JP3243627B2 - Method for producing 1,2,3,4-butanetetracarboxylic acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 1,2,3,4-butanetetracarboxylic acid, and more particularly to a method for producing 1,2,3,4-butanetetracarboxylic acid by hydrogen peroxide oxidation of tetrahydrophthalic anhydride or its hydrous acid.
The present invention relates to a method for producing 1,2,3,4-butanetetracarboxylic acid in a method for producing 2,3,4-butanetetracarboxylic acid by efficiently separating and recovering a catalyst and repeating the production of the catalyst in high yield.

[0002]

2. Description of the Related Art Tungstic acid or phosphotungstic acid or a salt thereof is often used as a catalyst when an organic compound is oxidized using a peroxide, and 1,2,3,4-butane is used. The method for producing tetracarboxylic acid is also an example. In other words, Tokuho 2-220
No. 56 discloses that tetrahydrophthalic anhydride or its hydrous acid is oxidized with hydrogen peroxide using tungstic acid or phosphotungstic acid or a salt thereof as a catalyst. , 4-butanetetracarboxylic acid are described as being obtained.

However, in the above method for producing 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid is crystallized and separated from the reaction solution after completion of the reaction. In addition, due to the effect of tungstate ions or phosphotungstate ions coexisting in the liquid,
Since the crystal habit of 3,4-butanetetracarboxylic acid changes and the crystal is hindered from growing, needle-like crystals or fine plate-like crystals are generated. These crystals have poor solid-liquid separation properties and a large amount of mother liquor adhered to the separated crystals, resulting in low crystal purity and a large loss of catalyst taken out of the system together with the crude crystals. Therefore,
In order to recover high-purity crystals and to effectively use the catalyst, prior to the step of isolating 1,2,3,4-butanetetracarboxylic acid crystals from the reaction mixture solution, selective isolation from the reaction mixture solution is performed. The step of separating the catalyst is indispensable.

[0004] Also, suppose that 1,2,3,4-
Even if the growth of butanetetracarboxylic acid crystals is promoted and the solid-liquid separation property is improved, in the reaction in which this shake-out mother liquor is reused,
Due to the decrease in catalytic activity due to accumulation of reaction by-products other than the catalyst contained in the mother liquor, the reaction yield of 1,2,3,4-butanetetracarboxylic acid is extremely low, and the reaction Results in an increase in the amount of by-products mixed in. Further, the metal catalyst is expensive, and it is extremely important in terms of economics to efficiently recover the metal catalyst removed from the reaction mixture and reuse it for the next reaction.

Conventionally, a method for separating and recovering a catalyst from a solution of an organic acid or a salt thereof, such as the desired product of the present invention, involves preparing a reaction solution containing at least eight times the amount of acetone, tetrahydrofuran, dioxane, n-propanol. , Isopropanol, etc. to precipitate and recover the catalyst (Japanese Patent Publication No. 46-41526), a method in which a catalyst dissolved in a cis-epoxysuccinic acid synthesis reaction solution is adsorbed on a strongly basic anion exchange resin, A method of eluting with an aqueous solution of an alkali metal oxide or a basic alkali metal salt and circulating and using this aqueous solution of a catalyst-containing alkali metal hydroxide or a basic alkali metal salt in a reaction system (Japanese Patent Publication No. 54-27327), tartaric acid or To an aqueous solution containing tartrate and tungstic acid, molybdic acid or their salts, add calcium sulfate to tartaric acid or The solution in which tartrate is precipitated and separated as a calcium salt is brought into contact with an anion exchange resin to adsorb the metal catalyst, and then a basic aqueous solution is brought into contact with the anion exchange resin to convert the metal acid or a salt thereof into a base. A method of recovering as an aqueous solution (Japanese Patent Publication No. 55-4449) is known.

