JP2000281608A - Production of bisphenol a - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably producing bisphenol A at a low cost while preventing the deterioration of a catalyst through the stable exhibition of purifying effect on phenol used as a raw material when producing bisphenol A by bringing phenol into contact with a storing acid-type cation exchange resin, and then by reacting the phenol obtained by distillation treatment with acetone in the presence of a solid acid catalyst having mercapto group- containing hydrocarbon group. SOLUTION: When producing bisphenol A by bringing phenol into contact with a strong acid-type cation exchange resin, by subjecting the phenol to distillation treatment and by reacting the treated phenol with acetone in the presence of a solid acid catalyst having mercapto group-containing hydrocarbon group, this method is to feed the reactant phenol subjected to distillation treatment into a reactor without bringing it into contact with oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bisphenol A
And a method for producing the same. More specifically, the present invention relates to a method for producing bisphenol A by reacting acetone and phenol in the presence of an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group.

[0002]

2. Description of the Related Art Bisphenol A [2,2-bis (4-
[Hydroxyphenyl) propane] is generally produced by subjecting phenol and acetone to a dehydration condensation reaction in the presence of an acid catalyst.

As a typical acid catalyst, a sulfonic acid type cation exchange resin is used. Further, by coexisting a compound containing a mercapto group in the reaction system, the catalyst activity and selectivity can be improved. It is known that it can be done. Specifically, a method of flowing a free mercapto group-containing compound such as alkyl mercaptan together with phenol and acetone as raw materials in a fixed bed reactor filled with a sulfonic acid type cation exchange resin (Japanese Patent Publication No. 45-1)
No. 0337), a method of covalently bonding a part of a sulfonic acid group of a sulfonic acid type cation exchange resin to a mercapto group-containing compound, and a method of combining a part of a sulfonic acid group of a sulfonic acid type cation exchange resin with a mercapto group-containing compound Are bonded by an ionic bond. The method of binding a mercapto group-containing compound to a part of the sulfonic acid groups of the sulfonic acid type cation exchange resin (hereinafter referred to as a modified ion exchange resin method) is compared with a method in which a free mercapto group-containing compound is present in a reaction system. Therefore, there are advantages that the loss of the mercapto group-containing compound is small and that there is no need to recover the mercapto group-containing compound.

However, in the modified ion exchange resin method, the catalytic activity is deteriorated, and a decrease in acetone conversion and a decrease in bisphenol A selectivity are observed during use.

Further, an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group is obtained by bonding a mercapto group-containing compound to a solid acid catalyst other than a sulfonic acid type cation exchange resin. Catalysts have been reported (JP-A-8-208545, JP-A-9-110767, JP-A-9-110989, JP-A-10-225638). This method has higher activity and higher selectivity than the modified ion exchange resin method, and is excellent as a catalyst for producing bisphenol A. However, phenol produced by the ordinary cumene method or toluene oxidation method remains untreated. When used, the degradation rate of the catalyst is higher than in the modified ion exchange resin method, and a decrease in acetone conversion and a decrease in bisphenol A selectivity are observed. Since this catalyst is more expensive than the sulfonic acid type cation exchange resin, it is desired to maintain the catalyst life longer.

As a method for preventing catalyst deterioration of a modified ion exchange resin, a method for producing bisphenol A, which comprises contacting phenol used as a raw material with a sulfonic acid type cation exchange resin in advance (JP-A-57-72927).
No.), contacting the phenol with an acidic ion exchange resin at least partially modified with a compound having an acidic reactive group and a mercapto group, and removing the compound comprising a carbonyl group and / or an unsaturated group from the phenol. Method (Japanese Patent Application Laid-Open No. 58-79942), using, as acetone, a substance subjected to distillation treatment and containing substantially no dissolved oxygen, and using, as phenol, a substance subjected to distillation treatment after contact with a strong acid-type ion exchange resin. Characteristic method for producing bisphenol A (Japanese Patent Laid-Open No. 6-3405)
No. 64). In any of these methods, the catalyst is less deteriorated than the method using untreated phenol as it is, but the effect of the above treatment may not be sufficiently exhibited depending on the method of handling phenol after distillation.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a phenol obtained by contacting with a strong acid type cation exchange resin in the presence of a solid acid catalyst having a mercapto group-containing hydrocarbon group, and further subjecting the phenol to a distillation treatment. In the method for producing bisphenol A by reacting phenol and acetone, a stable and low-cost production method of bisphenol A is provided by stably exhibiting the purification effect of phenol used as a raw material to prevent catalyst deterioration. Things.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, when producing bisphenol A using a solid acid catalyst having a mercapto group-containing hydrocarbon group, The present inventors have found that the catalyst can be prevented from deteriorating by contacting a purified phenol obtained by contacting a strong acid type cation exchange resin with phenol as a phenol and further subjecting the phenol to a distillation treatment, thereby completing the present invention.

