A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde

Abstract

The invention relates to a method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde. In the method, butanone oxime and a catalyst molybdate sulfonic acid resin are added to a reactor under a nitrogen atmosphere, stirred and mixed, acetaldehyde is slowly added dropwise while stirring, and after the reaction is completed, the catalyst is filtered to remove, and the filtrate is subjected to reduced pressure rectification to obtain acetaldehyde oxime; the molybdate sulfonic acid resin is subjected to a sulfonic acid resin, acryloyl chloride, DMF and pyridine, and after stirring and reacting, the product is filtered and washed to obtain an allyl sulfonic acid resin; the allyl sulfonic acid resin is added to water, ammonium molybdate tetrahydrate and 4-(2-carboxyethylene)phenylboric acid are added, sodium hydroxide is slowly added, the pH value is adjusted to 9-10, and after the reaction is completed, the product is filtered and washed with deionized water until the pH value of the washing liquid reaches 7 to obtain a sodium-type molybdate sulfonic acid resin; and the sodium-type molybdate sulfonic acid resin is treated with a hydrochloric acid solution to transform it into a hydrogen-type resin. The method can effectively improve the selectivity of acetaldehyde oxime and the conversion rate of butanone oxime.

Description

Technical Field

[0001] The invention relates to the technical field of acetaldehyde oxime synthesis, in particular to a method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde. Background Art

[0002] Acetaldehyde oxime is an important raw material for the preparation of the pesticides methomyl and thiodicarb, and is also an important organic synthesis reagent and analytical reagent. It has a large market demand and broad development prospects.

[0003] Chinese patent CN111943866A: discloses a method for continuously producing acetaldehyde oxime using a fixed bed, comprising the following steps: S1, filling the activated carbon additive after activation treatment into the fixed bed, and dissolving the catalyst in butanone oxime, wherein the mass fraction of the catalyst in the butanone oxime is 0.01-1%; S2, at a certain reaction temperature and pressure, simultaneously adding butanone oxime and acetaldehyde dissolved with the catalyst into the fixed bed in step S1 for reaction, wherein the molar ratio of butanone oxime to acetaldehyde is 1:1.5-5, the reaction temperature is 10-55°C, and the pressure is 0-0.5MPa.

[0004] Chinese patent CN112409208A: discloses a method for preparing acetaldehyde oxime by a continuous process, wherein the method is as follows: first, quartz sand is loaded into a reactor, and then raw materials such as hydroxylamine hydrochloride aqueous solution, acetaldehyde, and ammonia water are introduced into the reactor, and the reaction temperature and reaction pressure are controlled to adjust the pH.

[0005] Chinese Patent CN112574063A: relates to the chemical industry. The present invention provides a method for preparing acetaldehyde oxime, comprising: oximation reaction, stripping separation, distillation purification and other steps; The present invention provides a method for preparing acetaldehyde oxime. The method uses a modified titanium silicon molecular sieve catalyst prepared by the present invention to catalyze the oximation reaction of acetaldehyde and hydroxylamine hydrochloride.

[0006] At present, the Raschig method and oxime exchange method are mainly used to prepare acetaldehyde oxime; the Raschig method reaction process is relatively complicated, with many side reactions and serious environmental pollution; during the reaction process of the oxime exchange method, acetaldehyde oxime is unstable in the air and easily oxidized, and both butanone oxime and acetaldehyde are easily volatile, which affects the quality of acetaldehyde oxime. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, and the operating steps are as follows:

[0008] S1: Under a nitrogen atmosphere, 80-90 parts of butanone oxime and 5-10 parts of a catalyst molybdate sulfonic acid resin are added to a reaction kettle, stirred and mixed, and 160-180 parts of acetaldehyde are slowly added dropwise while stirring. After the addition is completed, the reaction is continued for 180-240 minutes;

[0009] S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is subjected to vacuum distillation to obtain acetaldehyde oxime;

[0010] The molybdate-based sulfonic acid resin is prepared by an addition reaction between acryl styrene-based sulfonic acid resin, ammonium molybdate tetrahydrate and 4-(2-carboxyvinyl)phenylboronic acid.

