WO2004050593A1 - Process for producing bisphenol a - Google Patents

Abstract

A process for producing bisphenol A which comprises using as a catalyst an acid-form ion-exchange resin partially modified with a sulfurized amine compound to react phenol with acetone, wherein the acid-form ion-exchange resin is washed with phenol before initiation of the reaction. By the process, high-purity bisphenol A of high quality can be produced which is reduced in coloration.

Description

 Description Bisphenol A Production Method

Technical field '

 The present invention relates to a method for producing bisphenol A [2,2-bis (4-hydroxyphenyl) pulp bread], and more particularly to a method for producing high-quality and high-purity bisphenol A with little coloring. Background art

 Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin or epoxy resin, and its demand has been increasing in recent years. You.

 It is known that bisphenol A is produced by condensing excess phenol and acetone in the presence of an acidic catalyst and optionally a cocatalyst such as a sulfur compound.

 In the past, inorganic acids such as sulfuric acid and hydrogen chloride have been used as the acid catalyst used in this reaction, but in recent years cation exchange resins have attracted attention and have been used industrially.

On the other hand, as the sulfur compound used as a cocatalyst, mercaptans having or not having a substituent, such as methyl mercaptan, ethyl mercaptan, and thiodaricholic acid, are known to be effective. The mercaptans have the effect of increasing the reaction rate and increasing the selectivity. For example, in the production of bisphenol A, 2- (2-hydroxyphenyl) -12- (4-hydroxyphenyl) propane (o, p-form) is mainly produced as a reaction by-product, and trisphenol, Polyfunor and the like are produced. In particular, when used as a raw material such as a polycarbonate resin or a polyarylate resin, bisphenol A with high purity and low content of these by-products without coloring is required. Therefore, while increasing the reaction rate, the generation of the above by-products is suppressed, and the selectivity is increased. In order to increase the catalyst, mercaptans are used as a promoter.

 However, these mercaptans cause environmental corrosion such as corrosion of equipment and odors. Therefore, in recent years, instead of using the above cation exchange resin and mercapbutans in combination, acid-type catalysts have been used as catalysts. Various modified acid-type ion exchange resins in which an i-containing group is introduced into a part of the sulfonic acid groups of the ion exchange resin are used.

 As one of the modified acid-type ion-exchange resins, an acid-type ion-exchange resin partially modified with an iodiamine-containing compound is known (for example, Japanese Patent Application Laid-Open No. 57-35533, Kaihei 1 1 1 2 4 6 4 5 8 Reference). However, the acid-type ion-exchange resin partially modified with the iodiamine-containing compound has a problem that the quality of the product is degraded when impurities containing iodine or nitrogen flow out of the resin. Disclosure of the invention

 The present invention has been made in view of the above situation, and uses an acid-type ion exchange resin partially modified with an iodamine-containing compound as a catalyst to react phenol and acetone to produce high-quality, high-purity with less coloring. It is an object of the present invention to provide a method for producing bisphenol A.

 As a result of intensive studies, the inventors have found that, when an acid-type ion-exchange resin partially modified with an iodiamine-containing compound is used as a catalyst, phenol and acetone are reacted to produce bisphenol A. The inventors have found that the object of the present invention can be efficiently achieved by washing the acid-type ion exchange resin with phenol, and have completed the present invention.

 That is, the gist of the present invention is as follows.

 1. In the production of bisphenol A by reacting phenol and acetone using an acid-type ion exchange resin partially modified with a diamine-containing compound as a catalyst, the above-mentioned acid-type ion exchange is carried out before starting the reaction. A method for producing bisphenol A, which comprises washing the resin with phenol.

2. Nitrogen content in phenol used for cleaning is in the range of 0.01 to 5 ppm 2. The method for producing bisphenol A according to the above item 1, wherein the washing is performed until the washing is completed.

 3. The process for producing bisphenol A according to 1 above, wherein the washing is carried out until the nitrogen content in the phenol used for washing is in the range of 0.05 to 3 ppm.

 4. Phenol washing of the acid-type ion exchange resin is performed at the liquid hourly space velocity (L H SV).

0 2-5 wherein 1 bisphenol A manufacturing method according is performed in the range of hr ^1.

