WO2005042154A1

WO2005042154A1 - Method of preparing modified catalyst for bisphenol a production

Info

Publication number: WO2005042154A1
Application number: PCT/JP2004/015700
Authority: WO
Inventors: Masahiro Iwahara; Jun Mase; Shuichi Masuda; Hideki Sato
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2003-11-04
Filing date: 2004-10-22
Publication date: 2005-05-12
Also published as: TWI337179B; JP2005137950A; TW200519077A; JP4452058B2

Abstract

A method of preparing a modified catalyst for bisphenol A production that is free from damaging of strongly acidic ion exchange resin, realizes uniform modification of strongly acidic ion exchange resin and excels in catalytic performance. There is provided a method of preparing a modified catalyst for bisphenol A production resulting from partial modification of a strongly acidic ion exchange resin with a sulfurated amine compound, comprising charging a fixed bed reactor with a strongly acidic ion exchange resin and effecting injection of an aqueous solution containing an acid and a sulfurated amine compound therein and circulation therethrough so as to modify the strongly acidic ion exchange resin, wherein after the injection of the aqueous solution or while circulating the same or while temporarily stopping the circulation, an inert gas is bubbled from an underpart of the fixed bed reactor to thereby agitate the strongly acidic ion exchange resin.

Description

Specification

Preparation of modified catalyst for bisphenol A production

Technical field

The present invention relates to a method for preparing a catalyst used for producing bisphenol A [2,2-bis (4-hydroxyphenyl) propane]. More specifically, the present invention relates to a diamine compound containing a strongly acidic ion exchange resin. Background Art on Preparation Method of Partially Modified Modified Catalyst for Production of Bisphenol A

[0002] Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate and polyarylate, and epoxy resin, and the demand for it is increasing in recent years. Tend to.

In the production of this bisphenol A, a strongly acidic ion-exchange resin partially modified with a diamine-containing conjugate is used as a catalyst, and such a catalyst is prepared in a fixed-bed reactor in a fixed-bed reactor. In addition, a method is used in which a sulfonic acid-type ion exchange resin is denatured by batch addition of a diamine-containing conjugate.

Usually, in a fixed-bed reactor, the sulfonic acid-type ion-exchange resin is modified all at once by adding the diamine-containing conjugate to the sulfonic acid-type ion-exchange resin. Transfers sulfonic acid groups (adsorption to sulfonic acid groups, desorption and transfer from sulfonic acid groups). At this time, the sulfonic acid-type ion-exchange resin is not uniformly denatured by a single transfer of the iodiamine-containing compound from the inlet to the outlet of the fixed-bed reactor by a single force. In other words, the concentration of the diamine-containing compound during the transfer of the diamine-containing compound is high at the outlet of the fixed-bed reactor (denaturation rate is about 30 to 80%, high denaturation rate). Is low (denaturation rate is as low as about 5-30%), so that the sulfonic acid type ion exchange resin cannot be uniformly denatured by only one transfer.

The cation-exchange resin fixed bed neutralized with the diamine-containing conjugate has been prepared by various methods. A method for preparing a fixed bed (for example, see Patent Documents 1 to 14) is disclosed. Also, circulate an aqueous solution of iodamine compound containing hydrochloric acid in the resin fixed bed. Although a method (for example, see Patent Document 5) is disclosed, if a large amount of hydrochloric acid is used, the equipment may be corroded.

Further, as a method for preparing a catalyst for producing bisphenols, a method of injecting a dilute solution of a diamine-containing conjugate while stirring an ion exchange resin in a reaction vessel (for example, see Patent Document 6), The acidic cation exchange resin is filled with the acidic cation exchange resin, and while the aqueous solution of the diamine-containing conjugate is being charged or after being charged, the lower portion of the reactor is circulated to uniformly distribute the acid cation exchange resin. A method of summing is disclosed (for example, see Patent Document 7). However, in the former case, a large-scale dilute solution storage facility is required, and the batch-type production using impeller agitation causes damage to the ion-exchange resin. Need to be refilled. In the latter case, since the preparation is carried out at a pH of 6 or more, it is difficult to homogenize the diamine-containing conjugate, which results in a non-uniform modified catalyst, and thus has a problem that the catalytic performance is reduced.

