JP4578999B2 - Method for producing hydroxylamine - Google Patents

Description

  The present invention relates to a method for producing high-purity hydroxylamine when producing hydroxylamine.

  Hydroxylamine and its salts are used in a wide range of industrial applications such as raw materials for medical and agrochemical intermediates, reducing agents, metal surface treatment agents, fiber treatment, and dyeing. In general, relatively stable salts of hydroxylamine are produced and used because they have very unstable properties such as being easily decomposed under conditions such as high temperature or high concentration in the presence of (especially heavy metal ions). Has been.

  However, in many applications, hydroxylamine is preferred over hydroxylamine salts. In the electronics industry, high-purity hydroxylamine with less metal impurities is required. Therefore, attempts have been made to produce high-purity hydroxylamine aqueous solutions.

  For example, in Japanese Translation of PCT International Publication No. 2002-503633 (Patent Document 1), a hydroxyl group-type anion exchanger is treated at least once, a stabilizer is added to the treated hydroxylamine solution, and then the hydroxylamine solution is acidified. A method for producing an aqueous hydroxylamine solution substantially free of metal ions, which is treated at least once with a cation exchanger of

  In JP-T-2001-510133 (Patent Document 2), an aqueous solution of hydroxylamine is passed through a strong acid ion exchange resin bed, and then passed through a strong base anion exchange resin bed to produce a hydroxylamine solution containing no metal ions. A method is described.

However, the above method has a problem that the removal is insufficient depending on the type of impurities.
JP-T-2002-503633 JP 2001-510133 A

  An object of the present invention is to provide a method for producing hydroxylamine having a high purity by purifying hydroxylamine.

  As a result of intensive studies to solve the above problems, the present inventors have found that a high-purity hydroxylamine can be produced by purifying a hydroxylamine solution through a monobed resin bed, thereby completing the present invention. It came.

By using the method for producing hydroxylamine of the present invention, high-purity hydroxylamine can be obtained. Such knowledge was discovered for the first time by the present inventors.
The present invention has been made based on the above findings, and relates to the following [1] to [19].
[1] A method for producing hydroxylamine, comprising a purification step 1 in which a hydroxylamine solution is purified by passing through a monobed resin bed.
[2] The method for producing hydroxylamine according to [1], wherein the purification step 1 is performed within a range of 0 ° C to 70 ° C.
[3] It includes a purification step 2 for purification by passing a hydroxylamine solution through at least one ion exchange resin bed selected from the group consisting of a cation exchange resin bed, an anion exchange resin bed and a chelate resin bed [1] Or the manufacturing method of the hydroxylamine as described in [2].
[4] The method for producing hydroxylamine according to [3], wherein the purification step 2 is performed within a range of 0 ° C to 70 ° C.
[5] The method for producing hydroxylamine according to any one of [1] to [4], wherein the hydroxylamine solution is obtained by a reaction step in which a hydroxylamine salt is reacted with an alkali compound.
[6] The method for producing hydroxylamine according to [5], wherein the reaction step is a step in which a salt of hydroxylamine is added to a reaction solution containing an alkali compound.
[7] The method for producing hydroxylamine according to [5] or [6], wherein the reaction step is performed while maintaining the pH of the reaction solution at 7 or more.
[8] The method for producing hydroxylamine according to any one of [5] to [7], wherein the reaction temperature in the reaction step is in the range of 0 ° C to 80 ° C.
[9] The method for producing hydroxylamine according to any one of [5] to [8], wherein the reaction step is performed in the presence of a solvent containing water and / or alcohol.
[10] The salt of hydroxylamine is any one of [5] to [9], which is at least one compound selected from the group consisting of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate, and hydroxylamine phosphate. A method for producing the hydroxylamine as described.
[11] The hydroxylamine according to any one of [5] to [9], wherein the alkali compound is at least one compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, ammonia and amines. Production method.
[12] The method for producing hydroxylamine according to any one of [1] to [11], which includes a separation step of separating hydroxylamine and an insoluble substance.
[13] The method for producing hydroxylamine according to [12], wherein the separation step is performed within a range of 0 ° C to 80 ° C.
[14] The method for producing hydroxylamine according to any one of [1] to [13], comprising a distillation step of distilling the hydroxylamine solution and obtaining hydroxylamine by the distillation.
[15] The method for producing hydroxylamine according to [14], wherein the distillation step is performed within a range of 0 ° C to 70 ° C.
[16] The method for producing hydroxylamine according to [14], wherein each step of producing the hydroxylamine is performed in the order of a reaction step, a separation step, a purification step 2, a purification step 1 and a distillation step.
[17] The method for producing hydroxylamine according to [16], further comprising a purification step 1 after the distillation step.
[18] The method for producing hydroxylamine according to [16] or [17], further comprising the purification step 2 after the distillation step.
[19] The method for producing hydroxylamine according to any one of [1] to [18], wherein each of the steps is performed in the presence of a stabilizer.

