JP3528859B2 - Synthetic method of ketazine - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial method for producing ketazine. Ketazine is used as an intermediate raw material for hydrazine hydrate.

[0002]

2. Description of the Related Art Ketazine is generally synthesized by oxidizing ammonia in the presence of a ketone with an oxidizing agent such as sodium hypochlorite or hydrogen peroxide. Kirk Osmer 3rd Edition,
Vol. 12, pp. 734-755, describes a process for synthesizing ketazine from hydrogen peroxide, ammonia and a ketone, and further producing hydrazine hydrate by hydrolysis of ketazine. In this process, an aqueous solution containing acetamide and sodium hydrogen phosphate is used as a working fluid to synthesize ketazine, and methyl ethyl ketone is used as a ketone. After the generated ketazine and the working liquid are separated, the working liquid is subjected to a concentration operation to remove water produced by the reaction and water as a solvent that has entered the reaction system together with hydrogen peroxide, and is reused by circulation. In this process, since the activity of the working fluid gradually decreases due to continuous operation, it is necessary to prepare and supplement a new working fluid in order to stably produce ketazine. It is described in the official gazette. However, preparation of hydraulic fluid
Replenishment generally requires complicated and complicated operations.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and more specifically, it is an industrial use of ketazine that does not essentially require supplementation with a new hydraulic fluid. To provide a simple manufacturing method.

[0004]

Means for Solving the Problems The inventors of the present invention have earnestly studied a method for regenerating a working fluid, and as a result, in particular, the working fluid after the reaction is heated to a temperature of 60 ° C. or higher to remove the reaction water, Furthermore, at any stage where the working fluid is circulated and reused, the recycled working fluid is purified by removing impurities in the working fluid with an ion exchange resin, so that the activity of the catalyst is maintained and the ketazine is stably and continuously produced. The present invention has been completed by discovering that they can be synthesized synthetically. That is, the present invention is a method for producing ketazine from hydrogen peroxide, ammonia and a ketone, in which ketazine is synthesized by bringing a working fluid into contact with hydrogen peroxide, ammonia and a ketone (step (a)), and the resulting ketazine is produced. And the working fluid are separated (step (b)), and then the separated working fluid is separated into 6
Of ketazine, which comprises heating to a temperature of 0 ° C. or higher to remove water of reaction (step (c)), and then returning the working liquid to step (a) for recycling and reuse (step (d)). It is a synthetic method.

The reaction in step (a) can be represented by the following formula.

## EQU1 ## 2NH ₃ + 2R ₁ R ₂ C = O + H ₂ O ₂ → R ₁ R ₂ C = N-N = CR ₁ R ₂ + 4H ₂ O Hydrogen peroxide is an ordinary commercial product, for example, 30 to 90% by weight. H ₂ O ₂ aqueous solution can be used. Hydrogen peroxide generally includes stabilizers of conventional peroxide solutions, such as phosphoric acid,
It is preferable to add one or more of pyrophosphoric acid, citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ammonium salts or alkali metal salts of these acids, or the like. The amount of these stabilizers used is preferably 1 to 100 ppm, and more preferably 5 to 25 ppm of the total amount of the reactant and working fluid at the inlet of the reactor. As the ammonia, ammonia gas or aqueous ammonia solution can be used.

The ketone used in the present invention is R ₁ R ₂ C═O
It is expressed by the formula. Here, R ₁ and R ₂ are an alkyl group containing 1 to 12 carbon atoms, a branched alkyl group containing 3 to 12 carbon atoms or a cycloalkyl group, an aromatic group containing 6 to 12 carbon atoms. Represents a radical or a straight-chain or branched alkylene radical containing 3 to 12 carbon atoms, these radicals being halogen, NO ₂ , hydroxy, alkoxy or carboxylic acid esters, preferably Cl, NO ₂ or CH _3. It may be replaced by O. R ₁ and R ₂ may be the same or different from each other. Examples of the ketone include acetone, 2-pentanone, 3-pentanone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl cyclohexyl ketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone and cyclohexanone. In particular, use of acetone, methyl ethyl ketone and methyl isobutyl ketone is preferable for obtaining hydrazine from ketazine. Although each reaction product can be used in a stoichiometric amount, a ketone is 0.2 to 5 mol, preferably 1.5 to 4 mol, and ammonia is 0.1 to 1 mol of hydrogen peroxide.
10 mol, preferably 1.5 to 4 mol can be used. The amount of working fluid is 0.1 to 1 mol of hydrogen peroxide.
It is in the range of 1 kg.