It is important for the denaturation catalyst that the ion exchange resin is uniformly denatured. If the denaturation is not uniform, sufficient catalytic activity cannot be obtained and the catalyst life will be shortened. In the method, particularly in a fixed-bed reactor, it is not possible to stir the strongly acidic ion-exchange resin by publishing an inert gas from the lower part of the fixed-bed reactor during catalyst preparation in order to perform uniform denaturation. We didn't.

[0003] Patent Document 1: JP-A-6-296871

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-286770

Patent Document 3: JP-A-8-40961

Patent Document 4: JP 2001-288132 A

Patent Document 5: JP-A-53-14680

Patent Document 6: JP-A-9-24279

Patent Document 7: JP-A-2000-254523

Disclosure of the invention

Problems to be solved by the invention

[0004] The present invention has been made in view of the above circumstances, and a bisphenol A in which a strongly acidic ion exchange resin is uniformly modified and which has excellent catalytic performance without breaking of the strongly acidic ion exchange resin. It is an object of the present invention to provide a method for preparing a modified catalyst for production.

Means for solving the problem

[0005] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, filled a fixed-bed reactor with a strongly acidic ion-exchange resin, and injected and circulated an aqueous solution containing an acid and an iodiamine-containing compound. In order to uniformly denature the strongly acidic ion exchange resin, while circulating the aqueous solution or temporarily suspending the circulation, the inert gas is bubbled from the lower part of the fixed bed reactor. It has been found that the above object can be achieved by stirring the above strongly acidic ion exchange resin. That is, by stirring the strongly acidic ion-exchange resin in this manner, the concentration of the diamine-containing conjugate is averaged. It has been found that a strongly acidic ion exchange resin is uniformly denatured in a short time. The present invention has been completed based on strong knowledge.

That is, the present invention relates to 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 a diamine conjugate containing a strongly acidic ion exchange resin. After filling the exchange resin and injecting and circulating an aqueous solution containing an acid and an iodamine compound therein, when denaturing the strongly acidic ion exchange resin, after injecting or circulating the above aqueous solution or temporarily. A modified catalyst for the production of bisphenol A, characterized in that the inert gas is bubbled from the lower part of the fixed bed reactor while the circulation is stopped and the strongly acidic ion exchange resin is stirred. It provides a method of preparation.

The invention's effect

According to the present invention, it is possible to prepare a modified catalyst for producing bisphenol A in a short time, in which a strongly acidic ion exchange resin that does not break the strongly acidic ion exchange resin is uniformly modified and has excellent catalytic performance. it can.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The strongly acidic ion-exchange resin used in the present invention includes sulfonates such as a snorephonated styrenedivinylbenzene copolymer, a sulfonated crosslinked styrene polymer, phenolformaldehyde hydrosulfonic acid resin, and benzeneformaldehyde-sulfonic acid resin. Acid form Ion-exchange resins and the like. Strongly acidic ion exchange resin is charged into a fixed bed reactor. Since the fixed bed is directly filled with ion exchange resin, the ion exchange resin will not be damaged in the denaturation process of the ion exchange resin, and there will be no transfer of batch reactors or modified catalyst preparation tanks. It is economically 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, 2 mercaptoalkylamines such as mercaptoethylamine, and 2,2-dimethylthiazolidine. Thiazolidine, etc .; aminothiofolones, such as 4-aminothiol, and pyridinalkanethiols, 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 diamine-containing conjugate is usually about 5 to 45%, preferably 8 to 35%, more preferably 10 to 30%. By setting the upper limit of this modification rate to about 45%, the catalyst activity is not reduced, and by setting the lower limit to about 5%, the catalyst life is shortened and the catalyst activity and selectivity are reduced. There is no. Here, the “denaturation rate” of the strongly acidic ion exchange resin means the molar modification rate of the strongly acidic ion exchange resin by the iodiamine 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 benzenesulfonic acid, paratoluenesulfonic acid and xylenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid and ethanesulfonic acid, acetic acid and formic acid. Of these, p-toluenesulfonic acid, which is more preferred by aromatic sulfonic acids, is more preferred. Further, an acidic aqueous solution obtained by washing the sulfonic acid type ion exchange resin with water is also suitable. Examples of the inorganic acid include phosphoric acid, boric acid, and sulfuric acid, and phosphoric acid is preferable. The use of aromatic sulfonic acids or phosphoric acid has the advantage of almost no equipment corrosion.