  According to the present invention, high-purity hydroxylamine can be produced.

According to the present invention, high-purity hydroxylamine can be produced by a method including purification step 1 in which a hydroxylamine solution is purified by passing through a monobed resin bed.
Hereinafter, the method for producing hydroxylamine according to the present invention will be described in more detail.
Purification step 1;
The method for producing hydroxylamine of the present invention includes purification step 1 in which the hydroxylamine solution is purified by passing through a monobed resin bed.

  In the production method of the present invention, the monobed resin used in the monobed resin bed is not particularly limited as long as it is commercially available or industrially available, but preferably has few metal impurities. This is because the presence of metal impurities may accelerate the decomposition of hydroxylamine. However, it may contain impurities as long as it does not promote the decomposition of hydroxylamine and can be removed by a purification process or the like, or has no problem in the use of the produced hydroxylamine.

  The monobed resin used in the present invention is a resin obtained by mixing a cation exchange resin and an anion exchange resin, preferably a resin obtained by mixing a strong acid cation exchange resin and a strongly basic anion exchange resin. It is done. For example, Amberlite (manufactured by Organo Corporation, manufactured by Rohm and Haas), Diaion (manufactured by Mitsubishi Chemical Corporation), Ionac (manufactured by Sibron Chemicals) and the like can be mentioned.

The mixing ratio of the cation exchange resin and the anion exchange resin is not particularly limited, and can be determined, for example, depending on the amount of the impurity cation or anion.
In the purification step 1, hydroxylamine is used as a hydroxylamine solution.

The concentration of the hydroxylamine solution is not particularly limited, but is preferably 0.1% by mass to 80% by mass, and more preferably 1.0% by mass to 60% by mass.
Moreover, water and / or an organic solvent can be used for the solvent of a hydroxylamine solution. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols, and the like. In these, it is preferable to use water and / or alcohol.

The refinement | purification process 1 can be performed by a well-known method, for example, a batch type, a semibatch type, a continuous type etc.
The space velocity of the hydroxylamine solution in the purification step 1 is not particularly limited, but is preferably 0.01 h ^{−1 to} 100 h ⁻¹ , more preferably 0.1 h ^{−1 to} 10 h ⁻¹ . If the space velocity is greater than 100 h ⁻¹ , problems such as insufficient removal of impurities and rapid breakthrough may occur. On the other hand, when the space velocity is less than 0.01 h ⁻¹ , problems such as a decrease in productivity may occur.

  As temperature which performs the refinement | purification process 1, 0 to 70 degreeC is preferable, More preferably, it exists in the range of 5 to 50 degreeC. When the temperature is higher than 70 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the temperature is lower than 0 ° C., there may be a problem that energy required for cooling increases.

  The monobed resin bed used in the purification step 1 is effective for removing impurities that are difficult to remove even when a cation exchange resin bed and an anion exchange resin bed are combined. Examples of impurities that are difficult to remove include amphoteric compounds such as Zn.

  The monobed resin bed is preferably pretreated, but is preferably separated into a cation exchange resin and an anion exchange resin before the pretreatment. The method for separating the cation exchange resin and the anion exchange resin can be performed using, for example, the density difference between the cation exchange resin and the anion exchange resin.

Further, it is preferable that the separated cation exchange resin is pretreated with an acid to form an H type, and the separated anion exchange resin is pretreated with an alkali to obtain an OH type.
The H-type cation exchange resin and the OH-type anion exchange resin are preferably washed. As the liquid to be washed, it is preferable to use the same solvent as the hydroxylamine solution.

The space velocity in the pretreatment and washing is not particularly limited, but is preferably 0.01 h ^{−1 to} 100 h ⁻¹ , more preferably 0.1 h ^{−1 to} 10 h ⁻¹ . When the space velocity is greater than 100 h ⁻¹ , problems such as an increase in the amount of liquid used for cleaning may occur. On the other hand, when the space velocity is less than 0.01 h ⁻¹ , there may be a problem that it takes time for cleaning.

The pretreatment and washing can be performed by a known method, for example, a batch system, a semi-batch system, a continuous system, or the like.
And as temperature of pre-processing and washing | cleaning, 0 to 70 degreeC is preferable, More preferably, it exists in the range of 5 to 50 degreeC. When the temperature is higher than 70 ° C., problems such as decomposition of the monobed resin may occur. On the other hand, when the temperature is lower than 0 ° C., there may be a problem that energy required for cooling increases.

