JP4578988B2 - Method for producing hydroxylamine - Google Patents

Description

  The present invention relates to a method for producing hydroxylamine safely and in high yield when producing hydroxylamine.

  Hydroxylamines are used in a wide range of industrial applications such as raw materials for pharmaceutical and agrochemical intermediates, reducing agents, metal surface treatment agents, fiber treatment, and dyeing. In general, a relatively stable salt of hydroxylamine is produced and used because it has very unstable properties such as being easily decomposed under conditions such as high temperature or high concentration in the presence of heavy metal ions). Yes.

  However, for many applications, hydroxylamine is preferred over hydroxylamine salts, and high concentrations of aqueous hydroxylamine are often required. In the electronics industry, high-purity hydroxylamine with less metal impurities is required. Therefore, an attempt has been made to produce a safe and highly pure hydroxylamine aqueous solution.

  For example, JP-B-52-48118 discloses a hydroxylamine and / or a salt thereof, or an aromatic compound having a hydroxyl group at each of two or more consecutive carbon atoms on an aromatic ring in a solution containing hydroxylamine. Stabilization methods are described in which is added as a stabilizer.

  However, this publication describes a method of stabilizing hydroxylamine by adding a stabilizer in the crystal or solution of hydroxylamine, which is added during the production of hydroxylamine to produce hydroxylamine. There is no mention of performing stabilization.

Similarly, WO 03/031330 describes that 2,3-dihydroxybenzoic acid is added to stabilize the hydroxylamine solution, which is also added when producing hydroxylamine. There is no mention of what to do.
Japanese Patent Publication No. 52-48118 International Publication No. 03/031330 Pamphlet

  An object of the present invention is to provide a method for producing hydroxylamine safely and in high yield when producing hydroxylamine by reaction of a salt of hydroxylamine with an alkali compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that in the presence of at least one stabilizer selected from aromatic compounds having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring. The present inventors have found a method in which a high concentration of hydroxylamine can be produced safely in a high yield by reacting a hydroxylamine salt with an alkali compound. These findings have been found for the first time by the present inventors.

This invention is made | formed based on the said knowledge, and relates to the following (1)-(22).
(1) Hydroxylamine salt is reacted with an alkali compound in the presence of at least one stabilizer selected from aromatic compounds having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring to produce hydroxyl. A method for producing hydroxylamine, comprising a reaction step of obtaining an amine.
(2) The stabilizer is catechol, 4-tert-butylcatechol, 2,3-dihydroxynaphthalene, 2,3-dihydroxybenzoic acid, 1,2,4-benzenetriol, 3,4-dihydroxybenzoic acid, 3 The method for producing hydroxylamine according to (1) above, which is at least one compound selected from the group consisting of 1,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzonitrile, and 3,4,5-trihydroxybenzoic acid.
(3) The stabilizer is 1,2,4-benzenetriol, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzonitrile, 3,4,5-trihydroxybenzoic acid. The method for producing hydroxylamine according to the above (1) or (2), which is at least one compound selected from the group consisting of:
(4) The method for producing hydroxylamine according to any one of (1) to (3), wherein the reaction step is performed by adding a hydroxylamine salt to a reaction solution containing an alkali compound.
(5) The method for producing hydroxylamine according to any one of (1) to (4), wherein the reaction step is performed while maintaining the pH of the reaction solution at 7 or more.
(6) The method for producing hydroxylamine according to any one of (1) to (5), wherein the reaction temperature in the reaction step is in the range of 0 ° C to 80 ° C.
(7) The method for producing hydroxylamine according to any one of (1) to (6), wherein the reaction step is performed in the presence of a solvent containing water and / or alcohol.
(8) Any of the above (1) to (7), wherein the salt of hydroxylamine is at least one compound selected from the group consisting of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate, and hydroxylamine phosphate. A method for producing hydroxylamine as described in 1. above.
(9) The hydroxylamine according to any one of (1) to (8), wherein the alkali compound is at least one compound selected from the group consisting of an alkali metal compound, an alkaline earth metal compound, ammonia, and an amine. Manufacturing method.
(10) The method for producing hydroxylamine according to any one of (1) to (9) above, comprising a purification step for purifying hydroxylamine by ion exchange and a concentration step for concentrating hydroxylamine at the bottom of the column by distillation.
(11) The method for producing hydroxylamine according to (10), wherein the purification step is performed within a range of 0 ° C to 70 ° C.
(12) In the above (10) or (11), at least a part of the hydroxylamine solution obtained by the purification step is used as a solvent for dissolving or suspending a salt of hydroxylamine and / or an alkali compound as a reaction raw material. A method for producing the hydroxylamine as described.
(13) The method for producing hydroxylamine according to (10), wherein the concentration step is performed within a range of 0 ° C to 70 ° C.
(14) In the above (10) or (13), at least a part of the hydroxylamine solution obtained by the concentration step is used as a solvent for dissolving or suspending a salt of hydroxylamine and / or an alkali compound as a reaction raw material. A method for producing the hydroxylamine as described.
(15) The method for producing hydroxylamine according to any one of (10) to (14), wherein each of the steps is performed in the order of the reaction step, the purification step, and the concentration step.
(16) The method for producing hydroxylamine according to any one of (1) to (15) above, which comprises a separation step of separating hydroxylamine and insoluble material.
(17) The method for producing hydroxylamine according to (16), wherein the separation step is performed within a range of 0 ° C to 80 ° C.
(18) The above (16) or (17), wherein at least a part of the reaction solution from which the insoluble material has been separated in the separation step is used as a solvent for dissolving or suspending the salt of hydroxylamine and / or the alkali compound as a reaction raw material. A method for producing hydroxylamine as described in 1. above.
(19) The method for producing hydroxylamine according to any one of (16) to (18), wherein each step is performed in the order of the reaction step, the separation step, the purification step, and the concentration step.
(20) The method for producing hydroxylamine according to (19), further comprising a purification step of purifying hydroxylamine by ion exchange after the concentration step.
(21) The method for producing hydroxylamine according to (20), wherein the purification step after the concentration step is performed within a range of 0 ° C to 70 ° C.
(22) The method for producing hydroxylamine according to any one of (10) to (21), wherein each step is performed in the presence of a stabilizer.

  According to the present invention, since a hydroxylamine salt and an alkali compound are reacted in the presence of the stabilizer of the present invention, a high concentration of hydroxylamine can be safely obtained in a high yield.

Hereinafter, the method for producing hydroxylamine according to the present invention will be described in more detail.
Reaction step;
The method for producing hydroxylamine of the present invention comprises a hydroxylamine salt in the presence of at least one stabilizer selected from aromatic compounds each having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring; A reaction step of reacting with an alkali compound to obtain hydroxylamine.

