A method for preparing a hydroxylamine aqueous solution

Abstract

A method for preparing an aqueous hydroxylamine solution belongs to the technical field of hydroxylamine preparation. Specifically, the method comprises adding an aqueous hydroxylamine sulfate solution to a raw material supply chamber, adding an aqueous sodium hydroxide solution to an alkali supply chamber, adding weakly alkaline water to a desalting chamber, adding a sulfuric acid solution to a concentrating chamber, circulating the sodium hydroxide solution between the anodic and cathodic chambers, and performing electrodialysis at room temperature to prepare the aqueous hydroxylamine solution. Furthermore, a method for preparing a stabilizer is provided, which can improve the stability of the aqueous hydroxylamine solution and reduce the damage to the hydroxylamine by metal ions.

Description

Technical Field

[0001] The invention relates to the technical field of hydroxylamine preparation, in particular to a method for preparing a hydroxylamine aqueous solution. Background Art

[0002] Hydroxylamine is an important chemical raw material. It acts as a reducing agent in organic synthesis, condensing with carbonyl compounds to form oximes. These oximes are primarily used in the synthesis of caprolactam (for the production of nylon-6), the pharmaceutical intermediate hydroxylamine-O-sulfonic acid, and in the synthesis of pesticides, pharmaceuticals, fragrances, and fuels. In the semiconductor industry, hydroxylamine is also used as a component in photoresist dissolving agents and can be used to selectively cleave asparagine-glycine peptide bonds.

[0003] Patent document CN110482505B discloses a method for preparing hydroxylamine using nitrogen, which is applied to a hydroxylamine preparation device. The method comprises: nitrogen stored in a nitrogen storage device is introduced into water stored in a water storage device through a first pipeline, and the humidified nitrogen is introduced into a discharge reaction chamber through a second pipeline; a high-voltage power supply is turned on and a high voltage is applied to a discharge array needle plate, causing the needle tips of the discharge array needle plate to generate water radical cation clusters. The formed water radical cation clusters react with nitrogen to produce hydroxylamine radical cations and nitroxyl radicals, which are transferred to a cathode plate to form hydroxylamine; the hydroxylamine formed on the cathode plate is output and collected through a product output channel. The present invention can solve the problem of harsh reaction conditions and the need for high temperature and high pressure (high gas pressure) when preparing hydroxylamine in the prior art. At the same time, this method realizes the conversion of inert gas nitrogen into hydroxylamine under normal temperature and pressure conditions for the first time.

[0004] Patent document PCT / EP2002 / 007273 relates to a method for preparing a salt-free aqueous hydroxylamine solution by reacting an aqueous solution of a hydroxylammonium salt with a base to obtain a mixture and separating the salt-free aqueous hydroxylamine solution from the mixture by distillation. The method is characterized in that an aqueous solution of a mixture of NaOH and KOH is used as the base, wherein NaOH in the mixture is + ∶K + The molar ratio is 70:30-95:5 and Na + and K + The total concentration is 0.1-10 m / m % based on the total amount of the mixture.

[0005] Patent document CN115595217A provides a stable solution containing hydroxylamine, a semiconductor cleaning solution containing hydroxylamine, and methods for preparing and using the same. The stable solution contains the following components in the following proportions by weight: 5-30 parts of hydroxylamine and its derivatives; 1-5 parts of a chelating agent; and 5-20 parts of a cucurbituril and its derivatives. The present invention uses cucurbituril and its derivatives to encapsulate hydroxylamine molecules, preventing them from direct contact with metal ions and acidic or alkaline media. The chelating agent complexes the metal ions, ensuring that the hydroxylamine molecules released from the cucurbituril and its derivatives are not catalyzed by the metal ions and decomposed. The present invention also discloses a semiconductor cleaning solution containing hydroxylamine, comprising the stable solution containing hydroxylamine, an alkali, a water-soluble organic solvent, and ultrapure water. The semiconductor cleaning solution containing hydroxylamine of the present invention can avoid the decomposition of hydroxylamine caused by metal ion catalysis and prevent decomposition caused by high temperature and alkalinity, making it widely applicable for semiconductor cleaning.

