A method for preparing a hydroxylamine aqueous solution by neutralizing a hydroxylamine salt

Abstract

The application discloses a method for preparing a hydroxylamine aqueous solution by a hydroxylamine salt neutralization method, and belongs to the technical field of hydroxylamine aqueous solution preparation. Specifically, a hydroxylamine salt is added into a reaction container, and is dissolved in a proper amount of deionized water; stirring is started under normal pressure; an alkali solution is added dropwise to perform a neutralization reaction; after the neutralization reaction is completed, the reaction solution is reduced-pressure filtered; a proper amount of a stabilizer is added into the filtrate; and then, reduced-pressure distillation is performed; and a distillate is the hydroxylamine aqueous solution. In the method, a pyrazolone type stabilizer is adopted, a mercapto imidazole sodium propyl sulfonate is introduced as a chelating agent, and a piperazine functional group is introduced, so that the stabilizing effect of the stabilizer can be effectively increased.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydroxylamine aqueous solution preparation, and particularly relates to a method for preparing hydroxylamine aqueous solution by hydroxylamine salt neutralization. BACKGROUND

[0002] Hydroxylamine and its salts are important chemical raw materials, which are widely used in the fields of medicine synthesis, developing technology, semiconductor cleaning and the like. Hydroxylamine can be thermally decomposed into ammonia, nitrogen, water, nitrogen oxide and the like at about 15 DEG C, so its stability is poor, and it usually exists in the form of aqueous solution.

[0003] The application file with the publication number CN115595217A provides a stable solution containing hydroxylamine, a semiconductor cleaning solution containing hydroxylamine, a preparation method and use thereof. The stable solution containing hydroxylamine includes the following components in a weight ratio: 5-30 parts of hydroxylamine and its derivatives; 1-5 parts of chelating agent; and 5-20 parts of cucurbituril and its derivatives. The hydroxylamine molecules are encapsulated by cucurbituril and its derivatives in the present application, so that the direct contact of the hydroxylamine molecules with metal ions and acidic or alkaline medium is avoided; the metal ions are complexed by using the chelating agent, so that the hydroxylamine molecules released from the cucurbituril and its derivatives will not be catalyzed to decompose by the metal ions. The present application also discloses a semiconductor cleaning solution containing hydroxylamine, which includes the stable solution containing hydroxylamine, alkali, water-soluble organic solvent and ultrapure water.

[0004] The application file with the publication number CN104129764B provides a method for preparing hydroxylamine or hydroxylamine salt from ketone, ammonia and hydrogen peroxide. The basic characteristics are as follows: the ketone is used as a circulating reaction medium, the organic solvent which is insoluble or slightly soluble in water is used as a circulating solvent medium, the heterogeneous catalytic ammonium oximation technology and the hydrolysis-extraction coupling technology are integrated, and the hydroxylamine and / or hydroxylamine salt are prepared by using ammonia, hydrogen peroxide and inorganic acid as basic raw materials.

[0005] The application file with the publication number CN110983370A relates to a method for preparing free hydroxylamine solution by electrolytic electrodialysis. The device used includes four compartments, which are an anode chamber, a raw material chamber, a product chamber and a cathode chamber, and are separated by a partition. The partitions of the four compartments are clamped and fixed in pairs, the clamped partitions are hollow frame structures, and three groups of clamped partitions are respectively fixed with a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane. An anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber. The method is as follows: continuously inputting ultrapure water into the anode chamber; continuously inputting a mixed solution of one or more of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate or hydroxylamine phosphate into the raw material chamber; continuously inputting ultrapure water into the product chamber; continuously inputting ultrapure water into the cathode chamber; and applying a constant voltage for electrolysis.

[0006] The technical material for preparing hydroxylamine based on the above disclosure can find that it causes environmental pollution in the preparation process, and also has problems of corroding equipment, introducing metal impurities affecting product quality, poor production efficiency, etc. SUMMARY

[0007] The present application aims to provide a method for preparing hydroxylamine aqueous solution by hydroxylamine salt neutralization method to solve at least one of the technical problems in the above technical background.

[0008] A method for preparing hydroxylamine aqueous solution by hydroxylamine salt neutralization method, the operation steps are:

[0009] A1: 30-50 parts by mass of hydroxylamine salt is added to a reaction vessel, dissolved with an appropriate amount of deionized water, and stirred under normal pressure. Add alkali solution dropwise and carry out neutralization reaction.