However, in these methods, Japanese Patent Publication No.
The method described in JP-A-6-41526 is not industrially advantageous because a large amount of a highly volatile solvent is used.
Further, the method described in Japanese Patent Publication No. 54-27327 is characterized in that the catalyst is adsorbed on a strongly basic anion exchange resin. Contains cis-epoxysuccinic acid, indicating that cis-epoxysuccinic acid is adsorbed on the strongly basic anion exchange resin together with the catalyst in the adsorption step. Further, in the method described in JP-B-55-4459, calcium sulfate is added to an aqueous solution of tartaric acid or tartrate containing tungstic acid, molybdic acid or a salt thereof before contacting the solution with an anion exchange resin. It is necessary to remove tartaric acid or tartaric acid as a calcium salt in advance, and the operation is complicated and it is difficult to say that it is the best industrial method.

An object of the present invention is to oxidize tetrahydrophthalic anhydride or its hydrous acid with hydrogen peroxide in the presence of a catalyst comprising tungstic acid or phosphotungstic acid or a salt thereof. In the method for producing butanetetracarboxylic acid, the catalyst metal ion is removed and recovered from the reaction-terminated liquid or a solution of crude 1,2,3,4-butanetetracarboxylic acid obtained by solid-liquid separation from the reaction liquid. In doing so, the metal catalyst is separated and recovered efficiently without subjecting the liquid to any special pretreatment, and without loss of the target product 1,2,3,4-butanetetracarboxylic acid. It is an object of the present invention to provide a method capable of producing 1,2,3,4-butanetetracarboxylic acid with high yield by reusing it for the next reaction and repeating it.

[0008]

According to the present invention, tetrahydrophthalic anhydride or its hydrous acid is prepared in the presence of a catalyst comprising tungstic acid, phosphotungstic acid or a salt thereof.
In the method for producing 1,2,3,4-butanetetracarboxylic acid which is oxidized using hydrogen peroxide , the reaction-completed solution or crude 1,2,3,4 obtained by solid-liquid separation from the reaction-completed solution
Contacting a solution of -butanetetracarboxylic acid with a weakly basic anion exchange resin to obtain an aqueous solution of 1,2,3,4-butanetetracarboxylic acid containing no anion of the catalytic metal acid, By contacting a weakly basic anion exchange resin adsorbing anions with an aqueous solution of an alkali metal hydroxide or ammonium hydroxide,
The catalyst metal acid anion-containing aqueous solution containing no 1,2,3,4-butanetetracarboxylic acid is eluted, and this solution is subjected to 1,2,3 oxidation of tetrahydrophthalic anhydride or its hydrated acid with hydrogen peroxide. Characterized by being reused as a catalyst for a 1,4-butanetetracarboxylic acid synthesis reaction
This is a method for producing 2,3,4-butanetetracarboxylic acid.

According to the present invention, an aqueous solution of 1,2,3,4-butanetetracarboxylic acid in which tungstic acid or phosphotungstic acid or a salt thereof obtained in the above oxidation reaction coexists can be efficiently and selectively selected. Catalyst and 1,2,
In addition to separating 3,4-butanetetracarboxylic acid, the recovered catalyst has sufficient activity in the reaction system, and can be reused as it is as the oxidation reaction catalyst.

[0010] 1, containing tungstic acid or phosphotungstic acid or a salt thereof obtained in the above reaction
A 2,3,4-butanetetracarboxylic acid aqueous solution is different from an organic aqueous solution containing only a low concentration of metal ions,
Both are highly concentrated electrolyte solutions in the form of a competitive anion, and the 1,2,3,4-butanetetracarboxylate anion is present in large excess with respect to the metal catalyst anion. It has been conventionally thought that it is difficult to selectively separate only the metal catalyst anion by a simple ion exchange operation.