[0006] However, existing electrodialysis methods for preparing aqueous hydroxylamine salt solutions contain impurities in the ppm range, such as sodium sulfate and other metal compounds, which limits their use in the electronics industry. Free hydroxylamine is highly unstable and readily decomposes in the presence of metal ions, at high temperatures, or at high concentrations. Hydroxylamine solutions containing diethylenetriamine-5-acetic acid or triethylenetetramine-6-acetic acid, quercetin, 8-hydroxyquinoline, benzylamine oxime, isocyanates, N-phenyl-N-hydroxythiourea, reductone, and / or reductone salts as stabilizers have been shown to be ineffective in inhibiting hydroxylamine decomposition at high temperatures, high concentrations, or even when metal impurities such as Fe are present. Summary of the Invention

[0007] To solve at least one of the technical problems in the above technical background, the present invention provides a method for preparing a hydroxylamine aqueous solution, wherein an anion and cation exchange membranes are alternately arranged on an electrodialysis device, and hydroxylamine sulfate is used as a raw material to prepare a hydroxylamine salt aqueous solution by electrodialysis.

[0008] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0009] The invention relates to a method for preparing a hydroxylamine aqueous solution by adding 800-1600 parts by mass of an aqueous hydroxylamine sulfate solution to a raw material supply chamber, adding 1500-3000 parts by mass of an aqueous sodium hydroxide solution to an alkali supply chamber, adding 300-600 parts by mass of weakly alkaline water to a desalting chamber, adding a sulfuric acid solution to a concentrating chamber, circulating the sodium hydroxide solution in the anode chamber and the cathode chamber, and performing electrodialysis at room temperature.

[0010] In some embodiments of the present invention, the content of the hydroxylamine phosphate water is not higher than 0.1%.

[0011] In some embodiments of the present invention, the preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from left to right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0012] In some embodiments of the present invention, two adjacent chambers of the electrodialysis device are separated by an anion and cation exchange membrane, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by an anion exchange membrane, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by a cation exchange membrane.

[0013] In some embodiments of the present invention, the initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5-35.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5-13.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5-2.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8-12%.

[0014] In some embodiments of the present invention, the circulation speed of the concentration chamber, the raw material supply chamber, the desalination chamber, and the alkali supply chamber is 5-30 L / h.

[0015] In some embodiments of the present invention, the current density during the electrodialysis process is 2-6 A / dm2, and the electrodialysis time is 5-10 h.

[0016] In some embodiments of the present invention, the hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the added amount is 5*10-4 to 1% by mass of hydroxylamine, especially 5*10-3 to 5*10-2%.

[0017] In some embodiments of the present invention, the stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 100-120:3-10.

[0018] In some embodiments of the present invention, the crown ether stabilizer is prepared by:

[0019] In a stirred reactor, 10-18 parts by weight of 4-vinylbenzo-18-crown-6 are placed in 200-280 parts of DMF, followed by 3-8 parts of sodium dimercaptosuccinate and 5-10 parts of triethylamine. The mixture is heated to 70-78°C and stirred for reaction for 100-150 minutes. 0.01-0.5 parts of 2,4,6-trimercapto-1,3,5-triazine are then added, stirred for reaction for 20-40 minutes, and DMF is removed by distillation to obtain a crown ether stabilizer.

[0020] The reaction mechanism of the above crown ether stabilizer is:

[0021] 4-vinylbenzo-18-crown-6 reacts with sodium dithiosuccinate to undergo a thiol addition reaction, and excess 4-vinylbenzo-18-crown-6 reacts with 2,4,6-trimercapto-1,3,5-triazine to undergo a thiol addition reaction to obtain a crown ether stabilizer.

