WO2005021155A1

WO2005021155A1 - Method of preparing modified catalyst for bisphenol a production

Info

Publication number: WO2005021155A1
Application number: PCT/JP2004/012861
Authority: WO
Inventors: Masahiro Iwahara; Jun Mase; Shuichi Masuda; Hideki Sato
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2003-09-01
Filing date: 2004-08-30
Publication date: 2005-03-10
Also published as: KR20060117905A; JP2005074332A; TWI370017B; CN102886277A; KR101083168B1; TW200510064A; CN102886277B; JP4298438B2; CN1845790A

Abstract

A method of preparing a modified catalyst for bisphenol A production by partially modifying a strongly acid ion-exchange resin with a sulfurized amine compound. It comprises packing a strongly acid ion-exchange resin into a fixed-bed reactor, introducing therein an aqueous acid solution, and further introducing a sulfurized amine compound in such an amount that its concentration in the aqueous acid solution reaches equilibrium to thereby modify the strongly acid ion-exchange resin. By the method, the strongly acid ion-exchange resin is evenly modified without breaking, and a modified catalyst for bisphenol A production which has excellent catalytic performance can be prepared.

Description

Method for preparing modified catalyst for production of bisphenol A

The present invention relates to a method for preparing a catalyst used for producing bisphenol A [2,2-bis (4-hydroxyphenyl) propane]. Specifically, the present invention relates to a method for partially modifying a strongly acidic ion-exchange resin with a diamine compound containing iodine. Technology for the preparation of modified catalysts for the production of bisphenol A

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

In the production of this bisphenol A, a strongly acidic ion-exchange resin partially modified with an iodiamine-containing compound is used as a catalyst. A method for preparing such a catalyst includes a fixed-bed reactor in a fixed-bed reactor. A method is employed in which a sulfonic acid-type ion exchange resin is modified by adding an iodiamine-containing compound at a time. Usually, when a sulfonate-type ion-exchange resin is denatured by batch addition of a diopamine compound in a fixed-bed reactor, the sulfonate compound in the fixed-bed resin is modified with an acid. Transfer (adsorption to sulfonic acid group, desorption and transfer from sulfonic acid group). At this time, the iodiamine-containing compound moves from the inlet to the outlet of the fixed-bed reactor, but the sulfonate-type ion-exchange resin is not uniformly denatured by a single transfer. In other words, the concentration of the iodiamin-containing compound during the transfer of the iodiamin-containing compound is determined by the fixed-bed reactor. Of the fixed bed reactor has a low concentration (denaturation rate is about 5 to 30%), resulting in a high concentration (denaturation rate of about 30 to 80%). There is a problem that the sulfonic acid-type ion exchange resin is not uniformly denatured by only one transfer.

Various methods have been used to prepare fixed beds of cation exchange resins neutralized with iodiamin-containing compounds.For example, preparation of fixed beds of acidic cation exchange resins in which acidic cation exchange resins are neutralized with iodiamin-containing compounds. The method (see, for example, JP-A-6-296871, JP-A-2001-286770, JP-A-8-40961 and JP-A-2001-288138) is described. It has been disclosed. Further, a method of circulating an aqueous solution of an iodamine compound containing hydrochloric acid in a fixed resin bed is disclosed (see, for example, JP-A-53-14680). Corrosion may occur.

Further, as a method for preparing a catalyst for producing bisphenols, a method of injecting a dilute solution of an iodamine-containing compound while stirring an ion exchange resin in a reaction vessel (for example, see JP-A-9-124279), The reactor is filled with acidic cation exchange resin, and while or after the aqueous solution of iodamine compound is charged, bubbles are passed from the lower part of the reactor to uniformly neutralize the acidic cation exchange resin. (See, for example, JP-A-2000-254523). However, in the former case, a large-scale diluted solution storage facility is required, and the batch-type production using impeller agitation causes damage to the ion-exchange resin. Requires refilling. In the latter case, since the preparation is carried out at pH 6 or higher, it is difficult to homogenize the diamine-containing compound, and this results in a heterogeneous modified catalyst, which degrades the catalytic performance. Disclosure of the invention

The present invention has been made in view of the above circumstances, and is intended to prepare a modified catalyst for producing bisphenol A, which has no damage to a strongly acidic ion exchange resin, uniformly modifies the strongly acidic ion exchange resin, and has excellent catalytic performance. It is intended to provide a method.

