PL201330B1 - Method of obtaining bisphenol A - Google Patents

Abstract

The method of obtaining bisphenol A from phenol and acetone in the presence of an acid ion exchange resin with the flow of the reaction mixture from the bottom to the top of the reactor is based on the fact that the mixture of phenol and acetone (1) containing not less than 0.7% by weight, preferably 0.9-1.5% by weight of water, is dosed into the condensation reactor divided into two parts, the lower part of the reactor consists of a bed of acid ion exchange resin in which 12-25% of sulfonic groups are neutralized promoter, and the upper part of the reactor contains an acidic ion exchange resin in which 10-20% of the sulfone groups are neutralized with the promoter, and the temperature increase between the stream inlet (1) and the outlet stream (3) from the reactor is not exceeds 15 ° K. Part of the post-reaction mixture (2) is taken from the boundary between both parts of the synthesis reactor and is combined with the feed mixture into reactor (1), and the remaining part after passing through the upper part of the reactor as stream n ( 3) is directed to the distillation system in which acetone, water and phenol are distilled off, obtaining crude bisphenol A (4), which is directed to fractional crystallization and the residue (6) after crystallization. PL PL PL

Description

(21) Application number: 347705 j

C07C 37/20 (2006.01) C07C 39/16 (2006.01) (22) Date of notification: 23/05/2001

Patent Office of the Republic of Poland (54)

Method of obtaining bisphenol A (43) Application was announced:

02.12.2002 BUP 25/02 (73) The holder of the patent:

Institute of Heavy Organic Synthesis BLACHOWNIA, Kędzierzyn-Koźle, PL Kiedik Maciej, Kędzierzyn-Koźle, PL Matyja Stanisław, Kędzierzyn-Koźle, PL Pokorska-Zofia, Kędzierzyn-Koźle, PL Rdesińska-Ćwik Teresa, Kędzierzyn-Koźle, PL Grzywa Edward, Warsaw, PL Kałędkowska Małgorzata, Kędzierzyn-Koźle, PL Kościu k Ryszard, Kędzierzyn-Koźle, PL Rzodeczko Anna, Kędzierzyn-Koźle, PL Kołt Józef, Zabrze, PL

Smolnik Ryszard, Kędzierzyn-Koźle, PL Mróz Jerzy, Kędzierzyn-Koźle, PL (45) The following was announced about the grant of the patent:

31.03.2009 WUP 03/09 (72) Inventor (s):

Maciej Kiedik, Kędzierzyn-Koźle, PL Stanisław Matyja, Kędzierzyn-Koźle, PL Zofia Pokorska, Kędzierzyn-Koźle, PL Teresa Rdesińska-Ćwik, Kędzierzyn-Koźle, PL Edward Grzywa, Warsaw, PL Małgorzata Kałędkowska, Kędzierzyn-Koźle, PL Ryszard Kościuk , Kędzierzyn-Koźle, PL Anna Rzodeczko, Kędzierzyn-Koźle, PL Józef Kołt, Zabrze, PL

Ryszard Smolnik, Kędzierzyn-Koźle, PL Jerzy Mróz, Kędzierzyn-Koźle, PL (74) Representative:

Renata Fiszer, ICSO BLACHOWNIA (57) The method of washing bisphenol A from phenol and acetone in the presence of acidic resin ion exchange during the flow of the reaction mixture from the bottom to the top of the reactor is based on the fact that a mixture of phenol and acetone (1) containing not less than 0.7% by weight , preferably 0.9-1.5% by weight of water, is dosed into the condensation reactor divided into two parts, the lower part of the reactor contains a bed of acidic ion exchange resin in which 12-25% of the sulpho groups are neutralized by the promoter, and the upper part of the reactor contains the bed acidic ion exchange resin in which 10-20% of sulfo groups are neutralized by the promoter, and the temperature increase between the inlet of stream (1) and the outlet of stream (3) from the reactor does not exceed 15 ° K. Part of the post-reaction mixture (2) is taken from the boundary between both parts of the synthesis reactor and is combined with the batch mixture to the reactor (1), and the remaining part, after passing through the upper part of the reactor as stream (3), is directed to the distillation system, where it distills acetone, water and phenol are combined to give crude bisphenol A (4), which is sent to fractional crystallization, and residue (6) after crystallization.