[0011] The pressure of nitrogen in the reactor is controlled at 0.1-0.2 MPa.

[0012] The acetaldehyde dropping time is 50-70 minutes.

[0013] The reaction temperature is 25-35°C.

[0014] The operating pressure of the vacuum distillation is -0.08~-0.09MPa, and the reflux ratio is 2-3.

[0015] The preparation method of the molybdate-based sulfonic acid resin is:

[0016] A1: 100-140 parts of sulfonic acid resin (the factory type is sodium type) and 30-50 parts of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1000-1200 parts of DMF and 4-8 parts of pyridine are added to the reaction kettle, stirred and reacted at 15-25°C for 4-7h, and the product is filtered and washed to obtain propylene sulfonic acid resin;

[0017] A2: Add 100-140 parts of propylene sulfonic acid resin to 1000-1200 parts of water, add 3-6 parts of ammonium molybdate tetrahydrate, 0.03-0.6 parts of 4-(2-carboxyvinyl)phenylboric acid, slowly add sodium hydroxide, adjust the pH value to 9-10, promote the reaction, continue stirring for 6-10 hours to ensure that the reaction is complete, filter and wash the product with deionized water until the pH value of the washing liquid reaches 7, to obtain a sodium molybdate sulfonic acid resin;

[0018] A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows:

[0019] The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

[0020] The sulfonic acid resin is a styrene sulfonic acid resin.

[0021] The styrene sulfonic acid resin is one of D006 styrene sulfonic acid resin, D008 styrene sulfonic acid resin and A15 styrene sulfonic acid resin.

[0022] The mass concentration of the hydrochloric acid solution of A3 is 2-5%.

[0023] The amount of the hydrochloric acid solution of A3 is 2-4 times the volume of the resin, and the soaking time is 2-4 hours.

[0024] Reaction mechanism

[0025] 1. An amino-olefin addition reaction occurs between acryl styrene sulfonic acid resin, ammonium molybdate tetrahydrate and 4-(2-carboxyvinyl)phenylboronic acid to generate a solid heteropoly acid resin catalyst containing molybdate, phenylboronic acid and sulfonic acid.

[0026] 2. Catalyst structure: The catalyst contains molybdic acid groups, phenylboronic acid groups and sulfonic acid groups; these groups work together to provide acidic sites and redox active centers, which help the catalytic reaction proceed.

[0027] During the reaction, the amino group of butanone oxime undergoes a nucleophilic addition reaction with the carbonyl group of acetaldehyde to generate an intermediate; then, the intermediate is converted into acetaldehyde oxime under the action of a catalyst; the molybdic acid group in the catalyst plays a redox role, while the sulfonic acid group provides a proton to promote the reaction.

[0028] Technical Effects

[0029] The present invention discloses a method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde. Compared with the prior art, the present invention has the following significant effects:

[0030] 1. Improve reaction efficiency: In the reaction of butanone oxime and acetaldehyde to efficiently synthesize acetaldehyde oxime, the solid heteropoly acid resin catalyst containing molybdate, phenylboronic acid and sulfonic acid significantly improves the reaction efficiency and selectivity by providing acid sites and redox active centers, thereby significantly increasing the yield of acetaldehyde oxime.

[0031] 2. Enhanced stability: The phenylboronic acid group and sulfonic acid group in the catalyst structure enhance the stability of the catalyst through π-π interaction and electrostatic repulsion, preventing the catalyst from degrading during the reaction.

[0032] 3. Easy to separate: Since the catalyst is in solid form, it can be separated from the reaction system by simple filtration or centrifugation after the reaction is completed, which is convenient for the recovery and reuse of the catalyst. DETAILED DESCRIPTION

[0033] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples:

[0034] Acetaldehyde oxime was detected by gas chromatography, and the detection results are shown in Table 1.