The present inventors have conducted intensive studies to solve the above problems, and as a result, filled a fixed-bed reactor with a strongly acidic ion-exchange resin, and contained an acid aqueous solution and a concentration that would be equilibrium in the acid aqueous solution. It has been found that the above object can be achieved by injecting a diopamine compound and modifying the strongly acidic ion exchange resin. The present invention has been completed based on such findings.

That is, the present invention provides a method for preparing a modified catalyst for the production of bisphenol A, which is obtained by partially modifying a strongly acidic ion exchange resin with an iodamine compound, wherein the fixed bed reactor is filled with the strongly acidic ion exchange resin. A method for preparing a modified catalyst for the production of bisphenol A, characterized by injecting an aqueous solution and an iodiamine-containing compound in a concentration equilibrium in the aqueous acid solution to modify the strongly acidic ion exchange resin. Is what you do. BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the strongly acidic ion exchange resin used in the present invention include a sulfonic acid type ion exchange resin such as a sulfonated styrene divinyl benzene copolymer, a snorehonig crosslinked styrene polymer, a phenol formaldehyde sulfonic acid resin, and a benzene formaldehyde sulfonic acid resin. Can be The strongly acidic ion exchange resin is charged to a fixed bed reactor. Since the fixed bed is directly filled with the ion exchange resin, the ion exchange resin is not damaged during the denaturation process of the ion exchange resin, and there is no transfer from the patch reactor or denaturing catalyst preparation tank. Is advantageous. In the present invention, examples of the iodamine-containing compound used for modifying the strongly acidic ion exchange resin include mercaptopyridines such as 3-mercaptopyridine, mercaptoalkylamines such as 2-mercaptoethylamine, and 2,2-dimethyl. Examples thereof include thiazolidines such as thiazolidine, aminothiophenols such as 4-aminothiophenol, and pyridinealkanethiols such as 4-pyridineethanethiol. Of these, 4-pyridineethanethiol, 2,2-dimethylthiazolidine and 2-mercaptoethylamine are preferred. These can be used alone or in combination of two or more.

The rate of modification of the strongly acidic ion exchange resin with the iodiamine-containing compound is usually about 5 to 45%, preferably 8 to 35%, more preferably 10 to 30%. By setting the upper limit of the modification rate to about 45%, the catalyst activity does not decrease, and by setting the lower limit to about 5%, the catalyst life is shortened, and the catalyst activity and selectivity are reduced. It does not get lower. Here, the “denaturation rate” of the strongly acidic ion exchange resin means a molar modification rate of the strongly acidic ion exchange resin by the iodamine compound containing the strongly acidic ion exchange group.

As the acid, an organic acid or an inorganic acid can be used. Examples of the organic acid include aromatic sulfonic acids such as benzenesnolephonic acid, paratonolenesnolephonic acid, and xylene zolefonic acid, alkyl sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, acetic acid, and formic acid. Can be Of these, aromatic sulfonic acids are preferred, and paratoluenesulfonic acid is more preferred. Further, an acidic aqueous solution obtained by washing the sulfonate-type ion exchange resin with water is also suitable. Examples of the inorganic acid include phosphoric acid, boric acid and sulfuric acid, with phosphoric acid being preferred. The use of aromatic sulfonic acids or phosphoric acid has the advantage of almost no equipment corrosion.

The concentration of the aqueous acid solution is selected from aromatic sulfonic acids, alkyl sulfonic acids and sulfuric acid. When a strong acid such as an acid is used, it is usually about 0.01 to 5% by mass, preferably 0.03 to 2% by mass. / ₀ . When a weak acid such as acetic acid, formic acid or phosphoric acid is used, it is usually about 0.01 to 8% by mass, preferably 0.05 to 3% by mass. By setting the upper limit of the acid concentration to about 5% by mass in the case of a strong acid, or to about 8% by mass in the case of a weak acid, the concentration of the diamine compound which equilibrates in an aqueous acid solution (hereinafter, referred to as “ ), Which is economically preferable because the amount of acid used and the loss of the iodiamin compound are small. By setting the lower limit of the acid concentration to about 0.01% by mass, the equilibrium concentration of the diamine-containing compound does not become too low, so that the time required for denaturation does not become too long.