In the present invention, however, surprisingly, by treating the mixed solution with a weakly basic anion exchange resin, 1,2,3,4-butanetetracarboxylic acid is not adsorbed at all. Only the metal ions are selectively adsorbed and removed, and a weak basic anion exchange resin adsorbing tungstate ions or phosphotungstate ions is converted to a base containing at least one of alkali metal hydroxide or ammonium hydroxide. By contacting with a neutral aqueous solution, the metal salt anion containing no 1,2,3,4-butanetetracarboxylic acid can be easily desorbed and eluted. The aqueous solution is neutralized or neutralized with sulfuric acid to a pH of 2 or less, and then tetrahydrophthalic anhydride or its hydrous hydrogen peroxide When used in 1,2,3,4-butane tetracarboxylic acid production process reaction catalyst by, it exhibits a remarkable effect that a similar reaction yield in the case of using a new catalyst obtained.

Still referring to the advantages of the present invention, in the conventional method, the mother liquor obtained by solid-liquid separation of 1,2,3,4-butanetetracarboxylic acid from the reaction-terminated liquid is recovered and reused as it is in the reaction step. However, in this method, not only the catalyst contained in the mother liquor but also by-products other than the catalyst are recovered and recycled. Therefore, as the mother liquor is reused, the target product 1,2,3,4 -The reaction yield of butanetetracarboxylic acid gradually decreases. In contrast, in the present invention,
Since only the catalyst is separated from the reaction solution alone and reused in the next reaction, there is no adverse effect on the catalytic activity due to accumulation of reaction by-products other than the catalyst, and 1,2,3,4-butanetetracarboxylic acid is recovered. The catalyst can be used repeatedly without any reduction in the rate.

The catalyst used in the present invention is tungstic acid, phosphotungstic acid or a salt thereof, and specific examples thereof include tungstic acid, sodium tungstate, ammonium tungstate, phosphotungstic acid,
And sodium phosphotungstate. The use amount of these catalysts is not particularly limited as long as the activity as a catalyst can be exhibited effectively, but is usually 0.5 to 10% by weight based on tetrahydrophthalic anhydride or its hydrate as a raw material. , Preferably 1 to 5% by weight.

The amount of hydrogen peroxide used is theoretically the same as that of starting compound 1.
4 moles per mole, but slightly (eg about 10-50%)
It is preferable to use it in excess. The concentration of hydrogen peroxide to be added is 3 to 70% by weight, preferably 50 to 60% by weight, and particularly preferably 60% by weight in view of reactivity and cost. Water is suitable as the reaction solvent. A low molecular weight organic solvent miscible with water, for example, a lower alcohol such as methanol, a lower carboxylic acid such as acetic acid, acetonitrile and the like can be used. The reaction temperature is usually from 80 to 120 ° C from the viewpoint of the reaction rate, but it is desirable to carry out the reaction at a reflux temperature of 100 to 110 ° C which does not require temperature control. Thus, in the presence of tungstic acid or phosphotungstic acid or a salt thereof,
Tetrahydrophthalic anhydride or its hydrous acid is oxidized with hydrogen peroxide to obtain 1,2,3,4-butanetetracarboxylic acid.

In the present invention, the reaction-terminated solution comprising the aqueous solution of 1,2,3,4-butanetetracarboxylic acid containing the catalyst metal anion thus obtained, or the reaction-terminated solution is cooled to solid-liquid. The crude 1,2,3,4-butanetetracarboxylic acid crude crystals containing the catalyst obtained by separation are redissolved in water, and the re-dissolved aqueous solution obtained is brought into contact with a weakly basic anion exchange resin for treatment. . In this case, the concentration of 1,2,3,4-butanetetracarboxylic acid contained in the aqueous solution to be treated is usually 10 to 30% by weight, preferably 15 to 25% by weight.
It is. The concentration of tungstic acid or phosphotungstic acid or a salt thereof is usually 0.1 to 1.0% by weight.
It is. As the weakly basic anion exchange resin used in the present invention, a weakly basic anion exchange resin whose terminal ion exchange group is a polyamine group or a dimethylamine group is preferable. As the terminal anion at the time of use, any of Cl-type and OH-type can be adopted, but use of OH-type is preferred in order to avoid mixing of Cl ions into the liquid to be treated.