The hydroxylamine salt used in the present invention includes hydroxylamine sulfate, hydrochloride, nitrate, phosphate, hydrobromide, sulfite, phosphite, perchlorate, carbonate, carbonate, Examples include salts of inorganic acids such as hydrogen salts, and salts of organic acids such as formate, acetate, propionate. Among them, hydroxylamine sulfate (NH ₂ OH · 1 / 2H ₂ S
O ₄ ), hydrochloride (NH ₂ OH · HCl), nitrate (NH ₂ OH · HNO ₃ ) and phosphate (NH ₂ OH · 1 / 3H ₃ PO ₄ ) Is preferred.

  The hydroxylamine salt is not particularly limited as long as it is commercially available or industrially available, but preferably has a small amount of metal impurities. This is because the presence of metal impurities may promote the decomposition of the hydroxylamine salt or hydroxylamine formed. However, it may contain impurities as long as it does not promote decomposition of the hydroxylamine salt or hydroxylamine and can be removed by a purification process or the like, or does not cause a problem in the use of the produced hydroxylamine.

  The hydroxylamine salt may be used as a solid, or may be used by dissolving or suspending in a solvent. As such a solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbons, ethers, alcohols and the like, but are not limited to these as long as the reaction is not affected. In these, the solvent containing water and / or alcohol is preferable. In addition, at least a part of the filtrate from which an insoluble salt or the like generated by the reaction between a hydroxylamine salt and an alkali compound is separated may be used as a solvent.

The amount of the solvent may be appropriately selected according to the conditions such as the amount of hydroxylamine salt used and the reaction temperature. Usually, the mass ratio of the solvent to the hydroxylamine salt (solvent / hydroxylamine salt) is It is in the range of 0.1 to 1000, preferably 1 to 100.

  The alkali compound used in the present invention is preferably at least one compound selected from the group consisting of a compound containing an alkali metal, a compound containing an alkaline earth metal, ammonia and an amine.

  Examples of the compound containing an alkali metal include oxides, hydroxides and carbonates of lithium, sodium, potassium, rubidium or cesium, preferably sodium or potassium hydroxides or carbonates.

  Examples of the compound containing an alkaline earth metal include oxides, hydroxides and carbonates of beryllium, magnesium, calcium, strontium or barium, and preferably oxides or hydroxides of magnesium, calcium, strontium or barium. Things.

Ammonia may be used as a gas or a solution in which ammonia is dissolved, for example, an aqueous ammonia solution.
As amines, primary amines, secondary amines and tertiary amines can be used. The amine may be a monoamine, a polyamine such as a diamine or triamine having two or more amino groups in the molecule, and a cyclic amine.

  Examples of the monoamine include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, i-propylamine, and di-i-propylamine. , Tri-i-propylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, i-butylamine, di-i-butylamine, tri-i-butylamine, sec-butylamine, di-sec-butylamine, Tri-sec-butylamine, tert-butylamine, di-tert-butylamine, tri-tert-butylamine, allylamine, diallylamine, triallylamine, cyclohexylamine, dicyclohexylamine, tricyclohexylamine , N-octylamine, di-n-octylamine, tri-n-octylamine, benzylamine, dibenzylamine, tribenzylamine, diaminopropylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propyl Amine, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (diethylamino) propylamine, bis (2-ethylhexyl) amine, 3- (dibutylamino) propylamine, α-phenylethylamine, β-phenylethylamine, aniline N-methylaniline, N, N-dimethylaniline, diphenylamine, triphenylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-chloroaniline, m- Chloroa Phosphorus, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline, 2,4,6- Examples thereof include trinitroaniline, p-aminobenzoic acid, sulfanilic acid, sulfanilamide, monoethanolamine, diethanolamine, and triethanolamine.

Examples of the diamine include 1,2-diaminoethane, N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N, N, N ′, N′-tetraethyl-1,2-diamino. Ethane, 1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,2-diaminopropane, N, N, N ′, N′-tetraethyl-1,2-diaminopropane, 1, 4-diaminobutane, N-methyl-1,4-diaminobutane, 1,2-diaminobutane, N, N, N ′, N′-tetramethyl-1,2-diaminobutane, 3-aminopropyldimethylamine, Examples include 1,6-diaminohexane, 3,3-diamino-N-methyldipropylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, and benzidine.

  Examples of the triamine include 2,4,6-triaminophenol, 1,2,3-triaminopropane, 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,3, 5-triaminobenzene and the like can be mentioned.

Examples of tetraamine include β, β ′, β ″ -triaminotriethylamine and the like.
Examples of the cyclic amine include pyrrole, pyridine, pyrimidine, pyrrolidine, piperidine, purine, imidazole, oxazole, thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline, carbazole, piperazine, pyridazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,3-triazole, 1,2,5-triazole, 1,2,4-triazole, 1,3,4-triazole, morpholine, etc. Is mentioned.

  The amine that can be used as the alkali compound in the present invention is not limited to the above-mentioned compound, and may be an asymmetric compound having different types of substituents such as ethylmethylamine. Moreover, an amine may be used individually by 1 type and may be used in combination of 2 or more type.

  The alkali compound used in the present invention is not particularly limited as long as it is commercially available or industrially available, but preferably has a small amount of metal impurities, like the hydroxylamine salt.

  The equivalent ratio of the alkali compound to the hydroxylamine salt (alkali compound / hydroxylamine salt) is in the range of 0.1 to 100, preferably 0.5 to 10, and more preferably 1 to 2. The equivalent weight is calculated as 1 for an alkali metal, 1 for an alkaline metal, 2 for an alkaline earth metal, 1 for ammonia, 1 for an amine, and 2 for a diamine, for example. .

  If the equivalent ratio is greater than 100, problems such as decomposition of hydroxylamine by an excessive alkali compound and recovery of a large amount of unreacted alkali compound may occur. On the other hand, if the equivalent ratio is less than 0.1, there may be a problem that a large amount of unreacted hydroxylamine salt needs to be recovered.

  The alkaline compound can be used by dissolving or suspending it in a solvent. As such a solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbons, ethers, alcohols and the like, but are not limited to these as long as the reaction is not affected. In these, it is preferable to use water and / or alcohol. In addition, at least a part of the filtrate from which an insoluble salt or the like generated by the reaction between a hydroxylamine salt and an alkali compound is separated may be used as a solvent.

  The amount of the solvent may be appropriately selected according to conditions such as the amount of the alkali compound to be used and the reaction temperature, and the mass ratio of the solvent to the alkali compound (solvent / alkali compound) is usually 0.5 to 1000, Preferably it is 0.8-100.

The stabilizer used in the method for producing hydroxylamine of the present invention is selected from aromatic compounds having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring (hereinafter also referred to as “specific stabilizer”).

