KR101132932B1 - Catalyst for bisphenol production - Google Patents

Abstract

Provided are a catalyst for producing a bisphenol and a method for producing a bisphenol using the catalyst, which can be prepared by a simple operation using a sulfur-containing amine compound contained in wastewater discharged from a bisphenol production process. The present invention relates to a catalyst for producing bisphenols obtained by adsorbing a sulfur-containing amine compound contained in wastewater discharged from a bisphenol production process to an acidic cation exchange resin and a method for producing bisphenols using the catalyst.

Description

Catalyst for producing bisphenols {CATALYST FOR BISPHENOL PRODUCTION}

The present invention comprises a catalyst for producing bisphenols and a method for producing bisphenols using the catalyst, and more particularly, an acidic cation exchange resin adsorbing a sulfur-containing amine compound contained in wastewater discharged from a bisphenol production process. It relates to a catalyst for producing bisphenols and a method for producing bisphenols using the catalyst.

Bisphenols are known to be important compounds as polymer raw materials, and bisphenol A, which is a typical compound among bisphenols, is used as a raw material for engineering plastics such as polycarbonate resins and polyarylate resins, or for epoxy resins. Tends to grow more and more.

It is known that bisphenols including bisphenol A are prepared by reacting phenols with a carbonyl compound using a fixed phase of an acidic cation exchange resin as a catalyst. In this case, for example, bisphenol A is used as the sulfur-containing amine in the acidic cation exchange resin in order to suppress by-products such as isomer 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane. It is also known to use what adsorbed a compound as a catalyst.

By the way, when the catalyst is prepared in the apparatus for producing bisphenols, that is, when the sulfur-containing amine compound is adsorbed to the acidic cation exchange resin, the waste water containing the sulfur-containing amine compound is discharged. In addition, when preparing the catalyst, the sulfur-containing amine compound may leak. Such wastewater containing the sulfur-containing amine compound discharged from the apparatus for producing bisphenols is difficult to treat activated sludge because the BOD value of the sulfur-containing amine compound contained therein is low. There is a method of liquid incineration by incineration without sending the wastewater to a wastewater treatment facility using activated sludge. However, in this case, the capital investment is expensive and a large amount of fuel for burning organic matter in water is required.

Therefore, it is desired to remove the sulfur-containing amine compound by simple means from the waste water containing the sulfur-containing amine compound.

A wastewater treatment method comprising amines, the method comprising contacting wastewater containing water-soluble amines with a weak acid ion exchange resin, regenerating a weak acid ion exchange resin adsorbed with amines with an inorganic acid, and neutralizing the regeneration solution with alkali. The wastewater treatment method containing the amine which consists of a process is disclosed (for example, refer patent document 1). However, this method has a problem that the operation is cumbersome, consisting of three steps including a regeneration step.

Patent Document 1: Japanese Patent Application Laid-Open No. 1983-30387

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

The present invention has been made under such circumstances, and it is possible to prepare a bisphenol catalyst and a bisphenol using the catalyst which can be prepared in a simple operation using a sulfur-containing amine compound contained in the wastewater discharged from the bisphenol production process. It is an object to provide a manufacturing method.

Means to solve the problem

As a result of intensive studies, the present inventors have found that the object can be achieved by adsorbing a sulfur-containing amine compound contained in the wastewater discharged from the bisphenols production process to an acidic cation exchange resin. The present invention has been completed according to this finding.

That is, the present invention,

(1) a catalyst for producing bisphenols formed by adsorbing a sulfur-containing amine compound contained in wastewater discharged from a bisphenol production process to an acidic cation exchange resin;

(2) the catalyst for producing bisphenols according to the above (1), wherein the wastewater discharged from the bisphenol production process is wastewater discharged from the catalyst preparation step;

(3) a catalyst for producing bisphenols comprising a catalyst comprising an acidic cation exchange resin obtained by adsorbing a sulfur-containing amine compound prepared in a catalyst preparation step, and the catalyst according to the above (1);

(4) a catalyst for producing bisphenols comprising a catalyst comprising an acidic cation exchange resin obtained by adsorbing a sulfur-containing amine compound prepared in a catalyst preparation step, and the catalyst according to (2) above;

(5) the catalyst for producing bisphenols according to the above (1), wherein the acidic cation exchange resin is a gel-type strongly acidic cation exchange resin;

(6) the catalyst for producing bisphenols according to the above (2), wherein the acidic cation exchange resin is a gel-type strongly acidic cation exchange resin;

(7) the catalyst for producing bisphenols according to the above (3), wherein the acidic cation exchange resin is a gel-type strongly acidic cation exchange resin;