The above-mentioned 1,2 containing the catalytic metal acid anion
The method of contacting the aqueous solution of 2,3,4-butanetetracarboxylic acid with the weakly basic anion exchange resin can be carried out without any problem using a commonly used fixed bed column system, but is not particularly limited to this system. Absent. If the fixed bed column method is adopted, the treatment rate of the aqueous solution is usually 0.1 to 20 times / hour, particularly 0.5 to 10 times / hour, based on the volume of the weakly basic anion exchange resin. Is preferred. The contact temperature is higher than the precipitation temperature of the dissolved component in the aqueous solution,
Any temperature may be used as long as the temperature is lower than the heat-resistant temperature of the ion exchange resin.
° C, particularly preferably 30 ° C to 60 ° C.

When the metal acid anion adsorbed on the ion exchange resin is desorbed, a basic aqueous solution comprising an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide or ammonium hydroxide is subjected to the ion exchange. By contacting with a resin, it can be easily recovered as a basic aqueous solution containing a tungstate or phosphotungstate anion. At this time, the method of contacting the ion exchange resin with the basic eluate is not particularly limited, but a fixed bed column method filled with the ion exchange resin is generally used, and at this time, the basic eluate is The flow rate is 1 to 10 times the volume of the ion exchange resin /
Time, particularly 1 to 7 times / hour, is preferred. The contact temperature is not particularly limited as long as it is equal to or lower than the heat-resistant temperature of the ion exchange resin, but preferably 20 ° C to 60 ° C.

The relative amounts of the tungstate or phosphotungstate anion and the weakly basic anion exchange resin in the present invention are determined by the form of the ion exchange resin, the degree of crosslinking, the particle size, the form of the packed tower, the flow rate of the liquid to be treated, Temperature, concentration of 1,2,3,4-butanetetracarboxylic acid in the liquid to be treated,
Although slightly influenced by the concentration of the metal anion, the effect of the present invention can be sufficiently exerted by using a weakly basic anion exchange resin having a total exchange capacity of 2 to 20 equivalents per equivalent of the metal anion. . The aqueous solution containing tungstate or phosphotungstate anions thus obtained is then reused as a catalyst for the oxidation of tetrahydrophthalic anhydride or its hydrous acid with hydrogen peroxide.

[0019]

The present invention will be further clarified with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

COMPARATIVE EXAMPLE 1 100.3 g of tetrahydrophthalic anhydride and 4.0 g of phosphotungstic acid were dissolved in 350 g of pure water while heating, and 188.1 g of 60% by weight hydrogen peroxide was added and reacted under reflux for 7 hours. Thus, 642 g of an aqueous solution containing 20.5% by weight of 1,2,3,4-butanetetracarboxylic acid, 0.62% by weight of phosphotungstic acid and other reaction by-products were obtained. 1,2,3 for tetrahydrophthalic anhydride
The reaction yield of 4-butanetetracarboxylic acid was 85.2%. The reaction solution was cooled and crystallized at 10 ° C., and then separated into a solid and a liquid. 142 g of crude crystals (59.0% by weight of 1,2,3,4-butanetetracarboxylic acid, 38.2% by weight of water, 0% of phosphotungstic acid) 0.35% by weight, other 2.45% by weight)
Then, 498 g of a reaction mother liquor containing 9.0% by weight of 1,2,3,4-butanetetracarboxylic acid, 0.70% by weight of phosphotungstic acid and other reaction by-products were obtained. The total amount of the reaction mother liquor was added to 100.
After adding 3 g, 0.4 g of phosphotungstic acid and 188.0 g of 60% hydrogen peroxide and reacting under reflux for 7 hours, 1,2,3,4-butanetetracarboxylic acid in the reaction solution was increased. As a result of measuring the amount, the reaction yield with respect to newly added tetrahydrophthalic anhydride was 30.2%.