  The aromatic compound having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring is preferably catechol, 4-tert-butylcatechol, 2,3-dihydroxynaphthalene, 2,3-dihydroxybenzoic acid, 1,2,4-benzenetriol, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzonitrile, 3,4,5-trihydroxybenzoic acid, and more preferably 1 , 2,4-benzenetriol, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzonitrile, 3,4,5-trihydroxybenzoic acid, more preferably 3,4-dihydroxybenzoic acid. 4-dihydroxybenzoic acid, 3,4-dihydroxybenzaldehyde, 3,4- Hydroxybenzonitrile. Particularly preferred examples include 3,4-dihydroxybenzoic acid.

  The stabilizer is not particularly limited as long as it is commercially available or industrially available, but preferably has a low metal impurity. This is because the presence of metal impurities may accelerate the decomposition of hydroxylamine. In the electronic industry, high-purity hydroxylamine with few metal impurities is preferable. The stabilizer may be a hydrate.

  The said stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type. By reacting a hydroxylamine salt with an alkali compound in the presence of a stabilizer, the decomposition of the hydroxylamine salt or hydroxylamine by a metal impurity or the like can be suppressed.

  According to the method for producing hydroxylamine of the present invention, in the above reaction for obtaining hydroxylamine by reacting a hydroxylamine salt with an alkali compound, hydroxylamine can be safely produced in a high yield by the presence of the stabilizer. Can be obtained at In this reaction step, since there are many metal impurities derived from the raw material, there is a high possibility that the produced hydroxylamine is decomposed. However, the stabilizer described above has a particularly high effect of suppressing the decomposition of the hydroxylamine.

The mass ratio between the stabilizer and the hydroxylamine salt (stabilizer / hydroxylamine salt) is preferably 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. ing. When the mass ratio is smaller than 1.0 × 10 ⁻⁹ , the effect of suppressing the decomposition reaction of hydroxylamine salt or hydroxylamine by metal impurities may not be obtained. If it is too large, it may be necessary to remove and recover the excess stabilizer.

  In the reaction step in the method for producing hydroxylamine of the present invention, the method for adding the stabilizer is not particularly limited, and a known method can be used. For example, a stabilizer may be introduced into the reactor in advance to start the reaction, and may be added during the reaction as necessary. The stabilizer may be used as it is, or may be used after being dissolved in a solvent. As such a solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols and the like, but are not limited to these as long as the reaction is not affected. In these, it is preferable to use water and / or alcohol. The amount of the solvent can be appropriately selected according to the conditions such as the type and amount of the stabilizer used and the reaction temperature.

Specifically, the stabilizer can be added to either or both of a hydroxylamine salt and an alkali compound which are starting materials in the above reaction step.
The reaction step in the method for producing hydroxylamine of the present invention is preferably carried out by adding a salt of hydroxylamine to a reaction solution in which an alkali compound is dissolved or suspended in a solvent. Thus, by using a method of adding a hydroxylamine salt to a reaction solution containing an alkali compound, it is difficult for the produced hydroxylamine to form a complex with a by-product salt, and a by-product is insoluble. It is difficult to be adsorbed or taken into the salt.

  In this specification, the term “reaction liquid” refers to a liquid (solution or suspension) during the reaction between a hydroxylamine salt and an alkali compound, as well as a liquid used in the reaction (that is, a hydroxylamine salt or alkali). It may mean a liquid containing only one of the compounds) or a liquid obtained by the reaction (that is, a liquid after the reaction).

  Further, when adding the hydroxylamine salt to the reaction solution containing an alkali compound, the pH of the reaction solution is preferably 7 or more, more preferably 7.5 or more, and even more preferably 8 or more, while maintaining the pH of the hydroxylamine. It is desirable to add salt. By maintaining the pH of the reaction solution in the above range, the produced hydroxylamine is less likely to form a complex with the by-product salt, and is less likely to be adsorbed or taken up by the insoluble salt produced as a by-product.

  Furthermore, the reaction step in the method for producing hydroxylamine of the present invention may be a reaction step in which a hydroxylamine salt and an alkali compound are simultaneously supplied and reacted. At that time, it is desirable to adjust the addition amount of the hydroxylamine salt and the alkali compound while keeping the pH of the reaction solution at preferably 7 or more, more preferably 7.5 or more, and even more preferably 8 or more. The hydroxylamine salt and / or alkali compound may be added as a solid, or may be added after dissolved or suspended in a solvent. Further, when the alkali compound is ammonia or the like, it may be introduced by gas.

  In the reaction step, the reaction temperature is preferably 0 ° C to 80 ° C, more preferably 5 ° C to 50 ° C. When the reaction temperature is higher than 80 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the reaction temperature is lower than 0 ° C., the reaction rate becomes slow and problems such as a decrease in productivity may occur.

  The reaction temperature generated in the reaction between the hydroxylamine salt of the present invention and the alkali compound is discharged out of the system through water, hot water or a heat medium, whereby the reaction temperature can be maintained within a certain range. Moreover, it is preferable to use the heat | fever discharged | emitted out of the system with water, warm water, or a heat medium as a heat source of another installation.

The reaction step in the method for producing hydroxylamine of the present invention can be performed by a known method, for example, a batch system, a semi-batch system, a continuous system, or the like.
Furthermore, by combining the reaction step with the following steps, it is possible to obtain hydroxylamine with higher concentration and higher purity.
Separation step;
The method for producing hydroxylamine of the present invention preferably includes a separation step for separating hydroxylamine and insoluble material.

This insoluble substance is, for example, an insoluble substance deposited in the reaction solution in the above reaction step.
Examples of the insoluble substance include a salt produced by the reaction of a hydroxylamine salt with an alkali compound in the above reaction step, a hydroxylamine salt, an alkali compound, and the like.

That is, in the case where the salt formed by the reaction of hydroxylamine salt and alkali compound in the above reaction step, hydroxylamine salt, alkali compound, etc. is precipitated as an insoluble substance due to its concentration higher than the solubility, it is insoluble. It is preferable to include a separation step for separating the substance.

Further, insoluble substances precipitated in steps other than the reaction step can be similarly separated.
As a separation method, known methods such as filtration, squeezing, centrifugation, sedimentation separation, and flotation separation can be used. For example, the separation by filtration may be performed by any of natural filtration, pressure filtration, or vacuum filtration, and the separation by sedimentation separation may be performed by any of clarification separation or precipitation concentration, by floating separation. Separation may be performed by any method of pressure levitation and ionization levitation.

