Clean production process for co-producing diacetylmonoxime and acetaldehyde oxime

Abstract

The invention relates to a clean production process for co-producing diacetylmonoxime and acetaldehyde oxime. The method comprises the following steps: adding a modified catalyst, solvent water and butanone into a reaction kettle, starting to stir and heat under the protection of nitrogen, slowly introducing ammonia gas, then slowly adding a hydrogen peroxide aqueous solution, and after the reaction is finished, carrying out centrifugal separation to obtain diacetylmonoxime; the preparation method comprises the following steps: adding hydroxylamine hydrochloride and water into a reaction kettle, stirring to dissolve the hydroxylamine hydrochloride and the water, dropwise adding acetaldehyde under cooling of an ice-water bath, and reacting; dropwise adding alkali liquor, and stirring to obtain an acetaldehyde oxime water solution; the method comprises the following steps: extracting an acetaldoxime aqueous solution with dichloromethane, drying an extract liquid with anhydrous sodium sulfate, fractionating at normal pressure to obtain most of a solvent, fractionating at reduced pressure, and collecting fractions to obtain anhydrous acetaldoxime; the modified catalyst disclosed by the invention is obtained by reacting a TS-1 molecular sieve, mercapto siloxane, (E)-1-allyl potassium trifluoroborate, allyl trimethyl stannane, methylbenzene and sodium ethoxide; the diacetylmonoxime and acetaldehyde oxime prepared by the invention have higher purity.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical synthesis, in particular to a clean production process for co-producing butanone oxime and acetaldehyde oxime. Background Art

[0002] Both butanone oxime and acetaldehyde oxime are important organic chemical raw materials. Butanone oxime can be used as an anti-skinning agent for coatings and inks and is also the primary raw material for the synthesis of the organosilicon crosslinkers methyltributylanoximesilane and vinyltributylanoximesilane. Acetaldehyde oxime is a low-toxic reducing agent and a novel, low-pollution, and effective scavenger. It is also an important intermediate in the synthesis of the pesticides methomyl and thiodicarb.

[0003] Chinese patent CN113230986B: Provides an apparatus for industrially preparing butanone oxime, and a method for preparing butanone oxime using the apparatus. The apparatus comprises a butanone ammoximation reactor, a feeding system, a product separation system, and a tail gas absorption system. The feeding system is used to feed reactants including hydrogen peroxide, butanone, gaseous ammonia, and a catalyst into the butanone ammoximation reactor; the product separation system is used to separate the mixed slurry output from the butanone ammoximation reactor; and the tail gas absorption system is used to absorb and separate the gaseous products output from the butanone ammoximation reactor.

[0004] Chinese patent CN1939897A: discloses a method for preparing ketone oxime using ketone as raw material through heterogeneous ammoximation. The method comprises: in the presence of a water-immiscible or slightly soluble solvent, subjecting ketone, hydrogen peroxide and ammonia to a heterogeneous catalytic oximation reaction to produce ketone oxime; after the oximation reaction products are phase-separated, part of the water is separated from the heavy phase product and recycled.

[0005] Chinese patent CN115974720B discloses a method and apparatus for preparing ketoxime using ketone, ammonia, and hydrogen peroxide as raw materials through a two-stage ammoximation reaction. The method comprises: in the presence of a solid catalyst and deionized water, reacting ketone, hydrogen peroxide, and ammonia to produce ketoxime; extracting the reaction solution with an organic solvent; separating the catalyst and a small amount of water by hydrocyclone separation and membrane filtration; and recycling the catalyst and a small amount of water back to the reactor; removing the majority of the water and oil phases and treating the system.