The washed cation exchange resin and anion exchange resin are preferably mixed uniformly and then contacted with a hydroxylamine solution.
A part of the hydroxylamine solution obtained in the purification step 1 may be used as a solvent for dissolving or suspending the hydroxylamine salt and / or alkali compound as a reaction raw material.

In the method for producing hydroxylamine of the present invention, the purification step 1 can be performed in the presence of a stabilizer. A well-known thing can be used for a stabilizer. For example, 8-hydroxyquinoline, N-hydroxyethylethylenediamine-N, N, N′-triacetic acid, glycine, ethylenediaminetetraacetic 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-hydroxyethylimino Diacetic acid, N, N′-dihydroxyethylglycine, diethylenetriaminepentaacetic acid, ethylenebis (oxyethylenenitrilo) tetraacetic acid, bishexamethylenetriaminepentaacetic acid, hexamethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, tris (2-amino) Ethyl) amine hexaacetic acid, iminodiacetic acid, polyethyleneimine, polypropyleneimine, -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, benzo Triazole, flavone, morin, quercetin, gossypetin, robitinen, luteolin, fisetin, apigenin, galangin, chrysin, flavonol, pyrogallol, oxyanthraquinone, 1,2-dioxyanthraquinone, 1,4-dioxyanthraki 1,2,4-trioxyanthraquinone, 1,5-dioxyanthraquinone, 1,8-dioxyanthraquinone, 2,3-dioxyanthraquinone, 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
-Of dihydroxyquinaldine, anthocyan, pelargonidin, cyanidin, delphinidin, peonidin, petunidin, malvidin, catechin, sodium thiosulfate, nitrilotriacetic acid, 2-hydroxyethyl disulfide, 1,4-dimercapto-2,3-butanediol, thiamine Hydrochloride, catechol, 4-t-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, 2-hydroxypyridine-N-oxide, 1,2-dimethyl-3-hydroxypyridin-4-one, 4-methylpyridine-N -Oxide, 6-me Rupyridine-N-oxide, 1-methyl-3-hydroxypyridin-2-one, 2-mercaptobenzothiazole, 2-mercaptocyclohexylthiazole, 2-mercapto-6-t-butylcyclohexylthiazole, 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, thiopropiona Imide, 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-thiobarbi Tool acid, thiocyanuric acid, 2-mercaptoquinoline, thiocoumazone, thiocumothiazone, thiosaccharin, 2-mercaptobenzimidazole, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, trimethyl phosphite, triethyl phosphite , Like triphenylphosphine.

  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 hydroxylamine by metal impurities or the like can be suppressed.

The stabilizer used in the refining step 1 is not particularly limited as long as it is commercially available or industrially available, but preferably has few metal impurities.
The mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) is suitably 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. 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 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. 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 purification temperature.
Purification step 2;
The method for producing hydroxylamine according to the present invention is a purification in which a hydroxylamine solution is passed through at least one ion exchange resin bed selected from the group consisting of a cation exchange resin bed, an anion exchange resin bed and a chelate resin bed. Step 2 is preferably included.

In the refinement | purification process 2, purification by a cation exchange resin bed can be performed by well-known methods, such as a strong acidic cation exchange resin and a weak acidic cation exchange resin. It is preferable to use the cation exchange resin in an H-type by performing an acid treatment in advance.

  Purification by the anion exchange resin bed 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.

  Further, purification using a chelate exchange resin bed 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 a cation exchange resin bed, an anion exchange resin bed, and a chelate exchange resin bed. For example, an anion exchange resin bed may be combined after the cation exchange resin bed, and a cation exchange resin bed may be combined after the anion exchange resin bed.

In purification step 2, hydroxylamine is used as a hydroxylamine solution.
The concentration of the hydroxylamine solution is not particularly limited, but is preferably 0.1% by mass to 80% by mass, and more preferably 1.0% by mass to 60% by mass.

  Moreover, water and / or an organic solvent can be used for the solvent of a hydroxylamine solution. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols, and the like. In these, it is preferable to use water and / or alcohol.

The refinement | purification process 2 can be performed by a well-known method, for example, a batch type, a semibatch type, a continuous type etc.
The space velocity of the hydroxylamine solution in the purification step 2 is not particularly limited, but is preferably 0.01 h ^{−1 to} 100 h ⁻¹ , more preferably 0.1 h ^{−1 to} 10 h ⁻¹ . If the space velocity is greater than 100 h ⁻¹ , problems such as insufficient removal of impurities and rapid breakthrough may occur. On the other hand, when the space velocity is less than 0.01 h ⁻¹ , problems such as a decrease in productivity may occur.

