JPH07126235A - Production of ketazine - Google Patents

Abstract

PURPOSE:To provide an industrially simple and economically advantageous process for producing ketazine continuously and stably. CONSTITUTION:In the production of ketazine by reaction of hydrogen peroxide, ammonia and a ketone in the presence of a solution containing the catalyst, the catalyst solution is reused by circulation and treated with anion- and cation- exchange resins to remove the impurities causing adverse effects on the reaction and maintain the reaction stably for a long period of time.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing ketazine. Ketazine is a compound useful as an intermediate for the synthesis of hydrazine.

[0002]

2. Description of the Related Art As a method for producing ketazine, various methods for producing ketazine have been developed. That is, in reacting hydrogen peroxide, ammonia and a ketone, a method using an organic arsenic compound as a catalyst (Japanese Patent Publication No. 61-41509) and a method using a carboxylic acid amide and an alkali metal phosphate as a catalyst ( Tokusho Sho 6
1-2654), a method using nitriles as a catalyst (Japanese Patent Publication No. 51-33083), and the like.
Usually, these catalysts are circulated and reused in the form of an aqueous solution, an alcohol solution or a mixed solution of water and alcohol.
"Kirk Osmer" Third Edition, Volume 12, 734-755
The page describes a process for actually producing ketazine in the presence of an aqueous solution containing hydrogen peroxide, ammonia, methyl ethyl ketone, acetamide and sodium phosphate (hereinafter referred to as a working fluid). As this process is continuously operated, reaction by-products accumulate in the working fluid,
The activity of the catalyst in the working fluid is reduced. In addition, components such as an ionic or non-volatile stabilizer introduced into the reaction may be accumulated in the hydraulic fluid and interfere with the process. For example, the accumulation of acids such as phosphoric acid and nitric acid can adversely affect the reaction and ions such as sodium can cause the precipitation of catalyst components. Therefore, in the conventional method, the ratio of each component contained in the working fluid is always increased by going through a complicated process such as discarding or regenerating the accumulated material outside the system together with a part of the working fluid and replenishing with a new catalyst component. Has to be kept constant. In industrial practice, adjustment of these hydraulic fluid components requires extremely complicated and difficult operations.

[0003]

An object of the present invention is to provide an industrially convenient and economically advantageous method for continuously and stably producing ketazine. Specifically, one object of the present invention is to prevent the accumulation of reaction by-products in the working fluid to maintain the activity of the catalyst in the working fluid. Another object of the present invention is to prevent components such as ionic or non-volatile stabilizer introduced into the reaction from accumulating in the working fluid and causing precipitation of catalyst components in the working fluid. Is.

[0004]

The method for producing ketazine of the present invention is a method for producing ketazine from hydrogen peroxide, ammonia and ketone in the presence of a working fluid containing a catalyst,
It is characterized in that the working fluid to be circulated and reused is purified by an ion exchange resin. The manufacturing method of the present invention comprises the following four steps. That is, (a) a step of producing ketazine by reacting ammonia, hydrogen peroxide, and a ketone in the presence of a catalyst-containing working fluid, (b) a step of separating the ketazine and the working fluid in the obtained mixture. , (C) Step of removing reaction water contained in the working fluid after the reaction, (d) Step of removing reaction by-products accumulated in the working fluid by an ion exchange resin, and returning the working fluid to the ketazine production process Is.

As the hydrogen peroxide used as the reaction product in the step (a), a commercially available aqueous solution of 30 to 90% by weight of H ₂ O ₂ can be used. The peroxide solution used contains, as a stabilizer, for example, one or more of phosphoric acid, pyrophosphoric acid, citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid or ammonium salts or alkali metal salts of these acids. It doesn't matter. The content of these stabilizers is preferably 1 to 100 ppm, and more preferably 5 to 25 ppm, based on the total mixture of the reactant and working fluid in the reactor. As ammonia, gaseous ammonia or an aqueous ammonia solution is used.

The ketone is represented by the general formula 2, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone.