[0035] Example 1

[0036] A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, the operating steps of which are:

[0037] S1: Under a nitrogen atmosphere, 80 g of butanone oxime and 5 g of a catalyst molybdate sulfonic acid resin were added to a reaction kettle, stirred and mixed, and 160 g of acetaldehyde was slowly added dropwise while stirring. After the addition was completed, the reaction was continued for 180 min;

[0038] S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is distilled under reduced pressure to obtain acetaldehyde oxime;

[0039] The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0040] The pressure of nitrogen in the reactor is controlled at 0.1 MPa.

[0041] The acetaldehyde dropping time is 50 minutes.

[0042] The reaction temperature is 25°C.

[0043] The operating pressure of the vacuum distillation is -0.08MPa, and the reflux ratio is 2.

[0044] The preparation method of the molybdate-based sulfonic acid resin is:

[0045] A1: 100 g of sulfonic acid resin (the factory type is sodium type) and 30 g of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1000 g of DMF and 4 g of pyridine are added to the reaction kettle, stirred and reacted at 15° C. for 4 h, and the product is filtered and washed to obtain propylene sulfonic acid resin;

[0046] A2: 100 g of propylene sulfonic acid resin was added to 1000 g of water, 3 g of ammonium molybdate tetrahydrate and 0.03 g of 4-(2-carboxyvinyl)phenylboronic acid were added, sodium hydroxide was slowly added, the pH value was adjusted to 9, the reaction was promoted, stirring was continued for 6 h to ensure that the reaction was complete, the product was filtered and washed with deionized water until the pH value of the washing solution reached 7, and a sodium-type molybdate-based sulfonic acid resin was obtained;

[0047] A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows:

[0048] The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

[0049] The sulfonic acid resin is a styrene sulfonic acid resin.

[0050] The styrene sulfonic acid resin is D006 styrene sulfonic acid resin.

[0051] The mass concentration of the hydrochloric acid solution of A3 is 2%.

[0052] The amount of the hydrochloric acid solution A3 used is twice the volume of the resin, and the immersion time is 2 hours.

[0053] Example 2

[0054] A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, the operating steps of which are:

[0055] S1: Under a nitrogen atmosphere, 83 g of butanone oxime and 6 g of a catalyst molybdate sulfonic acid resin were added to a reaction kettle, stirred and mixed, and 165 g of acetaldehyde was slowly added dropwise while stirring. After the addition was completed, the reaction was continued for 200 min;

[0056] S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is distilled under reduced pressure to obtain acetaldehyde oxime;

[0057] The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0058] The pressure of nitrogen in the reactor is controlled at 0.15 MPa.

[0059] The acetaldehyde dropping time is 55 minutes.

[0060] The reaction temperature is 28°C.

[0061] The operating pressure of the vacuum distillation is -0.085MPa, and the reflux ratio is 2.

[0062] The preparation method of the molybdate-based sulfonic acid resin is:

[0063] A1: 110 g of sulfonic acid resin (the factory type is sodium type) and 35 g of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1050 g of DMF and 5 g of pyridine are added to the reaction kettle, stirred and reacted at 18°C ​​for 5 h, and the product is filtered and washed to obtain propylene sulfonic acid resin;

[0064] A2: 110 g of propylene sulfonic acid resin was added to 1050 g of water, 4 g of ammonium molybdate tetrahydrate and 0.2 g of 4-(2-carboxyvinyl)phenylboronic acid were added, sodium hydroxide was slowly added, the pH value was adjusted to 9, the reaction was promoted, stirring was continued for 7 h, and the reaction was ensured to be complete, and the product was filtered and washed with deionized water until the pH value of the washing solution reached 7 to obtain a sodium-type molybdate-based sulfonic acid resin;

[0065] A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows:

[0066] The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

[0067] The sulfonic acid resin is a styrene sulfonic acid resin.

[0068] The styrene sulfonic acid resin is D008 styrene sulfonic acid resin.

[0069] The mass concentration of the hydrochloric acid solution of A3 is 3%.

[0070] The amount of the A3 hydrochloric acid solution used is 3 times the volume of the resin, and the immersion time is 2.5 hours.