PL 201 330 B1

Description of the invention

The subject of the invention is a method of obtaining bisphenol A used as a raw material in the production of resins, mainly epoxy and polycarbonate.

Bisphenol A, with the chemical formula OH-C6H ₄ -C (CH3) 2-C ₆ H ₄ -OH, is obtained by the condensation of phenol with acetone in the presence of a strongly acid cation exchanger as a catalyst, followed by separation of the reaction mixture by distillation and crystallization. The unreacted raw materials are returned to the process. The by-products are catalytically decomposed and the raw materials thus recovered are also returned to the process.

There are many processes for obtaining bisphenol A known in the patent literature.

In EP 0313165, acetone and phenol are condensed with recycle isomerization products against a cation exchange resin at 50-90 ° C, the reaction mixture is concentrated to recover unreacted acetone and phenol, which are recycled to the reaction. The bisphenol A product is crystallized to form a suspension of the bisphenol A adduct with phenol. The adduct is separated from the by-product mother liquor from the adduct suspension in the separator. The adduct is directed to the flux and the mother liquor is isomerized at 60-90 ° C in the presence of a mercaptan-modified acid cation exchange resin. The reaction mixture enriched in bisphenol A is returned to the condensation reactor.

EP 0332203 discloses a process for the preparation of high purity bisphenol A. Bisphenol A is obtained in the main process in the reaction of phenol with acetone, the post-reaction mixture is processed until the assumed concentration of bisphenol A is obtained, then the following steps are taken:

- the first stage of crystallization of the adduct of bisphenol A with phenol,

- the first stage of separating the adduct from the mother liquor,

- removing phenol from the adduct.

This is followed by the so-called sub-process in which p-isopropenylphenol is condensed with phenol and the resulting reaction mixture is subjected to successively:

- treatment to obtain the assumed concentration of bisphenol A,

- second crystallization of the adduct of bisphenol A with phenol,

- the second separation of the adduct from the parent tug.

Adduct crystals from the sub-process are routed to the main process. The main process mother liquor is passed to the sub-process and p-propenylphenol and phenol are separated from the sub-process mother liquor.

Patent EP 0332203 also protects a variant for the preparation of bisphenol A, in which the main process conducts the condensation of phenol and acetone, the catalyst is removed, then the bisphenol A adduct is precipitated in the crystallization, the adduct crystals are separated from the mother liquor and phenol is removed from the adduct crystals. In the sub-process, on the other hand, condensation of p-isopropenylphenol with phenol is carried out, the catalyst is removed, the unreacted phenol is removed, and from the raw bisphenol A obtained, the lower and higher boiling substances are separated from bisphenol A. The fractions containing lower and higher boiling substances are processed to obtain p-propenylphenol and phenol. The mother liquor from the main process goes to the sub-process and bisphenol A from the sub-process to the main process.

EP 0812815 describes a method of obtaining bisphenol A by condensation of acetone and phenol in the presence of an ion exchange resin as a catalyst, in which the post-reaction mixture is directed to a phenol separating stripper, and bisphenol A is subjected to alloying crystallization in a falling film dynamic crystallizer. Bisphenol A is flaked and the crystallization residue containing bisphenol A, tar and isomers is returned to the recovery node; the bisphenol A obtained in this way is directed to the melt distillation, and the tar and isomers to the thermal decomposition node. Thermal decomposition is carried out in the reactor-distillation column system, in the presence of a catalyst such as sodium hydroxide or sulfonic acids. The recovered phenol is recycled to the reaction and the residue is burned. The process protected by patent EP 0812815 proceeds as follows:

1.phenol condenses with a ketone in the presence of an ion exchange resin as a catalyst,

2. the fraction of unreacted phenol is removed from the reaction mixture,

3.water and acetone are removed from the unreacted phenol fraction and the dry phenol is recycled to condensation,

4.with fi ^^^ ccj of water and acetone obtained in node 3, water is separated, and acetone is returned to the condensation factor,

PL 201 330 B1

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3 is a process flowchart including condensation, distillation, fractional crystallization, thermal decomposition and rearrangement nodes.