When a strong acid such as an aromatic sulfonic acid, an alkylsulfonic acid or sulfuric acid is used, the acid concentration of the aqueous solution is usually about 0.01 to 5% by mass, preferably 0.03 to 2% by mass. 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 0.05-3% by mass. By setting the upper limit of the acid concentration to about 5% by mass in the case of a strong acid and to about 8% by mass in the case of a weak acid, the concentration of the diamine-containing compound dissolved in the acid solution does not increase. It is economically preferable because the amount of acid used and the amount of mouth of the diamine-containing conjugate are small. By setting the lower limit of the acid concentration to about 0.01% by mass, the concentration of the iodamine-containing compound does not become too low, so that the time required for denaturation does not become too long.

In the present invention, prior to denaturation of the strongly acidic ion exchange resin, the water contained in the fixed bed (strongly acidic ion exchange resin) of the fixed bed reactor may be replaced with an aqueous solution containing the above acid. preferable. 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, an effect is obtained in which the acid concentration is kept constant when the aqueous solution that has flowed out of the reactor is circulated and recycled.

The temperature for preparing the catalyst (modification of the strongly acidic ion-exchange resin with the diamine-containing conjugate) is usually about 0 to 120 ° C, preferably 20 to 100 ° C. By setting the upper limit of the catalyst preparation temperature at about 120 ° C., the ion exchange resin does not decompose, and by setting the lower limit at about 0 ° C., the solidification of the acid aqueous solution causes no problem! /.

From the viewpoint of acid concentration and preparation time, the circulation amount of the aqueous solution containing an acid and an iodamine compound is usually about 0.1 to 20 h- ¹ in LHSV (liquid hourly space velocity), preferably 0.2 to ¹⁰ h_1, more preferably 0. 4-5h ^1. The linear velocity of the aqueous solution is usually about 0.01 to 100 mZh, preferably 0.05 to 50 m / h, and more preferably 0.1 to 20 m / h.

[0010] The time required for preparing the catalyst is determined by the concentration of the acid and the type of the acid contained in the aqueous solution, the concentration of the diamine-containing compound, the modification rate of the strongly acidic ion-exchange resin with the diamine-containing conjugate, LHSV, and the like. . The amount of the diamine-containing conjugate to be consumed in the preparation of the catalyst is determined by the conversion.

Next, an example of a preferred embodiment of the catalyst preparation method of the present invention will be described. First, a solution obtained by dissolving the diamine-containing conjugate in an aqueous solution containing an acid is injected from the inlet of the fixed bed reactor, and then an aqueous solution containing an acid is injected. By circulating, the aqueous solution containing the acid and the iodamine compound is also discharged at the outlet of the fixed bed reactor. In the present invention, After injecting or circulating an aqueous solution containing the acid and the diamine-containing conjugate of the above, while the circulating is temporarily stopped, an inert gas is bubbled from the lower part of the fixed bed reactor, The above strongly acidic ion exchange resin is stirred. When publishing the inert gas while the circulation of the aqueous solution is stopped, the circulation is performed again after the publishing is completed. The stirring time is usually about 11 to 120 minutes, preferably 5 to 60 minutes. The timing of stirring depends on the time required for catalyst preparation, but is usually performed after the time required for catalyst preparation has passed about 1Z10-3Z4. Further, publishing of the inert gas may be performed twice or more. Examples of the inert gas include helium, argon, and nitrogen, among which nitrogen is preferred. The flow rate of the inert gas is usually 2 to 50 times (volume) Zh, preferably 5 to 50 times the internal volume of the reactor or the amount of catalyst, depending on the diameter of the reactor and the gas injection mode. 30 times (volume) Zh. For example, at the level of an actual apparatus, a gas flow rate of 700 m ³ / h is preferable for a catalyst of 50 m ³ (reactor diameter 4 m). After publishing, it is preferable to stir the mixture so that the ion exchange resin is completely mixed.

