A method for preparing hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime

Abstract

A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime belongs to the technical field of hydroxylamine preparation. The present invention uses low-temperature catalytic hydrolysis of butanone oxime and extraction and separation to obtain a hydroxylamine aqueous solution; the catalyst undergoes a sulfhydryl addition reaction with vinylguanamine and 4-allylcatechol through a macroporous styrene thiol resin to obtain a guanidine resin, which is then sulfonated to obtain a guanidine solid acid catalyst. The guanidine solid acid catalyst has higher acid strength and stronger catalytic activity, can more effectively promote the hydrolysis of butanone oxime, can significantly increase the hydrolysis rate and conversion rate of butanone oxime, and has good economic benefits.

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 catalytic hydrolysis of butanone oxime. 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 discloses a method for preparing a high-purity free-state hydroxylamine aqueous solution. The method involves concentrating the dilute hydroxylamine aqueous solution in a tower, extracting hydroxylamine-containing vapor from the tower bottom via a side stream, and condensing the vapor to obtain high-purity hydroxylamine. The method is simple, employs mild conditions, and can be used for large-scale production to produce "electronic-grade" hydroxylamine.

[0004] Chinese patent CN200710068003.9 discloses a method for producing high-purity hydroxylamine and its active alkaline aqueous solution. Hydroxylamine phosphate is thermally decomposed under 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 of the active alkaline aqueous solution, and their metal ion content is extremely low, fully meeting the needs of the pharmaceutical and electronics industries. The method of the present invention is simple in equipment and operation, avoids the high-vacuum distillation and concentration process of low-concentration aqueous solutions, and eliminates the explosion hazard associated with the concentration process, thus possessing high industrial application value.

[0005] Chinese patent CN02813522.9 discloses 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 of Na is 70:30 to 95:5 and Na + and K + The total concentration is 0.1-10 m / m % based on the total amount of the mixture.

[0006] However, existing public patents and production 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 the product. Summary of the Invention

[0007] In order to solve at least one technical problem in the above technical background, the present invention provides a method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime. The hydroxylamine aqueous solution is obtained by low-temperature catalytic hydrolysis of butanone oxime and extraction and separation. The operation is simple and environmentally friendly.

[0008] The technical solution of the present invention is:

[0009] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0010] S1: Add 2-8 parts by mass of butanone oxime and 30-50 parts of deionized water to a hydrolysis kettle to completely dissolve the butanone oxime;

[0011] S2: Add 0.1-3 parts of catalyst, stir, and react under reduced pressure;

[0012] 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.

[0013] In some embodiments of the present invention, the catalyst is a guanidine-based solid acid catalyst, and a guanidine-based resin is obtained by subjecting a macroporous styrene-based thiol resin to a thiol addition reaction with vinylguanamine and 4-allylcatechol, respectively; and then sulfonated to obtain a guanidine-based solid acid catalyst.

[0014] Furthermore, the preparation method of the guanidine-based solid acid catalyst is:

[0015] A1: Weigh 100-180 parts by weight of a macroporous styrene-mercapto resin, 500-1000 parts of ethylene dichloride, 0.2-2 parts of vinylguanamine, and 2-5 parts of sodium ethoxide in a stirred reactor. Stir at 40-50°C for 10-30 minutes. Then, add 10-18 parts of 4-allylcatechol, stir for 60-120 minutes, and filter to obtain a guanidine resin.

[0016] A2: The guanidine resin obtained in step A1 is charged into a stirred tank, 1000-1300 parts of 80%-98% sulfuric acid is introduced, and the mixture is stirred at 70-80°C for 15-20 hours. The mixture is filtered, and the mixture is stirred with 50%-60% sulfuric acid for 1-3 hours; 20%-40% sulfuric acid is stirred for 1-3 hours; and deionized water is stirred for 1-3 hours. The mixture is filtered and dried to obtain a guanidine solid acid catalyst.

[0017] In some embodiments of the present invention, the macroporous styrene-mercapto resin is a commercially available product, such as HAD30 resin; D190 macroporous styrene-mercapto resin.

[0018] In some embodiments of the present invention, the reactor is connected to a distillation column and a vacuum pump decompression device, and the sealing of the entire device is ensured.

[0019] In some embodiments of the present invention, the stirring rate is 300-600 rpm.