The working fluid is an organic or inorganic oxygen acid, its ammonium salt and their derivatives such as anhydrides,
It can be prepared by bringing one or more compounds selected from esters, amides, nitriles, acyl peroxides or mixtures thereof into solution. Preference is given to using amides, ammonium salts or nitriles. Examples of preferred amides are formamide, acetamide, monochloroacetamide, and propionamide. Of the ammonium salts, formates, acetates, monochloroacetates, propionates, especially cacodylates are preferred. Examples of preferable nitriles include acetonitrile and propionitrile. A compound selected from organic or inorganic oxyacids, their ammonium salts and their derivatives such as anhydrides, esters, amides, ammonium salts, nitriles, acyl peroxides or mixtures thereof in order to maintain the ketazine production reaction. It may be contained in the hydraulic fluid.

The working fluid can be an aqueous solution, an alcohol solution or a mixed solution of water and alcohol. As the alcohol in this case, it is preferable to use a saturated aliphatic alcohol having 1 to 6 carbon atoms, particularly 1 to 2 carbon atoms. Also, diols, especially 2
It is also preferred to use diols having ˜5 carbon atoms. For example, glycol, propylene glycol, 1,
Included are 3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
The amount of the amide, the acid, the ammonium salt or the nitrile introduced into the water, the alcohol or the mixture of water and the alcohol is 40 to 80 of the working fluid at the inlet of the step (a).
% By weight.

The contact of the reactant containing hydrogen peroxide, ammonia and ketone with the working fluid can be carried out by any method.
Preferably, one operates in a homogeneous medium or a medium in which each reactant can be solubilized sufficiently to give ketazine. The above reaction can be carried out in an extremely wide range of temperature, for example, 30 to 110 ° C, preferably 45 to 70 ° C. Further, although this reaction can be carried out at any pressure, it is easier to operate at atmospheric pressure. Each reactant can be added to the working fluid either simultaneously or individually in any order. Also, any type of reactor can be used. The reactor may be a simple container, but it is preferable to attach a stirring device.

Separation of ketazine and working fluid in step (b) can be carried out by any known method such as liquid-liquid extraction, distillation or a combination thereof. Preferred is a liquid / liquid separation method using a mixer / settler or a centrifuge.

After the working fluid containing the reaction water is separated from ketazine, in the treatment of step (c), the reaction water is removed by raising the temperature to 60 ° C. or higher. In the step (c), water is removed from the working fluid by heating and can be industrially performed in a distillation column. In the step (c), the ammonia dissolved in water can be recovered.
The treatment in step (c) can be carried out in a heat exchanger or a reboiler in a distillation column. When a distillation column which is a preferred embodiment of the present invention is used, the working liquid supply temperature is preferably 30 to 50 ° C, and the bottom temperature is 60 ° C or higher, preferably 60 to 129 ° C, more preferably 65. ~ 100
C., most preferably 70 to 90.degree. From the viewpoint of heat energy cost, lower temperature is more economical in the above range, but the bottom of the distillation column for concentrating the working fluid is maintained at at least 60 ° C. The distillation column is preferably operated under reduced pressure in order to surely boil the kettle liquid, and the column top is operated at 10 to 500 torr, more preferably 50 to 250 torr. At the top of the tower, water is extracted to keep the volume of the working fluid constant. The distillation column preferably has 5 to 50 theoretical plates, and the working liquid is preferably fed to the 3rd to 20th plates from the bottom.
The residence time of the working fluid in the step (c) is preferably 1 to 30 minutes, and in particular, the shorter the retention time is, the better in order to prevent deterioration of the catalyst.

In the step (d), the main part of the hydraulic fluid that has been subjected to the step (c) is recycled and reused in the step (a). An advantage of the present invention is that a major part of the hydraulic fluid can be recycled and reused without reducing the yield of ketazine only by the treatment in step (c).

Further, it is more preferable to purify the recycled working fluid by removing impurities in the working fluid with a resin at an arbitrary stage where the working fluid is circulated and reused.
Anion exchange resins and cation exchange resins are preferably used to adsorb and remove impurities accumulated in the working fluid to be recycled for the purpose of purifying the working fluid. In this case, it is not always necessary to purify the entire working fluid coming out of step (c), and it is sufficient to partially purify the working fluid. The amount of working fluid to be treated depends on the amount of impurities in the working fluid, but the amount of impurities in the working fluid depends on the synthesis conditions of ketazine and the amount of impurities already present in ammonia, hydrogen peroxide, and ketones. Dependent.