Embedded image R ₁ —CO—R ₂ (R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, or
It represents a phenyl group, and R ₁ and R ₂ may be bonded to each other to form a ring with the carbon atom of the carbonyl group, and the phenyl group may be a lower alkyl group or a lower alkoxyl group which is stable in the reaction system. Alternatively, it may be substituted with a halogen atom. In addition, when the method of the present invention is carried out as one step for synthesizing hydrazine, easiness of implementation for hydrolyzing the obtained ketazine to hydrazine and recovering a ketone as a by-product, From the viewpoint of economic efficiency, it is preferable to use acetone, methyl ethyl ketone or methyl isobutyl ketone as the raw material ketone. When synthesizing ketazine, each reactant can be used in a stoichiometric amount, but the above-mentioned ketone is 0.2 to 5 mol, preferably 1.
5 to 4 mol, and ammonia can be used in an amount of 0.1 to 10 mol, preferably 1.5 to 4 mol.

The catalyst-containing working liquid is a solution of water containing a catalyst, alcohol, or a mixed liquid of water and alcohol. This catalyst is represented by the general formula 3.

Embedded image Q-XY = Z (wherein Q is hydrogen, an alkali metal or ammonium, X and Z are oxygen atoms or nitrogen atoms, and Y
Is a carbon atom, a nitrogen atom, an arsenic atom, an antimony atom, a phosphorus atom, a sulfur atom, a selenium atom, or a tellurium atom, and the X, Y, and Z atoms have substituents necessary for satisfying the valence rule. is doing. ) As the catalyst Q-XY = Z,
Ammonium or alkali metal phosphates, phosphites,
Examples thereof include phosphonates, pyrophosphonates, arsenic salts, phenylarsonates, cacodylates, bicarbonates, antimonates, phosphates and sulfates. further,
It is also possible to use the corresponding esters, especially the esters of aliphatic alcohols containing 1 to 5 carbon atoms. Particularly preferred is the ammonium salt of acetic acid or cacodylic acid.

The alcohol used as a solvent in the catalyst-containing working fluid is a saturated aliphatic monoalcohol having 1 to 6 carbon atoms, preferably a saturated aliphatic monoalcohol having 1 to 2 carbon atoms, Or a saturated aliphatic diol having 2 to 6 carbon atoms, preferably
Saturated aliphatic diols having 2 to 4 carbon atoms are preferably used. Examples thereof include methanol, ethanol, ethylene glycol, propion glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. The amount of working fluid is 0.1 to 1 mol of hydrogen peroxide.
It is in the range of 1 kg. By reacting at the above ratio, hydrogen peroxide can be effectively utilized for the reaction, and 50% or more of the hydrogen peroxide used, or 90% in some cases, can be used.
% Are available for ketazine synthesis.

The contact of hydrogen peroxide, ammonia, and ketone with the working fluid can be carried out by any method that allows good contact.
It can be done in any way. The reaction temperature is 0 to 1
It can be carried out in the range of 00 ° C, but is preferably 30 to 70 ° C.
Further, this reaction can be performed at any pressure, but it is easier to operate at atmospheric pressure. Hydrogen peroxide, ammonia and ketone can be added to the working fluid simultaneously or individually and in any order. As the reaction apparatus, a stirring and mixing tank or a fluidized tank, which allows good contact between hydrogen peroxide, ammonia, and a ketone, and a working fluid is preferable.

Separation of ketazine and working fluid in the step (b) can be carried out by any known method, for example, a mixer / settler, a centrifuge or a combination thereof. The treatment in the step (c) is an operation of removing the reaction water from the working liquid separated in the step (b). The reaction water can be removed by a distillation operation. By the distillation operation, highly volatile components, that is, ammonia and ketone can be recovered. The distillation operation is preferably under reduced pressure. That is, the pressure is preferably 10 to 500 torr, and 50 to 250 torr.
Torr is more preferred. Further, the type of distillation column is such that water and a product more volatile than water are obtained at the head, and the volume of the working fluid is adjusted to a constant value by the amount of water withdrawn from this.