[0020] In some embodiments of the present invention, the reaction temperature is 18-42°C.

[0021] In some embodiments of the present invention, the reaction operating pressure is -0.05 to -0.09 MPa.

[0022] In some embodiments of the present invention, the reaction time is 45-100 minutes.

[0023] In some embodiments of the present invention, the extractant is ethanol, ether or acetone.

[0024] Technical effects:

[0025] The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime of the present invention has the following significant effects compared with the prior art:

[0026] Solid acid catalysts have higher acid strength and stronger catalytic activity, which can more effectively promote the hydrolysis of butanone oxime. Compared with traditional liquid acid hydrolysis methods, this method can significantly increase the hydrolysis rate and conversion rate of butanone oxime, while also avoiding the corrosiveness of liquid acids. It also improves the stability of the hydroxylamine aqueous solution. DETAILED DESCRIPTION

[0027] 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.

[0028] The formula for calculating the product yield in the examples is as follows: the molar yield is calculated by weighing the mass of the product obtained and the mass of the raw materials used and calculating the amount of substance.

[0029] Example 1

[0030] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0031] S1: Add 2 kg of butanone oxime to the hydrolysis kettle and add 30 kg of deionized water to completely dissolve the butanone oxime;

[0032] S2: Add 0.1 kg of catalyst, stir, and react under reduced pressure;

[0033] 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.

[0034] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0035] A1: 100 g of macroporous styrene-mercapto resin, 500 g of ethylene dichloride, 0.2 g of vinylguanamine, and 2 g of sodium ethoxide were weighed and placed in a stirred reactor. The mixture was stirred at 40°C for 10 minutes. 10 g of 4-allylcatechol was then added, stirred for 60 minutes, and filtered to obtain a guanidine-based resin.

[0036] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1000 g of 80% sulfuric acid was introduced, and the mixture was stirred at 70°C for 15 hours. The mixture was filtered and stirred with 50% sulfuric acid for 1 hour; 20% sulfuric acid was stirred for 1 hour; deionized water was stirred for 1 hour; filtered, and dried to obtain a guanidine solid acid catalyst.

[0037] The macroporous styrene mercapto resin is a commercially available product, namely HAD30 resin.

[0038] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0039] The stirring rate is 300 rpm.

[0040] The reaction temperature is 18°C.

[0041] The reaction operating pressure is -0.05Mpa.

[0042] The reaction time is 45 minutes.

[0043] The extractant is ethanol.

[0044] In this example, the product yield was 98.9% based on the butanone oxime fed, and the product conversion rate was 88.7%.

[0045] Example 2

[0046] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0047] S1: Add 4 kg of butanone oxime to the hydrolysis kettle and add 35 kg of deionized water to completely dissolve the butanone oxime;

[0048] S2: Add 1 kg of catalyst, stir, and react under reduced pressure;

[0049] 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.

[0050] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0051] A1: 125 g of macroporous styrene-mercapto resin, 650 g of ethylene dichloride, 0.9 g of vinylguanamine, and 3.5 g of sodium ethoxide were weighed and added to a stirred reactor. The mixture was stirred at 45° C. for 15 minutes. 12 g of 4-allylcatechol was then added, stirred for 80 minutes, and filtered to obtain a guanidine-based resin.

[0052] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1100 g of 86% sulfuric acid was introduced, and the mixture was stirred at 70°C for 16 hours. The mixture was filtered and stirred with 50% sulfuric acid for 3 hours; 40% sulfuric acid for 3 hours; and deionized water for 3 hours. The mixture was filtered and dried to obtain a guanidine solid acid catalyst.

[0053] The macroporous styrene mercapto resin is a commercially available product, namely HAD30 resin.

[0054] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0055] The stirring rate is 450 rpm.

[0056] The reaction temperature is 28°C.

[0057] The reaction operating pressure is -0.07 MPa.

[0058] The reaction time is 65 min.

[0059] The extractant is ether.

[0060] In this example, the product yield was 99.3% based on the butanone oxime fed, and the product conversion rate was 91.3%.

[0061] Example 3

[0062] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0063] S1: Add 6 kg of butanone oxime to the hydrolysis kettle, add 40 kg of deionized water, and completely dissolve the butanone oxime;

[0064] S2: Add 2.3 kg of catalyst, stir, and react under reduced pressure;

[0065] 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.