[0022] Technical effect:

[0023] The method for preparing a hydroxylamine aqueous solution of the present invention has the following significant effects compared with the prior art:

[0024] 4-Vinylbenzo-18-crown-6 reacts with 2,4,6-trimercapto-1,3,5-triazine to form a thiol addition reaction. The triazine functional group is highly stable and reactive, and the triazine ring structure is also incorporated into the crown ether structure. This allows for the formation of more stable complexes with metal ions. Therefore, these functional groups can enhance the stability of hydroxylamine aqueous solutions, maintaining stability over a wide pH range. This complexation reduces the damage of hydroxylamine by metal ions and maintains its stability over a wide pH range. DETAILED DESCRIPTION

[0025] The essential features and significant effects of the present invention can be reflected in the following embodiments, but they do not limit the present invention in any way. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the present invention. The present invention is further described below through specific embodiments.

[0026] Example 1

[0027] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0028] 800 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 1500 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 300 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anode chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0029] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0030] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0031] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0032] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8%.

[0033] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 5L / h.

[0034] The current density during the electrodialysis process is 2A / dm 2 , the electrodialysis time is 5h.

[0035] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the amount added is 5*10% of the mass percentage of hydroxylamine. -4 .

[0036] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 100:3.

[0037] The preparation method of the crown ether stabilizer is as follows:

[0038] In a stirred reactor, 10 g of 4-vinylbenzo-18-crown-6 was placed in 200 g of DMF, followed by 3 g of sodium dimercaptosuccinate and 5 g of triethylamine. The mixture was heated to 70°C and stirred for 100 minutes. 0.1 g of 2,4,6-trimercapto-1,3,5-triazine was then added and stirred for 20 minutes. DMF was then removed by distillation to obtain a crown ether stabilizer.

[0039] Example 2

[0040] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0041] 1200 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 2000 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 400 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anodic chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0042] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0043] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0044] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0045] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 31.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 10.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 2N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 9%.

[0046] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 10L / h.

[0047] The current density during the electrodialysis process is 3A / dm 2 , the electrodialysis time is 7h.

[0048] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the amount added is 5*10% of the mass percentage of hydroxylamine. -3 .

[0049] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 120:3.

[0050] The preparation method of the crown ether stabilizer is as follows:

[0051] In a stirred reactor, 12 g of 4-vinylbenzo-18-crown-6 was placed in 220 g of DMF, followed by 5 g of sodium dimercaptosuccinate and 7 g of triethylamine. The mixture was heated to 72°C and stirred for 120 minutes. 0.25 g of 2,4,6-trimercapto-1,3,5-triazine was then added and stirred for 30 minutes. DMF was then removed by distillation to obtain a crown ether stabilizer.

[0052] Example 3

[0053] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0054] 1400 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 2500 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 500 g of weak alkaline water was added to the desalination chamber, sulfuric acid solution was added to the concentration chamber, the sodium hydroxide solution was circulated in the anode chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0055] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0056] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0057] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0058] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 32.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 11.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 2N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 11%.

[0059] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 20L / h.

[0060] The current density during the electrodialysis process is 5A / dm 2 , the electrodialysis time is 8h.

[0061] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the amount added is 5*10% of the mass percentage of hydroxylamine. -2 %.

[0062] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 120:3.

[0063] The preparation method of the crown ether stabilizer is as follows:

[0064] In a stirred reactor, 16 g of 4-vinylbenzo-18-crown-6 was placed in 260 g of DMF, followed by 7 g of sodium dimercaptosuccinate and 8 g of triethylamine. The mixture was heated to 76°C and stirred for 140 minutes. 0.4 g of 2,4,6-trimercapto-1,3,5-triazine was then added and stirred for 35 minutes. DMF was then removed by distillation to obtain a crown ether stabilizer.

[0065] Example 4

[0066] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0067] 1600 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 3000 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 600 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anodic chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0068] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0069] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0070] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0071] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 35.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 13.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 2.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 12%.

[0072] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 30L / h.

[0073] The current density during the electrodialysis process is 6A / dm 2 , the electrodialysis time is 10h.

[0074] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the added amount is 1% of the mass percentage of hydroxylamine.

[0075] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 120:10.

[0076] The preparation method of the crown ether stabilizer is as follows:

[0077] In a stirred reactor, 18 g of 4-vinylbenzo-18-crown-6 was placed in 280 g of DMF, followed by 8 g of sodium dimercaptosuccinate and 10 g of triethylamine. The mixture was heated to 78°C and stirred for 150 minutes. 0.5 g of 2,4,6-trimercapto-1,3,5-triazine was then added and stirred for 40 minutes. DMF was then removed by distillation to obtain a crown ether stabilizer.