[0006] Currently, the production processes for butanone oxime and acetaldehyde oxime present numerous challenges. Prior art processes for preparing butanone oxime and acetaldehyde oxime are often complex, involving multiple reactions and complex separation and purification steps, resulting in high production costs. Furthermore, the purity and selectivity of the products need to be further improved, making it difficult to meet growing market demand. Furthermore, traditional processes generate large amounts of wastewater, waste gas, and waste residue during production, causing significant environmental pollution and failing to align with current green chemistry and clean production concepts. Therefore, developing a production process that can efficiently and cleanly co-produce butanone oxime and acetaldehyde oxime is of great practical significance. Summary of the Invention

[0007] In order to solve the above problems, the present invention provides a clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are as follows:

[0008] S1: Add 2-10 parts of modified catalyst, 180-240 parts of solvent water, and 40-60 parts of butanone to a reactor. Under the protection of nitrogen, stir and heat. Slowly introduce 30-50 parts of ammonia gas, and then slowly add aqueous hydrogen peroxide solution. After the reaction is completed, centrifuge to obtain butanone oxime;

[0009] S2: Add 50-90 parts of hydroxylamine hydrochloride and 100-140 parts of water to a reaction kettle, stir to dissolve, and add 35-50 parts of acetaldehyde dropwise under ice-water bath cooling to react;

[0010] S3: then add alkali solution dropwise and stir for 20-30 minutes to obtain an acetaldehyde oxime aqueous solution;

[0011] S4: The acetaldehyde oxime aqueous solution is extracted with dichloromethane. After the extract is dried over anhydrous sodium sulfate, most of the solvent is first distilled off under normal pressure, and then fractionated under reduced pressure to collect the 76-78°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime.

[0012] The mass concentration of the hydrogen peroxide aqueous solution is 20-30%.

[0013] The reaction temperature of S1 is 40-60°C, and the reaction time is 3-6h.

[0014] The reaction temperature of S2 is 5-8°C, and the reaction time is 4-7h.

[0015] The alkali solution consists of 30-40 parts of sodium hydroxide and 40-50 parts of water.

[0016] The temperature of S3 is 10-15°C.

[0017] The modified catalyst preparation method is:

[0018] T1: Add 100-150 parts of TS-1 molecular sieve and 5-10 parts of mercaptosiloxane to 1200-1300 parts of water, stirring at room temperature, filtering, and drying to obtain mercapto TS-1 molecular sieve;

[0019] T2: Add 100-150 parts of mercapto TS-1 molecular sieve, 2.4-4.8 parts of (E)-1-propenyl potassium trifluoroborate, and 0.03-0.3 parts of allyltrimethylstannane to 1000-1200 parts of toluene, stir and mix until uniform, then add 2-5 parts of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

[0020] The mercaptosiloxane is one of γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0021] The reaction time of T1 is 100-120 min.

[0022] The reaction temperature of T2 is 70-90°C and the reaction time is 60-120 minutes.

[0023] Reaction mechanism

[0024] 1. Mercapto-olefin addition reaction: The mercapto group (-SH) in the mercapto TS-1 molecular sieve reacts with the olefin group in (E)-1-propenyltrifluoroborate and allyltrimethylstannane; (E)-1-propenyltrifluoroborate and allyltrimethylstannane respectively combine with the mercapto groups on the mercapto TS-1 molecular sieve to form new chemical bonds; these newly formed chemical bonds firmly anchor the modifiers (i.e., (E)-1-propenyltrifluoroborate and allyltrimethylstannane) on the surface or skeleton of the TS-1 molecular sieve, thereby changing its catalytic performance.

[0025] 2. Formation of active sites: The modified TS-1 catalyst exhibits higher catalytic efficiency in ammoximation reactions due to the introduction of new active sites or the enhancement of the activity of existing active sites. The catalytic performance of the TS-1 molecular sieve is enhanced by modifying its acidity, pore structure, or by adding specific functional groups.

[0026] Technical Effects

[0027] The present invention provides a clean production process for the co-production of butanone oxime and acetaldehyde oxime. Compared with the prior art, the present invention has the following significant effects:

[0028] 1. Improve catalytic activity

[0029] Enhanced active sites: The modified TS-1 catalyst exhibits higher catalytic efficiency in the ammoximation reaction due to the introduction of new active sites or the enhancement of the activity of the original active sites.

[0030] 2. Enhanced stability

[0031] Carbon deposition resistance: The modification process also enhances the thermal and chemical stability of the TS-1 catalyst, enabling it to maintain stable catalytic performance under more demanding reaction conditions. The modified TS-1 catalyst's enhanced carbon deposition resistance and improved regeneration performance significantly extend its service life. This is crucial for reducing catalyst replacement frequency, lowering production costs, and improving production efficiency.