In addition, by washing the insoluble material separated in the separation step of the present invention with a solvent, hydroxylamine attached to or taken in by the insoluble material can be recovered.
As the solvent for washing the insoluble substance (hereinafter also referred to as “washing solvent”), the same solvent as that used in the reaction step may be used, or another solvent may be used. As such a washing solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols and the like, but are not limited to these as long as the recovery of hydroxylamine is not affected. In these, it is preferable to use water and / or alcohol as a washing | cleaning solvent. The amount of the washing solvent can be appropriately selected according to the type and amount of the insoluble substance, conditions such as separation.

  The temperature at which the insoluble material is separated in the separation step is preferably 0 ° C to 80 ° C, more preferably 5 ° C to 50 ° C. When the temperature at the time of separation is higher than 80 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the temperature of the reaction solution is lower than 0 ° C., there may be a problem that energy required for cooling increases. A part or all of the filtrate from which the insoluble substances have been separated in the separation step and / or the filtrate from which the insoluble substances have been washed may be used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as the reaction raw material. Good.

The separation step is preferably performed in the presence of a stabilizer as in the purification step and the concentration step described later. A stabilizer may be newly added in the separation step, or the stabilizer used in the previous step may be used as it is. A well-known thing can be used for a stabilizer. Examples of the stabilizer other than the specific stabilizer (hereinafter also referred to as “other stabilizer”) include, for example, 8-hydroxyquinoline, N-hydroxyethylethylenediamine-N, N, N′-triacetic acid, glycine, and ethylenediamine Acetic acid, cis-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, trans-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, N, N ′ -Di (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, N-hydroxyethyliminodiacetic acid, N, N'-dihydroxyethylglycine, diethylenetriaminepentaacetic acid, ethylenebis (oxyethylenenitrilo) tetraacetic acid, bis Hexamethylenetriaminepentaacetic acid, hexamethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, tris (2-aminoethyl) a Hexaacetic acid, iminodiacetic acid, polyethyleneimine, polypropyleneimine, o-aminoquinoline, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 5-phenyl-1 , 10-phenanthroline, hydroxyanthraquinone, 8-hydroxyquinoline-5-sulfonic acid, 8-hydroxymethylquinoline, thioglycolic acid, thiopropionic acid, 1-amino-2-mercapto-propionic acid, 2,2-dipyridyl, 4 , 4-dimethyl-2,2-dipyridyl, ammonium thiosulfate, benzotriazole, flavone, morin, quercetin, gossypetin, robitinen, luteolin, fisetin, apigenin, galangin, chrysin, flavonol, pyrogallol, oxyant Laquinone, 1,2-dioxyanthraquinone, 1,4-dioxyanthraquinone, 1,2,4-trioxyanthraquinone, 1,5-dioxyanthraquinone, 1,8-dioxyanthraquinone, 2,3-di Oxyanthraquinone, 1,2,6-trioxyanthraquinone, 1,2,7-trioxyanthraquinone, 1,2,5,8-tetraoxyanthraquinone, 1,2,4,5,8-pentaoxyanthraquinone, 1 , 6,8-dioxy-3-methyl-6-methoxyanthraquinone, quinalizarin, flavan, lactone, 2,3-dihydrohexono-1,4-lactone, 8-hydroxyquinaldine, 6-methyl-8-hydroxyquinaldine, 5,8-dihydroxyquinaldine, anthocyan, pelargonidin, cyanidin, delphinidin Peonidin, petunidin, malvidin, catechin, sodium thiosulfate, nitrilotriacetic acid, 2-hydroxyethyl disulfide, 1,4-dimercapto-2,3-butanediol, thiamine hydrochloride, 2-hydroxypyridine-N-oxide, 1 , 2-dimethyl-3-hydroxypyridin-4-one, 4-methylpyridine-N-oxide, 6-methylpyridine-N-oxide, 1-methyl-3-hydroxypyridin-2-one, 2-mercaptobenzothiazole 2-mercaptocyclohexyl thiazole, 2-mercapto-6-t-butylcyclohexyl thiazole, 2-mercapto-4,5-dimethylthiazoline, 2-mercaptothiazoline, 2-mercapto-5-t-butylthiazoline, tetramethylthiuram disulfide Tetra n-butylthiuram disulfide, N, N′-diethylthiuram disulfide, tetraphenylthiuram disulfide, thiuram disulfide, thiourea, N, N′-diphenylthiourea, di-o-tolylthiourea, ethylenethiourea, thiocetamide, 2-thiouracil , Thiocyanuric acid, thioformamide, thioacetamide, thiopropionamide, thiobenzamide, thionicotinamide, thioacetanilide, thiobenzanilide, 1,3-dimethylthiourea, 1,3-diethyl-2-thiourea, 1-phenyl- 2-thiourea, 1,3-diphenyl-2-thiourea, thiocarbazide, thiosemicarbazide, 4,4-dimethyl-3-thiosemicarbazide, 2-mercaptoimidazoline, 2-thiohydantoin, 3-thiourazole, 2 Thiouramil, 4-thiouramil, thiopentanol, 2-thiobarbituric acid, thiocyanuric acid, 2-mercaptoquinoline, thiocoumazone, thiococciazone, thiosaccharin, 2-mercaptobenzimidazole, trimethyl phosphite, triethyl phosphite, triphenyl phosphite , Trimethylphosphine, triethylphosphine, triphenylphosphine, and the like.

  The said stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type. By adding a stabilizer, the decomposition of the hydroxylamine salt or hydroxylamine by metal impurities or the like can be suppressed.

The stabilizer is not particularly limited as long as it is commercially available or industrially available, but preferably has a low metal impurity.
The stabilizer may be used as a solid or may be used after being dissolved in a solvent. As such a solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols and the like, but are not limited to these as long as the reaction is not affected. In these, it is preferable to use water and / or alcohol. The amount of the solvent can be appropriately selected according to conditions such as the type and amount of the stabilizer used and the reaction temperature.

  As the stabilizer, use the same type of stabilizer used in the reaction process (specific stabilizer) or a different type (other stabilizer) for the separation process and the use of the hydroxylamine produced. Can be selected accordingly. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities and the like are suppressed, and the production efficiency of hydroxylamine is improved.

The stabilizer has a mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use in such an amount. When the mass ratio is less than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of hydroxylamine by metal impurities may not be obtained. When the mass ratio is greater than 1.0, excessive stability Removal or recovery of the agent may be necessary.

The separation step in the method for producing hydroxylamine of the present invention can be performed by a known method, for example, a batch system, a semi-batch system, a continuous system, or the like.
Purification step;
The method for producing hydroxylamine of the present invention preferably includes, for example, a purification step of purifying the hydroxylamine obtained as described above by ion exchange.

The ion exchange can be performed by a known method such as cation exchange, anion exchange, or chelate exchange.
Purification by cation exchange can be performed by a known method using a strong acid cation exchange resin, a weak acid cation exchange resin, or the like. It is preferable to use the cation exchange resin in an H-type by performing an acid treatment in advance.