[0010] A2: After the neutralization reaction is completed, the reaction liquid is reduced pressure filtration, an appropriate amount of stabilizer is added to the filtrate, and then reduced pressure distillation is carried out. The distillate is hydroxylamine aqueous solution.

[0011] In some embodiments of the present application, the hydroxylamine salt in A1 is selected from at least one of hydroxylamine sulfate, hydroxylamine phosphate or hydroxylamine hydrochloride.

[0012] In some embodiments of the present application, the molar ratio of hydroxylamine salt to deionized water in A1 is 1:5-18.

[0013] In some embodiments of the present application, the alkali solution in A1 is selected from at least one of sodium hydroxide solution, potassium hydroxide solution or ammonia water, and the molar ratio of alkali to hydroxylamine salt is 1:0.9-1.3, and the molar amount of alkali is calculated as hydroxide.

[0014] In some embodiments of the present application, the reaction temperature in A1 is -15 to 15℃, and the reaction time is 0.1-2h.

[0015] In some embodiments of the present application, the reduced pressure distillation temperature in A2 is 50-60℃, and the reduced pressure distillation pressure is 0.01-0.1MPa.

[0016] In some embodiments of the present application, the amount of stabilizer added in A2 is 0.01-0.1wt% of the reaction system.

[0017] In some embodiments of the present application, the preparation method of the stabilizer in A2 is:

[0018] B1: by weight parts, 32-64 parts of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 300-500 parts of N,N-dimethyl-m-aniline, then 9-18 parts of mercaptoimidazole sodium propanesulfonate, 3-6 parts of ethanolamine are added, heated to 75-95℃, and reacted for 2-6h;

[0019] B2: 6-9 parts of 4-allylpiperazine-1-amine are further added, stirred for 15-60min, and N,N-dimethyl-m-aniline is removed by distillation to obtain a modified pyrazolone stabilizer.

[0020] The preparation mechanism of the above-mentioned modified pyrazolone stabilizer involves the following processes:

[0021] 1. Addition reaction of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone and mercaptoimidazole sodium propanesulfonate.

[0022] 2. Excess 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone further adds to the amino group in N-aminoethylpiperazine, and then successfully introduces piperazine into the modified pyrazolone stabilizer to increase the stability.

[0023] Compared with the prior art, the method for preparing a hydroxylamine aqueous solution by a hydroxylamine salt neutralization method has the following remarkable effects: pyrazolone type stabilizers are used, mercaptoimidazole sodium propanesulfonate is introduced as a chelating agent, and a piperazine functional group is introduced, which can effectively increase the stability of the stabilizer. DETAILED DESCRIPTION

[0024] The essential features and remarkable effects of the present application can be embodied in the following examples, but they do not limit the present application in any way, and those skilled in the art can make some non-essential improvements and adjustments according to the content of the present application. The present application is further described below through specific embodiments.

[0025] Example 1

[0026] A method for preparing a hydroxylamine aqueous solution by a hydroxylamine salt neutralization method, the operation steps are:

[0027] A1: 30kg of hydroxylamine salt is added to a reaction container, dissolved with an appropriate amount of deionized water, and stirred under normal pressure. An alkali solution is added dropwise to perform a neutralization reaction.

[0028] A2: After the neutralization reaction is completed, the reaction liquid is reduced pressure filtration, an appropriate amount of stabilizer is added to the filtrate, and then reduced pressure distillation is performed. The distillate is the hydroxylamine aqueous solution.

[0029] The hydroxylamine salt in A1 is selected from hydroxylamine sulfate.

[0030] The molar ratio of the hydroxylamine salt to deionized water in A1 is 1:5.

[0031] The alkali solution in A1 is selected from sodium hydroxide solution, and the molar ratio of alkali to hydroxylamine salt is 1:0.9, and the molar amount of alkali is calculated based on hydroxide.

[0032] The reaction temperature in A1 is -15℃, and the reaction time is 2h.

[0033] The reduced pressure distillation temperature in A2 is 50℃, and the reduced pressure distillation pressure is 0.01MPa.

[0034] The amount of stabilizer added in A2 is 0.01wt% of the reaction system.