(8) the catalyst for producing bisphenols according to the above (4), wherein the acidic cation exchange resin is a gel-type strongly acidic cation exchange resin;

(9) the catalyst for producing bisphenols according to the above (5), wherein the gel-type strong acid cation exchange resin has a crosslinking degree of 2 to 8%;

(10) the catalyst for producing bisphenols according to the above (6), wherein the crosslinking degree of the gel-type strongly acidic cation exchange resin is 2 to 8%;

(11) the catalyst for producing bisphenols according to the above (7), wherein the gel-type strongly acidic cation exchange resin has a crosslinking degree of 2 to 8%;

(12) the catalyst for producing bisphenols according to the above (8), wherein the crosslinking degree of the gel-type strongly acidic cation exchange resin is 2 to 8%;

(13) The catalyst for producing bisphenols according to any one of the above (1) to (12), wherein the bisphenols are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A];

(14) A method for producing bisphenols using the catalyst according to any one of (1) to (12) above, and

(15) It provides the manufacturing method of bisphenols using the catalyst of said (13).

Effects of the Invention

According to the present invention, there is provided a catalyst for producing bisphenols and a method for producing bisphenols using the catalyst which can be prepared in a simple operation using a sulfur-containing amine compound contained in the wastewater discharged from the bisphenols manufacturing process and must be removed. can do. In addition, the wastewater containing the sulfur-containing amine compound discharged after preparing the catalyst for producing bisphenols of the present invention can be sent to the wastewater treatment facility as it is.

Best Mode for Carrying Out the Invention

Bisphenols to which the catalyst for producing bisphenols of the present invention are applied are produced by condensation of phenols and carbonyl compounds.

As said phenols, those having no substituent at the p-position relative to the hydroxyl group, for example, phenol, o-cresol, m-cresol, o-tert-butyl phenol, 2,6-xyleneol, 2,6 Alkyl phenols such as di-tert-butyl phenol; halogenated phenols such as o-chlorophenol, m-chlorophenol and 2,6-dichlorophenol.

On the other hand, examples of the carbonyl compound include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, acetophenone and cyclohexanone; Aldehydes, such as formaldehyde, acetaldehyde, and benzaldehyde, etc. are mentioned. In particular, the catalyst of the present invention is suitably applicable to the preparation of bisphenol A obtained by condensation of phenol and acetone.

It is preferable that the acidic cation exchange resin used in this invention is a sulfonic acid type | system | group which is a strongly acidic cation exchange resin, and as resin used as a parent | base, styrene- vinylbenzene copolymer resin, a perfluoroethylene-type copolymer resin, and a phenol- Although there are formaldehyde polymer resins and the like, styrene-divinylbenzene copolymer resins are preferable. These resins can be either gel or porous, but gel is preferred, and the degree of crosslinking is preferably relatively low, for example, from 2 to 8%.

In the present invention, the acidic cation exchange resin is charged to a reactor to form a fixed phase. The sulfur-containing amine compound contained in the aqueous solution is adsorbed to the acidic cation exchange resin by injecting an aqueous solution of a sulfur-containing amine compound, which is a drainage discharged from the bisphenol production process, into the fixed bed reactor to modify the resin. A production catalyst (hereinafter also referred to simply as "catalyst") is prepared.

Here, as said sulfur-containing amine compound, For example, mercaptopyridines, such as 3-mercaptopyridine; Mercaptoalkylamines such as 2-mercaptoethylamine; Thiazolidines such as 2,2-dimethylthiazolidine; Aminothiophenols such as 4-aminothiophenol; Pyridine alkane thiols, such as 4-pyridine ethane thiol, etc. are mentioned. Of these, 4-pyridineethanethiol, 2,2-dimethylthiazolidine and 2-mercaptoethylamine are suitable. In the present invention, only one kind of such sulfur-containing amine compound may be included in the waste water, or two or more kinds thereof may be included.

The method of preparing a catalyst by contacting the aqueous sulfur-containing amine compound solution with an acidic cation exchange resin, adsorbing the sulfur-containing amine compound contained therein to the acidic cation exchange resin and modifying the acidic cation exchange resin is not particularly limited. For example, it is also possible to perform batchwise, but it is common to prepare a catalyst in a reactor prior to the reaction, and the following method may be mentioned.

(1) An acidic cation exchange resin is charged to the reactor, and an aqueous solution of a sulfur-containing amine compound is simply injected from the top.

(2) An acidic cation exchange resin is charged to the reactor, and an aqueous solution of the sulfur-containing amine compound is injected from the top while circulating a part of the outflowed aqueous solution.