[0078] Comparative Example 1

[0079] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0080] 800 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 1500 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 300 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anode chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0081] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0082] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0083] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0084] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8%.

[0085] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 5L / h.

[0086] The current density during the electrodialysis process is 2A / dm 2 , the electrodialysis time is 5h.

[0087] Comparative Example 2

[0088] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0089] 800 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 1500 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 300 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anode chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0090] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0091] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0092] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0093] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8%.

[0094] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 5L / h.

[0095] The current density during the electrodialysis process is 2A / dm 2 , the electrodialysis time is 5h.

[0096] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the amount added is 5*10% of the mass percentage of hydroxylamine. -4 .

[0097] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 100:3.

[0098] The crown ether stabilizer is prepared by placing 3 g of sodium dimercaptosuccinate in 200 g of DMF in a stirred reactor, adding 5 g of triethylamine, heating to 70° C., and stirring for 100 minutes; then adding 0.1 g of 2,4,6-trimercapto-1,3,5-triazine, stirring for 20 minutes, and distilling off the DMF to obtain the crown ether stabilizer.

[0099] Comparative Example 3

[0100] A method for preparing a hydroxylamine aqueous solution, characterized in that the operating steps are:

[0101] 800 g of hydroxylamine sulfate aqueous solution was added to the raw material supply chamber, 1500 g of sodium hydroxide aqueous solution was added to the alkali supply chamber, 300 g of weak alkaline water was added to the desalting chamber, sulfuric acid solution was added to the concentrating chamber, the sodium hydroxide solution was circulated in the anode chamber and the cathode chamber, and electrodialysis was performed at room temperature to prepare a hydroxylamine aqueous solution.

[0102] The content of the hydroxylamine phosphate water is not higher than 0.1%.

[0103] The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which is separated from the left to the right by an anion exchange membrane including an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

[0104] The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

[0105] The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8%.

[0106] The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 5L / h.

[0107] The current density during the electrodialysis process is 2A / dm 2 , the electrodialysis time is 5h.

[0108] The hydroxylammonium salt solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine, and the amount added is 5*10% of the mass percentage of hydroxylamine. -4 .

[0109] The stabilizer is selected from 8-hydroxyquinoline:crown ether stabilizer in a mass ratio of 100:3.

[0110] The preparation method of the crown ether stabilizer is as follows:

[0111] In a stirred reactor, 10 g of 4-vinylbenzo-18-crown-6 was placed in 200 g of DMF, and then 3 g of sodium dithiosuccinate and 5 g of triethylamine were added. The mixture was heated to 70°C and stirred for 120 minutes. DMF was distilled off to obtain a crown ether stabilizer.

[0112] Evaluation of Examples

[0113] The 50 wt % hydroxylamine aqueous solutions prepared in Examples 1-4 and Comparative Examples 1-3 were placed in a 500 ml container made of PFA with a lid, and the container was placed in a thermostatic chamber at 60° C. after the lid was fixed.

[0114] After 30 days, the color of the hydroxylamine aqueous solution was visually determined. The hydroxylamine concentration was then measured by hydrochloric acid titration, and the decomposition rate of hydroxylamine was obtained by the following expression.

[0115] Hydroxylamine decomposition rate (%) = (50-A) / 50×100

[0116] A = Hydroxylamine concentration (mass %) after 30 days.

[0117] The results are listed in Table 1:

[0118]

[0119]

[0120] The 50 wt% hydroxylamine aqueous solution prepared in Examples 1-4 and Comparative Examples 1-3 was placed in a 500 ml container with a lid made of PFA, and then Fe 3+ The Fe content was adjusted to a specific concentration, and then the container was placed in a constant temperature chamber at 60°C after securing the lid.

[0121] After 30 days, the color of the hydroxylamine aqueous solution was visually determined. The hydroxylamine concentration was then measured by hydrochloric acid titration, and the decomposition rate of hydroxylamine was obtained by the following expression.