  Purification by anion exchange can be performed by a known method using a strongly basic anion exchange resin, a weakly basic anion exchange resin, or the like. It is preferable that the anion exchange resin is used after being alkali-treated in advance to form an OH type.

  Purification by chelate exchange can be performed by a known method using a chelate exchange resin or the like. The chelate exchange resin is preferably subjected to acid treatment in advance and used as an H type.

  You may refine | purify combining cation exchange, anion exchange, and chelate exchange. For example, anion exchange may be performed after cation exchange, and cation exchange may be performed after anion exchange. Moreover, it is also possible to use a monobed resin or a mixed bed resin in which a cation exchange resin and an anion exchange resin are mixed.

  The ion exchange temperature is preferably 0 ° C to 70 ° C, more preferably 5 ° C to 50 ° C. When the temperature of ion exchange is higher than 70 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the ion exchange temperature is lower than 0 ° C., there may be a problem that energy required for cooling becomes large.

  A part of the hydroxylamine solution obtained by the purification step may be used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as a reaction raw material.

  The purification step is preferably performed in the presence of a hydroxylamine stabilizer as in the reaction step. A stabilizer may be newly added in the purification step, or the stabilizer used in the previous step may be used as it is.

  As the stabilizer, the same type of stabilizer used in the reaction step (specific stabilizer), or a different type as described in the separation step (other stabilizers), the status and production of the separation step It can be selected depending on the use of the hydroxylamine to be prepared. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities and the like are suppressed, and the production efficiency of hydroxylamine is improved.

The stabilizer has a mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use in such an amount. When the mass ratio is less than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of hydroxylamine by metal impurities may not be obtained. When the mass ratio is greater than 1.0, excessive stability Removal or recovery of the agent may be necessary.

The step of purification by ion exchange in the method for producing hydroxylamine of the present invention can be performed by a known method, for example, a batch system, a semi-batch system, a continuous system, or the like.
A concentration step;
Furthermore, the method for producing hydroxylamine of the present invention preferably includes a concentration step in which hydroxylamine is concentrated at the bottom of the column by distillation.

Distillation can be performed by a known method such as simple distillation, multistage distillation, steam distillation, or flash distillation.
For example, a hydroxylamine solution having a high hydroxylamine concentration can be obtained from the bottom of the column by simple distillation or multistage distillation.

As the distillation column, a general plate column such as a bubble bell tray column, a stitch plate column, or a general packing such as a Raschig ring, a pearl ring, and a saddle body may be provided.
The distillation temperature is preferably 0 to 70 ° C., more preferably 5 to 60 ° C. at the bottom of the column. When the temperature at the bottom of the column is higher than 70 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the temperature at the bottom of the column is lower than 0 ° C., there may be a problem that a large amount of cooling energy is required.

Although the distillation pressure is determined by the relationship with temperature, the pressure at the bottom of the column is preferably 0.5 to 60 kPa, more preferably 0.8 to 40 kPa.
A part of the hydroxylamine solution obtained by the concentration step may be used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as a reaction raw material.

  In addition, a low concentration hydroxylamine solution may be obtained from the top or side of the distillation column, but a part or all of this dissolves or suspends the hydroxylamine salt and / or alkali compound as a reaction raw material. It may be used as a solvent.

  The concentration step is preferably performed in the presence of a hydroxylamine stabilizer as in the reaction step. A stabilizer may be newly added in the concentration step, or the stabilizer used in the previous step may be used as it is.

  As the stabilizer, the same type of stabilizer used in the reaction step (specific stabilizer), or a different type as described in the separation step (other stabilizer), the status of the concentration step and the production It can be selected depending on the use of the hydroxylamine to be prepared. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities and the like are suppressed, and the production efficiency of hydroxylamine is improved.

The stabilizer has a mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use in such an amount. When the mass ratio is less than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of hydroxylamine by metal impurities may not be obtained. When the mass ratio is greater than 1.0, excessive stability Removal or recovery of the agent may be necessary.

The concentration step of concentration at the bottom of the column by distillation in the method for producing hydroxylamine of the present invention can be performed by a known method, for example, a batch method, a semi-batch method, a continuous method, or the like.
Furthermore, the method for producing hydroxylamine of the present invention may include a purification step for purifying the hydroxylamine obtained by the concentration step by ion exchange.

The ion exchange can be performed by a known method such as cation exchange, anion exchange, or chelate exchange.
Purification by cation exchange can be performed by a known method using a strong acid cation exchange resin, a weak acid cation exchange resin, or the like. It is preferable to use the cation exchange resin in an H-type by performing an acid treatment in advance.

  Purification by anion exchange can be performed by a known method using a strongly basic anion exchange resin, a weakly basic anion exchange resin, or the like. It is preferable that the anion exchange resin is used after being alkali-treated in advance to form an OH type.

  Purification by chelate exchange can be performed by a known method using a chelate exchange resin or the like. The chelate exchange resin is preferably subjected to acid treatment in advance and used as an H type.

  You may refine | purify combining cation exchange, anion exchange, and chelate exchange. For example, anion exchange may be performed after cation exchange, and cation exchange may be performed after anion exchange.

Moreover, it is also possible to use a monobed resin or a mixed bed resin in which a cation exchange resin and an anion exchange resin are mixed.
The ion exchange temperature is preferably 0 ° C to 70 ° C, more preferably 5 ° C to 50 ° C. When the temperature of ion exchange is higher than 70 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the ion exchange temperature is lower than 0 ° C., there may be a problem that energy required for cooling becomes large.

  A part of the hydroxylamine solution obtained in the purification step after the concentration step may be used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as a reaction raw material.

  The purification step after the concentration step is preferably performed in the presence of a hydroxylamine stabilizer as in the reaction step. In the purification step (2), a stabilizer may be newly added, or the stabilizer used in the previous step may be used as it is.

  As the stabilizer, the same type of stabilizer as used in the reaction step (specific stabilizer) or a different type as described in the separation step (other stabilizer) is used in the purification step (2). It can be selected depending on the situation and the use of hydroxylamine to be produced. By adding a stabilizer, side reactions such as decomposition of hydroxylamine by metal ions and the like are suppressed, and the production efficiency of hydroxylamine is improved.

The stabilizer has a mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use in such an amount. When the mass ratio is less than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of hydroxylamine by metal impurities may not be obtained. When the mass ratio is greater than 1.0, excessive stability Removal or recovery of the agent may be necessary.

The method for producing hydroxylamine of the present invention comprises:
(1) A hydroxylamine salt is reacted with an alkali compound in the presence of at least one stabilizer selected from aromatic compounds having a hydroxyl group at each of two or more consecutive carbon atoms on the aromatic ring to produce hydroxyl. Including the reaction step of obtaining the amine,
(2) a purification step for purifying hydroxylamine by ion exchange;
(3) a concentration step of concentrating hydroxylamine at the bottom of the column by distillation;
The above step is preferably performed in the order of the reaction step, the purification step, and the concentration step.