Alternatively, either residue 6 or residue 9 is subjected to thermal decomposition.

If the residue decomposition is used, static crystallization is not performed.

P r z y k ł a d l

The condensation process is carried out continuously at the temperature of 331-339 ° K in a special, two-zone reactor enabling the collection of reaction products at various levels. The lower part of the reactor is filled with 30 m ³ of a sulfonated copolymer of styrene with 4 mol% of divinylbenzene, whose 20% of sulfonic groups neutralized with 2,2-dimethylthiazolidine is, the upper part of the reactor is filled with 15 m3 of copolymerized styrene and 5% divinyl benzene, which 15% of sulfonic groups neutralized with is 2,2 dimethylthiazolidine. Purolit CT-124 is used as the base cation exchanger. From the bottom into the reactor with a capacity of 90 mr ³ , 71 421 kg / hour of raw materials 1 having the following composition are introduced:

acetone 3.24% by weight phenol 87.05% by weight bisphenol A 8.36% by-products 0.44% by weight!

water 0.91% by weight!

From the boundary of both parts of the catalyst bed, the stream of the reaction mixture 2 in the amount of 55,886 kg / hour is led through slot-filtration nozzles and returned to the stream of raw materials 1. The dosing of the reactants, the size and the degree of cooling of the recycle stream are selected so that the temperature difference between the raw materials inlet to the reactor and the recycle stream of the reaction mixture outlet does not exceed 6 ° K. From the upper part of the reactor, a stream 3 of the reaction mixture is led to the distillation system, in the first stage of which a fraction containing acetone, water and phenol is distilled off, obtaining a crude bisphenol A 4 as a cubic residue, which is sent for crystallization. In the second stage of the evaporation system, the acetone and water fraction are distilled off to obtain a phenol stream 5 as cubic residue, and in the third stage, acetone is distilled off, which is recycled to the feed stream 1, and phenolic water. The stream 4 of crude bisphenol A is directed to fractionated alloy crystallization which produces 1736.1 kg / hour of pure, crystallized bisphenol A with purity:

content of bisphenol A content of 2,4-isomer of bisphenol A content of trisphenol color in 50% methanol solution color in a molten state

99.96 wt% 42 ppm 17 ppm APHA unit 10 APHA units

The residue 6 after the melt crystallization containing by-products is diluted with a phenolic stream 12 in the ratio 1: 1.4 and subjected to static crystallization, the adduct of bisphenol A with phenol 7 obtained in the crystallization is directed to the distillation system together with the reaction mixture 3, and from the crystallization residues At static 8, phenol 10 is distilled off, which is directed to the dilution of stream 11, and the residue 9 is thermally decomposed in the presence of sodium bicarbonate catalyst at 513 ° K under a vacuum of 11 mbar for a residence time of 5 hours. The solid waste of 52.1 kg / hour is removed, the distillate 11 is diluted with stream 10 and pure phenol in a ratio of 1: 4.5 and subjected to a rearrangement reaction in which, in the presence of the macroporous cation exchanger Amberlyst 15 at a temperature of 333-338 ° K , bisphenol A is formed from p-isopropenylphenol and its dimers and oligomers in reaction with phenol, and the obtained reaction mixture 12 is returned to the dilution of the batch for static crystallization. The selectivity of the process is 97%.

P r z x l a d II

The process is carried out in the same apparatus and in the same way as in example 1, in a two-zone reactor enabling the reception of reaction products at different levels, the lower part of the reactor is filled with 30 m3 of sulphonated copolymer of styrene with 4% by weight of divinylbenzene, 25% of which are sulphonic groups is neutralized with 2,2 dimethylthiazolidine, and the upper part of the reactor is filled with 15 m 3 of a styrene copolymer with 4% divinylbenzene, 12% of the sulfonic groups of which are neutralized with 2,2 dimethylthiazolidine. The dosing of the raw materials, the size and the degree of cooling of the recycle stream are selected so that the temperature difference between the raw materials inlet to the reactor and the recycle stream of the reaction mixture outlet does not exceed 5 ° K.