[0071] Example 3

[0072] A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, the operating steps of which are:

[0073] S1: Under a nitrogen atmosphere, 88 g of butanone oxime and 9 g of a catalyst molybdate sulfonic acid resin were added to a reaction kettle, stirred and mixed, and 175 g of acetaldehyde was slowly added dropwise while stirring. After the addition was completed, the reaction was continued for 220 min;

[0074] S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is distilled under reduced pressure to obtain acetaldehyde oxime;

[0075] The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0076] The pressure of nitrogen in the reactor is controlled at 0.15 MPa.

[0077] The acetaldehyde dropping time is 65 minutes.

[0078] The reaction temperature is 33°C.

[0079] The operating pressure of the vacuum distillation is -0.085MPa, and the reflux ratio is 3.

[0080] The preparation method of the molybdate-based sulfonic acid resin is:

[0081] A1: 130 g of sulfonic acid resin (the factory type is sodium type) and 45 g of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1150 g of DMF and 7 g of pyridine are added to the reaction kettle, stirred and reacted at 23° C. for 6 h, and the product is filtered and washed to obtain propylene sulfonic acid resin;

[0082] A2: 130 g of propylene sulfonic acid resin was added to 1150 g of water, 5 g of ammonium molybdate tetrahydrate and 0.4 g of 4-(2-carboxyvinyl)phenylboronic acid were added, sodium hydroxide was slowly added, the pH value was adjusted to 10, the reaction was promoted, stirring was continued for 9 h to ensure that the reaction was complete, the product was filtered and washed with deionized water until the pH value of the washing solution reached 7, and a sodium-type molybdate-based sulfonic acid resin was obtained;

[0083] A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows:

[0084] The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

[0085] The sulfonic acid resin is a styrene sulfonic acid resin.

[0086] The styrene sulfonic acid resin is D008 styrene sulfonic acid resin.

[0087] The mass concentration of the hydrochloric acid solution of A3 is 4%.

[0088] The amount of the A3 hydrochloric acid solution used is 3 times the volume of the resin, and the immersion time is 3.5 hours.

[0089] Example 4

[0090] A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, the operating steps of which are:

[0091] S1: Under a nitrogen atmosphere, 90 g of butanone oxime and 10 g of a catalyst molybdate sulfonic acid resin were added to a reaction kettle, stirred and mixed, and 180 g of acetaldehyde was slowly added dropwise while stirring. After the addition was completed, the reaction was continued for 240 min;

[0092] S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is distilled under reduced pressure to obtain acetaldehyde oxime;

[0093] The coagulant is prepared by the reaction between ferrocenyl hexanethiol and benzofuranyl-containing acrylamide.

[0094] The pressure of nitrogen in the reactor is controlled at 0.2 MPa.

[0095] The acetaldehyde dropping time is 70 minutes.

[0096] The reaction temperature is 35°C.

[0097] The operating pressure of the vacuum distillation is -0.09MPa, and the reflux ratio is 3.

[0098] The preparation method of the molybdate-based sulfonic acid resin is:

[0099] A1: 140 g of sulfonic acid resin (the factory type is sodium type) and 50 g of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1200 g of DMF and 8 g of pyridine are added to the reaction kettle, and the reaction is stirred at 25°C for 7 hours, and the product is filtered and washed to obtain propylene sulfonic acid resin;

[0100] A2: 140 g of propylene sulfonic acid resin was added to 1200 g of water, 6 g of ammonium molybdate tetrahydrate and 0.6 g of 4-(2-carboxyvinyl)phenylboronic acid were added, sodium hydroxide was slowly added, the pH value was adjusted to 10, the reaction was promoted, stirring was continued for 10 h, and the reaction was ensured to be complete, and the product was filtered and washed with deionized water until the pH value of the washing solution reached 7 to obtain a sodium-type molybdate-based sulfonic acid resin;

[0101] A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows:

[0102] The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

[0103] The sulfonic acid resin is a styrene sulfonic acid resin.

[0104] The styrene sulfonic acid resin is A15 styrene sulfonic acid resin.

[0105] The mass concentration of the hydrochloric acid solution of A3 is 5%.

[0106] The amount of the hydrochloric acid solution of A3 used is 4 times the volume of the resin, and the immersion time is 4 hours.