Moreover, after performing the process of (1), you may perform each process of these (1)-(3) in any order, and may perform the same process twice or more.
The method for producing hydroxylamine of the present invention includes:
(4) A separation step of separating hydroxylamine and insoluble material may be included, and this step is preferably performed between the reaction step and the purification step.

Therefore, the method for producing hydroxylamine of the present invention is most preferably performed in the order of the reaction step, the separation step, the purification step, the concentration step, and the purification step.
The concentration of hydroxylamine in the hydroxylamine solution obtained by using the method of the present invention is 10% by mass or more. Further, a hydroxylamine solution having a concentration of 20% by mass or more can be obtained, and a hydroxylamine solution having a concentration of 40% by mass or more can also be obtained.

  In the hydroxylamine obtained by using the method of this invention, content of each metal contained as an impurity is 1 mass ppm or less, respectively. Moreover, the hydroxylamine whose content of each metal is 0.1 mass ppm or less can be obtained, respectively, and the hydroxylamine whose content of each metal is 0.01 mass ppm or less can also be obtained. Examples of the metal that can be contained in hydroxylamine include alkali metal derived from the alkali compound used in the reaction step, alkaline earth metal, Fe that significantly promotes decomposition of hydroxylamine, and the like.

  In the hydroxylamine obtained by using the method of the present invention, the content of each anion contained as an impurity is 100 mass ppm or less. Moreover, the hydroxylamine whose content of each anion is 10 mass ppm or less can be obtained, respectively, and the hydroxylamine whose content of each anion is 1 mass ppm or less can also be obtained, respectively. Examples of the anion that can be contained in hydroxylamine include sulfate ion, chloride ion, nitrate ion and the like derived from the salt of hydroxylamine as a raw material.

To the hydroxylamine obtained using the production method of the present invention, a stabilizer may be newly added, or the stabilizer used in the previous step may be used as it is.
<Example>
Hereinafter, although it demonstrates more concretely using an Example, this invention is not limited to these Examples.
[Example 1-1]
CaO 30.8 g (0.550 mol), 3,4-dihydroxybenzoic acid 0.0206
g (0.133 mmol) and 175 g (9.70 mol) of H ₂ O were charged into a 1 L glass reactor and stirred at 20 ° C. The pH of the reaction solution at this time was 12.8. While stirring this reaction solution, 82.1 g (1.0 mol) of hydroxylamine sulfate was added to H ₂ O 123.
A solution dissolved in g (6.83 mol) was added while keeping the pH of the reaction solution at 7 or more. The time required for the addition was about 40 minutes. After the addition, the mixture was further reacted at 20 ° C. for 3 hours. The final pH of the reaction solution was 12.2.

As a result of analyzing the obtained reaction liquid by hydrochloric acid titration, hydroxylamine in the reaction liquid was 3
It was 2.7 g (0.99 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 99%.
[Example 1-2]
1 L of 30.8 g (0.550 mol) of CaO and 175 g (9.70 mol) of H ₂ O
Were stirred at 20 ° C. The pH of the reaction solution at this time was 12.8. While stirring this reaction solution, 82.1 g (1.0 mol) of hydroxylamine sulfate was used.
A solution prepared by dissolving 0.0205 g (0.133 mmol) of 3,4-dihydroxybenzoic acid in 123 g (6.83 mol) of H ₂ O was added while maintaining the pH of the reaction solution at 7 or more. It was. The time required for the addition was about 40 minutes. After the addition, the mixture was further reacted at 20 ° C. for 3 hours. The final pH of the reaction solution was 12.2.

As a result of analyzing the obtained reaction liquid by hydrochloric acid titration, the hydroxylamine in the reaction liquid was 32.7 g (0.99 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 99%. It was.
[Example 1-3]
CaO 30.8 g (0.550 mol), 3,4-dihydroxybenzoic acid 0.0206
g (0.133 mmol) and 175 g (9.70 mol) of H ₂ O were charged into a 1 L glass reactor and stirred at 20 ° C. The pH of the reaction solution at this time was 12.8. While stirring this reaction solution, 82.1 g (1.0 mol) of hydroxylamine sulfate and 0.0205 g (0.133 mmol) of 3,4-dihydroxybenzoic acid were added to 123 g (6.83 mol) of H ₂ O. The solution dissolved in was added while keeping the pH of the reaction solution at 7 or higher. The time required for the addition was about 40 minutes. After the addition, the mixture was further reacted at 20 ° C. for 3 hours. The final pH of the reaction solution was 12.2.

As a result of analyzing the obtained reaction liquid by hydrochloric acid titration, the hydroxylamine in the reaction liquid was 32.7 g (0.99 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 99%. It was.
[Example 1-4]
The reaction was carried out in the same manner as in Example 1-1, and the resulting reaction solution at 20 ° C. after completion of the reaction was filtered under reduced pressure to separate an insoluble solid from the reaction solution. The solid was further washed 5 times with 33.0 g (1.83 mol) of H ₂ O at 20 ° C.

As a result of analyzing the liquid obtained by mixing the reaction liquid from which the insoluble solid had been separated and the liquid from which the solid after separation was washed (hereinafter also referred to as “mixed liquid”) by hydrochloric acid titration, the hydroxylamine concentration of the mixed liquid was 7 It was 6 mass%. Therefore, the obtained hydroxylamine was 32.4 g (0.98 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 98%.
[Example 1-5]
Na-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Corporation)
Was packed into a polytetrafluoroethylene column, and a 1N-HCl aqueous solution was passed through it to convert it into an H type, and further, it was sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by using the same method as in Example 1-4 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ]. As a result of analyzing the obtained aqueous solution by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), each concentration of impurities Na and Ca was 10 mass ppb or less.

[Example 1-6]
A similar result was obtained when the same operation as in Example 1-5 was performed except that a 1N—H ₂ SO ₄ aqueous solution was used instead of the 1N—HCl aqueous solution.

[Example 1-7]
Cl type strongly basic anion exchange resin (Amberlite IRA900 manufactured by Organo Corporation)
J) was packed in a polytetrafluoroethylene column, and a 1N-NaOH aqueous solution was passed through it to convert it into an OH type, followed by sufficient washing with H ₂ O. Through this strong basic anion exchange resin, an aqueous solution of hydroxylamine from which the cation of impurities obtained by the same method as in Example 1-5 was removed was circulated at a space velocity (SV) = 1 [h ⁻¹ ]. I let you.