[0066] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0067] A1: 160 g of macroporous styrene-mercapto resin, 800 g of ethylene dichloride, 1.5 g of vinylguanamine, and 4 g of sodium ethoxide were weighed and added to a stirred reactor. The mixture was stirred at 50° C. for 10 minutes. 16 g of 4-allylcatechol was then added, stirred for 100 minutes, and filtered to obtain a guanidine-based resin.

[0068] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1250 g of 92% sulfuric acid was introduced, and the mixture was stirred at 80°C for 15 hours. The mixture was filtered and stirred with 60% sulfuric acid for 1 hour; 40% sulfuric acid for 1 hour; deionized water for 2 hours; filtered, and dried to obtain a guanidine solid acid catalyst.

[0069] The macroporous styrene-mercapto resin is a commercially available product, namely D190 macroporous styrene-mercapto resin.

[0070] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0071] The stirring rate is 520 rpm.

[0072] The reaction temperature is 36°C.

[0073] The reaction operating pressure is -0.08Mpa.

[0074] The reaction time is 85 min.

[0075] The extractant is acetone.

[0076] In this example, the product yield was 99.5% based on the butanone oxime fed, and the product conversion rate was 94.2%.

[0077] Example 4

[0078] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0079] S1: Add 8 kg of butanone oxime to the hydrolysis kettle, add 50 kg of deionized water, and completely dissolve the butanone oxime;

[0080] S2: Add 3 kg of catalyst, stir, and react under reduced pressure;

[0081] 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.

[0082] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0083] A1: 180 g of macroporous styrene-mercapto resin, 1000 g of ethylene dichloride, 2 g of vinylguanamine, and 5 g of sodium ethoxide were weighed and added to a stirred reactor. The mixture was stirred at 50° C. for 30 minutes. 18 g of 4-allylcatechol was then added, stirred for 120 minutes, and filtered to obtain a guanidine-based resin.

[0084] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1300 g of 98% sulfuric acid was introduced, and the mixture was stirred at 80°C for 20 hours. The mixture was filtered and stirred with 60% sulfuric acid for 3 hours; 40% sulfuric acid was stirred for 3 hours; deionized water was stirred for 3 hours; filtered, and dried to obtain a guanidine solid acid catalyst.

[0085] The macroporous styrene-mercapto resin is a commercially available product, namely D190 macroporous styrene-mercapto resin.

[0086] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0087] The stirring rate is 600 rpm.

[0088] The reaction temperature is 42°C.

[0089] The reaction operating pressure is -0.09 MPa.

[0090] The reaction time is 100 min.

[0091] The extractant is ethanol.

[0092] In this example, the product yield was 99.4% based on the butanone oxime fed, and the product conversion rate was 92.5%.

[0093] Comparative Example 1

[0094] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0095] S1: Add 2 kg of butanone oxime to the hydrolysis kettle and add 30 kg of deionized water to completely dissolve the butanone oxime;

[0096] S2: Add 0.1 kg of catalyst, stir, and react under reduced pressure;

[0097] 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.

[0098] The catalyst is aminosulfonic acid.

[0099] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0100] The stirring rate is 300 rpm.

[0101] The reaction temperature is 18°C.

[0102] The reaction operating pressure is -0.05Mpa.

[0103] The reaction time is 45 minutes.

[0104] The extractant is ethanol.

[0105] In this example, the product yield was 95.6% based on the butanone oxime fed, and the product conversion rate was 70.8%.

[0106] Comparative Example 2

[0107] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0108] S1: Add 2 kg of butanone oxime to the hydrolysis kettle and add 30 kg of deionized water to completely dissolve the butanone oxime;

[0109] S2: Add 0.1 kg of catalyst, stir, and react under reduced pressure;

[0110] 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.

[0111] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0112] A1: Weigh 100 g of macroporous styrene-mercapto resin, 500 g of ethylene dichloride, and 2 g of sodium ethoxide into a stirred reactor. Stir at 40°C for 10 minutes. Then, add 10 g of 4-allylcatechol, stir for 60 minutes, and filter to obtain a guanidine-based resin.

[0113] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1000 g of 80% sulfuric acid was introduced, and the mixture was stirred at 70°C for 15 hours. The mixture was filtered and stirred with 50% sulfuric acid for 1 hour; 20% sulfuric acid was stirred for 1 hour; deionized water was stirred for 1 hour; filtered, and dried to obtain a guanidine solid acid catalyst.