  As temperature which performs the refinement | purification process 2, 0 to 70 degreeC is preferable, More preferably, it is desirable to exist in the range of 5 to 50 degreeC. When the temperature is higher than 70 ° C., problems such as decomposition of hydroxylamine may occur. On the other hand, when the temperature is lower than 0 ° C., there may be a problem that energy required for cooling increases.

  A part of the hydroxylamine solution obtained in the purification step 2 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 2 is preferably carried out in the presence of a hydroxylamine stabilizer as in the purification step 1. A stabilizer may be added in the purification step 2, or the stabilizer from the previous step may be used as it is.

  As the stabilizer, the same type as the stabilizer used in the purification step 1 or a different type can be selected according to the situation and use. 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 amount of stabilizer is such that the mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) is in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use so that it becomes inside. 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 purification step 2 may be performed in any order in combination with the purification step 1, and the purification step 1 and the purification step 2 may be performed twice or more.
In the method for producing hydroxylamine of the present invention, the hydroxylamine solution that can be used in the purification step 1 or 2 can be obtained, for example, by the following reaction step.
Reaction step;
The reaction step for obtaining a hydroxylamine solution is preferably a reaction step for reacting a hydroxylamine salt with an alkali compound.

The hydroxylamine salt used in the above reaction step includes hydroxylamine sulfate, hydrochloride, nitrate, phosphate, hydrobromide, sulfite, phosphite, perchlorate, carbonate, Examples include salts of inorganic acids such as hydrogen carbonate, and salts of organic acids such as formate, acetate, and propionate. Among these, hydroxylamine sulfate (NH ₂ OH · 1 / 2H ₂ SO ₄ ), hydrochloride (NH ₂ OH · HCl), nitrate (NH ₂ OH · HNO ₃ ) and phosphate (NH ₂ OH) • At least one salt selected from the group consisting of 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, impurities may be contained as long as they do not affect the decomposition of the hydroxylamine salt or hydroxylamine and can be removed by a purification process or the like, or have no problem in using 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. Moreover, you may use at least one part of the filtrate which isolate | separated the insoluble salt etc. which arose in reaction 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 reaction step is preferably at least one compound selected from the group consisting of compounds containing alkali metals, compounds containing alkaline earth metals, ammonia and amines.

  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. It is a thing.

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 reaction step is not limited to the above 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 above reaction step 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 excess alkali compounds and recovery of many unreacted alkali compounds 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. Moreover, you may use at least one part of the filtrate which isolate | separated the insoluble salt etc. which arose in reaction 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.

  In the method for producing hydroxylamine of the present invention, the reaction step of obtaining a hydroxylamine solution by reacting a hydroxylamine salt with an alkali compound is preferably performed in the presence of a stabilizer. A well-known thing can be used for a stabilizer. For example, the same type or different type of stabilizer used in the purification step 1 can be selected depending on the situation of the reaction step, the use of the hydroxylamine to be produced, and the like. By selecting 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 salt (stabilizer / hydroxylamine salt) of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.00. It is suitable to use in an amount that is within the range of 1. When the mass ratio is smaller than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of the hydroxylamine salt or hydroxylamine by metal impurities may not be obtained, and the mass ratio is larger than 1.0. In some cases, it may be necessary to remove or recover excess stabilizer.

  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.

  The method for adding the stabilizer in the reaction step is not particularly limited and can be performed by a known method. For example, it may be introduced into the reactor in advance to start the reaction, or may be added during the reaction as necessary. Further, the stabilizer may be added by dissolving or suspending it in a solvent together with an alkali compound and / or a hydroxylamine salt.

  The hydroxylamine solution is preferably obtained by a reaction step in which a hydroxylamine salt is added and reacted in a reaction solution in which an alkali compound is dissolved or suspended in a solvent as described above. 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 becomes difficult to be adsorbed or taken in by the salt.

  Furthermore, when adding a hydroxylamine salt to a 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 the hydroxylamine salt is maintained. It is desirable to add. 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-produced salt, and is difficult to be adsorbed or incorporated into the by-produced insoluble salt.

However, in the above reaction step, an alkali compound may be added to the reaction solution in which the hydroxylamine salt is dissolved or suspended to cause the reaction.
Furthermore, the reaction step may be a reaction step in which a hydroxylamine salt and an alkali compound are supplied and reacted simultaneously. 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 from 0 ° C to 80 ° C, more preferably from 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 heat generated with the reaction between the salt of hydroxylamine and the alkali compound can be kept out of the system with water, hot water or a heat medium, so that the reaction temperature can be kept 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.