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 7% by mass. Moreover, as a result of analyzing the obtained aqueous solution by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), the respective concentrations of impurity sulfate ion and chlorine ion were 1.0 mass ppm or less. It was. Similarly, the obtained aqueous solution was analyzed by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.). As a result, the concentration of Fe as an impurity was 10 mass ppb or less.
[Example 1-8]
3,4-Dihydroxybenzoic acid was added to an aqueous solution of hydroxylamine obtained by the same method as in Example 1-7 so as to be 600 ppm by mass with respect to hydroxylamine, and further concentrated by distillation under reduced pressure. . The degree of vacuum was adjusted so that the tower bottom temperature was 30 ° C. or less, water was extracted from the tower top, and an aqueous solution having a higher hydroxylamine concentration was recovered from the tower bottom.

As a result of analyzing the obtained tower bottom liquid by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%.
[Example 1-9]
Na-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Corporation)
Was packed into a polytetrafluoroethylene column, and a 1N-HCl aqueous solution was passed through it to convert it into an H type, and further, it was sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained in the same manner as in Example 1-8 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. Moreover, as a result of analyzing the obtained aqueous solution by ICP-MS (Seiko Instruments Co., Ltd. SPQ-900 type | mold), each concentration of impurity Na and Ca was 10 mass ppb or less.
[Example 1-10]
Cl type strongly basic anion exchange resin (Amberlite IRA900 manufactured by Organo Corporation)
J) was packed in a polytetrafluoroethylene column, and a 1N-NaOH aqueous solution was passed through it to convert it into an OH type, followed by sufficient washing with H ₂ O. Through this strong basic anion exchange resin, an aqueous solution of hydroxylamine obtained by removing impurities cations obtained by the same method as in Example 1-9 was distributed at a space velocity (SV) = 1 [h ⁻¹ ]. I let you.

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. Moreover, as a result of analyzing the obtained aqueous solution by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), each concentration of the sulfate ion and the chlorine ion as impurities was 1.0 mass ppm or less. . Similarly, the obtained aqueous solution was analyzed by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.). As a result, the concentration of Fe as an impurity was 10 mass ppb or less.
[Example 1-11]
A monobed resin (Ultrapure Water Amberlite ESG-1 manufactured by Organo Corporation) was packed in a polytetrafluoroethylene column and thoroughly washed with H ₂ O. An aqueous solution of hydroxylamine obtained in the same manner as in Example 1-8 was added to this monobed resin with a space velocity (
SV) = 1 [h ⁻¹ ].

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. As a result of analysis by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), each concentration of impurity Na, Ca and Fe was 10 mass ppb or less. As a result of analysis by anion chromatography (SHODEX IC SI-90 4E manufactured by Showa Denko KK), the respective concentrations of impurity sulfate ions and chloride ions were 1.0 mass ppm or less.
[Example 2-1]
220 g of 20% by mass NaOH aqueous solution (1.1 mol of NaOH) and 0.0220 g (0.143 mmol) of 3,4-dihydroxybenzoic acid were charged into a 1 L glass reactor and stirred at 20 ° C. While stirring this reaction solution, 82.1 g of hydroxylamine sulfate (
1.0 mol) in 465 g (25.8 mol) of H ₂ O was added over about 40 minutes. After the addition, the mixture was further reacted at 20 ° C. for 3 hours.

As a result of analyzing the reaction solution by hydrochloric acid titration, the hydroxylamine concentration was 4.2% by mass. Therefore, the obtained hydroxylamine was 32.4 g (0.98 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 98%.
[Example 2-2]
220 g of 20% by mass NaOH aqueous solution (1.1 mol of NaOH) was charged into a 1 L glass reactor and stirred at 20 ° C. While stirring this reaction solution, hydroxylamine sulfate 8
A solution prepared by dissolving 2.1 g (1.0 mol) and 3,47-dihydroxybenzoic acid 0.0547 g (0.355 mmol) in 465 g (25.8 mol) of H ₂ O was added over about 40 minutes. And added. After the addition, the mixture was further reacted at 20 ° C. for 3 hours.

As a result of analyzing the reaction solution by hydrochloric acid titration, the hydroxylamine concentration was 4.2% by mass. Therefore, the obtained hydroxylamine was 32.4 g (0.98 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 98%.
[Example 2-3]
220 g of 20% by mass NaOH aqueous solution (1.1 mol of NaOH) and 0.0220 g (0.143 mmol) of 3,4-dihydroxybenzoic acid were charged into a 1 L glass reactor and stirred at 20 ° C. While stirring this reaction solution, 82.1 g of hydroxylamine sulfate (
1.0 mol), and 0.0547 g (0.355 mmol) of 3,4-dihydroxybenzoic acid dissolved in 465 g (25.8 mol) of H ₂ O are added over about 40 minutes. It was. After the addition, the mixture was further reacted at 20 ° C. for 3 hours.

As a result of analyzing the reaction solution by hydrochloric acid titration, the hydroxylamine concentration was 4.2% by mass. Therefore, the obtained hydroxylamine was 32.4 g (0.98 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 98%.
[Example 2-4]
Na-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Corporation)
Was packed into a polytetrafluoroethylene column, and a 1N-HCl aqueous solution was passed through it to convert it into an H type, and further, it was sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by using the same method as in Example 2-1 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ]. As a result of analyzing the obtained aqueous solution by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), each concentration of impurities Na and Ca was 10 mass ppb or less.
[Example 2-5]
A similar result was obtained when the same operation as in Example 2-4 was performed except that a 1N—H ₂ SO ₄ aqueous solution was used instead of the 1N—HCl aqueous solution.
[Example 2-6]
Cl type strongly basic anion exchange resin (Amberlite IRA900 manufactured by Organo Corporation)
J) was packed in a polytetrafluoroethylene column, and a 1N-NaOH aqueous solution was passed through it to convert it into an OH type, followed by sufficient washing with H ₂ O. Through this strong basic anion exchange resin, an aqueous solution of hydroxylamine obtained by removing impurities cations obtained by the same method as in Example 2-4 was circulated at a space velocity (SV) = 1 [h ⁻¹ ]. I let you.

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 4.0% by mass. Moreover, as a result of analyzing the obtained aqueous solution by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), each concentration of the sulfate ion and the chlorine ion as impurities was 1.0 mass ppm or less. . Similarly, the obtained aqueous solution was analyzed by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.). As a result, the concentration of Fe as an impurity was 10 mass ppb or less.
[Example 2-7]
3,4-Dihydroxybenzoic acid was added to an aqueous solution of hydroxylamine obtained by the same method as in Example 2-6 so as to be 600 ppm by mass with respect to hydroxylamine, and further concentrated by distillation under reduced pressure. . The degree of vacuum was adjusted so that the tower bottom temperature was 30 ° C. or less, water was extracted from the tower top, and an aqueous solution having a higher hydroxylamine concentration was recovered from the tower bottom.