5. The phenol wash acid type ion exchange resin, a liquid hourly space velocity (LHSV) 0. 0 5~2 said one bisphenol A manufacturing method according is performed in the range of hr ^1.

 6. The process for producing bisphenol A according to 1 above, wherein phenol washing of the acid-type ion exchange resin is carried out at a temperature of 45 to 110 ° C.

 7. The process for producing bisphenol A according to the above item 1, wherein phenol washing of the acid-type ion exchange resin is performed at a temperature of 55 to 90 ° C. BEST MODE FOR CARRYING OUT THE INVENTION

 The method of the present invention is a method for producing bisphenol A by using an acid-type ion-exchange resin partially modified with an iodiamine-containing compound as a catalyst to cause a condensation reaction between phenol and acetone to produce bisphenol A. The base acid-type ion exchange resin used for the type ion-exchange resin is not particularly limited, and those conventionally used as a catalyst for bisphenol A can be used. Sulfonic acid ion exchange resins which are strongly acidic are preferred.

 The sulfonic acid type ion exchange resin is not particularly limited as long as it is a strongly acidic ion exchange resin having a sulfonic acid group. Examples thereof include a sulfonated styrene divinyl benzene copolymer, a snolephonated cross-linked styrene polymer, and a phenol phenol resin. Mualdehyde sulfonic acid resin, benzeneformaldehyde sulfonic acid resin and the like can be mentioned.

On the other hand, the iodiamin-containing compound used for the partial modification of the above-mentioned acid-type ion exchange resin is not particularly limited, and any one of conventionally known compounds which can be used for the modification of the acid-type ion exchange resin is appropriately selected. Can be used. The Examples of iodiamine-containing compounds include 3-mercaptomethylpyridine,

Mercaptoalkylpyridines such as (2-mercaptoethyl) pyridine and 4- (2-mercaptoethyl) pyridine, 2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine, etc. Thiazolidines such as mercaptoalkylamines, thiazolidine, 2,2-dimethylthiazolidine, 2-methyl-2-phenylthiazolidine, and 3-methylthiazolidine; and aminothiophenols such as 4-aminothiophenol. Of these, 2-mercaptoethylamine, 2,2-dimethylthiazolidin, and 4- (2-mercaptoethyl) pyridine are preferred. These diamine-containing compounds may be in a free form, an addition salt of an acidic substance such as hydrochloric acid, and a quaternary ammonium salt.

 There is no particular limitation on the method of partially modifying the above-mentioned acid-type ion-exchange resin as a base by using these iodiamine-containing compounds, and a conventionally known method can be used.

 For example, denaturation is performed by reacting an acid-type ion exchange resin with an iodamine compound in a suitable solvent, preferably an aqueous solvent such as water, so as to obtain a desired modification ratio (10 to 65%). be able to. The reaction may be carried out at room temperature or, if necessary, with heating. By this reaction, the sulfonic acid group, which is an ion exchange group, and the amino group in the ioamine compound react with each other, and an io group is introduced into a part of the ion exchange group to be modified. The modification ratio means a molar modification ratio of the sulfonic acid group of the acid-type ion-exchange resin with the diol amine compound.

 In the present invention, after an acid-type ion exchange resin partially modified with a diamine compound containing a catalyst (hereinafter, simply referred to as an ion exchange resin) is charged into a fixed-bed reactor, before the reaction is started, the ion-exchange resin is used. Must be washed with phenol.

The temperature in the washing conditions of the ion exchange resin is preferably in the range of 45 to 110 ° C, more preferably in the range of 55 to 90 ° C. 4 5. If the temperature is lower than C, the phenol may solidify.If the temperature exceeds 110 ° C, the ion exchange resin is decomposed. May advance.

The liquid hourly space velocity (LHSV) is preferably in the range of 0.02 to 5 hr—more preferably 0.05 to 2 hr. If it is less than 0.02 hr ¹ , it may take a long time and the efficiency may be poor. If it exceeds 5 hr- ¹ , a large amount of phenol may be required.