[0032] 3. Improve selectivity

[0033] Adjusting Catalytic Performance: By precisely controlling the modification process, the selectivity of the TS-1 catalyst can be adjusted to favor the target product over byproducts. This helps improve product purity and yield, while reducing production costs. The modified TS-1 catalyst effectively suppresses side reactions, thereby improving the selectivity and yield of the target product. DETAILED DESCRIPTION

[0034] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in conjunction with the embodiments and comparative examples:

[0035] 1. Determination of butanone oxime content: The sample is vaporized and passed through a chromatographic column to separate butanone oxime from other components. The sample is monitored by a flame ionization detector and the mass fraction of butanone oxime is calculated by the area normalization method.

[0036] 2. Acetaldehyde oxime is detected by gas chromatography.

[0037] The test and calculation results are shown in Table 1.

[0038] Example 1

[0039] A clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are as follows:

[0040] S1: Add 2g of modified catalyst, 180g of solvent water, and 40g of butanone to a reactor. Under the protection of nitrogen, stir and heat, slowly introduce 30g of ammonia gas, and then slowly add aqueous hydrogen peroxide solution. After the reaction is completed, centrifuge to obtain butanone oxime;

[0041] S2: Add 50 g of hydroxylamine hydrochloride and 100 g of water to a reaction kettle, stir to dissolve, and add 35 g of acetaldehyde dropwise under ice-water bath cooling to react;

[0042] S3: then add alkali solution dropwise and stir for 20 min to obtain an acetaldehyde oxime aqueous solution;

[0043] S4: The acetaldehyde oxime aqueous solution is extracted with dichloromethane. After the extract is dried over anhydrous sodium sulfate, most of the solvent is first distilled off at atmospheric pressure, and then fractionated under reduced pressure to collect the 76°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime.

[0044] The mass concentration of the hydrogen peroxide aqueous solution is 20%.

[0045] The reaction temperature of S1 is 40° C. and the reaction time is 3 h.

[0046] The reaction temperature of S2 is 5°C and the reaction time is 4 hours.

[0047] The alkali solution consists of 30g of sodium hydroxide and 40g of water.

[0048] The temperature of S3 is 10°C.

[0049] The modified catalyst preparation method is:

[0050] T1: 100 g of TS-1 molecular sieve and 5 g of mercaptosiloxane were added to 1200 g of water, and then stirred at room temperature for reaction, filtered, and dried to obtain mercapto TS-1 molecular sieve;

[0051] T2: Add 100 g of mercapto TS-1 molecular sieve, 2.4 g of (E)-1-propenyl potassium trifluoroborate, and 0.03 g of allyltrimethylstannane to 1000 g of toluene, stir and mix until evenly mixed, then add 2 g of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

[0052] The mercaptosiloxane is gamma-mercaptopropyltrimethoxysilane.

[0053] The reaction time of T1 is 100 min.

[0054] The reaction temperature of T2 is 70° C. and the reaction time is 60 min.

[0055] Example 2

[0056] A clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are as follows:

[0057] S1: 4 g of modified catalyst, 190 g of solvent water, and 43 g of butanone were added to a reactor. Under nitrogen protection, stirring and heating were started. 33 g of ammonia gas was slowly introduced, and then an aqueous hydrogen peroxide solution was slowly added. After the reaction was completed, the mixture was centrifuged to obtain butanone oxime.

[0058] S2: Add 55g of hydroxylamine hydrochloride and 105g of water to a reaction kettle, stir to dissolve, and add 38g of acetaldehyde dropwise under ice-water bath cooling to react;

[0059] S3: Alkali solution is then added dropwise and stirred for 25 minutes to obtain an acetaldehyde oxime aqueous solution;

[0060] S4: The acetaldehyde oxime aqueous solution is extracted with dichloromethane. After the extract is dried over anhydrous sodium sulfate, most of the solvent is first distilled off at atmospheric pressure, and then fractionated under reduced pressure to collect the 77°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime.

[0061] The mass concentration of the hydrogen peroxide aqueous solution is 23%.

[0062] The reaction temperature of S1 is 45° C. and the reaction time is 4 h.

[0063] The reaction temperature of S2 is 6°C and the reaction time is 5 hours.

[0064] The alkali solution consists of 33g of sodium hydroxide and 43g of water.