(3) An acidic cation exchange resin is charged to the reactor, an aqueous solution of a sulfur-containing amine compound is injected, or after the injection, air bubbles are passed through the reactor from the bottom of the reactor (Japanese Patent Laid-Open No. 2000-254523).

(4) After filling the reactor with an acidic cation exchange resin to form a fixed phase, it is washed with water before the start of the reaction, and an aqueous solution in which the sulfur-containing amine compound is dissolved in the spilled washings is injected into the reactor and circulated (Japanese Patent) Publication No. 2001-286770).

On the other hand, the filling amount of the acidic cation exchange resin is appropriately selected depending on the concentration of the sulfur-containing amine compound in the drainage to be passed through, the amount of passing through, and the type and concentration of the acid contained in the drainage.

In addition, the catalyst preparation may be carried out at room temperature, or may be carried out by heating if necessary. In this catalyst preparation treatment, a sulfonic acid group, which is an ion exchange group, and an amino group in a sulfur-containing amine compound react to introduce a sulfur-containing group into a part of the ion exchange group, thereby producing a desired modification ratio (5 to 50%, preferably 8 to 30%). Is denatured. On the other hand, "modification rate" means the molar conversion rate by the sulfur-containing amine compound of the sulfonic acid group of the acidic cation exchange resin.

In the first invention of the present application, the sulfur-containing amine compound-containing drainage discharged during the preparation of the catalyst or the leaked sulfur-containing amine compound-containing drainage discharged during the preparation of the catalyst as described above is injected into the fixed bed made of an acidic cation exchange resin, The present invention relates to a catalyst formed by adsorbing a sulfur-containing amine compound on an acidic cation exchange resin.

In the present invention, as the catalyst for producing bisphenols, as described above, only a catalyst formed by adsorbing a sulfur-containing compound in wastewater to an acidic cation exchange resin can be used, or an acid formed by adsorbing a sulfur-containing amine compound prepared in a catalyst preparation step. The catalyst consisting of a cation exchange resin and the catalyst can be used in combination.

2nd invention of this application is a manufacturing method of bisphenols characterized by using the said catalyst. As a typical example, the manufacturing method of bisphenol A is demonstrated.

Condensation reaction of phenol and acetone can use the fixed-phase continuous reaction system which continuously supplies and reacts phenol and acetone to the reaction tower which filled the catalyst mentioned above. At this time, one reaction column may be sufficient, and two or more reaction towers may be arrange | positioned in series or parallel. Industrially, it is particularly advantageous to employ a fixed bed multistage continuous reaction system by connecting two or more reactor-packed reaction towers in series.

The reaction conditions in this fixed-phase continuous reaction system are demonstrated.

First, the acetone / phenol molar ratio is usually selected in the range of 1/30 to 1/3, preferably 1/20 to 1/5. If the molar ratio is smaller than 1/30, the reaction rate may be too slow. If the molar ratio is larger than 1/30, the generation of impurities may increase and the selectivity of bisphenol A tends to decrease.

Further, the reaction temperature is usually selected in the range of 40 to 150 ° C, preferably 55 to 100 ° C. If the temperature is less than 40 ° C, the reaction rate is slow, the viscosity of the reaction solution is very high, and there is a risk of solidification in some cases. If the temperature is higher than 150 ° C, the reaction control is difficult and the selectivity of bisphenol A is lowered. May decompose or deteriorate. In addition, the LHSV (liquid space velocity) of the raw material mixture is usually selected in the range of 0.2 to 30 hr ⁻¹ , preferably 0.5 to 20 ^{hr −1} .

In the method of the present invention, the reaction mixture discharged from the reaction column is post-treated by a known method to separate bisphenol A. Next, an example of the post-treatment will be described. First, the reaction mixture is concentrated before crystallization. There is no particular limitation regarding the concentration condition, but it is usually concentrated under the conditions of a temperature of 130 to 170 ° C and a pressure of 13 to 53 kPa. If the temperature is lower than 130 ° C, high vacuum is required. If the temperature is higher than 170 ° C, impurities may increase or cause coloring. Moreover, it is advantageous that the density | concentration of bisphenol A of a concentrated balance exists in the range of 25-40 mass%. If this concentration is less than 25 mass%, the recovery rate of bisphenol A is low, and if it exceeds 40 mass%, there exists a possibility that the conveyance of the slurry after crystal precipitation may become difficult.