In the preparation of the catalyst, the flow of the aqueous solution containing the acid and the diamine-containing conjugate in the fixed-bed reactor may be either a downflow or an upflow. In the case of an upflow, a large flow of the aqueous solution increases the development (floating, flowing, etc.) of the ion exchange resin. Therefore, a 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 preparing the catalyst (LHSV and linear velocity). The proportion of phenol and acetone used is not particularly limited, 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 and the economical efficiency. It is advantageous to use phenol in excess of the stoichiometric amount. Usually, about 3 to 30 mol, preferably 5 to 15 mol of phenol is used per 1 mol of acetone. The reaction temperature is usually in the range of about 40 to 150 ° C, preferably 60 to 110 ° C.

The condensation reaction between phenol and acetone may be carried out in batch or continuous manner. The reaction may be carried out by continuously supplying phenol and acetone to a reaction tower filled with a denaturation catalyst. The fixed bed continuous reaction method is preferred.

Example

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

Example Reference Example 1 and Comparative Example 1

The reactor has an inner diameter of 50 mm, a length of 250 mm, and the outlet side and the inlet side are connected by an external pipe so that the discharged liquid from the reactor is circulated to the inlet side, and nitrogen publishing is performed from the lower part of the reactor. The reactor used was able to carry out the reaction. This reactor was charged with 200 ml of a water-swelled sulfonic acid type cation exchange resin (trade name: Diaion SK 104, manufactured by Mitsubishi Idani Gakusha), and washed with 1000 ml of distilled water by down flow. did . Next, water in the reactor and the piping was replaced with a 1.0% by mass aqueous solution of paratoluenesulfonic acid. At 25 ° C, 5.9 g of 2,2-dimethylthiazolidine (target modification rate: 20%) was dissolved in 50 ml of a 1.0% by mass aqueous solution of p-toluenesulfonic acid, and the solution was added to the above ion exchange resin over 30 minutes. Injected. Thereafter, circulation of a 1.0% by mass aqueous solution of paratoluenesulfonic acid was started at 400 ml (ZMLHSV = 2 h—linear velocity = 0.20 mZh). After 4 hours, the circulation was temporarily stopped, and nitrogen gas was flowed from the lower part of the reactor at 150 milliliters Zmin, and publishing was performed for 20 minutes. Thereafter, a 1.0% by mass aqueous solution of paratoluenesulfonic acid was further circulated at 400 ml Zh (LHSV = ^2h_1 , linear velocity = ^0.20 m / h) for 4 hours.

Reactor power The denaturing catalyst was divided into five parts, extracted, and the aqueous solution of paratoluenesulfonic acid was removed with distilled water. The modified catalyst was the first catalyst on the inlet side of the reactor, and hereinafter the second, third, fourth and fifth catalysts. The modified catalyst was dried, the acid equivalent was measured by titration using an aqueous sodium hydroxide solution, the neutralization rate was calculated based on the following equation, and the neutralization rate was defined as the modification rate. The results are shown in Table 1.

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

In the catalyst preparation step, the modification rate of the ion exchange resin when the circulation of the acid aqueous solution was temporarily stopped was determined in the same manner as described above (Reference Example 1). Furthermore, the above catalyst preparation The denaturation of the modified catalyst obtained by circulating a 1.0% by mass aqueous solution of p-toluenesulfonic acid at the same flow rate as described above and for the same time as that required for the preparation of the catalyst, without publishing with nitrogen gas. The ratio was determined in the same manner as above (Comparative Example 1). Table 1 shows these results.

The circulated acid aqueous solution can be reused after preparing the catalyst. In addition, since 2,2-dimethylthiazolidine is hydrolyzed to produce acetone as a by-product, acetone is contained in the circulated acid aqueous solution. Practically, when this acid aqueous solution is discarded, it is general that the acetone is removed by steam stripping and then treated in a wastewater treatment facility.