Said reaction process can be performed by a well-known method, for example, a batch type, a semibatch type, a continuous type etc.
Separation step;
The method for producing hydroxylamine of the present invention preferably includes a step of 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. A separation step of separating the substance may be included.

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 with a solvent, hydroxylamine attached or taken into the insoluble material can be recovered.
As the solvent for washing the insoluble substance, 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 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 hydroxylamine stabilizer as in the reaction step. A new stabilizer may be added in the separation step, or the stabilizer from the previous step may be used as it is.

  As the stabilizer, the same type as the stabilizer used in the reaction step or a different type can be selected according to the situation and use. 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 amount of stabilizer is such that the mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) is in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use so that it becomes inside. When the mass ratio is smaller than 1.0 × 10 ^{−9, the} effect of suppressing the decomposition reaction of hydroxylamine by metal impurities may not be obtained, and the mass ratio is 1
. If it is greater than 0, it may be necessary to remove or recover excess stabilizer.

Said separation process can be performed by a well-known method, for example, a batch type, a semibatch type, a continuous type.
Each process for producing the hydroxylamine is preferably performed in the order of a reaction process, a separation process, a purification process 2 and a purification process 1.
Distillation step;
The method for producing hydroxylamine of the present invention preferably includes a distillation step of distilling a hydroxylamine solution and obtaining hydroxylamine by the distillation.

As a distillation method in the distillation step, a known method such as simple distillation, multistage distillation, steam distillation, or flash distillation can be used.
Further, hydroxylamine can be obtained at the top, side or bottom of the distillation column depending on the purpose.

  For example, a hydroxylamine solution can be obtained from the top of the column by simple distillation, steam distillation or the like. Further, for example, by distilling water from the top of the column by multistage distillation, a hydroxylamine solution having a high concentration can be obtained from the bottom of the column.

  As the distillation column, a known distillation column such as a plate type distillation column or a packed distillation column can be used. Examples of the structure of the shelf of the shelf type distillation column include a bubble bell tray, a perforated plate tray, a valve tray, a super flack tray, and a max fract tray. Moreover, as a packing of a packed distillation column, a regular packing and an irregular packing are mentioned. Examples of the regular packing include a metal plate mold, a wire mesh mold, and a grid mold. Examples of the irregular packing include Raschig rings, Lessing rings, Berle saddles, Interlocks saddles, terralet, pole rings, flexi rings, cascade rings, and the like.

  The temperature in the distillation step is preferably from 0 to 70 ° C., more preferably from 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 pressure of a distillation process is decided by relationship with temperature, 0.5-60 kPa is preferable at the pressure of a tower bottom part, More preferably, it exists in the range of 0.8-40 kPa.
A part of the hydroxylamine solution obtained at the bottom of the column in the distillation step may be used as a solvent for dissolving or suspending a hydroxylamine salt and / or an alkali compound preferably used as a reaction raw material for hydroxylamine.

  In addition, a part or all of the hydroxylamine solution obtained from the top or side of the distillation column is used as a solvent for dissolving or suspending a hydroxylamine salt and / or alkali compound that is preferably used as a reaction raw material for hydroxylamine. It may be used.

The said distillation process can be performed by well-known methods, such as a batch type, a semibatch type, and a continuous type.
It is preferable to perform the said distillation process in presence of the stabilizer of a hydroxylamine similarly to each said process. A new stabilizer may be added in the distillation step, or the stabilizer from the previous step may be used as it is.

As the stabilizer, the same type as the stabilizer used in each step or a different type can be selected depending on the situation and use. 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 amount of stabilizer is such that the mass ratio of stabilizer to hydroxylamine (stabilizer / hydroxylamine) is in the range of 1.0 × 10 ^{−9 to} 1.0, preferably 1.0 × 10 ^{−8 to} 0.1. It is suitable to use so that it becomes inside. 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.

Each process for producing the hydroxylamine is preferably performed in the order of a reaction process, a separation process, a purification process 2, a purification process 1, and a distillation process.
Furthermore, in the method for producing hydroxylamine of the present invention, it is preferable to further perform a purification step 1 in which the hydroxylamine obtained by the distillation step is purified by passing the hydroxylamine solution through a monobed resin bed.

  In the method for producing hydroxylamine of the present invention, the hydroxylamine obtained by the distillation step is at least one ion exchange selected from the group consisting of a cation exchange resin bed, an anion exchange resin bed, and a chelate resin bed. It is preferable to further perform a purification step 2 of purification by passing a hydroxylamine solution through the resin bed.