[0035] The preparation method of the stabilizer in A2 is:

[0036] B1: 32g of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 300g of N,N-dimethyl-m-aniline, 9g of sodium mercaptoimidazole propyl sulfonate and 3g of ethanolamine are added, heated to 75℃, and reacted for 2h;

[0037] B2: 6g of 4-allyl piperazine-1-amine is added, stirred for 15min, and N,N-dimethyl-m-aniline is removed by distillation to obtain a modified pyrazolone stabilizer.

[0038] In this example, the hydroxylamine aqueous solution is determined by potassium permanganate method, and the result is 1.42mol / L.

[0039] Example 2

[0040] A method for preparing a hydroxylamine aqueous solution by neutralizing a hydroxylamine salt, the operation steps of which are:

[0041] A1: 35kg of hydroxylamine salt is added to a reaction container, dissolved with an appropriate amount of deionized water, and stirred under normal pressure. An alkali solution is added dropwise to carry out neutralization reaction.

[0042] A2: After the neutralization reaction is completed, the reaction liquid is reduced pressure filtration, an appropriate amount of stabilizer is added to the filtrate, and then reduced pressure distillation is carried out. The distillate is the hydroxylamine aqueous solution.

[0043] The hydroxylamine salt in A1 is selected from hydroxylamine sulfate.

[0044] The molar ratio of the hydroxylamine salt to deionized water in A1 is 1:9.

[0045] The alkali solution in A1 is selected from sodium hydroxide solution, and the molar ratio of alkali to hydroxylamine salt is 1:1.0, and the molar amount of alkali is calculated based on hydroxide.

[0046] The reaction temperature in A1 is -5℃, and the reaction time is 1.4h.

[0047] The reduced pressure distillation temperature in A2 is 50℃, and the reduced pressure distillation pressure is 0.04MPa.

[0048] The amount of the stabilizer added in A2 is 0.04wt% of the reaction system.

[0049] The preparation method of the stabilizer in A2 is:

[0050] B1: 48g of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 360g of N,N-dimethyl-m-toluidine, 12g of sodium mercaptoimidazole propyl sulfonate and 4g of ethanolamine are further added, heated to 80℃, and reacted for 3h;

[0051] B2: 7g of 4-allyl piperazine-1-amine is further added, stirred for 30min, and N,N-dimethyl-m-toluidine is removed by distillation to obtain a modified pyrazolone stabilizer.

[0052] In this example, the hydroxylamine aqueous solution is determined by the potassium permanganate method, and the result is 1.49mol / L.

[0053] Example 3

[0054] A method for preparing a hydroxylamine aqueous solution by neutralizing a hydroxylamine salt, the operation steps of which are:

[0055] A1: 45kg of hydroxylamine salt is added to a reaction container, dissolved with an appropriate amount of deionized water, and stirred under normal pressure. An alkali solution is added dropwise to perform a neutralization reaction.

[0056] A2: After the neutralization reaction is completed, the reaction liquid is reduced pressure filtered, an appropriate amount of stabilizer is added to the filtrate, and then reduced pressure distillation is performed. The distillate is a hydroxylamine aqueous solution.

[0057] The hydroxylamine salt in A1 is selected from hydroxylamine phosphate.

[0058] The molar ratio of the hydroxylamine salt to deionized water in A1 is 1:13.

[0059] The alkali solution in A1 is selected from potassium hydroxide solution, and the molar ratio of the alkali to the hydroxylamine salt is 1:1.1. The molar amount of the alkali is calculated based on hydroxide.

[0060] The reaction temperature in A1 is 5℃, and the reaction time is 0.8h.

[0061] The reduced pressure distillation temperature in A2 is 60℃, and the reduced pressure distillation pressure is 0.07MPa.

[0062] The amount of the stabilizer added in A2 is 0.07wt% of the reaction system.

[0063] The preparation method of the stabilizer in A2 is:

[0064] B1: 56 g of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 450 g of N,N-dimethyl-m-toluidine, 16 g of sodium mercaptoimidazole propanesulfonate, 5 g of ethanolamine are added, heated to 90°C, and reacted for 5 h;

[0065] B2: 8 g of 4-allylpiperazine-1-amine is further added, stirred for 50 min, and N,N-dimethyl-m-toluidine is distilled off to obtain a modified pyrazolone stabilizer.