Here, the equilibrium concentration of the iodiamine-containing compound in the acid aqueous solution is determined as follows. For example, an acid solution is added to a water-swollen strongly acidic ion exchange resin, and the mixture is repeatedly stirred and filtered to replace water with the acid solution. Then, a 10% by mass aqueous solution of a diamine-containing compound is replaced with an ion exchange resin. Add slowly with stirring. Up to this point, the preparation of the catalyst using a patch has been described. Then, a part of this aqueous solution is sampled, and the total nitrogen analysis is performed, and the concentration of the diopamine compound is determined from the total nitrogen concentration.

In the present invention, prior to denaturation of the strongly acidic ion exchange resin, it is preferable to replace the water contained in the fixed bed (strongly acidic ion exchange resin) of the fixed bed reactor with an aqueous acid solution. This is because the water-swelling type of the gel-type ion exchange resin usually used as a strongly acidic ion exchange resin contains about 50% by mass of water. By performing such substitution, when the acid aqueous solution flowing out of the outlet of the reactor is circulated and recycled, an effect is obtained that the acid concentration is kept constant.

The temperature of the catalyst preparation (denaturation of the strongly acidic ion-exchange resin with a diamine-containing compound) is usually about 0 to 120 ° C, preferably 20 to 100 ° C. Touch By setting the upper limit of the medium preparation temperature to about 120 ° C, the ion exchange resin is not decomposed, and by setting the lower limit to about 0 ° C, the problem of solidification of the acid aqueous solution does not occur.

The injection of the acid aqueous solution and the iodamine compound is usually performed by injecting a prepared solution in which the iodamine compound is dissolved in the acid aqueous solution. From the viewpoint of acid concentration and preparation time, the injection amount of the aqueous solution is usually about ¹ to 20 h1 in LHSV (liquid hourly space velocity), preferably 0.2 to 10 h- ¹ , more preferably 0.4. ~ 5 h- ¹ . The linear velocity of the prepared solution is usually about 0.1 to 10 OmZh, preferably 0.2 to 5 OmZh, and more preferably 0.5 to 2 OmZh.

The time required for preparing the catalyst is determined by the concentration and type of acid in the aqueous acid solution, the equilibrium concentration of the diamine compound, the modification ratio of the strongly acidic ion exchange resin with the diamine compound, LHSV, and the like. The amount of the diamine compound to be consumed in the preparation of the catalyst is determined by the modification ratio. The concentration of the iodamine-containing compound injected into the fixed bed reactor is the equilibrium concentration of the iodamine-containing compound.

In the preparation of the catalyst, a fixed amount of the prepared solution obtained by dissolving the iodamine compound in an aqueous acid solution was injected from the inlet of the fixed bed reactor, and the prepared solution passed through the strongly acidic ion-exchange resin filled in this reactor was fixed. It flows out of the outlet of the bed reactor. As a treatment of this prepared solution, there is a method of discarding or circulating and recycling it.However, the method of circulating and recycling is used because the amount of waste solution becomes small and the amount of iodamine-containing compound and acid used becomes small. I like it. In the case of cyclic recycling, measure the concentration of the iodamine compound in the preparation liquid flowing out from the outlet of the fixed bed reactor, and add an amount of the iodamine compound that is equivalent to the equilibrium concentration of the iodamine compound. The concentration of the iodamine-containing compound is determined by measuring the nitrogen concentration in the preparation containing the iodamine compound and the acid. Can be obtained by doing Since the total injection time is roughly determined by the equilibrium concentration of the ioamine compound to be injected and the denaturation ratio of the ion exchange resin, the measurement interval of the ioamine compound concentration can be usually set to every 2 to 20 hours. When circulating the preparation solution containing the iodamine-containing compound and the acid, the injection amount (circulation amount) to the fixed bed reactor can be the same LHSV and linear velocity as described above.

In the preparation of the catalyst, the flow of the preparation solution containing the acid and the ioamine compound in the fixed bed reactor may be either a down flow or an up flow. However, in the case of an upflow, the expansion (floating, flowing, etc.) of the ion-exchange resin increases as the injection amount of the preparation liquid increases. Therefore, the downflow is preferred in the present invention.