That is, the present invention relates to a method of reacting phenol and acetone obtained by contacting with a strong acid type cation exchange resin in the presence of a solid acid catalyst having a mercapto group-containing hydrocarbon, followed by a further distillation treatment. Let's bisphenol A
In the method for producing bisphenol A, the phenol is subjected to a distillation treatment and then introduced into a reactor without contacting with oxygen.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The phenol used as a raw material in the present invention has been previously treated with a strong acid type cation exchange resin. As the phenol treated with the strong acid type cation exchange resin, commercially available industrial phenol can be used. Industrial phenols include those manufactured by the cumene method or the toluene oxidation method, but may be manufactured by any method. Generally, phenols with a purity of 98% or more are commercially available.

As the strong acid type cation exchange resin, those which can be usually obtained may be used. Examples thereof include Diaion manufactured by Mitsubishi Chemical Corporation, Amberlite and Amberlyst manufactured by Rohm and Haas, and Levatit manufactured by Bayer Corporation. As the strong acid type cation exchange resin, any of a gel type and a macroporous type can be used.
It is preferable to use an 8% gel type because it can be used stably for a long period of time.

[0012] The phenol is treated continuously or batchwise with the strong acid type cation exchange resin as described above. A method in which the strong acid type cation exchange resin is packed in a packed column and the phenol is continuously flowed is used. It is preferable because crushing is small and phenol can be efficiently treated. Processing temperature is 41 ~ 1
The temperature is 50C, preferably 50C to 120C. The time for treating phenol with a strong acid type cation exchange resin is 5 minutes to
10 hours, preferably 10 minutes to 2 hours. The phenol thus obtained is further distilled. The distillation method is not particularly limited, but the pressure is normal pressure to 10 mmH
g, preferably at a temperature of 70 to 200 ° C.

[0013] The purified phenol obtained by such treatment is introduced into the reactor without contact with oxygen. When the purified phenol is brought into contact with oxygen before being introduced into the reactor, the catalyst deteriorates with time more than in the case where it is not brought into contact with oxygen. The reason for this is not clear, but phenol comes into contact with oxygen to produce a small amount of catalyst deterioration-causing substances, or the phenol that is slightly remaining in the purified phenol and does not affect catalyst deterioration comes into contact with oxygen. It is thought to be due to the change to a catalyst deterioration-causing substance. The purified phenol may be sent directly to the reactor and reacted with acetone, or may be used in another step in a series of bisphenol A production processes and then sent to the reactor and reacted with acetone. For example, after separating the equimolar adduct crystals of bisphenol A and phenol generated by cooling the reaction solution from the mother liquor, washing the adduct crystals with purified phenol, sending the washing solution to the reactor as a phenol source and reacting with acetone. May be. What is important is that the phenol purified by contact with the strong acid cation exchange resin and further distillation treatment does not come into contact with oxygen before being sent to the reactor. Before sending the purified phenol to the reactor, it may be temporarily stored in a tank or the like. In this case, the gas phase of the tank is replaced with an inert gas such as nitrogen, and the oxygen concentration is reduced to 1%.
%, Preferably 0.1% or less. Also, it is preferable that the piping until the purified phenol is sent to the reactor is sufficiently replaced with an inert gas such as nitrogen before use. Instead of the inert gas, a solvent such as phenol from which oxygen has been sufficiently removed may be used.

The acetone used in the present invention is not particularly limited, and commercially available commercially available acetone may be used. Generally, those having a purity of 99% or more are available.