[0065] The temperature of S3 is 12°C.

[0066] The modified catalyst preparation method is:

[0067] T1: 110 g of TS-1 molecular sieve and 6 g of mercaptosiloxane were added to 1240 g of water, and then stirred at room temperature for reaction, filtered, and dried to obtain mercapto TS-1 molecular sieve;

[0068] T2: Add 110 g of mercapto TS-1 molecular sieve, 3.5 g of (E)-1-propenyl potassium trifluoroborate, and 0.1 g of allyltrimethylstannane to 1050 g of toluene, stir and mix well, then add 3 g of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

[0069] The mercaptosiloxane is γ-mercaptopropyltrimethoxysilane

[0070] The reaction time of T1 is 105 min.

[0071] The reaction temperature of T2 is 75° C. and the reaction time is 80 min.

[0072] Example 3

[0073] A clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are as follows:

[0074] S1: 6 g of modified catalyst, 210 g of solvent water, and 48 g of butanone were added to a reactor. Under the protection of nitrogen, stirring and heating were started. After 38 g of ammonia gas was slowly introduced, an aqueous hydrogen peroxide solution was slowly added. After the reaction was completed, centrifugation was performed to obtain butanone oxime;

[0075] S2: Add 65g of hydroxylamine hydrochloride and 115g of water to a reaction kettle, stir to dissolve, and add 43g of acetaldehyde dropwise under ice-water bath cooling to react;

[0076] S3: Alkali solution is then added dropwise and stirred for 25 minutes to obtain an acetaldehyde oxime aqueous solution;

[0077] S4: The acetaldehyde oxime aqueous solution is extracted with dichloromethane. After the extract is dried over anhydrous sodium sulfate, most of the solvent is first distilled off at atmospheric pressure, and then fractionated under reduced pressure to collect the 77°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime.

[0078] The mass concentration of the hydrogen peroxide aqueous solution is 25%.

[0079] The reaction temperature of S1 is 55° C. and the reaction time is 5 h.

[0080] The reaction temperature of S2 is 7° C. and the reaction time is 6 h.

[0081] The alkali solution consists of 38g sodium hydroxide and 48g water.

[0082] The temperature of S3 is 14°C.

[0083] The modified catalyst preparation method is:

[0084] T1: 140 g of TS-1 molecular sieve and 8 g of mercaptosiloxane were added to 1280 g of water, and then stirred at room temperature for reaction, filtered, and dried to obtain mercapto TS-1 molecular sieve;

[0085] T2: Add 140 g of mercapto TS-1 molecular sieve, 4.3 g of (E)-1-propenyl potassium trifluoroborate, and 0.2 g of allyltrimethylstannane to 1150 g of toluene, stir and mix well, then add 4 g of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

[0086] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0087] The reaction time of T1 is 115 min.

[0088] The reaction temperature of T2 is 85° C. and the reaction time is 100 min.

[0089] Example 4

[0090] A clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are as follows:

[0091] S1: Add 10g of modified catalyst, 240g of solvent water, and 60g of butanone to a reactor. Under the protection of nitrogen, stir and heat, slowly introduce 50g of ammonia gas, and then slowly add aqueous hydrogen peroxide solution. After the reaction is completed, centrifuge to obtain butanone oxime;

[0092] S2: Add 90g of hydroxylamine hydrochloride and 140g of water to a reaction kettle, stir to dissolve, and add 50g of acetaldehyde dropwise under ice-water bath cooling to react;

[0093] S3: then add alkali solution dropwise and stir for 30 min to obtain an acetaldehyde oxime aqueous solution;

[0094] S4: The acetaldehyde oxime aqueous solution is extracted with dichloromethane. After the extract is dried over anhydrous sodium sulfate, most of the solvent is first distilled off at atmospheric pressure, and then fractionated under reduced pressure to collect the 78°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime.

[0095] The mass concentration of the hydrogen peroxide aqueous solution is 30%.

[0096] The reaction temperature of S1 is 60° C. and the reaction time is 6 h.

[0097] The reaction temperature of S2 is 8°C and the reaction time is 7h.

[0098] The alkali solution consists of 40g of sodium hydroxide and 50g of water.

[0099] The temperature of S3 is 15°C.