PL 201 330 B1

The stream 4 obtained in the amount of 1736.1 kg / h of pure, crystallized bisphenol A after fractionated melt crystallization had the purity:

bisphenol A content 99.95% by weight 2,4-isomer content 38 ppm trisphenol content 15 ppm color in 50% methanol solution 2 APHA units melt color 10 APHA units

The residue 6 after melt-crystallization, containing by-products, is directed to an evaporator, in which phenol 10 is distilled off and directed to the dilution of stream 11, and residue 9 is subjected to thermal decomposition in the presence of sodium bicarbonate as catalyst at a temperature of 510 ° K under vacuum 8 hPa with a residence time of 5.5 hours. The solid waste in the amount of 65.2 kg / hour is removed, the distillate 11, after dilution with phenolic stream, is rearranged against the Purolite CT-175 cation exchanger at a temperature of 331-337 ° K, and the resulting reaction mixture 12 is sent to the distillation system along with the stream post-reaction mixture 3 from the condensation reactor. The selectivity of the process is 96%.

Claims (7)

Patent claims 1. The method of obtaining bisphenol A from phenol and acetone in the presence of acidic yorK ^ \ in ^ rmem ^ ^ ^ jj resin with the flow of the reaction mixture from the bottom to the top of the reactor with the use of distillative separation of reaction products, crystallization, and catalytic thermal decomposition of by-products, characterized by that a mixture of phenol and acetone containing not less than 0.7% by weight, preferably 0.9-1.5% by weight of water, is dosed into the condensation reactor divided into two parts, the lower part of the reactor contains a bed of acidic ion exchange resin in which -25% of the sulfone groups are neutralized by the promoter, and the upper part of the reactor contains an acidic ion exchange resin bed, in which 10-20% of the sulfone groups are neutralized by the promoter, and the temperature increase between the feed mixture inlet to the reactors (1) and the stream outlet (3) from the reactor does not exceed 15 ° K, with a part of the post-reaction mixture (2) taken from the boundary between both parts of the synthesis reactor and combined with with the batch mixture to the reactor (1), and the remaining part after passing through the upper part of the reactor as stream (3) is directed to the distillation system, where the fraction containing acetone, water and phenol is distilled off, obtaining as a cubic residue crude bisphenol A (4) containing not more than 3 wt.% phenols, preferably not more than 1 wt.% phenol, which is fed to the fractional melt crystallization to obtain bisphenol A and residue (6) mainly containing bisphenol A and by-products. 2. The method according to zassrz. A process as claimed in claim 1, characterized in that the residual content (6) after the crystalline allization is diluted with a phenolic stream and subjected to static crystallization, obtaining an adduct of bisphenol A with phenol (7), which is directed to the distillation system together with the stream (3) of the reaction mixture with the condensation reactor, and the static crystallization residue (8) which, after distilling off the phenol, is withdrawn from the process as stream (9). 3. The method according toSrz. A process according to claim 1, characterized in that the fractionated crystallization j6) after phenol distillation is subjected to thermal decomposition in the presence of basic catalysts, and the distillate (11) obtained as a result of decomposition is diluted with phenolic stream (10) and phenol, and then contacted with a macroporous cation exchanger, and the product (12) of the rearrangement reaction is directed to the distillation system along with the reaction mixture stream from the condensation reactor. 4. The method according to zassrz. j, characterized in that the ratio of the lower volume to the upper one is from 1/2 to 2. 5. The method according to the merits. j, characterized in that the acidic ion exchange vein is a sulfonated styrene copolymer with 2-6% divinylbenzene. 6. The method according to principles A method as claimed in claim 1, characterized in that 2, 2 dimethylthiazolidine or cysteamine is used in the RH promotot. 7. The method according to p. 2, characterized by the fact that the residual content (9) after the suction crystallization after phenol distillation is subjected to thermal decomposition in the presence of basic catalysts, and the distillate (11) obtained as a result of decomposition is diluted with phenolic stream (10) and pure phenol, after whereby it is contacted with the macroporous cation and the rearrangement reaction product (12) is directed to the dilution of the static crystallization feed.