[0122] Hydroxylamine decomposition rate (%) = (50-B) / 50×100

[0123] B = hydroxylamine concentration (mass %) after 30 days.

[0124] The results are listed in Table 2:

[0125] Implementation Method <![CDATA[Fe 3+ Concentration (mass ppm)]]> Decomposition rate of hydroxylamine (%) Example 1 10 34 Implementation rate 2 10 28 Implementation rate 3 10 22 Implementation rate 4 10 25 Comparative Example 1 10 100 Comparative Example 2 10 54 Comparative Example 3 10 49

[0126] In summary, a stable aqueous hydroxylamine solution can be prepared by this method, and a certain stability can be maintained in the presence of metal ions.

[0127] The preferred embodiments of the present invention have been described in detail above. It should be understood that numerous modifications and variations based on the concepts of the present invention are possible without inventive effort by those skilled in the art. Therefore, any technical solution that can be derived by one skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A method for preparing a hydroxylamine aqueous solution, characterized in that: The operation steps are: 800-1600 parts by mass of an aqueous solution of hydroxylamine sulfate are added to a raw material supply chamber, 1500-3000 parts of an aqueous solution of sodium hydroxide are added to an alkali supply chamber, 300-600 parts of weakly alkaline water are added to a desalting chamber, a sulfuric acid solution is added to a concentrating chamber, the sodium hydroxide solution is circulated in the anodic chamber and the cathode chamber, and electrodialysis is performed at room temperature to prepare an aqueous solution of hydroxylamine; The hydroxylamine sulfate aqueous solution contains a stabilizer that forms a chelate with the metal ion of hydroxylamine; The stabilizer is selected from 8-hydroxyquinoline: crown ether stabilizer mass ratio = 100-120:3-10; The preparation method of the crown ether stabilizer is as follows: In a stirred reactor, 10-18 parts by weight of 4-vinylbenzo-18-crown-6 are placed in 200-280 parts of DMF, followed by the addition of 3-8 parts of sodium dimercaptosuccinate and 5-10 parts of triethylamine. The mixture is heated to 70°C-78°C and stirred for reaction for 100-150 minutes. 0.01-0.5 parts of 2,4,6-trimercapto-1,3,5-triazine are then added, stirred for reaction for 20-40 minutes, and the DMF is removed by distillation to obtain a crown ether stabilizer.

2. The method for preparing a hydroxylamine aqueous solution according to claim 1, wherein: The preparation of the hydroxylamine aqueous solution is carried out in an electrodialysis device, which comprises, from left to right, an anode chamber, a concentration chamber, a raw material supply chamber, a desalination chamber, an alkali supply chamber and a cathode chamber.

3. The method for preparing a hydroxylamine aqueous solution according to claim 2, wherein: The adjacent two chambers of the electrodialysis device are separated by anion and cation exchange membranes, wherein the anode chamber and the concentration chamber, the raw material supply chamber and the desalination chamber, and the alkali supply chamber and the cathode chamber are separated by anion exchange membranes, and the concentration chamber and the raw material supply chamber, and the desalination chamber and the alkali supply chamber are separated by cation exchange membranes.

4. The method for preparing a hydroxylamine aqueous solution according to claim 1, wherein: The initial concentration of the hydroxylamine sulfate aqueous solution in the raw material supply chamber is 28.5-35.5%, the initial concentration of the sodium hydroxide solution in the alkali supply chamber is 8.5-13.5%, the initial concentration of the sulfuric acid solution in the concentration chamber is 1.5-2.5N, and the concentration of the sodium hydroxide solution in the anode chamber and the cathode chamber is 8-12%.

5. The method for preparing a hydroxylamine aqueous solution according to claim 1, wherein: The circulation speed of the concentration chamber, raw material supply chamber, desalination chamber and alkali supply chamber is 5-30 L / h.

6. The method for preparing a hydroxylamine aqueous solution according to claim 1, wherein: The current density during the electrodialysis process is 2-6A / dm 2 , the electrodialysis time is 5-10h.

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