The method for producing hydroxylamine of the present invention includes, for example,
(1) A reaction step in which a hydroxylamine salt is reacted with an alkali compound to obtain a hydroxylamine solution.
(2) Purification step 1 for purification by passing a monobed resin bed through a hydroxylamine solution.
It is preferable to contain.

And the manufacturing method of the hydroxylamine of this invention,
(3) Purification step 2 for purification by passing a hydroxylamine solution through at least one ion exchange resin bed selected from the group consisting of a cation exchange resin bed, an anion exchange resin bed and a chelate resin bed.
It is preferable to contain.

Moreover, it is preferable that the manufacturing method of the hydroxylamine of this invention includes the distillation process which obtains a hydroxylamine by (4) distillation.
Furthermore, the method for producing hydroxylamine of the present invention may include (5) a separation step for separating hydroxylamine and an insoluble substance, and this step is preferably performed after the reaction step.

Each of the above steps may be performed in any order after performing the step (1), and the same step may be performed twice or more.
By using the method of the present invention, a hydroxylamine having a concentration of 10% by mass or more can be obtained. Moreover, the hydroxylamine of the density | concentration of 20 mass% or more can also be obtained, and also the hydroxylamine of the density | concentration of 40 mass% or more can also be obtained.

  By using the method of the present invention, a hydroxylamine having a content of each metal contained as an impurity of 1 mass ppm or less can be obtained. Moreover, the hydroxylamine whose content of each metal is 0.1 mass ppm or less can also be obtained, and also the hydroxylamine whose content of each metal is 0.01 mass ppm or less can be obtained. Examples of metals that may be included as impurities include alkali metals derived from the alkali compounds used in the reaction process, alkaline earth metals, and Fe that significantly accelerates the decomposition of hydroxylamine.

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

  To the hydroxylamine finally obtained by the present invention, a stabilizer may be newly added, or the stabilizer from the previous step may be used as it is. As the stabilizer, the same type as the stabilizer used in the reaction step or a different type can be selected according to the situation and use. By adding a stabilizer, side reactions such as decomposition of hydroxylamine due to metal impurities and the like are suppressed, and the stability of hydroxylamine is improved.

<Example>
Hereinafter, although it demonstrates more concretely using an Example, this invention is not limited to these Examples.

[Example 1-1]
61.7 g (1.1 mol) of CaO, 1.45 g (0.01 mol) of 8-hydroxyquinoline and 332 g (18.4 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, a solution prepared by dissolving 164 g (2.0 mol) of hydroxylamine sulfate in 246 g (13.7 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 65.4 g (1.98 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 99%. It was.

[Example 1-2]
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 66.1 g (3.67 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 by hydrochloric acid titration, the hydroxylamine concentration of the liquid mixture was 7.4% by mass. Therefore, the obtained hydroxylamine was 64.7 g (1.96 mol), and the yield of hydroxylamine based on hydroxylamine sulfate was 98%.

[Example 1-3]
A monobed resin (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 by using the same method as in Example 1-2 was passed through this monobed 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, Ca, Fe, and Zn was 10 mass ppb or less. Anion chromatography (SHODEX IC manufactured by Showa Denko KK)
As a result of analysis by SI-90 4E), the respective concentrations of impurity sulfate ions and chloride ions are 1.
It was 0 mass ppm or less.

[Example 1-4]
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 1-2 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

Next, Cl type strongly basic anion exchange resin (Amberlite IRA manufactured by Organo Corporation)
900J) was packed into 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. The aqueous solution of hydroxylamine obtained by passing through the strong acid cation exchange resin was passed through the strongly basic anion exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

Furthermore, a monobed resin (Ultrapure Water Amberlite ESG-1 manufactured by Organo Corp.) was packed in a polytetrafluoroethylene column and sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by passing through this monobed resin through a strongly basic anion exchange resin was passed 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, Ca, Fe, and Zn was 10 mass ppb or less. Anion chromatography (SHODEX I manufactured by Showa Denko KK)
As a result of analysis by CSI-90 4E), the respective concentrations of impurity sulfate ion and chlorine ion were 1.0 mass ppm or less.

[Example 1-5]
The same results were obtained as in Example 1-4, except that a 1N—H ₂ SO ₄ aqueous solution was used instead of the 1N—HCl aqueous solution.

[Example 1-6]
An aqueous solution of hydroxylamine obtained by the same method as in Example 1-4 was further concentrated by distillation under reduced pressure. The degree of vacuum was adjusted so that the tower bottom temperature was 40 ° 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%. As a result of analysis by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), impurity Na concentration is 30 mass ppb, Ca concentration is 20 mass ppb, Fe concentration is 15 mass ppb, and Zn concentration is 15 mass. ppb. Furthermore, as a result of analysis by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), the impurity sulfate ion concentration was 1.5 mass ppm and the chlorine ion concentration was 1.5 mass ppm or less. .