[0114] The macroporous styrene mercapto resin is a commercially available product, namely HAD30 resin.

[0115] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0116] The stirring rate is 300 rpm.

[0117] The reaction temperature is 18°C.

[0118] The reaction operating pressure is -0.05Mpa.

[0119] The reaction time is 45 minutes.

[0120] The extractant is ethanol.

[0121] In this example, the product yield was 97.4% based on the butanone oxime fed, and the product conversion rate was 80.4%.

[0122] Comparative Example 3

[0123] A method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime, the operating steps are:

[0124] S1: Add 2 kg of butanone oxime to the hydrolysis kettle and add 30 kg of deionized water to completely dissolve the butanone oxime;

[0125] S2: Add 0.1 kg of catalyst, stir, and react under reduced pressure;

[0126] 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.

[0127] The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows:

[0128] A1: Weigh 100 g of macroporous styrene-mercapto resin, 500 g of ethylene dichloride, 0.2 g of vinylguanamine, and 2 g of sodium ethoxide, add them to a stirred reactor, stir at 40°C for 70 minutes, and filter to obtain a guanidine-based resin;

[0129] A2: The guanidine resin obtained in step A1 was charged into a stirred tank, 1000 g of 80% sulfuric acid was introduced, and the mixture was stirred at 70°C for 15 hours. The mixture was filtered and stirred with 50% sulfuric acid for 1 hour; 20% sulfuric acid was stirred for 1 hour; deionized water was stirred for 1 hour; filtered, and dried to obtain a guanidine solid acid catalyst.

[0130] The macroporous styrene mercapto resin is a commercially available product, namely HAD30 resin.

[0131] The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

[0132] The stirring rate is 300 rpm.

[0133] The reaction temperature is 18°C.

[0134] The reaction operating pressure is -0.05Mpa.

[0135] The reaction time is 45 minutes.

[0136] The extractant is ethanol.

[0137] In this example, the product yield was 96.7% based on the butanone oxime fed, and the product conversion rate was 77.3%.

[0138] It can be seen from the above implementation scheme that the technical solution provided by the present invention significantly improves the conversion rate of butanone oxime compared with the traditional liquid acid hydrolysis method, improves the product yield to a certain extent, and improves economic efficiency.

[0139] 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 by catalytic hydrolysis of butanone oxime, the operating steps are: S1: Add 2-8 parts by mass of butanone oxime and 30-50 parts of deionized water to a hydrolysis kettle to completely dissolve the butanone oxime; S2: Add 0.1-3 parts of catalyst, stir, and react under reduced pressure; S3: After the reaction is completed, the system is restored to normal pressure, cooled to room temperature, and the reaction solution is extracted and separated to obtain a hydroxylamine aqueous solution; The catalyst is a guanidine-based solid acid catalyst, and its preparation method is as follows: A1: Weigh 100-180 parts by weight of a macroporous styrene-mercapto resin, 500-1000 parts of ethylene dichloride, 0.2-2 parts of vinylguanamine, and 2-5 parts of sodium ethoxide in a stirred reactor. Stir at 40-50°C for 10-30 minutes. Then, add 10-18 parts of 4-allylcatechol, stir for 60-120 minutes, and filter to obtain a guanidine resin. A2: The guanidine resin obtained in step A1 is charged into a stirred tank, 1000-1300 parts of 80%-98% sulfuric acid is introduced, and the mixture is stirred at 70-80°C for 15-20 hours. The mixture is filtered, and the mixture is stirred with 50%-60% sulfuric acid for 1-3 hours; 20%-40% sulfuric acid is stirred for 1-3 hours; and deionized water is stirred for 1-3 hours. The mixture is filtered and dried to obtain a guanidine solid acid catalyst.

2. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The reactor is connected to the distillation column and the vacuum pump decompression device, and the sealing of the entire device is ensured.

3. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The stirring rate of the step S2 is 300-600 rpm.

4. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The reaction temperature is 18-42°C.

5. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The reaction operating pressure is -0.05 to -0.09 MPa.

6. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The reaction time is 45-100 minutes.

7. The method for preparing a hydroxylamine aqueous solution by catalytic hydrolysis of butanone oxime according to claim 1, characterized in that: The extractant is ethanol, ether or acetone.