Using the modified catalyst prepared as described above, bisphenol A is produced using phenol and acetone as raw materials. The addition of the modified catalyst to the raw material in the fixed-bed reactor can be performed under almost the same conditions as when the catalyst was prepared (LHSV and linear velocity). There is no particular limitation on the ratio of phenol and acetone used, but it is desirable that the amount of unreacted acetone be as small as possible in view of the ease of purification of bisphenol A to be produced and the economical efficiency. Is advantageously used in excess of the stoichiometric amount. Usually, about 3 to 30 moles, preferably 5 to 15 moles of phenol are used per mole of acetone. The reaction temperature is usually about 40 to 150 ° C, preferably 60 to 110 ° C.

The condensation reaction between phenol and acetone may be any of a batch type and a continuous type, but a fixed bed continuous reaction system in which phenol and acetone are continuously supplied to a reaction tower filled with a denaturing catalyst and reacted. Is preferred.

According to the present invention, the strongly acidic ion exchange resin is not damaged, the strongly acidic ion exchange resin is uniformly denatured, the time for uniform denaturation is short, and the catalyst performance is improved. An excellent modified catalyst for producing bisphenol A can be prepared. .

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

Example 1

As a reactor, four reactors with an inner diameter of 1 O mm and a length of 1200 mm are connected in series, and the outlet side and the inlet side are connected by piping, and the prepared solution discharged from the reactor outlet Was circulated to the inlet side. This reactor was filled with 300 milliliters of a water-swelled sulfonic acid-type cation exchange resin (trade name: Diaion SK-104, manufactured by Mitsubishi Chemical Corporation), and distilled water was passed through a down port. Washed at 500 milliliters. Next, the water in the reactor and the piping was replaced with a 0.3% by mass aqueous solution of phosphoric acid. A 0.3% by weight aqueous solution of phosphoric acid and 2,2-dimethylthiazolidine in which 2,2-dimethylthiazolidine had a concentration of 117 ppm by mass were added to a reactor of 300 ml. The injection was performed at Z h (LHSV = 1 h—linear velocity = 3.8 m / h). The target denaturation rate with 2,2-dimethylthiazolidine was 2'3% .The above preparation was continuously injected for 298 hours, and the above ion exchange resin was modified at 25 ° C. . The above prepared solution flowing out from the outlet of the fourth reactor was circulated to the first reactor and recycled. At this time, the content of 2,21-dimethylthiazolidine in the preparation flowing out from the outlet of the fourth reactor was measured every 20 hours using a total nitrogen analyzer, and the amount of 2,21-dimethylthiazolidine was kept at 17 mass ppm. , 2-Dimethylthiazolidine was added.

After the injection of the prepared solution obtained by adding 2,2-dimethylthiazolidine to the phosphoric acid aqueous solution was completed, the denaturing catalyst was extracted from the reactor, and the phosphoric acid aqueous solution was removed with distilled water. The modified catalyst was dried, and the modification rate was measured by the following method. The results are shown in Table 1.

Measurement of denaturation rate> The acid equivalent was measured by a titration method using an aqueous sodium hydroxide solution, a neutralization ratio was calculated based on the following equation, and this neutralization ratio was defined as a modification ratio.

Neutralization rate (%) = 100 X {1-[acid equivalent of modified resin (meq./g) Z acid equivalent of unmodified resin (meq. / G)]}

Example 2

In Example 1, a prepared solution containing 4.4% by mass of 2,2-dimethylthiazolidine prepared using an aqueous solution of 1.0% by mass of phosphoric acid instead of the aqueous solution of 0.3% by mass of phosphoric acid was continuously used for 79 hours. A modified catalyst was obtained in the same manner as in Example 1 except that the injection was performed. The same evaluation as in Example 1 was performed on the resulting modified catalyst. The results are shown in Table 1.

Example 3

In Example 1, a preparation containing 52 mass ppm of 2-mercaptoethylamine instead of 2,2-dimethylthiazolidine was used, and a target denaturation rate of 15% was used. This preparation was continuously used for 280 hours. A modified catalyst was obtained in the same manner as in Example 1 except that the catalyst was injected. The same evaluation as in Example 1 was performed for the obtained modified catalyst. The results are shown in Table 1.

Example 4

In Example 1, a preparation solution containing 2,3-dimethylthiazolidine 13 1 mass ppm was prepared by using a 0.3 mass% paratoluenesulfonic acid aqueous solution instead of the 0.3 mass% phosphoric acid aqueous solution. A modified catalyst was obtained in the same manner as in Example 1, except that injection was continued for 6 hours. The same evaluation as in Example 1 was performed for the obtained modified catalyst. The results are shown in Table 1.