 The above washing is performed until the nitrogen content in the phenol used for washing is preferably in the range of 0.01 to 5 ppm, more preferably 0.05 to 3 ppm. If it is less than 0.1 ppm, the time required for cleaning and the amount of phenol used may increase, which may be economically disadvantageous. If it exceeds 5 ppm, the quality of the product may deteriorate.

 The condensation reaction between phenol and acetone in the present invention can be carried out by a fixed bed continuous reaction system in which phenol and acetone are continuously supplied to a reaction tower filled with the above-mentioned phenol-washed ion exchange resin and reacted. . At this time, the number of reaction towers may be one, or two or more may be arranged in series or in parallel. Industrially, it is particularly advantageous to employ a fixed bed multistage continuous reaction system in which two or more reaction towers filled with the ion exchange resin are connected in series.

 The reaction conditions in the fixed bed continuous reaction system will be described.

 First, the acetone / phenol molar ratio is usually selected in the range of 1 to 30 to 1/3, preferably 1/20 to 1Z5. If the molar ratio is less than 1/30, the reaction rate may be too slow. If the molar ratio is more than 1Z3, the generation of impurities increases, and the selectivity of bisphenol A tends to decrease.

The reaction temperature is usually selected in the range of 40 to 150 ° (preferably 55 to 100 ° C.) When the temperature is lower than 40 ° C., the reaction speed is slow and the viscosity of the reaction solution is extremely high. If the temperature exceeds 150 ° C., reaction control becomes difficult, the selectivity of bisphenol A decreases, and the ion exchange resin of the catalyst may decompose or deteriorate. , LHSV (liquid space-time velocity) of the raw material mixture is usually 0. 2 to 30 hr, preferably chosen in the range of 0. 5 to 20 hr ^1.

In the method of the present invention, the reaction mixture coming out of the reaction tower is subjected to a known method. Further post-treatment is performed to extract bisphenol A. Next, an example of the post-treatment will be described. First, concentration is performed prior to crystallization. The concentration conditions are not particularly limited, but the concentration is usually performed at a temperature of 130 to 170 ° C and a pressure of 13 to 53 kPa. If the temperature is lower than 130 ° C, a high vacuum is required. If the temperature is higher than 170 ° C, impurities may increase or coloring may occur. The concentration of Bisufu Wenoru A concentrated residual liquid is in the range of 2 5-4 0 weight _^0/0 are preferred. If the concentration is less than 25% by mass, the recovery of bisphenol A is low, and if it exceeds 40% by mass, it becomes difficult to transfer the slurry after crystallization.

 Crystallization of the adduct of bisphenol A and phenol from the concentrated residue is usually carried out by vacuum cooling crystallization, which uses the latent heat of vaporization of water under reduced pressure. In this vacuum cooling crystallization method, about 3 to 20% by mass of water is added to the concentrated residue, and crystallization is carried out at a normal temperature of 40 to 70 ° C and a pressure of 3 to 13 kPa. Processing is performed. If the amount of water added is less than 3% by mass, the heat removal ability is not sufficient, and the mass is 20%. /. If it exceeds 2,000, the dissolution loss of bisphenol A increases, which is not preferable. If the crystallization temperature is less than 40 ° C, the viscosity of the crystallization liquid may increase or solidify. If the crystallization temperature exceeds 70 ° C, the dissolution loss of bisphenol A increases, which is not preferable.

 Next, the adduct of bisphenol A and phenol thus crystallized is separated by a known method, and is usually subjected to a washing treatment with phenol. Next, the washed adduct is separated into bisphenol A and phenol, in which case the temperature is usually from 130 to 200 ° C, preferably from 150 to 180 ° C. The pressure is usually selected in the range of 3 to 20 kPa.

 Bisphenol A obtained by this separation treatment is substantially completely removed of the residual phenol therein by a method such as steam stripping, so that high-quality bisphenol A can be obtained.

 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

Cation exchange resin (Sumitomo Chemical Co., Ltd.) in a 1,000 milliliter flask 200 Duolite SC 400) (water swelling) and 400 ml of ion-exchanged water were suspended and stirred. Into this, a solution of 8 g of 4- (2-mercaptoethyl) pyridine hydrochloride and 50 milliliters of ion-exchanged water was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then the resin was separated by filtration. The acid content of the filtered resin was determined by titration and found that 17% of the acid sites had been modified.