In the step (d), the reaction by-product accumulated in the catalyst-containing working fluid to be recycled and reused is removed by the ion exchange resin, and the catalyst action and the operability of the catalyst-containing working fluid are kept constant. Reaction by-products removed in this step include compounds that can exist as ions in the working fluid, depending on the type of catalyst and ketone used in the synthesis of ketazine. As the ion exchange resin used in the present invention, a strongly acidic cation exchange resin or a weakly basic anion exchange resin is particularly preferable. In particular,
When the ion exchange resin is a porous ion exchange resin, both the cation exchange resin and the anion exchange resin have a pore volume of 0.1 to 1 mg / g and an average pore radius of 10
It is preferably from 0 to 1000 μm.

A cation exchange resin, particularly a strongly acidic cation exchange resin is effective in removing the cationic compound. As the strongly acidic cation exchange resin, it is particularly preferable to use a gel type or porous type acidic cation exchange resin having a sulfonic acid group as an exchange group. Anion exchange resins, especially weakly basic anion exchange resins, are effective in removing anionic compounds. The weakly basic anion exchange resin is a gel type basic anion exchange resin having a quaternary ammonium group as an exchange group or a porous basic anion exchange resin having a primary to tertiary amino group as an exchange group. Is particularly preferred.

In the present invention, the cation exchange resin treatment or the anion exchange resin treatment may be performed alone. Further, the strongly acidic cation exchange resin and the weakly basic anion exchange resin may be arranged in parallel to separate the working fluids, or may be arranged in series to sequentially treat the working fluids. good. There is no restriction on the order of treatment with the cation exchange resin and the anion exchange resin. Further, the cation exchange resin treatment and the anion exchange resin treatment may be performed in a mixed state of both resins. The treatment of the working fluid with the cation and anion exchange resin according to the method of the present invention can be carried out in a usual manner, but in particular, it can be carried out vertically from a high place to a low place (gravity column) by a continuous or intermittent method. The method of moving is preferable.
The ratio of the volume of working fluid to the volume of ion exchange resin and the treatment time depend on many parameters, in particular the type of reaction by-products and the type of ion exchange resin. Usually, the ratio of the volume of ion exchange resin to the volume of hydraulic fluid is 1/5.
˜1 / 50, and the processing time is preferably 30 to 300 minutes.

The treatment of the working fluid with the anion exchange resin and the cation exchange resin does not necessarily have to be carried out for the entire amount of the working fluid coming out of the step (c), but it is sufficient to carry out a purification treatment of a part of the working fluid. Is. The processing amount of the hydraulic fluid depends on the amount of impurities in the hydraulic fluid, but the amount of impurities in the hydraulic fluid is
It depends on the synthesis conditions of ketazine and the amount of impurities already present in ammonia, hydrogen peroxide, and ketones. When the exchange group of the ion exchange resin is saturated, a usual method is used. For the cation exchange resin, an acidic aqueous solution, for example, hydrochloric acid aqueous solution (1 to 10% by weight) is used, and for the anion exchange resin, an alkaline aqueous solution, for example, It is preferred to regenerate the ion exchange resin with an aqueous sodium hydroxide solution (1-10% by weight).

[0015]

INDUSTRIAL APPLICABILITY According to the present invention, ketazine can be produced industrially conveniently and economically.

[0016]

