A method for preparing hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by liquid organic acid

Abstract

The invention relates to the technical field of hydroxylamine preparation, and particularly to a method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime with a liquid organic acid. The method adopts low-temperature catalytic hydrolysis of acetone oxime and extraction and separation to obtain the hydroxylamine aqueous solution. The method adopts 1H-benzotriazole-6-methylamine and propylene thiourea to first undergo an amino addition reaction, and then the adduct is further subjected to an amino addition reaction with 3-acryloyloxyflavonoid to obtain a hydrolyzed hydroxylamine stabilizer. The method continuously distills and collects acetone, a product generated by the hydrolysis of acetone oxime, from the top of a distillation tower, thereby reducing the concentration of the product and promoting the rightward progress of the entire reaction, promoting the conversion of acetone oxime, and finally obtaining a high-purity hydroxylamine aqueous solution. The method has the advantages of simple operation, environmental friendliness, resource conservation, and the like.

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 by hydrolyzing acetone oxime catalyzed by a liquid organic acid. Background Art

[0002] Hydroxylamine is highly hygroscopic and slightly soluble in ether, benzene, carbon disulfide, and chloroform. Because hydroxylamine is unstable, its salts are commonly used in industry. Hydroxylamine and its salts are important chemical raw materials. Due to its oxidizing properties, hydroxylamine is not only used as an oxidizer in liquid propellants for spacecraft such as manned spacecraft, space shuttles, unmanned aircraft, and satellite launches, but also as a power source for intercontinental missiles, large-caliber artillery, and torpedoes. Hydroxylamine also has reducing properties, making it a highly efficient reducing agent. Furthermore, hydroxylamine is used as an analytical reagent for the detection of organic compounds such as aldehydes and ketones, for the microanalysis of sulfonic acids, and as a depolarizer in electroanalysis.

[0003] Chinese patent CN98806279.8: relates to a method for preparing a high-purity free-state hydroxylamine aqueous solution, wherein the dilute hydroxylamine aqueous solution is concentrated in a tower, and the vapor containing hydroxylamine is extracted from the bottom of the tower via a side stream, and the high-purity hydroxylamine is obtained by condensing the vapor.

[0004] Chinese Patent CN02813522.9: relates to a method for preparing a salt-free hydroxylamine aqueous solution by reacting an aqueous solution of a hydroxylamine salt with a base to obtain a mixture and separating the salt-free hydroxylamine aqueous 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 Na + ∶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] Chinese patent CN200710068003.9 discloses a method for producing high-purity hydroxylamine and its active alkaline aqueous solution. Hydroxylamine phosphate is thermally decomposed at a pressure of less than 30 mmHg and a temperature of 80-150°C, and the sublimates are collected to produce high-purity hydroxylamine crystals. These high-purity hydroxylamine crystals can be prepared to any desired concentration in the active alkaline aqueous solution and have an extremely low metal ion content, fully meeting the needs of the pharmaceutical and electronics industries.

[0006] The above-mentioned patents and existing processes have a series of problems such as many production steps, complex operating procedures, harsh reaction conditions, frequent side reactions, environmental pollution, and low economic benefits; the existing technology mainly uses inorganic acids (hydrochloric acid, sulfuric acid, etc.) as catalysts, but inorganic acids have disadvantages such as corrosiveness and are not conducive to separation from products. Summary of the Invention

[0007] Purpose of the invention: To overcome the deficiencies in the prior art, the present invention provides a method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime with a liquid organic acid catalyst. The acetone product generated by the hydrolysis of acetone oxime is continuously distilled and collected from the top of a distillation tower, thereby reducing the concentration of the product and promoting the rightward progress of the entire reaction, thereby promoting the conversion of acetone oxime and ultimately obtaining a high-purity hydroxylamine aqueous solution.