The above phenol and acetone are reacted in the presence of a solid acid catalyst having a mercapto group-containing hydrocarbon group to produce bisphenol. Examples of the catalyst used in the present invention include those in which a part of the sulfonic acid group of the sulfonic acid type cation exchange resin and a mercapto group-containing compound are bonded by a covalent bond, and the sulfonic acid of the sulfonic acid type cation exchange resin. An organic polymer siloxane having both a part of the group and a mercapto group-containing compound bonded by an ionic bond and an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group are exemplified. The organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group is a catalyst with higher activity and higher selectivity than the modified ion exchange resin, but without purifying phenol. When the synthesis reaction of bisphenol A is performed, the deterioration of the catalyst with time is more severe than that of the modified ion exchange resin,
When the purified phenol in contact with oxygen is used, the activity is greatly deteriorated. Therefore, when the method of the present invention is applied to a method for producing bisphenol A using an organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group, the effect is particularly large. Examples of the organic polymer siloxane catalyst having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group are described in JP-A-8-208545 and JP-A-9-11098.
No. 9 and JP-A-10-225638, a hydrocarbon group partially having a sulfonic acid group and a hydrocarbon group having a mercapto group are directly contained in a silica matrix comprising a siloxane bond. An organic polymer siloxane having a structure in which a silicon atom is bonded to a carbon-silicon bond is exemplified.

The reaction is usually carried out at a phenol to acetone molar ratio of 2 to 30, preferably 4 to 20. If the molar ratio of phenol to acetone is 2 or more, the residual amount of acetone after the reaction is small,
The generation of impurities such as mesityl oxide by-produced from acetone is reduced. When the molar ratio is 30 or less, the amount of unreacted phenol circulated is reduced, so that equipment such as a reactor and a crystallizer are reduced, and power required for circulation is reduced, which is economical. . The pressure may be such that the phenol and acetone as raw materials do not gasify since the reaction is carried out in a liquid phase, but is usually from normal pressure to 0.
It is performed in the range of 5 MPa. Reaction temperature is 40-200
° C, preferably 50 to 120 ° C. Reaction temperature 40
If the temperature is lower than 0 ° C., the reaction time becomes extremely long, and it becomes necessary to install a huge reactor. When the reaction temperature exceeds 200 ° C., an undesired side reaction occurs, and the selectivity decreases. The reaction time is generally 1 minute to 15 hours, preferably 10 minutes to
5 hours.

The reaction solution thus obtained is cooled after removing reaction water, unreacted acetone and a part of unreacted phenol, if necessary, and then cooling the mixture to obtain bisphenol A.
Bisphenol A is separated in the form of an equimolar adduct of phenol and phenol. Further, phenol is removed from this equimolar adduct and bisphenol A is isolated.

[0018]

Next, the present invention will be described in more detail with reference to examples.

Example 1 Commercially available industrial phenol was placed in a 50 L stainless steel container, kept at 50 ° C., and left for 20 hours while introducing nitrogen from an annular nozzle provided in the lower part of the container. This phenol is converted to a sulfonic acid type ion exchange resin (K1 manufactured by Bayer AG).
221) It was continuously supplied to a cylindrical reactor having an inner diameter of 50 mm filled with 500 ml so as to have a contact time of 30 minutes with the ion exchange resin, and treated at 70 ° C. further,
The obtained phenol was continuously distilled at a pressure of 40 mmHg and a temperature of the still of 160 ° C. to obtain a purified phenol. The obtained purified phenol was sent to a 50 L stainless steel container in which the inside was replaced with nitrogen and the oxygen concentration became 10 ppm or less, and stored at 50 ° C. This purified phenol 3
8.0 g / h and 2.3 g / h of acetone were continuously supplied to a reactor filled with 30 ml of Bayer K1221 in which 15% of sulfonic acid groups were uniformly modified with cysteamine. A synthesis reaction was performed. In addition, a plunger pump is used to send phenol from each stainless steel phenol storage container, and each device is connected with stainless steel piping. The reaction was performed without contact between phenol and oxygen.

After 24 hours from the start of the reaction, the conversion of acetone was 83.7%, and the selectivity of bisphenol A was 9%.
4.3%. Further, the reaction is continued in this state, and 5
When the analysis was carried out after 00 hours, the acetone conversion was 8
3.1%, bisphenol A selectivity was 94.2%.

Example 2 [Preparation of catalyst] According to the following procedures (a) and (b),
An organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group was prepared.