[0107] Comparative Example 1

[0108] No molybdate-based sulfonic acid resin was added, but sulfonic acid resin was added. Other steps were the same as in Example 1.

[0109] Comparative Example 2

[0110] Ammonium molybdate tetrahydrate was not added, and the rest was the same as in Example 1.

[0111] Comparative Example 3

[0112] The other steps were the same as in Example 1 except that 4-(2-carboxyvinyl)phenylboronic acid was not added.

[0113] Table 1

[0114] The conversion rate of butanone oxime reached / % The selectivity of acetaldehyde oxime is / % Example 1 98.56 97.91 Example 2 98.83 98.43 Example 3 99.18 98.85 Example 4 99.57 99.32 Comparative Example 1 89.22 88.54 Comparative Example 2 94.45 93.66 Comparative Example 3 95.04 94.23

[0115] Through the data analysis of the above embodiments and comparative examples, the present invention can effectively improve the selectivity of acetaldehyde oxime and the conversion rate of butanone oxime.

[0116] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde, the operating steps of which are: S1: Under a nitrogen atmosphere, 80-90 parts of butanone oxime and 5-10 parts of a catalyst molybdate sulfonic acid resin are added to a reaction kettle, stirred and mixed, and 160-180 parts of acetaldehyde are slowly added dropwise while stirring. After the addition is completed, the reaction is continued for 180-240 minutes; S2: After the reaction is completed, the catalyst is removed by filtration, and the filtrate is subjected to vacuum distillation to obtain acetaldehyde oxime; The molybdate-based sulfonic acid resin is prepared by an addition reaction between an acryl styrene-based sulfonic acid resin, ammonium molybdate tetrahydrate and 4-(2-carboxyvinyl)phenylboronic acid; The preparation method of the molybdate-based sulfonic acid resin is: A1: 100-140 parts of sulfonic acid resin (the factory type is sodium type) and 30-50 parts of acryloyl chloride are added to a stirring kettle and stirred and mixed, 1000-1200 parts of DMF and 4-8 parts of pyridine are added to the reaction kettle, stirred and reacted at 15-25°C for 4-7h, and the product is filtered and washed to obtain propylene sulfonic acid resin; A2: Add 100-140 parts of propylene sulfonic acid resin to 1000-1200 parts of water, add 3-6 parts of ammonium molybdate tetrahydrate, 0.03-0.6 parts of 4-(2-carboxyvinyl)phenylboric acid, slowly add sodium hydroxide, adjust the pH value to 9-10, promote the reaction, continue stirring for 6-10 hours to ensure that the reaction is complete, filter and wash the product with deionized water until the pH value of the washing liquid reaches 7, to obtain a sodium molybdate sulfonic acid resin; A3: Convert the sodium molybdate sulfonic acid resin into hydrogen type resin. The operation steps are as follows: The resin is treated with a hydrochloric acid solution to transform it from the sodium form to the hydrogen form; during the transformation process, the resin is stirred from time to time to ensure that the reaction proceeds evenly; after the transformation is completed, the resin is rinsed again with deionized water until the pH of the discharged water is close to 4, thereby obtaining a molybdate-based sulfonic acid resin.

2. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The pressure of the nitrogen is controlled at 0.1-0.2 MPa.

3. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The acetaldehyde dropping time is 50-70 minutes.

4. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The reaction temperature is 25-35°C.

5. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The operating pressure of the vacuum distillation is -0.08 to -0.09 MPa, and the reflux ratio is 2-3.

6. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The sulfonic acid resin is a styrene sulfonic acid resin.

7. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 6, characterized in that: The styrene sulfonic acid resin is one of D006 styrene sulfonic acid resin, D008 styrene sulfonic acid resin and A15 styrene sulfonic acid resin.

8. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The mass concentration of the hydrochloric acid solution of A3 is 2-5%.

9. The method for efficiently synthesizing acetaldehyde oxime from butanone oxime and acetaldehyde according to claim 1, characterized in that: The amount of the hydrochloric acid solution of A3 is 2-4 times the volume of the resin, and the soaking time is 2-4 hours.