As a result of analyzing the obtained tower bottom liquid by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%.
[Example 2-8]
Na-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Corporation)
Was packed into a polytetrafluoroethylene column, and a 1N-HCl aqueous solution was passed through it to convert it into an H type, and further, it was sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by using the same method as in Example 2-7 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. Moreover, as a result of analyzing the obtained aqueous solution by ICP-MS (Seiko Instruments Co., Ltd. SPQ-900 type | mold), each concentration of impurity Na and Ca was 10 mass ppb or less.
[Example 2-9]
Cl type strongly basic anion exchange resin (Amberlite IRA900 manufactured by Organo Corporation)
J) was packed in a polytetrafluoroethylene column, and a 1N-NaOH aqueous solution was passed through the column to convert it into an OH type, followed by sufficient washing with H ₂ O. Through this strong basic anion exchange resin, an aqueous solution of hydroxylamine obtained by removing impurities cations obtained by the same method as in Example 2-8 was distributed at a space velocity (SV) = 1 [h ⁻¹ ]. I let you.

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. Moreover, as a result of analyzing the obtained aqueous solution by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), each concentration of the sulfate ion and the chlorine ion as impurities was 1.0 mass ppm or less. . Similarly, the obtained aqueous solution was analyzed by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.). As a result, the concentration of Fe as an impurity was 10 mass ppb or less.
[Example 2-10]
A monobed resin (Ultrapure Water Amberlite ESG-1 manufactured by Organo Corporation) was packed in a polytetrafluoroethylene column and thoroughly washed with H ₂ O. An aqueous solution of hydroxylamine obtained in the same manner as in Example 2-7 was added to this monobed resin with a space velocity (
SV) = 1 [h ⁻¹ ].

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. As a result of analysis by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), each concentration of impurity Na, Ca and Fe was 10 mass ppb or less. As a result of analysis by anion chromatography (SHODEX IC SI-90 4E manufactured by Showa Denko KK), the respective concentrations of impurity sulfate ions and chloride ions were 1.0 mass ppm or less.
[Comparative Example 1]
30.8 g (0.550 mol) of CaO, 1,10-phenanthroline monohydrate
0226 g (0.114 mmol) and H ₂ O 175 g (9.70 mol) were charged into a 1 L glass reactor and stirred at 20 ° C. The pH of the reaction solution at this time was 12.8. While stirring this reaction solution, 82.1 g (1.0 mol) of hydroxylamine sulfate, 1
, 10-phenanthroline monohydrate 0.0226 g (0.114 mmol) dissolved in 123 g (6.83 mol) of H ₂ O was added while maintaining the pH of the reaction solution at 7 or higher. It was. The time required for the addition was about 40 minutes. After the addition, the mixture was further reacted at 20 ° C. for 3 hours. The final pH of the reaction solution was 12.2.

  As a result of analyzing the obtained reaction liquid by hydrochloric acid titration, the hydroxylamine in the reaction liquid was 31.3 g (0.95 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 95%. It was.

According to the production method of the present invention, a high concentration of hydroxylamine can be produced safely in a high yield, and the obtained hydroxylamine comprises a raw material for a pharmaceutical and agrochemical intermediate, a reducing agent, a metal surface treatment agent, It can be widely used in fiber processing, dyeing, electronic industry, and the like.

Claims (20)

In the presence of a stabilizer, by reacting a salt of hydroxylamine with an alkali compound saw including a reaction step of obtaining a hydroxylamine,
The stabilizer is 3,4-dihydroxybenzoic acid;
The method for producing hydroxylamine , wherein a mass ratio of the stabilizer to the salt of hydroxylamine (stabilizer / hydroxylamine salt) is 1.0 x ^{10-9 to} 1.0. . The method for producing hydroxylamine according to claim 1 , wherein the reaction step is performed by adding a hydroxylamine salt to a reaction solution containing an alkali compound. The method for producing hydroxylamine according to claim 1 or 2 , wherein the reaction step is performed while maintaining the pH of the reaction solution at 7 or more. The method for producing hydroxylamine according to any one of claims 1 to 3 , wherein a reaction temperature in the reaction step is in a range of 0C to 80C. The method for producing hydroxylamine according to any one of claims 1 to 4 , wherein the reaction step is performed in the presence of a solvent containing water and / or alcohol. The hydroxylamine salt according to any one of claims 1 to 5 , wherein the salt of hydroxylamine is at least one compound selected from the group consisting of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate and hydroxylamine phosphate. Production method. The method for producing hydroxylamine according to any one of claims 1 to 6 , wherein the alkali compound is at least one compound selected from the group consisting of an alkali metal compound, an alkaline earth metal compound, ammonia and an amine. The method for producing hydroxylamine according to any one of claims 1 to 7 , comprising a purification step for purifying hydroxylamine by ion exchange and a concentration step for concentrating hydroxylamine at the bottom of the column by distillation. The method for producing hydroxylamine according to claim 8 , wherein the purification step is performed within a range of 0C to 70C. 10. The production of hydroxylamine according to claim 8 or 9 , wherein at least part of the hydroxylamine solution obtained by the purification step is used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as a reaction raw material. Method. The method for producing hydroxylamine according to claim 8 , wherein the concentration step is performed within a range of 0 ° C to 70 ° C. The production of hydroxylamine according to claim 8 or 11 , wherein at least a part of the hydroxylamine solution obtained by the concentration step is used as a solvent for dissolving or suspending a salt of hydroxylamine and / or an alkali compound as a reaction raw material. Method. The method for producing hydroxylamine according to any one of claims 8 to 12 , wherein each of the steps is performed in the order of the reaction step, the purification step, and the concentration step. The method for producing hydroxylamine according to any one of claims 1 to 13 , further comprising a separation step of separating hydroxylamine from an insoluble substance. The method for producing hydroxylamine according to claim 14 , wherein the separation step is performed within a range of 0 ° C to 80 ° C. 16. The production of hydroxylamine according to claim 14 or 15 , wherein at least a part of the reaction liquid from which the insoluble substance has been separated in the separation step is used as a solvent for dissolving or suspending a salt and / or alkali compound of hydroxylamine as a reaction raw material. Method. The method for producing hydroxylamine according to any one of claims 14 to 16 , wherein each step is performed in the order of the reaction step, the separation step, the purification step, and the concentration step. The method for producing hydroxylamine according to claim 17 , further comprising a purification step of purifying hydroxylamine by ion exchange after the concentration step. The method for producing hydroxylamine according to claim 18 , wherein the purification step after the concentration step is performed within a range of 0 ° C to 70 ° C. The method for producing hydroxylamine according to any one of claims 8 to 19 , wherein each step is performed in the presence of a stabilizer.