Comparative Example 1

In Example 1, a total of 10.1 g of 2,2-dimethylthiazolidine was injected in 0.5 hours, and a 0.3% by mass phosphoric acid aqueous solution was circulated and recycled for the same time as in Example 1. A modified catalyst was obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed for the obtained modified catalyst. Table 1 shows the results.

Comparative Example 2

In Example 2, a total of 10.1 g of 2,2-dimethylthiazolidine was injected in 0.5 hours, and a 1.0% by mass aqueous phosphoric acid solution was circulated and recycled for the same time as in Example 2. In the same manner as in Example 2, a modified catalyst was obtained. The same evaluation as in Example 1 was performed for the obtained modified catalyst. Table 1 shows the results.

Comparative Example 3

In Example 3, a total amount of 4.2 g of 2,2-mereptethylamine used was injected in 0.5 hours, and a 0.3% by mass aqueous phosphoric acid solution was circulated for the same time as in Example 1. A modified catalyst was obtained in the same manner as in Example 3 except that the catalyst was recycled. The same evaluation as in Example 1 was performed for the obtained modified catalyst. Table 1 shows the results.

Comparative Example 4

In Example 4, a total amount of 10.1 g of 2,2-dimethylthiazolidine used was injected in 0.5 hours, and a 0.3% by mass aqueous phosphoric acid solution was circulated and recycled for the same time as in Example 4. In the same manner as in Example 4, a modified catalyst was obtained. The same evaluation as in Example 1 was performed for the obtained modified catalyst. Table 1 shows the results.

table 1

Industrial applicability

According to the present invention, a modified catalyst for producing bisphenol A having excellent catalytic performance can be provided.

Claims

The scope of the claims

1. In a method for preparing a modified catalyst for the production of bisphenol A, which is obtained by partially modifying a strongly acidic ion exchange resin with an iodiamine compound, a fixed bed reactor is charged with a strongly acidic ion exchange resin, and A method for preparing a modified catalyst for producing bisphenol A, which comprises injecting an acid aqueous solution and an ioamine compound containing an equilibrium concentration in the acid aqueous solution to modify a strongly acidic ion exchange resin.

2. The method according to claim 1, wherein the diamine-containing compound is at least one selected from mercaptoalkylamines, thiazolidines and mercaptoalkylpyridines.

3. The method according to claim 1, wherein the acid is an organic acid selected from aromatic sulfonic acids, alkyl sulfonic acids, acetic acid and formic acid.

4. The preparation method according to claim 3, wherein the acid is a 0.01 to 5% by mass aqueous solution of an aromatic sulfonic acid.

5. The preparation method according to claim 4, wherein the acid is a 0.03 to 2% by mass aqueous solution of an aromatic sulfonic acid.

6. The method according to claim 1, wherein the acid is an inorganic acid selected from phosphoric acid, boric acid and sulfuric acid.

7. The method according to claim 6, wherein the acid is a 0.1 to 8% by mass aqueous solution of phosphoric acid. Preparation method described in 1.

8. The preparation method according to claim 7, wherein the acid is a 0.05 to 3% by mass aqueous solution of phosphoric acid.

9. The preparation method according to claim 1, wherein the acid is an acidic aqueous solution obtained by washing the sulfonic acid type ion exchange resin with water.

10. The method according to claim 1, wherein the denaturation of the strongly acidic ion exchange resin with the iodiamine-containing compound is carried out at 0 to 120.

1 1. The preparation method according to claim 1, wherein the modification ratio of the strongly acidic ion exchange resin with the iodiamine-containing compound is 5 to 45%.

1 2. The injection of the acid aqueous solution and the iodamine compound is the injection of a prepared solution in which the iodamine compound is dissolved in the acid aqueous solution, and the injection amount of the prepared solution is 0.1 to LH SV (liquid space velocity). the preparation method according to any one of 20 h ¹ in the range of claims is the first term - the first (1).

1 3. Injection volume of preparation by dissolving a free Iowamin compound aqueous acid solution, preparation method according to the first two terms claims is 0. 2 to 1 0 h ¹ in LHS V (liquid hourly space velocity).