[0100] The modified catalyst preparation method is:

[0101] T1: 150 g of TS-1 molecular sieve and 10 g of mercaptosiloxane were added to 1300 g of water, and then stirred at room temperature for reaction, filtered, and dried to obtain mercapto TS-1 molecular sieve;

[0102] T2: Add 150 g of mercapto TS-1 molecular sieve, 4.8 g of (E)-1-propenyl potassium trifluoroborate, and 0.3 g of allyltrimethylstannane to 1200 g of toluene, stir and mix until evenly mixed, then add 5 g of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

[0103] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0104] The reaction time of T1 is 120 min.

[0105] The reaction temperature of T2 is 90° C. and the reaction time is 120 min.

[0106] Comparative Example 1

[0107] The TS-1 molecular sieve was not modified, and the other steps were the same as in Example 1.

[0108] Comparative Example 2

[0109] The same procedures as in Example 1 were followed except that potassium (E)-1-propenyltrifluoroborate was not added.

[0110] Comparative Example 3

[0111] Allyltrimethylstannane was not added, and the other procedures were the same as in Example 1.

[0112] Table 1

[0113] Purity of butanone oxime / % Purity of acetaldehyde oxime / % Example 1 99.90 99.89 Example 2 99.92 99.93 Example 3 99.95 99.94 Example 4 99.96 99.96 Comparative Example 1 85.69 86.02 Comparative Example 2 93.58 93.71 Comparative Example 3 95.21 95.31

[0114] Through the data analysis of the above examples and comparative examples, the butanone oxime and acetaldehyde oxime prepared by the present invention have high purity.

[0115] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. 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 clean production process for the co-production of butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 2-10 parts of modified catalyst, 180-240 parts of solvent water, and 40-60 parts of butanone to a reactor. Under the protection of nitrogen, stir and heat. Slowly introduce 30-50 parts of ammonia gas, and then slowly add aqueous hydrogen peroxide solution. After the reaction is completed, centrifuge to obtain butanone oxime; S2: Add 50-90 parts of hydroxylamine hydrochloride and 100-140 parts of water to a reaction kettle, stir to dissolve, and add 35-50 parts of acetaldehyde dropwise under ice-water bath cooling to react; S3: then add alkali solution dropwise and stir for 20-30 minutes to obtain an acetaldehyde oxime aqueous solution; S4: extracting the acetaldehyde oxime aqueous solution with dichloromethane, drying the extract over anhydrous sodium sulfate, first distilling off most of the solvent under normal pressure, and then fractionating under reduced pressure to collect the 76-78°C / 2×104Pa fraction to obtain anhydrous acetaldehyde oxime; The modified catalyst is prepared by reacting mercapto TS-1 molecular sieve, (E)-1-propenyl potassium trifluoroborate and allyltrimethylstannane.

2. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide aqueous solution is 20-30%.

3. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The reaction temperature of S1 is 40-60°C, and the reaction time is 3-6h.

4. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The reaction temperature of S2 is 5-8°C, and the reaction time is 4-7h.

5. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The alkali solution consists of 30-40 parts of sodium hydroxide and 40-50 parts of water.

6. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The temperature of S3 is 10-15°C.

7. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 1, characterized in that: The modified catalyst preparation method is: T1: Add 100-150 parts of TS-1 molecular sieve and 5-10 parts of mercaptosiloxane to 1200-1300 parts of water, stirring at room temperature, filtering, and drying to obtain mercapto TS-1 molecular sieve; T2: Add 100-150 parts of mercapto TS-1 molecular sieve, 2.4-4.8 parts of (E)-1-propenyl potassium trifluoroborate, and 0.03-0.3 parts of allyltrimethylstannane to 1000-1200 parts of toluene, stir and mix until uniform, then add 2-5 parts of sodium ethoxide, then heat and stir to react, filter, and dry to obtain a modified catalyst.

8. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 7, characterized in that: The mercaptosiloxane is one of γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

9. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 7, characterized in that: The reaction time of T1 is 100-120 min.

10. The clean production process for co-producing butanone oxime and acetaldehyde oxime according to claim 7, characterized in that: The reaction temperature of T2 is 70-90°C and the reaction time is 60-120 minutes.