[0013] Example 2, Reference Example 2, and Comparative Example 2

In Example 1, a 0.1% by mass aqueous solution of paratoluenesulfonic acid was used instead of the 1.0% by mass aqueous solution of paratoluenesulfonic acid, and the circulation was temporarily stopped 20 hours after the circulation of the acid solution was started. Then, a modified catalyst was obtained in the same manner as in Example 1 except that nitrogen gas was bubbled, and then a 0.1% by mass aqueous solution of paratoluenesulfonic acid was further circulated for 24 hours. The same evaluation as in Example 1 was performed for the obtained modified catalyst.

Further, in the catalyst preparation step, the modification rate of the ion exchange resin when the circulation of the acid aqueous solution was temporarily stopped was determined in the same manner as described above (Reference Example 2). Further, in the preparation of the above catalyst, a modification obtained by circulating a 0.1% by mass aqueous solution of phosphoric acid at the same flow rate as described above without publishing with nitrogen gas and at the same time as that required for the preparation of the above catalyst was carried out. The modification rate of the catalyst was determined in the same manner as above (Comparative Example 2). Table 2 shows the results.

Example 3, Reference Example 3, and Comparative Example 3

In Example 1, instead of circulating a 1.0% by mass aqueous solution of paratoluenesulfonic acid at 400 mL Zh, a 1.0% by mass aqueous solution of phosphoric acid was used, and seven hours have elapsed since the circulation of the aqueous solution of phosphoric acid was started. After that, the circulation was stopped, nitrogen gas was bubbled, and then a 1.0% by mass aqueous phosphoric acid solution was further circulated at 400 ml Zh for 3 hours. Obtained. The same evaluation as in Example 1 was performed on the resulting modified catalyst.

In the above catalyst preparation step, the ion The modification ratio of the exchange resin was determined in the same manner as described above (Reference Example 3). Further, in the preparation of the above catalyst, a modification obtained by circulating a 1.0% by mass aqueous solution of phosphoric acid at the same flow rate as described above and at the same time as that required for the preparation of the above catalyst, without publishing with nitrogen gas, was carried out. The modification rate of the catalyst was determined in the same manner as above (Comparative Example 3). Table 3 shows the results.

Example 4, Reference Example 4, and Comparative Example 4

In Example 1, the operation after replacing the water in the reactor and the pipe with a 1.0% by mass aqueous solution of paratoluenesulfonic acid was changed as follows to obtain a modified catalyst. That is,

At 25 ° C, 1. 0 mass ^_0/0 p-toluenesulfonic acid aqueous solution 50 ml, 2-mercapto Echiruamin 3. 9 g (target modification ratio 20%) was dissolved, the ion exchange resin over this 30 minutes Was injected. Next, nitrogen gas was flowed from the lower part of the reactor at 150 ml Zmin, and publishing was performed for 20 minutes. Thereafter, a 1.0% by mass aqueous solution of paratoluenesulfonic acid was circulated at 800 ml Zh for 3 hours. The same evaluation as in Example 1 was performed for the obtained modified catalyst.

In the catalyst preparation step, the modification rate of the ion exchange resin after the injection of the acid aqueous solution was determined in the same manner as described above (Reference Example 4). Further, in the preparation of the above catalyst, a cycling of a 1.0% by mass aqueous solution of paratoluenesulfonic acid was carried out at the same flow rate as above, without publishing with nitrogen gas, for the same time as that required for the preparation of the catalyst. The modification ratio of the modified catalyst thus obtained was determined in the same manner as above (Comparative Example 4). Table 4 shows the results.