[0066] In this example, the hydroxylamine aqueous solution is determined by the potassium permanganate method, and the result is 1.54 mol / L.

[0067] Example 4

[0068] A method for preparing a hydroxylamine aqueous solution by neutralizing a hydroxylamine salt, the operation steps of which are as follows:

[0069] A1: 50 kg of a hydroxylamine salt is added to a reaction container, dissolved with a proper amount of deionized water, and stirred under normal pressure. An alkali solution is added dropwise to perform a neutralization reaction.

[0070] A2: After the neutralization reaction is completed, the reaction solution is reduced pressure filtered, a proper amount of stabilizer is added to the filtrate, and then reduced pressure distillation is performed. The distillate is the hydroxylamine aqueous solution.

[0071] The hydroxylamine salt in A1 is selected from hydroxylamine hydrochloride.

[0072] The molar ratio of the hydroxylamine salt to deionized water in A1 is 1:18.

[0073] The alkali solution in A1 is selected from ammonia water, and the molar ratio of the alkali to the hydroxylamine salt is 1:1.3. The molar amount of the alkali is calculated based on hydroxide.

[0074] The reaction temperature in A1 is 15°C, and the reaction time is 0.2 h.

[0075] The reduced pressure distillation temperature in A2 is 60°C, and the reduced pressure distillation pressure is 0.1 MPa.

[0076] The amount of the stabilizer added in A2 is 0.1 wt% of the reaction system.

[0077] The preparation method of the stabilizer in A2 is as follows:

[0078] B1: 64 g of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 500 g of N,N-dimethyl-m-toluidine, 18 g of sodium mercaptoimidazole propanesulfonate, 6 g of ethanolamine are added, heated to 95°C, and reacted for 6 h;

[0079] B2: add 9 g 4-allyl piperazine-1-amine again, stir for 60 min, remove N,N-dimethyl-m-toluidine by distillation to obtain a modified pyrazolone stabilizer.

[0080] In this example, the hydroxylamine aqueous solution is determined by the potassium permanganate method, and the result is 1.50 mol / L.

[0081] Comparative Example 1

[0082] A method for preparing a hydroxylamine aqueous solution by neutralizing a hydroxylamine salt, the operation steps of which are as follows:

[0083] A1: add 30 kg of hydroxylamine salt to a reaction container, dissolve it with a proper amount of deionized water, open the stirring under normal pressure, add alkali solution dropwise, and carry out neutralization reaction;

[0084] A2: after the neutralization reaction is completed, the reaction solution is reduced pressure filtration, a proper amount of stabilizer is added to the filtrate, and then reduced pressure distillation is carried out, and the distillate is the hydroxylamine aqueous solution.

[0085] The hydroxylamine salt in A1 is selected from hydroxylamine sulfate.

[0086] The molar ratio of hydroxylamine salt to deionized water in A1 is 1:5.

[0087] The alkali solution in A1 is selected from sodium hydroxide solution, and the molar ratio of alkali to hydroxylamine salt is 1:0.9, and the molar amount of alkali is calculated based on hydroxide.

[0088] The reaction temperature in A1 is -15℃, and the reaction time is 2h.

[0089] The reduced pressure distillation temperature in A2 is 50℃, and the reduced pressure distillation pressure is 0.01 MPa.

[0090] The amount of stabilizer added in A2 is 0.01wt% of the reaction system.

[0091] The preparation method of the stabilizer in A2 is as follows:

[0092] B1: add 9 g of sodium mercaptoimidazole propanesulfonate and 3 g of ethanolamine to 300 g of N,N-dimethyl-m-toluidine, heat to 75℃, and react for 2h;

[0093] B2: add 6 g of 4-allyl piperazine-1-amine again, stir for 15 min, remove N,N-dimethyl-m-toluidine by distillation to obtain a modified pyrazolone stabilizer.

[0094] In this example, the hydroxylamine aqueous solution is determined by the potassium permanganate method, and the result is 1.34 mol / L.