[0014]

Industrial Applicability According to the present invention, it is possible to stably produce ketazine industrially without essentially requiring supplementation of a new hydraulic fluid.

[0015]

【Example】

Example 1 1500 cc using stainless steel (SUS304)
Into a reactor equipped with a stirrer, was charged 500 cc of a working liquid consisting of 5% by weight of cacodylic acid, 30% by weight of ammonium acetate and 50% by weight of propylene glycol, and the mixture was kept at 50 ° C. while continuously blowing ammonia gas, and 305 g of methyl ethyl ketone and phosphoric acid were added. 80% stabilized with sodium
90 g of a hydrogen peroxide aqueous solution was simultaneously added over 30 minutes and 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 hydraulic fluid is supplied to the 10th stage from the bottom of a stainless steel (SUS304) distiller (inner diameter 50 mm, height 1,000 mm, and has 20 stages of plates), and 70 torr.
The reaction product water and hydrogen peroxide medium water were distilled off at r and 70 ° C., and the working fluid was concentrated to 500 cc. 100 cc out of 500 cc of concentrated working fluid is a glass column (inner diameter 20 m
m, height 200 mm) weakly basic anion exchange resin (Mitsubishi Kasei, trade name: Diaion, WA30)
It was introduced into 10 cc from the upper part of the column at a flow rate of 50 cm ³ / hr. In addition, another 500 cc of the concentrated working fluid
00cc glass column (inner diameter 20mm, height 200m
m)) porous strong acid cation exchange resin (manufactured by Mitsubishi Kasei, trade name: Diaion, PK216) 10 cc
Was introduced from above the column at a flow rate of 50 cm ³ / hr.
The remaining concentrated working fluid of 300 cc was combined with the working fluid after each ion-exchange resin treatment to give 300 cc, which was reused in the ketazine synthesis reaction. The above-mentioned series of operations for synthesizing ketazine, concentrating the working fluid, and purifying the working fluid with an ion-exchange resin were repeated 100 times, and the ketazine yield was examined at predetermined intervals. As a result, the yield was not reduced.

Comparative Example 1 The same operation as in Example 1 was carried out under the condition that the working fluid was concentrated to 760 tons.
rr, 140 degreeC was implemented. As a result, the ketazine yield decreased with the number of repetitions and decreased to 30% at the 10th time. Comparative Example 2 The same operation as in Example 1 was carried out without performing the purification treatment of the working fluid with the ion exchange resin. As a result, the ketazine yield was 80% at the 50th repetition and decreased to 75% at the 100th repetition.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A 2-311448 (JP, A) JP-A 58-10547 (JP, A) JP-A 52-36615 (JP, A) JP-A 54- 141713 (JP, A) JP-A-7-126235 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 251/88 C07C 249/16

Claims (6)

(57) [Claims] 1. A method for producing ketazine from hydrogen peroxide, ammonia and a ketone, which comprises synthesizing ketazine by bringing a working fluid into contact with hydrogen peroxide, ammonia and a ketone (step (a)), and producing ketazine. The working fluid is separated from the working fluid (step (b)), and subsequently the separated working fluid is heated to a temperature of 60 to 100 ° C. to remove water (step (c)), and the working fluid after removing the water. Anion exchange
Purified with a replacement resin and a cation exchange resin, the purified working fluid is returned to the step (a) and reused by circulation (step (d))
A method for synthesizing ketazine, which comprises: 2. A method for producing ketazine from hydrogen peroxide, ammonia and a ketone, wherein hydrogen peroxide, ammonia and a ketone are mixed with cacodylic acid or cacodylic acid anion.
Was synthesized ketazine by contacting the working solution containing Moniumu ((a) step), the resulting ketazine and the hydraulic fluid is separated ((b) step), subsequently, the hydraulic fluid after separation 60-100 A method for synthesizing ketazine, which comprises heating to a temperature of ° C to remove water (step (c)), and then returning the working fluid to step (a) for reuse by circulation (step (d)). Wherein (c) is carried out step in a distillation column, the method according to any one of claims 1 to 2, the distillation column top section characterized by operating at 10～500Torr. 4. An anion exchange resin is a weakly basic anion exchange resin.
Cation exchange resin is a porous resin and is a strong acidic cation resin.
The method according to claim 1, which is an on-exchange resin. 5. The method according to claim 1, wherein the working fluid contains acetic acid amide, ammonium acetate or nitrile acetate. 6. The method according to claim 1, wherein the hydraulic fluid contains cacodylic acid or ammonium cacodylate.