[0008] Technical solution: To achieve the above-mentioned purpose, the first aspect of the present invention provides a method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0009] S1: Add 13-17 parts by weight of acetone oxime to a reactor and add 60-80 parts of distilled water to completely dissolve the acetone oxime;

[0010] S2: Add 1-3 parts of liquid organic acid, stir, and react under reduced pressure;

[0011] S3: After the reaction is completed and the system returns to normal pressure, it is cooled to room temperature, the reaction liquid is extracted and separated, and 0.05-0.2 parts of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0012] Optionally, the liquid organic acid is selected from one or more of sulfamic acid, formic acid, oxalic acid, terephthalic acid and trifluoroacetic acid.

[0013] Optionally, the reactor is connected to a distillation column and a vacuum pump decompression device, and the sealing of the entire device is ensured.

[0014] Optionally, the stirring rate is 300-500 rpm.

[0015] Optionally, the reaction temperature is 20-40°C.

[0016] Optionally, the reaction operating pressure is -0.08~-0.09Mpa.

[0017] Optionally, the reaction time is 45-90 min.

[0018] Optionally, the extractant is ethanol, ether or acetone.

[0019] The second aspect of the present invention provides a method for preparing a hydrolyzed hydroxylamine stabilizer, the steps of which are as follows:

[0020] S1: nitrogen is introduced into a stirred reactor, and 14-26 parts of 1H-benzotriazole-6-methylamine, 5-11 parts of propylene thiourea, 0.5-2.5 parts of triethylamine, and 100-150 parts of solvent are added to the reactor by weight, and stirred at 50-60°C for 100-200 minutes;

[0021] S2: Add 0.005-0.05 parts of 3-acryloyloxyflavone, stir at 40-50° C. for 30-100 minutes, and remove the solvent by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0022] Optionally, the solvent is selected from at least one of chloroform, carbon tetrachloride, acetonitrile, dimethylformamide, and cyclohexane.

[0023] Reaction mechanism: 1H-benzotriazole-6-methylamine and allylthiourea first undergo amino addition reaction, and then the adduct further undergoes amino addition reaction with 3-acryloyloxyflavonoid to obtain a hydrolyzed hydroxylamine stabilizer.

[0024] Beneficial effects: The method of preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid has the following advantages over the prior art:

[0025] 1. The present invention has the advantages of simple operation, environmental friendliness, and resource conservation;

[0026] 2. The present invention hydrolyzes acetone oxime to generate acetone, which is continuously distilled out from the top of the distillation tower and collected, thereby reducing the concentration of the product and promoting the rightward progress of the entire reaction, thereby promoting the conversion of acetone oxime and ultimately obtaining a high-purity hydroxylamine aqueous solution;

[0027] 3. Since hydroxylamine is easily decomposed into free amine and water in water, in order to improve the stability of the hydroxylamine aqueous solution, the hydrolyzed hydroxylamine stabilizer prepared by the present invention delays the decomposition of hydroxylamine, thereby improving the stability of hydroxylamine. DETAILED DESCRIPTION

[0028] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0029] In the embodiments of the present invention, the concentration of the free hydroxylamine solution is measured by titration. Example 1

[0030] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0031] S1: Add 13g of acetone oxime to a reactor and add 60g of distilled water to completely dissolve the acetone oxime;

[0032] S2: Add 1g of liquid organic acid, stir, and react under reduced pressure;

[0033] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.05 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0034] The liquid organic acid is selected from sulfamic acid.

[0035] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0036] The stirring rate is 300 rpm.

[0037] The reaction temperature is 20°C.

[0038] The reaction operating pressure is -0.08Mpa.

[0039] The reaction time is 45 minutes.

[0040] The extractant is ethanol.

[0041] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0042] S1: Nitrogen was introduced into a stirred autoclave, and 14 g of 1H-benzotriazole-6-methylamine, 5 g of propylene thiourea, 0.5 g of triethylamine, and 100 g of DMF were added to the autoclave and stirred at 50°C for 100 minutes;

[0043] S2: 0.005 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 40° C. for 30 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0044] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 47.8%. Example 2

[0045] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0046] S1: Add 14 g of acetone oxime to a reactor and add 65 g of distilled water to completely dissolve the acetone oxime;

[0047] S2: Add 2g of liquid organic acid, stir, and react under reduced pressure;

[0048] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.1 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0049] The liquid organic acid is selected from formic acid.