140 milliliters of this resin was passed through a fixed bed flow system at 23 ° C / 11 phenol at 70 ° (at LHSV 0.3 hr- ¹⁾ and washed for 72 hours. Nitrogen concentration in phenol at the end of washing Was 0.3 pm.

After the completion of the washing, 15 ml / h of acetone and 277 ml of phenol Zhr [acetone / phenol (molar ratio) = 1/15] were reacted at a reaction temperature of 75 ° C. and LHS V4 hr- ¹ . The reaction results were as follows: acetone conversion 98%, bisphenol A selectivity 96.5%, and o, p-isomer 2.5%. Unreacted acetone, some phenol, and generated water were removed by distillation to obtain a crystallization raw material at 130 ° C. After adding 10% by mass of water to the crystallization raw material and cooling to 80 ° C, it was cooled to 50 ° C while removing water under reduced pressure to further precipitate crystals. Next, solid-liquid separation was performed to obtain a phenol adduct of bisphenol A and a mother liquor (water content: 4% by mass). After further melting, the phenol was removed. The APHA color of the obtained bisphenol A at 250 ° C. for 10 minutes was measured and found to be 10. The purity of bisphenol A is 99.9 mass ⁰ /. The o, p-isomer was 240 ppm.

Example 2

 A modified catalyst was prepared in the same manner as in Example 1 using 2,2-dimethylthiazolidine. This catalyst had 23% of the acid sites modified.

140 milliliters of this catalyst was passed through a fixed bed flow system at a flow rate of 70 milliliters of phenol / 111: 1 with LHSVO.5 hr- ¹ and washed for 72 hours. The nitrogen concentration in the phenol at the end of the washing was 0.2 ppm.

After completion of washing, the reaction temperature was changed to 23 mil / liter of acetone and 277 milliliter / hour of phenol [acetone / phenol (molar ratio) = 1/10]. The reaction was carried out at 5 ° C and LHS V4 hr- ¹ . The reaction results were as follows: acetone conversion: 60%, bisphenol A selectivity: 96.2%, o, p-isomer: 2.8%.

Thereafter, purification was performed in the same manner as in Example 1. The APHA color of the obtained bisphenol A at 250 ° C. for 10 minutes was 10. The purity of the bis-phenol A 9 9.9 mass _^0/0, o, p- isomers been filed with 240 p pm.

 Regarding the above LHSV, when the denatured catalyst changes from water swelling to phenol swelling, it shrinks to about 56% and about 52%, respectively. It was determined for the raw material mixture. Industrial potential

 According to the process for producing bisphenol A of the present invention, high-quality, high-purity with little coloring is achieved by reacting phenol and acetone with an acid-type ion-exchange resin partially modified with an iodiamine-containing compound as a catalyst. Bisphenol A can be produced.

Claims

The scope of the claims 1 When bisphenol A is produced by reacting phenol and acetone using an acid-type ion-exchange resin partially modified with a diamine-containing compound as a catalyst, the above-mentioned acid-type ion-exchange resin is used before starting the reaction. A process for producing bisphenol A, which comprises washing phenol with phenol. 2. The process for producing bisphenol A according to claim 1, wherein the washing is carried out until the nitrogen content in the phenol used for washing falls within the range of 0.01 to 5 ppm. 3. The method for producing bisphenol A according to claim 1, wherein the washing is carried out until the nitrogen content in the phenol used for washing falls within the range of 0.05 to 3 ppm. 4 phenol wash acid type ion exchange resins, method for producing bisphenol A according to claim 1, wherein is performed in the range of liquid hourly space velocity (LHSV) 0. 0 2~5 hr 1. 5. The method for producing bisphenol A according to claim ¹ , wherein the phenol washing of the acid-type ion exchange resin is performed at a liquid hourly space velocity (LHSV) of 0.05 to 2 hr1. 6. The method for producing bisphenol A according to claim 1, wherein the phenol washing of the acid-type ion exchange resin is performed at a temperature of 45 to 110 ° C. 7 Wash the acid-type ion exchange resin with phenol at a temperature of 55-90. 2. The method for producing bisphenol A according to claim 1, which is performed in the range of C.