[Example 1-7]
A monobed resin (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 by using the same method as in Example 1-6 was passed through this monobed 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%. And as a result of analyzing by ICP-MS (SPQ-900 type | mold by Seiko Instruments Inc.), each concentration of impurity Na, Ca, Fe, and Zn was 10 mass ppb or less. Furthermore, anion chromatography (SHODEX I manufactured by Showa Denko KK)
As a result of analysis by CSI-90 4E), the respective concentrations of impurity sulfate ion and chlorine ion were 1.0 mass ppm or less.

[Practical example 1-8]
It carried out similarly to Example 1-7 except having used another monobed resin (Amberlite ESG-2 by Organo Corporation) instead of the monobed resin (Amberlite ESG-1 by Organo Corporation). .

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, Ca, Fe, and Zn was 10 mass ppb or less. Anion chromatography (SHODEX I manufactured by Showa Denko KK)
As a result of analysis by CSI-90 4E), the respective concentrations of impurity sulfate ion and chlorine ion were 1.0 mass ppm or less.

[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 by using the same method as in Example 1-6 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

Next, Cl type strongly basic anion exchange resin (Amberlite IRA manufactured by Organo Corporation)
900J) was packed into 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. An aqueous solution of hydroxylamine obtained by passing the strong basic anion exchange resin through the strongly acidic cation exchange resin was passed at a space velocity (SV) = 1 [h ⁻¹ ].

Furthermore, a monobed resin (Amberlite ESG-1 manufactured by Organo Corporation) was packed in a polytetrafluoroethylene column and sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by passing the monobasic resin through the strongly basic anion exchange resin was passed 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%. And as a result of analyzing by ICP-MS (SPQ-900 type | mold by Seiko Instruments Inc.), each concentration of impurity Na, Ca, Fe, and Zn was 10 mass ppb or less. Furthermore, as a result of analyzing by anion chromatography (SHODEX IC SI-90 4E manufactured by Showa Denko KK), each concentration of impurity sulfate ion and chloride ion was 1.0.
It was below mass ppm.

[Example 2-1]
220 g of 20 mass% NaOH aqueous solution (NaOH 1.1 mol) and 8-hydroxyquinoline 0.73 g (0.005 mol) were charged into a 1 L glass reactor and stirred at 20 ° C. While stirring this reaction solution, a solution prepared by dissolving 82.1 g (1.0 mol) of hydroxylamine sulfate 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]
A monobed resin (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 by using the same method as in Example 2-1 was passed through this monobed 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, Ca, Fe, and Zn 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 ion and chloride ion were 1.
It was 0 mass ppm or less.

[Example 2-3]
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 ].

Next, Cl type strongly basic anion exchange resin (Amberlite IRA manufactured by Organo Corporation)
900J) was packed into 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. An aqueous solution of hydroxylamine obtained by passing through the strong acid anion exchange resin was passed through the strongly basic anion exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

Furthermore, a monobed resin (Amberlite ESG-1 manufactured by Organo Corporation) was packed in a polytetrafluoroethylene column and sufficiently washed with H ₂ O. An aqueous solution of hydroxylamine obtained by passing the monobed resin through the strongly basic anion exchange resin was passed 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, Ca, Fe, and Zn was 10 mass ppb or less. Anion chromatography (SHODEX I manufactured by Showa Denko KK)
As a result of analysis by CSI-90 4E), the respective concentrations of impurity sulfate ion and chlorine ion were 1.0 mass ppm or less.

[Example 2-4]
A similar result was obtained when the same procedure as in Example 2-3 was performed except that a 1N—H ₂ SO ₄ aqueous solution was used instead of the 1N—HCl aqueous solution.

[Example 2-5]
An aqueous solution of hydroxylamine obtained by the same method as in Example 2-3 was further concentrated by distillation under reduced pressure. The degree of vacuum was adjusted so that the tower bottom temperature was 40 ° 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%. As a result of analysis by ICP-MS (SPQ-900 type manufactured by Seiko Instruments Inc.), impurity Na concentration was 30 mass ppb, Ca concentration was 20 mass ppb, Fe concentration was 15 mass ppb, and Zn concentration was 15 mass. ppb. Further, as a result of analysis by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), the impurity sulfate ion concentration was 1.5 mass ppm and the chlorine ion concentration was 1.5 mass ppm or less. .