[0050] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0051] The stirring rate is 400 rpm.

[0052] The reaction temperature is 25°C.

[0053] The reaction operating pressure is -0.08Mpa.

[0054] The reaction time is 60 min.

[0055] The extractant is ether.

[0056] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0057] S1: Nitrogen was introduced into a stirred autoclave, and 18 g of 1H-benzotriazole-6-methylamine, 7 g of allylthiourea, 1 g of triethylamine, and 110 g of DMF were added to the autoclave and stirred at 55°C for 140 minutes;

[0058] S2: 0.02 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 45° C. for 60 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0059] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 48.6%. Example 3

[0060] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0061] S1: Add 16g of acetone oxime to a reactor and add 75g of distilled water to completely dissolve the acetone oxime;

[0062] S2: Add 2g of liquid organic acid, stir, and react under reduced pressure;

[0063] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.15 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0064] The liquid organic acid is oxalic acid.

[0065] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0066] The stirring rate is 400 rpm.

[0067] The reaction temperature is 35°C.

[0068] The reaction operating pressure is -0.09Mpa.

[0069] The reaction time is 75 minutes.

[0070] The extractant is ether.

[0071] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0072] S1: Nitrogen was introduced into a stirred autoclave, and 22 g of 1H-benzotriazole-6-methylamine, 9 g of propylene thiourea, 2 g of triethylamine, and 140 g of DMF were added to the autoclave and stirred at 55° C. for 180 minutes.

[0073] S2: 0.04 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 45° C. for 90 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0074] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 49.8%. Example 4

[0075] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0076] S1: Add 17g of acetone oxime to a reactor and add 80g of distilled water to completely dissolve the acetone oxime;

[0077] S2: Add 3g of liquid organic acid, stir, and react under reduced pressure;

[0078] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.2 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0079] The liquid organic acid is selected from terephthalic acid.

[0080] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0081] The stirring rate is 500 rpm.

[0082] The reaction temperature is 40°C.

[0083] The reaction operating pressure is -0.09Mpa.

[0084] The reaction time is 90 min.

[0085] The extractant is acetone.

[0086] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0087] S1: Nitrogen was introduced into a stirred autoclave, and 26 g of 1H-benzotriazole-6-methylamine, 11 g of propylene thiourea, 2.5 g of triethylamine, and 150 g of DMF were added to the autoclave and stirred at 60°C for 200 minutes;

[0088] S2: 0.05 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 50° C. for 100 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0089] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 49.5%.

[0090] Comparative Example 1

[0091] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0092] S1: Add 13g of acetone oxime to a reactor and add 60g of distilled water to completely dissolve the acetone oxime;

[0093] S2: Add 1g of liquid organic acid, stir, and react under reduced pressure;

[0094] S3: After the reaction is completed, the system is restored to normal pressure and then cooled to room temperature. The reaction solution is extracted and separated to obtain a hydroxylamine aqueous solution.

[0095] The liquid organic acid is selected from sulfamic acid.

[0096] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0097] The stirring rate is 300 rpm.

[0098] The reaction temperature is 20°C.

[0099] The reaction operating pressure is -0.08Mpa.

[0100] The reaction time is 45 minutes.

[0101] The extractant is ethanol.

[0102] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 32.5%.

[0103] Comparative Example 2

[0104] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0105] S1: Add 13g of acetone oxime to a reactor and add 60g of distilled water to completely dissolve the acetone oxime;

[0106] S2: Add 1g of liquid organic acid, stir, and react under reduced pressure;

[0107] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.05 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0108] The liquid organic acid is selected from sulfamic acid.

[0109] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0110] The stirring rate is 300 rpm.

[0111] The reaction temperature is 20°C.

[0112] The reaction operating pressure is -0.08Mpa.

[0113] The reaction time is 45 minutes.

[0114] The extractant is ethanol.