Crystal precipitation of the adducts of bisphenol A and phenol from the concentrated residue is usually carried out by a vacuum cooled crystal precipitation method which cools using latent heat of evaporation of water under reduced pressure. In this vacuum cooling crystal precipitation method, about 3-20 mass% of water is added to the said concentrated residue, and a crystal precipitation process is performed on the conditions of the normal temperature of 40-70 degreeC, and the pressure of 3-13 kPa. If the amount of water added is less than 3% by mass, the heat removal ability is not sufficient. If the amount of water is more than 20% by mass, the dissolution loss of bisphenol A becomes large, which is not preferable. On the other hand, if the crystal precipitation temperature is less than 40 ° C, the viscosity of the crystal precipitation liquid may be increased or solidified. If it exceeds 70 ° C, the dissolution loss of bisphenol A becomes large, which is not preferable.

Subsequently, the adducts of bisphenol A and phenol precipitated in this way are separated by a known method, and thereafter, washing is usually performed by phenol. The washed adduct is then separated into bisphenol A and phenol, but in this case the temperature is usually selected in the range from 130 to 200 ° C., preferably from 150 to 180 ° C., while the pressure is usually in the range from 3 to 20 kPa. Is selected from.

The residual phenol in bisphenol A obtained by this separation treatment is substantially completely removed by a method such as steam stripping to obtain a high quality bisphenol A.

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by these Examples.

Reference Example 1

A glass column of 25 mm in diameter and 20 cm in length was charged with 50 cm ³ of sulfonic acid type cation exchange resin (DIAION SK-104, Mitsubishi Chemical Corporation) in a water-swelled state, and a circulation line and 2,2- A supply line of dimethylthiazolidine (hereinafter also referred to as DMT) was set up. In the circulation line, the solution of 170 mass ppm of DMT concentration and 0.4 mass% of phosphoric acid concentration was circulated at 200 mL / h. In order to maintain a 170 mass ppm DMT concentration, a 1.3 mass% DMT solution was supplied to the circulation line at 2.6 mL / h. Thus, 230 mL of wastewater was generated at the end of denaturation of the 50 cm ³ catalyst, the DMT concentration at the column outlet was 170 ppm, and the phosphoric acid concentration was 0.4 mass%. When 1,500 cm <^3> of cation exchange resin was processed using 30 glass columns in total, 7000 mL of waste water generate | occur | produced, the DMT concentration in waste water was 170 mass ppm, and the phosphoric acid concentration was 0.4 mass%. In addition, the modification rate of the cation was 23%. One glass column was used to evaluate the reaction performance. As conditions, reaction temperature was 75 degreeC, phenol / acetone (molar ratio) was 10/1, LHSV was performed at 6h <^-1> , and phenol conversion was 12.1% and bisphenol A selectivity was 93.5%.

Example 1

A glass column having an inner diameter of 25 mm and a length of 20 cm was filled with 50 cm ³ of sulfonic acid type cation exchange resin (Diion SK-104, Mitsubishi Chemical Corporation) in water swelling state, and 170 mass ppm of DMT concentration generated in Reference Example 1 and phosphoric acid concentration 0.4 mass% of drainage was injected at 400 mL / h. In total, 7,000 mL of the drainage was injected. The DMT concentration was measured regularly at the outlet, and the DMT concentration could be maintained at 5 mass ppm or less and the phosphoric acid concentration at 0.4 mass% until the treatment was completed. In addition, the modification rate of the cation was 16%. The reaction performance of this catalyst was carried out under the same conditions as in Reference Example 1, whereby the same results as in Reference Example 1 were obtained.

The catalyst for producing bisphenols of the present invention and the method for producing bisphenols using the catalyst can be prepared by a simple operation using a sulfur-containing amine compound contained in the wastewater discharged from the bisphenols production process and which must be removed. The wastewater containing the sulfur-containing amine compound discharged after preparing the catalyst for producing bisphenols of the present invention can be sent to the wastewater treatment facility as it is.

Claims (15)

In the method for producing a catalyst for producing bisphenols, comprising the step of adsorbing a sulfur-containing amine compound to an acidic cation exchange resin, the sulfur-containing amine compound contained in the waste water discharged from the preparation of the catalyst for producing bisphenols as the sulfur-containing amine compound. It is used, The manufacturing method of the catalyst for bisphenols manufacture. delete delete delete The method of claim 1, A method for producing a catalyst for producing bisphenols, wherein the acidic cation exchange resin is a gel-type strongly acidic cation exchange resin. delete delete delete The method of claim 5, A method for producing a catalyst for producing a bisphenol having a crosslinking degree of 2 to 8% of a gel-type strongly acidic cation exchange resin. delete delete delete The method according to any one of claims 1, 5 and 9, The manufacturing method of the catalyst for bisphenol manufacture whose bisphenols are 2, 2-bis (4-hydroxyphenyl) propane [bisphenol A]. delete delete