Example 1 After heating and dissolving 100.3 g of tetrahydrophthalic anhydride and 4.0 g of phosphotungstic acid in 350 g of pure water, 188.1 g of 60% by weight hydrogen peroxide was added and reacted under reflux for 7 hours. Thus, 642 g of an aqueous solution containing 20.5% by weight of 1,2,3,4-butanetetracarboxylic acid, 0.62% by weight of phosphotungstic acid and other reaction by-products were obtained. 1,2,3 for tetrahydrophthalic anhydride
The reaction yield of 4-butanetetracarboxylic acid was 85.2%. The reaction solution was cooled to 40 ° C. and passed through a vinyl chloride column filled with 30 ml of a dimethylamine type weakly basic anion exchange resin (Amberlite IRA-94S OH type, manufactured by Organo) (300 ml / hour). The residual liquid was extruded with 60 g of pure water. 1, 1 in the processing solution
2,3,4-butanetetracarboxylic acid content is 131,
3 g (recovery rate 99.8%), and the content of phosphotungstic acid was below the detection limit. Also, a 10% by weight aqueous solution of sodium hydroxide 3
After passing through 00 g (150 ml / hour), phosphotungstic acid adsorbed on the ion exchange resin was recovered. The content of phosphotungstate anions in the recovered liquid was 3.9 g (recovery rate of 9).
7.5%), 1,2,3,4-butanetetracarboxylic acid was not detected. 97% by weight sulfuric acid was added to the recovered solution to adjust the pH to 2, and the total amount was adjusted to 400 g with pure water. 100.3 g of tetrahydrophthalic anhydride was added and dissolved by heating. Then, 188.1 g of 60% by weight hydrogen peroxide was added. Then, the mixture was reacted under reflux for 7 hours. As a result, the reaction yield of 1,2,3,4-butanetetracarboxylic acid with respect to tetrahydrophthalic anhydride was 84.0%.

Example 2 A polyamine-type weakly basic anion exchange resin (Amberlite IRA-60 manufactured by Organo) was used as the anion exchange resin.
(OH type), the same reaction solution as in Example 1 was subjected to resin treatment and recovery under the same conditions as in Example 1, and as a result, the phosphotungstic acid concentration was 1, 2, 2,
Contains 3,4-butanetetracarboxylic acid (131.2 g)
An aqueous solution and a phosphotungstate anion having a 1,2,3,4-butanetetracarboxylic acid concentration of not more than the detection limit.
An alkaline aqueous solution containing 9 g was obtained. Pure water was added to this alkaline aqueous solution to make the total amount 400 g, and 100.3 g of tetrahydrophthalic anhydride was added and dissolved by heating.
When 188.1 g of 0% by weight hydrogen peroxide was added and reacted under reflux for 7 hours, the reaction yield of 1,2,3,4-butanetetracarboxylic acid with respect to tetrahydrophthalic anhydride was 84.3%. Met.

Example 3 A reaction was carried out in the same manner as in Example 1 except that 3.0 g of tungstic acid was used instead of phosphotungstic acid as a catalyst, and 1,2,3,4-butanetetracarboxylic acid 2
641 g of a reaction liquid containing 0.4% by weight, 0.47% by weight of tungstic acid, and other reaction by-products were obtained.
The reaction yield of 1,2,3,4-butanetetracarboxylic acid with respect to tetrahydrophthalic anhydride was 84.7%. As a result of performing resin treatment and recovery treatment on the reaction solution in the same manner as in Example 1, a 1,2,3,4-butanetetracarboxylic acid-containing (130.5 g) aqueous solution having a tungstic acid concentration of not more than a detection limit, An alkaline aqueous solution having a 1,2,3,4-butanetetracarboxylic acid concentration below the detection limit and containing 2.97 g of tungstate anion was obtained. Further, 97% by weight sulfuric acid was added to this alkaline aqueous solution to adjust the pH to 2, and the total amount was adjusted to 400 g with pure water, and 100.3 g of tetrahydrophthalic anhydride was added thereto and dissolved by heating. When 1 g was added and reacted under reflux for 7 hours, the reaction yield of 1,2,3,4-butanetetracarboxylic acid with respect to tetrahydrophthalic anhydride was 84.0%.