[0115] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0116] S1: Nitrogen was introduced into a stirred autoclave, 5 g of propylene thiourea, 0.5 g of triethylamine, and 100 g of DMF were added to the autoclave, and stirred at 50°C for 100 minutes;

[0117] S2: 0.005 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 40° C. for 30 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0118] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 37.6%.

[0119] Comparative Example 3

[0120] A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are as follows:

[0121] S1: Add 13g of acetone oxime to a reactor and add 60g of distilled water to completely dissolve the acetone oxime;

[0122] S2: Add 1g of liquid organic acid, stir, and react under reduced pressure;

[0123] S3: After the reaction is completed, the system is restored to normal pressure and cooled to room temperature. The reaction solution is extracted and separated, and 0.05 g of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution.

[0124] The liquid organic acid is selected from sulfamic acid.

[0125] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0126] The stirring rate is 300 rpm.

[0127] The reaction temperature is 20°C.

[0128] The reaction operating pressure is -0.08Mpa.

[0129] The reaction time is 45 minutes.

[0130] The extractant is ethanol.

[0131] The preparation method of the hydrolyzed hydroxylamine stabilizer is:

[0132] S1: Nitrogen was introduced into a stirred autoclave, and 14 g of 1H-benzotriazole-6-methylamine, 0.5 g of triethylamine, and 100 g of DMF were added to the autoclave and stirred at 50°C for 100 minutes;

[0133] S2: 0.005 g of 3-acryloyloxyflavone was added, and the mixture was stirred at 40° C. for 30 minutes. DMF was removed by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

[0134] After testing and analysis, the concentration of the hydroxylamine aqueous solution in this embodiment is 40.9%.

[0135] It can be seen from the data of the above examples and comparative examples that the addition of the hydrolyzed hydroxylamine stabilizer prepared by the present invention can effectively improve the stability of the hydroxylamine aqueous solution and delay the decomposition of hydroxylamine.

[0136] The applicant declares that the present invention uses the above-described embodiments to illustrate the detailed process equipment and process flow of the present invention. However, the present invention is not limited to the above-described detailed process equipment and process flow, and does not necessarily rely on the above-described detailed process equipment and process flow in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for the raw materials of the present invention's products, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid, the operating steps of which are: S1: Add 13-17 parts by weight of acetone oxime to a reactor and add 60-80 parts of distilled water to completely dissolve the acetone oxime; S2: Add 1-3 parts of liquid organic acid, stir, and react under reduced pressure; S3: After the reaction is completed and the system returns to normal pressure, it is cooled to room temperature, the reaction solution is extracted and separated, and 0.05-0.2 parts of hydrolyzed hydroxylamine stabilizer is added and stirred to obtain a hydroxylamine aqueous solution; The preparation method of the hydrolyzed hydroxylamine stabilizer is: A1: In a stirred autoclave, nitrogen is introduced, and 14-26 parts by weight of 1H-benzotriazole-6-methylamine, 5-11 parts of allylthiourea, 0.5-2.5 parts of triethylamine, and 100-150 parts of solvent are added to the autoclave. The mixture is stirred at 50-60°C for 100-200 minutes. A2: Add 0.005-0.05 parts of 3-acryloyloxyflavone, stir at 40-50° C. for 30-100 minutes, and remove the solvent by distillation under reduced pressure to obtain a hydrolyzed hydroxylamine stabilizer.

2. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The liquid organic acid is selected from one or more of sulfamic acid, formic acid, oxalic acid, terephthalic acid and trifluoroacetic acid.

3. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The reactor in S1 is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

4. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The stirring rate in S2 and S3 is 300-500 rpm.

5. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The reaction temperature is 20-40°C.

6. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The reaction operating pressure is -0.08 to -0.09 MPa.

7. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The reaction time is 45-90 minutes.

8. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The extraction agent used for the extraction and separation in S3 is ethanol, ether or acetone.

9. The method for preparing a hydroxylamine aqueous solution by hydrolyzing acetone oxime catalyzed by a liquid organic acid according to claim 1, characterized in that: The solvent is selected from at least one of chloroform, carbon tetrachloride, acetonitrile, dimethylformamide and cyclohexane.