[0095] Comparative Example 2

[0096] A method for preparing a hydroxylamine aqueous solution by a hydroxylamine salt neutralization method, the operation steps of which are as follows:

[0097] A1: 30 kg of hydroxylamine salt is added to a reaction container and dissolved with a proper amount of deionized water, and stirring is started under normal pressure, and then alkali solution is added dropwise for neutralization reaction;

[0098] A2: After the neutralization reaction is completed, the reaction solution is filtered under reduced pressure, and then a proper amount of stabilizer is added to the filtrate, and then reduced pressure distillation is carried out, and the distillate is the hydroxylamine aqueous solution.

[0099] The hydroxylamine salt in A1 is selected from hydroxylamine sulfate.

[0100] The molar ratio of the hydroxylamine salt to deionized water in A1 is 1:5.

[0101] The alkali solution in A1 is selected from sodium hydroxide solution, and the molar ratio of alkali to hydroxylamine salt is 1:0.9, and the molar amount of alkali is calculated based on hydroxide.

[0102] The reaction temperature in A1 is -15℃, and the reaction time is 2h.

[0103] The reduced pressure distillation temperature in A2 is 50℃, and the reduced pressure distillation pressure is 0.01 MPa.

[0104] The amount of stabilizer added in A2 is 0.01wt% of the reaction system.

[0105] The preparation method of the stabilizer in A2 is as follows:

[0106] B1: 32g of 1-(2,4,6-trichlorophenyl)-3-propenylamino-5-pyrazolone is added to 300g of N,N-dimethyl-m-toluidine, 3g of ethanolamine, heated to 75℃, and reacted for 2h;

[0107] B2: 6g of 4-allylpiperazine-1-amine is further added, stirred for 15min, and N,N-dimethyl-m-toluidine is removed by distillation to obtain a modified pyrazolone stabilizer.

[0108] In this example, the hydroxylamine aqueous solution is determined by the potassium permanganate method, and the result is 1.37mol / L.

[0109] The above detailed the preferred embodiments of the present application. It should be understood that those skilled in the art can make many modifications and changes without creative labor based on the concept of the present application. Therefore, any technical solution obtained by logical analysis, reasoning or limited experiment based on the prior art according to the concept of the present application shall be within the protection scope determined by the claims.

Claims

1. A method for preparing a hydroxylamine aqueous solution by a hydroxylamine salt neutralization method, comprising the following steps: A1: adding 30-50 parts of a hydroxylamine salt to a reaction container, dissolving the hydroxylamine salt in a proper amount of deionized water, and stirring under normal pressure, and then adding an alkali solution dropwise to perform a neutralization reaction; A2: after the neutralization reaction is completed, the reaction solution is reduced pressure filtered, a proper amount of a stabilizer is added to the filtrate, and then reduced pressure distillation is performed, and the distillate is the hydroxylamine aqueous solution; and the stabilizer preparation method in A2 is: B1: adding 32-64 parts of 1-(2, 4, 6-trichlorophenyl)-3-propenylamino-5-pyrazolone to 300-500 parts of N, N-dimethyl-m-toluidine, and then adding 9-18 parts of mercaptoimidazole sodium propanesulfonate and 3-6 parts of ethanolamine, heating to 75-95℃, and reacting for 2-6 hours; B2: adding 6-9 parts of 4-allylpiperazine-1-amine, stirring for 15-60 minutes, and removing the N, N-dimethyl-m-toluidine by distillation to obtain a modified pyrazolone stabilizer. The hydroxylamine salt in A1 is at least one selected from hydroxylamine sulfate, hydroxylamine phosphate, and hydroxylamine hydrochloride. The molar ratio of the hydroxylamine salt to the deionized water in A1 is 1:5-18. The alkali solution in A1 is at least one selected from a sodium hydroxide solution, a potassium hydroxide solution, and ammonia water, and the molar ratio of the alkali to the hydroxylamine salt is 1:0.9-1.3, and the molar amount of the alkali is calculated based on hydroxide. The reaction temperature in A1 is-15-15℃, and the reaction time is 0.1-2 hours. The reduced pressure distillation temperature in A2 is 50-60℃, and the reduced pressure distillation pressure is 0.01-0.1 MPa.

2. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: The amount of the stabilizer added in A2 is 0.01-0.1 wt% of the reaction system.

3. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: ​ 4. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: ​ 5. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: ​ 6. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: ​ 7. The method of claim 1, wherein the hydroxylamine aqueous solution is prepared by a hydroxylamine salt neutralization method, characterized in that: ​