Example 4 Crude crystals (1,2,3,4-butanetetracarboxylic acid 59.0) separated from the reaction solution according to the method described in Comparative Example 1.
% By weight, water content 38.2% by weight, phosphotungstic acid 0.1%.
(35% by weight, other 2.45% by weight) To 1100g, 2200g of pure water was added and dissolved at 35 ° C. Then, the resin was treated in the same manner as in Example 1 (with the exception that 100ml of ion exchange resin was used), and the phosphotungstic acid concentration was analyzed. Below the detection limit,
An aqueous solution containing 642 g of 1,2,3,4-butanetetracarboxylic acid was obtained. This aqueous solution was cooled and crystallized at 10 ° C., and then subjected to solid-liquid separation to obtain 359 g of wet crystals (92.1% by weight of 1,2,3,4-butanetetracarboxylic acid and 7.9% by weight of water). Further, 300 g of a 5% by weight aqueous solution of potassium hydroxide was passed through the ion-exchange resin that had been subjected to the above treatment (1.
(50 ml / hour), and the phosphotungstic acid adsorbed on the ion exchange resin was recovered. The phosphotungstate anion content in the recovered liquid was 3.8 g (recovery rate 98.7%),
1,2,3,4-butanetetracarboxylic acid was not detected. 97% by weight sulfuric acid was added to this recovered solution to adjust the pH to 2
After the preparation, the total amount was made 400 g with pure water, 100.3 g of tetrahydrophthalic anhydride was added and dissolved by heating, and then 188.1 g of 60% by weight hydrogen peroxide was added and reacted under reflux for 7 hours. The reaction yield of 1,2,3,4-butanetetracarboxylic acid with respect to tetrahydrophthalic anhydride was 84.4%.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 51/47 C07C 51/47 55/24 55/24 // C07B 61/00 300 C07B 61/00 300 (56) References Special JP-A-58-164541 (JP, A) JP-A-55-76839 (JP, A) JP-A-53-33979 (JP, A) JP-A-52-156814 (JP, A) (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 51/285 B01J 23/30 B01J 27/188 B01J 38/74 B01J 41/04 C07C 51/47 C07C 55/24 C07B 61 / 00 300 CASREACT (STN)

Claims (4)

(57) [Claims] 1,2,3,4-butane for oxidizing tetrahydrophthalic anhydride or its hydrous acid with hydrogen peroxide in the presence of a catalyst comprising tungstic acid, phosphotungstic acid or a salt thereof In the method for producing tetracarboxylic acid, the reaction-terminated liquid or a solution of crude 1,2,3,4-butanetetracarboxylic acid obtained by solid-liquid separation from the reaction-terminated liquid is treated with a weakly basic anion exchange resin. 1,2,3,4 containing no catalytic metal anion by contact
-Butanetetracarboxylic acid aqueous solution is obtained, and the weakly basic anion exchange resin adsorbing the catalyst metal acid anion is brought into contact with an aqueous solution of an alkali metal hydroxide or ammonium hydroxide to obtain 1,2,3,4 The catalyst metal acid anion-containing aqueous solution containing no butanetetracarboxylic acid is eluted, and this solution is subjected to 1,2,3,4 oxidation of tetrahydrophthalic anhydride or its hydrous acid with hydrogen peroxide.
-A process for producing 1,2,3,4-butanetetracarboxylic acid, which is reused as a catalyst for a butanetetracarboxylic acid synthesis reaction. 2. The method according to claim 1, wherein the weakly basic anion exchange resin is a weakly basic anion exchange resin having a polyamine group or a tertiary amine group as a terminal ion exchange group. 3. The method according to claim 1, wherein the alkali metal hydroxide is lithium hydroxide,
The method according to claim 1, which is sodium hydroxide or potassium hydroxide. 4. After neutralizing the eluted aqueous solution containing metal acid anions to pH 2 or less with sulfuric acid, tetrahydrophthalic anhydride or 1,2,2 by oxidation of hydrous acid with hydrogen peroxide.
The method according to claim 1, which is reused as a catalyst for a 3,4-butanetetracarboxylic acid synthesis reaction.