃ temperature, and the concentration of acetone is for by weight 1% to carrying out under 5% the condition by weight in reaction mixture.
In first reactive system and/or second reactive system of phenol condensation with acetone, circulate a part of postreaction mixture to the raw mix of condensation reaction by heat exchanger.
Method of the present invention also comprises the distillation drying of the postreaction mixture of the first condensation system.The light ends that contains acetone, water and phenol in the dehumidification system of phenol mother liquor is delivered to the regenerative process of phenol and acetone, and dry mixture is delivered in the raw material of second crystal system.
In the method for the invention, because reaction parameter such as temperature, concentration, the residence time and catalyst property and the active variation of reagent in the conversion zone of each (two) reactive system of acetone in reaction mixture, improved the selectivity of common dihydroxyphenyl propane preparation process.Because the two-step crystallization of bisphenol a/phenol adducts from phenol solution obtains highly purified dihydroxyphenyl propane under the situation that reduces investment of first crystallisation step and isolated adduct crystalline and running cost.In method, use effectively corresponding to their composition and the technology logistics of the phenol solution of purity.
Embodiment 1
The condensation that is used to prepare the equipment of dihydroxyphenyl propane partly comprises two reactive system 1a in parallel and 1b.
What use as catalyzer in reactive system 1a is to have added promotor 2, and the cationite Amberlyst 31 of 2-dimethylthiazole alkane is during the add-on of promotor is equivalent to and 12% cationite sulfo group.
Reaction mixture in this system comprises :-by product by weight 3.2%-acetone by weight the 2.1%-temperature of reaction be that 62-64 ℃-postreaction mixture color is 90APHA (Hazen unit)
As the catalyzer use in reactive system 1b is the cationite Amberlyst 31 that has not added promotor.
Reaction mixture in this system comprises :-by product by weight 14%-acetone by weight the 2.9%-temperature of reaction be that 76-78 ℃-postreaction mixture color is 1750APHA (in 4% methanol solution for 70APHA).
The postreaction mixture of second reactive system (1b) carries out crystallization under 40 ℃ temperature, the bisphenol a/phenol adducts crystallization that obtains is centrifugal, wash with phenol solution, add subsequently in the postreaction mixture of reactive system (1a), the raw material that obtains by this way carries out crystallization 42 ℃ temperature, bisphenol a/phenol adducts by centrifugation obtains washs with purified petroleum benzin phenol.
Remove beyond the adducts, go out phenol and remove phenol residues with stripping and separate final product by vacuum distilling.
The actual dihydroxyphenyl propane that obtains has following qualitative characteristics :-isomer neighbour-, right-content by weight the color 25 APHA-plant capacity 840kg dihydroxyphenyl propanes of the color 10 APHA-molten states of 0.03%-in 50% methanol solution/hour-general method selectivity 97% example II and EXAMPLE III
In the bisphenol production equipment of example I, catalyzer and the change reaction mixture of exchange in two reactive systems formed, and other technical parameter does not become.
The general selectivity of the comparative feature of the postreaction mixture in two reactive systems, quality, plant capacity and the method for final product is listed in the table 2.The explanation of gained by product during table 1 dihydroxyphenyl propane is synthetic
Table 2
| Example I example II reactive system reactive system | The EXAMPLE III reactive system | |||||
| 1a | 1b | 1a | 1b | 1a | 1b | |
| 1. degree (the %2 that neutralized by promoter of cation-exchanger sulfo group; 2-dimethylthiazole alkane) 2. in first | 12 ? ? - ? 3.2 ? - ? 64-66 2.1 90 | - ? ? - ? 14.1 ? ?- ? 76-78 2.9 1750 | 15 ? ? 0.6 ? 2.5 ? 0.5 ? 62-64 1.7 80 | 18 ? ? - ? 10.1 ? - ? 65-67 1.9 250 | 15 ? ? 1.1 ? 1.9 ? 0.5 ? 56-58 1.4 40 | 25 ? ? ?- ? 7.4 ? ?- ? 59-61 1.2 100 |
| ? 10 ? 25 0.03 ? 840 97 | ? 7.5 ? 15 0.100 ? 1630 95 | ? 2.5 ? 7.5 0.05 ? 1390 97 | ||||
Claims (10)
1. the method for preparing bisphenol A with high purity, the strong-acid cation exchanger that is reflected at of phenol and acetone carries out under existing as catalyzer, also crystallization is with the distillation that separates bisphenol a/phenol adducts and it and reclaim dihydroxyphenyl propane from the thermocatalysis decomposition course of process by product, it is characterized in that the phenol and the condensation reaction of acetone are that byproduct of reaction has in two reactive systems in parallel of different concns and carries out in reaction mixture, prerequisite is in first condensation reaction system (1a), use has added the cationite of promotor as catalyzer, the concentration of by product is by weight at the most 5% in reaction mixture, preferably by weight 1% to by weight 3%, and in second condensation reaction system (1b), the concentration of by product is by weight at the most 20% in reaction mixture, preferably by weight 6% to by weight 12%, subsequently, to carrying out crystallization from mixture after the reaction of second reactive system (1b), separate the bisphenol a/phenol adducts crystal, be used in the phenol solution washing in first crystal system (2), the adducts that obtains by this way joins after the reaction of first condensation reaction system (1a) in the mixture, it is carried out crystallization, separate the bisphenol a/phenol adducts crystal, be used in the wash phenol in second crystal system (3), can easily separate dihydroxyphenyl propane by going out phenol by distillation (4) in the adducts that obtains by this way, subsequently, carry out evaporate to dryness (5) at the phenol mother liquor that the bisphenol a/phenol adducts crystal separates and washing obtains in first crystal system (2), obtain phenol and regenerated acetone, be circulated to condensation reaction, from process, remove the water of phenol, the major portion of the phenol mother liquor of subsequent drying is circulated to second condensation reaction system (1b), the thermocatalysis that rest part is delivered to by product decomposes and rearrangement process (6), wherein from the process of dihydroxyphenyl propane, separate and remove the heavy distillation residue as refuse, reaction and by product rearrangement reaction the regenerate dihydroxyphenyl propane of the distillment that in the thermocatalysis of phenol mother liquor decomposes, obtains by carrying out phenol and right-isopropenyl phenol in the presence of as catalyzer at the strong-acid cation exchanger of macroporous structure, be circulated to second condensation reaction system (1b) and/or first crystal system (2) subsequently, prerequisite is to be circulated to two condensation reaction systems by the regenerated acetone that phenol mother liquor drying (5) obtains with fresh phenol, and the regeneration phenol that is obtained by phenol mother liquor drying (5) is circulated to first condensation reaction system (1a) with the phenol that washing bisphenol a/phenol adducts crystal in second crystal system (3) obtains.
2. according to the method for claim 1, it is characterized in that in the condensation reaction of phenol and acetone, using the cationite of gel structure as catalyzer.
3. according to the method for claim 1, it is characterized in that in the condensation reaction system of two phenol and acetone, using the Zeo-karb that contains reaction promotor.
4. according to the method for claim 1, it is characterized in that reaction mixture contacts with ion exchange resin before being delivered to first (1a) and/or second (1b) reactive system, the sulfo group of the 25%-90% of resin is neutralized by mercapto-amine.
5. according to the method for claim 1 or 3 or 4, it is characterized in that using 2, the sulfo group of 2-dimethylthiazole alkane or cysteamine neutralizing cation exchanger.
6. according to the method for claim 1, it is characterized in that being used for the promoted cationite of dihydroxyphenyl propane synthetic and contain 2-40%, preferred 15-25% is by mercapto-amine neutral sulfo group.
7. according to the method for claim 1, it is characterized in that the condensation reaction of phenol and acetone is carried out under 50-80 ℃ temperature, the concentration of acetone is by weight 1% to by weight 5% in reaction mixture.
8. according to the method for claim 1, it is characterized in that carrying out in the presence of the australol that is reflected at 0.5-3% p-tert-butylphenol and 0.5-2.5% in first system (1a).
9. according to the method for claim 1, it is characterized in that in first reactive system (1a) and/or second reactive system (1b), circulating a part of post reaction mixture to the raw mix of condensation reaction by heat exchanger.
10. according to the method for claim 1, it is characterized in that the post reaction mixture of the first condensation system (1a) is distilled drying (7), the cut that contains acetone, water and phenol subsequently is transported to the regenerative process of carrying out phenol and acetone in phenol mother liquor drying (5) system, and dry mixture is delivered in the raw material of second crystal system (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98109430 CN1229074A (en) | 1998-03-13 | 1998-03-13 | Method for obtaining bisphenol A |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98109430 CN1229074A (en) | 1998-03-13 | 1998-03-13 | Method for obtaining bisphenol A |
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| CN1229074A true CN1229074A (en) | 1999-09-22 |
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| CN 98109430 Pending CN1229074A (en) | 1998-03-13 | 1998-03-13 | Method for obtaining bisphenol A |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476572A (en) * | 2016-07-22 | 2019-03-15 | 沙特基础工业全球技术有限公司 | Method for continuously manufacturing bisphenol-A |
| CN109790095A (en) * | 2016-12-20 | 2019-05-21 | 沙特基础工业全球技术有限公司 | The method for manufacturing bisphenol-A |
-
1998
- 1998-03-13 CN CN 98109430 patent/CN1229074A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476572A (en) * | 2016-07-22 | 2019-03-15 | 沙特基础工业全球技术有限公司 | Method for continuously manufacturing bisphenol-A |
| CN109476572B (en) * | 2016-07-22 | 2022-02-11 | 沙特基础工业全球技术有限公司 | Process for the continuous production of bisphenol A |
| CN109790095A (en) * | 2016-12-20 | 2019-05-21 | 沙特基础工业全球技术有限公司 | The method for manufacturing bisphenol-A |
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