[Example 2-6]
A monobed resin (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 by using the same method as in Example 2-5 was passed through this monobed 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%. And as a result of analyzing by ICP-MS (SPQ-900 type | mold by Seiko Instruments Inc.), each concentration of impurity Na, Ca, Fe, and Zn was 1 mass ppb or less. Furthermore, as a result of analysis by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), the respective concentrations of impurity sulfate ion and chloride ion were 1.
It was 0 mass ppm or less.

[Practical example 2-7]
It carried out similarly to Example 2-6 except having used another monobed resin (Amberlite ESG-2 by Organo Co., Ltd.) instead of the monobed resin (Amberlite ESG-1 by Organo Co., Ltd.). .

As a result of analyzing the obtained aqueous solution by hydrochloric acid titration, the hydroxylamine concentration was 51 mass%. And as a result of analyzing by ICP-MS (SPQ-900 type | mold by Seiko Instruments Inc.), each concentration of impurity Na, Ca, Fe, and Zn was 1 mass ppb or less. Furthermore, as a result of analysis by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), the respective concentrations of impurity sulfate ion and chloride ion were 1.
It was 0 mass ppm or less.

[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 2-5 was passed through this strongly acidic cation exchange resin at a space velocity (SV) = 1 [h ⁻¹ ].

Next, Cl type strongly basic anion exchange resin (Amberlite IRA manufactured by Organo Corporation)
900J) was packed into 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. An aqueous solution of hydroxylamine obtained by passing the strong basic anion exchange resin through the strong acid cation exchange resin was passed at a space velocity (SV) = 1 [h ⁻¹ ].

In addition, a monobed resin (Ultrapure Water Amberlite ESG-1 manufactured by Organo Corp.) was packed in a polytetrafluoroethylene column and thoroughly washed with H ₂ O. An aqueous solution of hydroxylamine obtained by passing the monobasic resin through the strongly basic anion exchange resin was passed 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%. And as a result of analyzing by ICP-MS (SPQ-900 type | mold by Seiko Instruments Inc.), each concentration of impurity Na, Ca, Fe, and Zn was 1 mass ppb or less. Furthermore, as a result of analyzing by anion chromatography (SHODEX IC SI-904E manufactured by Showa Denko KK), each concentration of impurity sulfate ion and chlorine ion was 1.0 mass ppm or less.

  According to the production method of the present invention, high-purity hydroxylamine can be produced, and the obtained hydroxylamine is obtained from raw materials for medical and agrochemical intermediates, reducing agents, metal surface treatment agents, fiber treatment, dyeing, electronic It can be used widely in industry.

Claims (14)

A reaction step of reacting a hydroxylamine salt with an alkali compound to obtain a hydroxylamine solution;
A separation step for separating hydroxylamine and insoluble substances;
Purification step 2 for purification by passing a hydroxylamine solution through at least one ion exchange resin bed selected from the group consisting of a cation exchange resin bed, an anion exchange resin bed and a chelate resin bed;
Purification step 1 for purifying the hydroxylamine solution by passing it through a monobed resin bed , and
Distilling the hydroxylamine solution, it viewed including the distillation step <br/> obtaining a hydroxylamine from the bottom of the distillation column by the distillation, the each step, the reaction step, the separation step, purification step 2, the purification step 1 and distillation A method for producing hydroxylamine, which is performed in the order of steps .   The method for producing hydroxylamine according to claim 1, wherein the purification step 1 is performed within a range of 0C to 70C. The method for producing hydroxylamine according to claim 1 or 2 , wherein the purification step 2 is performed within a range of 0C to 70C. The method for producing hydroxylamine according to any one of claims 1 to 3, wherein the reaction step is a step in which a salt of hydroxylamine is added to a reaction solution containing an alkali compound. The method for producing hydroxylamine according to any one of claims 1 to 4, 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 5 , wherein a reaction temperature in the reaction step is within a range of 0 ° C to 80 ° C. The method for producing hydroxylamine according to any one of claims 1 to 6 , 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 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. Production method. The method for producing hydroxylamine according to any one of claims 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. The method for producing hydroxylamine according to any one of claims 1 to 9, wherein the separation step is performed within a range of 0C to 80C. The method for producing hydroxylamine according to any one of claims 1 to 10, wherein the distillation step is performed within a range of 0C to 70C. The method for producing hydroxylamine according to any one of claims 1 to 11, further comprising a purification step 1 after the distillation step. The method for producing hydroxylamine according to any one of claims 1 to 12, further comprising the purification step 2 after the distillation step. The method for producing hydroxylamine according to any one of claims 1 to 13 , wherein each step is performed in the presence of a stabilizer.