[Table 1]

[0017] [Table 2] 0.1% by mass p-toluenesulfonic acid aqueous solution

Reference Example 2 Example 2 Comparative Example 2

Nitrogen publishing,

Circulation after 20 hours Circulation after 24 hours Circulation after 44 hours From reactor inlet Denaturation rate (%) Denaturation rate (%) Denaturation rate (%)

1 86 21 68

2 14 20 31

3 0 19 1

4 0 20 0

5 0 20 0

[0018] [Table 3]

[0019] [

The reaction performance of the modified catalyst obtained as described above was evaluated. Evaluation of the reaction performance was performed by synthesizing bisphenol A in a flask using phenol and acetone as raw materials. The reaction temperature was 75 ° C., the phenol Z acetone (molar ratio) was 10Z1, the amount of the modified catalyst used was 5% by mass relative to the raw materials, and the reaction was carried out for 2 hours. Table 5 shows the results. [Table 5]

(note)

Selectivity: Ratio of bisphenol A to product

Catalyst 1: Reference Example 1, a mixture of catalysts from the reactor inlet to the first to fifth catalysts Catalyst 2: Example 1, Mixture of catalysts from the inlet to the first to fifth catalysts Catalyst 3: Reference Example 1: 5 from the inlet to the reactors Th catalyst

Catalyst 4: Reference Example 2, a mixture of catalysts 1 to 5 from the reactor inlet Catalyst 5: Example 2, Mixture of catalysts 1 to 5 from the reactor inlet Catalyst 6: Reference Example 3, 1 from the reactor inlet One-fifth catalyst mixture Catalyst 7: Example 3, from reactor inlet 1-Fifth catalyst mixture Catalyst 8: Reference Example 4, first catalyst from reactor inlet

Catalyst 9: Example 4, a mixture of catalysts 1 to 5 from the reactor inlet Catalyst 10: Comparative Example 1, a mixture of catalysts 1 to 5 from the reactor inlet Catalyst 11: Comparative Example 2, 1 from the reactor inlet Mixture of the 1st and 5th catalysts Catalyst 12: Comparative Example 3, a mixture of 1 to 5 catalysts from the reactor inlet Catalyst 13: Comparative Example 4, mixture of the 1st to 5th catalysts from the reactor inlet 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

[I] In a method for preparing a modified catalyst for producing bisphenol A, which is obtained by partially modifying a strongly acidic ion exchange resin with an iodiamine compound, a fixed bed reactor is filled with the strongly acidic ion exchange resin. Injecting and circulating an aqueous solution containing an acid and an iodamine compound therein to denature the strongly acidic ion-exchange resin, after injecting or circulating the aqueous solution, or temporarily stopping circulation. A method for preparing a modified catalyst for producing bisphenol A, characterized in that an inert gas is bubbled from a lower part of the fixed bed reactor and the strongly acidic ion exchange resin is stirred.

[2] The preparation method according to claim 1, which is at least one selected from the group consisting of mercaptoalkylamines, thiazolidines and mercaptoalkylpyridines.

[3] The method according to claim 1 or 2, wherein the acid is an organic acid selected from aromatic sulfonic acids, alkylsulfonic acids, acetic acid and formic acid.

[4] The method according to claim 3, wherein the aqueous solution contains 0.01 to 5% by mass of aromatic sulfonic acids.

[5] The preparation method according to claim 1 or 2, wherein the acid is an inorganic acid selected from phosphoric acid, boric acid and sulfuric acid.

[6] The preparation method according to claim 5, wherein the aqueous solution contains 0.01 to 8% by mass of phosphoric acid.

[7] The preparation method according to claim 1 or 2, wherein the aqueous solution is an acidic aqueous solution obtained by washing the sulfonic acid type ion exchange resin with water.

[8] The preparation method according to any one of claims 17 to 17, wherein the inert gas is nitrogen gas.

[9] The preparation method according to any one of [18] to [18], wherein the denaturation of the strongly acidic ion exchange resin with the iodiamine-containing compound is performed at 0 to 120 ° C.

[10] The preparation method according to any one of claims 11 to 19, wherein the modification ratio of the strongly acidic ion exchange resin with the diamine-containing conjugate is 5-45%.

[II] acid and containing Iouamini匕合product preparation method according to any one of claims 1 one 10 is 0. 1-20h ^_1 by injection 'circulation rate force LHSV (liquid hourly space velocity) of an aqueous solution containing.