【Example】

Example 1 1500 cc using stainless steel (SUS304)
Into a reactor equipped with a stirrer, was charged 500 cc of a working fluid containing 5% by weight of cacodylic acid, 30% by weight of ammonium acetate and 50% by weight of propylene glycol, and the temperature was kept at 50 ° C., while continuously blowing ammonia gas, 305 g of methyl ethyl ethane. And 90 g of 80% hydrogen peroxide aqueous solution stabilized with sodium phosphate are added simultaneously over 30 minutes,
The reaction was carried out for 4 hours. The reaction liquid was allowed to stand and separate into a methylethylketazine phase and a working liquid phase, and the amount of ketazine in each phase was quantified by instrumental analysis and volumetric analysis. As a result, ketazine was obtained in a yield of 85% with respect to the added hydrogen peroxide. The separated working fluid was supplied to the 10th stage from the bottom of a stainless steel (SUS304) distiller (inner diameter: 50 mm, height: 1,000 mm, having a plate of 20 stages), 70 torr,
The reaction product water and hydrogen peroxide medium water were distilled off at 70 ° C., and the working fluid was concentrated to 500 cc. Working fluid after concentration 500
Of cc, 100 cc is a glass column (inner diameter 20 mm,
Weakly basic anion exchange resin (manufactured by Mitsubishi Kasei Co., Ltd., trade name: Diaion-WA3) filled in a height of 200 mm)
0) It was introduced into 10 cc from the upper part of the column at a flow rate of 50 cm ³ / hr and then used for the ketazine synthesis reaction. In addition, another 100 cc of the above-mentioned concentrated working fluid of 500 cc
Porous strongly acidic cation exchange resin (trade name: Diaion-PK216, manufactured by Mitsubishi Kasei Co., Ltd.) 10c in which glass was packed in a glass column (inner diameter 20 mm, height 200 mm).
It was introduced into the column c from the top of the column at a flow rate of 50 cm ³ / hr and then used in the ketazine synthesis reaction. Remaining hydraulic fluid 300
Hydraulic fluid 100 which was treated with anion exchange resin in cc
hydraulic fluid treated with cc and cation exchange resin 1
00 cc was added to make 500 cc, which was used for the above ketazine synthesis. A series of steps for synthesizing ketazine, concentrating the working fluid, and purifying the working fluid with an ion exchange resin is performed in 100
Repeated times, the ketazine yield was examined at fixed intervals. As a result, the initial yield was maintained until the end. In addition, precipitation of the catalyst component was not recognized.

Example 2 The same operation as in Example 1 was carried out under the condition that the working fluid was concentrated to 100 tons.
It was carried out at rr and 80 ° C. The yield of ketazine is 85%
Therefore, the initial yield was maintained even after 100 repetitions.

Comparative Example 1 The same operation as in Example 1 was carried out without purifying the working fluid with an ion exchange resin. As a result, the ketazine yield was 80% at the 50th repetition, and the ketazine yield was reduced to 75% at the 100th repetition. In addition, a small amount of catalyst component deposition was observed at the 100th repetition.

Comparative Example 2 The same operation as in Example 1 was repeated, except that the weakly basic anion exchange resin was replaced with a gel type strongly basic anion exchange resin (trade name: Diaion-SA10A, manufactured by Mitsubishi Kasei Co., Ltd.). ) Was used. As a result, the ion-exchange resin was crushed at the 20th repetition and the purification process became difficult thereafter.

Comparative Example 3 The same procedure as in Example 1 was repeated except that the strongly acidic cation exchange resin was replaced with a porous weakly acidic cation exchange resin (Mitsubishi Kasei Co., Ltd.).
Manufactured, trade name: Diaion-WK10). As a result, the ketazine yield was 80% at the 65th repetition and the ketazine yield was 75% at the 100th repetition.
Fell to.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (6)

[Claims] 1. A method for producing ketazine from hydrogen peroxide, ammonia and a ketone in the presence of a catalyst-containing working fluid, characterized in that the working fluid to be recycled and reused is purified by an ion exchange resin. Method. 2. The method for producing ketazine according to claim 1, wherein the ion exchange resin is a weakly basic anion exchange resin. 3. The method for producing ketazine according to claim 1, wherein the ion exchange resin is a strongly acidic cation exchange resin. 4. The method for producing ketazine according to claim 1, wherein the ion exchange resin is a combination of a weakly basic anion exchange resin and a strongly acidic cation exchange resin. 5. The ion exchange resin has a pore volume of 0.1 to 10.
1 mg / g, and the average pore radius is 100 to 1000 μ
The method for producing ketazine according to claim 1, wherein the ketazine is a gel or porous ion exchange resin having m. 6. The ketazine according to claim 1, wherein the catalyst-containing working liquid is a solution containing water, alcohol or a mixed liquid of water and alcohol containing the catalyst represented by Chemical formula 1 as a solvent. Manufacturing method. Embedded image Q-XY = Z (wherein Q is hydrogen, an alkali metal or ammonium, X and Z are oxygen atoms or nitrogen atoms, and Y is Y).
Is a carbon atom, a nitrogen atom, an arsenic atom, an antimony atom, a phosphorus atom, a sulfur atom, a selenium atom, or a tellurium atom, and the X, Y, and Z atoms have substituents necessary for satisfying the valence rule. is doing. )