(A) Synthesis of sulfonic acid group-containing alkoxysilane 200 ml of methylene chloride was placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and 124.0 g (0.585 mol) of phenyltrichlorosilane was added thereto. Ice cooled. 46.8 g of sulfuric anhydride (0.585 g)
(mol) in 100 ml of methylene chloride was added dropwise over 30 minutes under a nitrogen stream, and the ice bath was removed, followed by stirring at room temperature for 5 hours to perform sulfonation. The dropping funnel was removed, and the mixture was heated to 100 ° C. using an oil bath under a nitrogen stream to distill off methylene chloride and unreacted sulfuric anhydride.
After allowing to cool, 160 g of ethanol was added dropwise at room temperature over 3 hours, followed by refluxing for 2 hours while bubbling with nitrogen to carry out an ethoxylation reaction while removing generated hydrogen chloride. Sulfonic acid component in the sol-gel preparation of the following organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group, using 237.7 g of an ethanol solution of phenyl sulfonic acid group-containing ethoxysilane containing the obtained impurities. Used as a raw material for

(B) Preparation of an organic high molecular siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group The above-mentioned sulfonic acid group-containing ethoxysilane was placed in a two-necked 500 ml round bottom flask equipped with a stirring bar. 26.0 g of ethanol solution and 35.5 g of tetraethoxysilane (1
70.7 mmol), 6.7 g (34.3 mmol) of mercaptopropyltrimethoxysilane, ethanol 30
ml and mixed. 7.5 g of water (0.42 m
ol) was added dropwise over 30 minutes. Then heat this,
Stirred at 65 ° C. for 4 hours. After cooling, an aqueous solution obtained by mixing 15 ml of 28% aqueous ammonia and 75 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. The mixture was further stirred at 65 ° C. for 3 days and aged. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. After filtration, the operation of washing with 500 ml of ion-exchanged water was repeated 10 times to remove hydrochloric acid. Finally, it was dried at 100 ° C. under reduced pressure for 6 hours.

By the above operation, 30 g of an organic high molecular siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group was obtained. It was 1.0 meq / g when the solid acid amount of this catalyst was measured.

[Synthesis reaction of bisphenol A] As a synthesis catalyst of bisphenol A, except that the organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group prepared as described above was used. The reaction was carried out in the same manner as in Example 1.

As a result, the conversion of acetone 24 hours after the start of the reaction was 95.3%, and the selectivity of bisphenol A was 96.
2%. After 500 hours of analysis, the conversion of acetone was 94.7% and the selectivity of bisphenol was 9%.
It was 6.1%.

Comparative Example 1 The procedure of Example 1 was repeated, except that a commercially available industrial phenol was treated with an ion-exchange resin, and after distillation, the tank for storing phenol was not replaced with nitrogen but had an air atmosphere.

As a result, the conversion of acetone after 24 hours from the start of the reaction was 83.5%, and the selectivity for bisphenol A was 94.5%.
3%. After 500 hours, the analysis showed that the conversion of acetone was 78.3% and the selectivity of bisphenol A was 8%.
It was 3.9%, and both the acetone conversion and the bisphenol A selectivity were significantly reduced as compared with the case where nitrogen substitution was performed.

Comparative Example 2 The procedure of Example 2 was repeated except that a commercially available industrial phenol was treated with an ion-exchange resin, and after distillation, the tank for storing phenol was not replaced with nitrogen but had an air atmosphere.

As a result, the conversion of acetone 24 hours after the start of the reaction was 95.2%, and the selectivity of bisphenol A was 96.
2%. Analysis was performed 500 hours later. As a result, the conversion of acetone was 93.3%, and the selectivity of bisphenol A was 96.0%. The decrease in the conversion of acetone was larger than that in Example 1.

[0031]

According to the method of the present invention, a phenol obtained by contacting with a strong acid type cation exchange resin and further subjecting to a distillation treatment can be stably stored, and the hydrocarbon containing a mercapto group can be stably stored. Deterioration of the solid acid catalyst having a group is prevented, and bisphenol A can be produced economically advantageously.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuyo Matsu 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F-term (reference) 4G069 AA02 BA22A BA22B BA24A BA24B BA45A BE21A BE21B BE22A BE22B BE32A BE32B CB01 CB25 CB70 DA05 4H006 AA02 AC25 BA33 BA36 BA68 BD10 DA64 FC52 FE13 FG29 4H039 CA19 CA60 CD10 CD40

Claims (3)

[Claims] 1. A phenol exchanged with a strong acid type cation exchange resin in the presence of a solid acid catalyst having a mercapto group-containing hydrocarbon group, and further subjected to a distillation treatment to react phenol with acetone to obtain bisphenol. A method for producing bisphenol A, wherein the phenol is subjected to a distillation treatment and then introduced into a reactor without contacting with oxygen. 2. The method according to claim 1, wherein the catalyst is an organic polymer siloxane having both a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. 3. The method according to claim 1, wherein the catalyst is obtained by binding a part of a sulfonic acid group of a sulfonic acid type cation exchange resin to a mercapto group-containing compound.