Continuous production technology of diacetylmonoxime and acetaldehyde oxime

Abstract

The invention relates to a continuous production technology of diacetylmonoxime and acetaldehyde oxime, and belongs to the technical field of organic chemical synthesis. According to the invention, butanone, tert-butyl alcohol, water, a TS-1 catalyst, ammonia water and hydrogen peroxide are adopted as raw materials to prepare diacetylmonoxime; acetaldehyde oxime is prepared from diacetylmonoxime, a catalyst and acetaldehyde; the method comprises the following steps: by taking quinolyl strong-acid ion exchange resin as a catalyst, firstly obtaining 4-isocyano strong-acid ion exchange resin through strong-acid ion exchange resin, dichloroethane, 4-isocyano benzoyl chloride and aluminum trichloride; and continuously reacting the 4-isocyano strong acid ion exchange resin, 2, 5-dihydroxyl-1, 4-benzene diphosphonic acid, 8-hydroxyquinoline-2-sulfonic acid, dichloroethane and dibutyltin diacetate to obtain the 2, 5-dihydroxyl-1, 4-benzene diphosphonic acid. The diacetylmonoxime and the acetaldehyde oxime prepared by the method have higher purity, and the acetaldehyde oxime has higher selectivity.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical synthesis, in particular to a continuous production technology of butanone oxime and acetaldehyde oxime. Background Art

[0002] Butanone oxime, also known as methyl ethyl ketone oxime, is a colorless or light yellow oily transparent liquid. It is an important organic synthesis intermediate and highly active reagent with a wide range of uses.

[0003] Acetaldehyde oxime is a low-toxic reducing agent, a novel oxygen scavenger characterized by low pollution, low price, and excellent deoxygenation performance. It is also an important reagent for organic synthesis and analysis. In the 1990s, acetaldehyde oxime replaced the highly toxic hydrazine as a boiler water deoxygenator. Its far superior deoxygenation performance led to its widespread application. Acetaldehyde oxime is an important intermediate in the synthesis of the pesticides methomyl and thiodicarb, which are excellent broad-spectrum insecticides. With the continuous growth of production, the market demand for acetaldehyde oxime has also increased.

[0004] Chinese patent CN1556096A relates to a process for producing acetone oxime or butanone oxime by oxidizing acetone or butanone. This process involves dissolving acetone or butanone in isopropyl alcohol or tert-butyl alcohol at a ratio of 100-200 g of solvent per mol of ketone. TS-1 catalyst at a ratio of 3-10 g of catalyst per mol of ketone and ammonia at a ratio of 1.2-2 mol of ammonia per mol of ketone are added to the acetone or butanone solution to prepare a reaction solution. Hydrogen peroxide at a ratio of 1.0-1.3 mol of hydrogen peroxide per mol of ketone is then slowly added dropwise to the reaction solution at a temperature of 50-120°C and a pressure of 0.1-1.0 MPa for 0.25-12 hours to produce the acetone oxime or butanone oxime product.

[0005] Chinese patent CN101624353B: A method for preparing anhydrous acetaldehyde oxime, comprising the following steps: adding a hydroxylamine solution, acetaldehyde, and a base to an oximation reactor equipped with a stirring or external circulation system for reaction to produce an acetaldehyde oxime solution; passing the acetaldehyde oxime solution obtained above through a cooler and then sent to a liquid-liquid separator, the upper oil phase being sent to a distillation tower A for rectification to obtain an acetaldehyde oxime aqueous solution with a mass percentage of about 50% and anhydrous acetaldehyde oxime, the lower phase being a solution containing inorganic salts being sent to a distillation tower B for rectification, and an acetaldehyde oxime aqueous solution with a mass percentage of about 50% being obtained at the top of the tower, and the bottom of the tower being an inorganic salt aqueous solution without acetaldehyde oxime.

[0006] Chinese Patent CN109400499A relates to the field of organic chemical synthesis technology, specifically to a method for preparing acetaldehyde oxime. The method comprises the following steps: 1) stirring and dissolving hydroxylamine and distilled water, then dropwise adding acetaldehyde and acetic acid as a catalyst in an ice-water bath, and stirring and reacting at 0-10°C for 10-30 minutes to produce an acetaldehyde oxime solution; 2) extracting the acetaldehyde oxime solution from step 1) with dichloromethane, drying the extract over anhydrous sodium sulfate, fractionally distilling the solvent at normal pressure, and then distilling under reduced pressure to collect the fractions to obtain a colorless, transparent liquid, namely acetaldehyde oxime.

[0007] The butanone oxime and acetaldehyde oxime prepared by the above patents and prior art have complex processes and high costs, and the purity and selectivity of butanone oxime and acetaldehyde oxime need to be further improved. Summary of the Invention

[0008] In order to solve the above problems, the present invention provides a continuous production technology of butanone oxime and acetaldehyde oxime, and its operating steps are as follows: S1: Add 25-30 parts of butanone, 40-60 parts of tert-butanol, 80-120 parts of water, 1-3 parts of TS-1 catalyst, and 40-60 parts of ammonia water into the autoclave, stir, pressurize, and heat; S2: Slowly add 60-70 parts of hydrogen peroxide dropwise for 1.5-4.5 hours, and continue the reaction for 90-120 minutes after the addition is complete; S3: After the reaction is completed, cool and filter; the filter cake is the catalyst, which is recovered for future use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 30-40 parts of diethyl ether. The combined four extracts were washed with 20-30 parts of a Na2S2O3 aqueous solution and 30-40 parts of water, respectively, and dried. S5: After drying, distill under normal pressure and reduced pressure, collect the fractions to obtain butanone oxime; S6: 160-200 parts of butanone oxime and 10-20 parts of a catalyst are added to a reaction kettle, and 350-400 parts of acetaldehyde are slowly added dropwise at room temperature under stirring and reflux, and the mixture is reacted for 5-7 hours under normal pressure to generate a crude acetaldehyde oxime product, which overflows into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower via the acetaldehyde tower feed pump for distillation separation under normal pressure; the material is condensed in two stages and then enters the distillate tank. The distillate is divided into two paths, one as reflux liquid and the other returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, where it is subjected to distillation separation at an absolute pressure of 50-60 kPa, a tower bottom temperature of 85-95°C, and a tower top temperature of 50-60°C. The tower top material is condensed in two stages and then sent to the butanone tank; S9: The bottom liquid of the butanone tower is pressurized by a pump and sent to the acetaldehyde oxime finished product tower 1, and is distilled and separated at an absolute pressure of 20-30 Pa, a bottom temperature of 75-85°C, and a top temperature of 50-60°C. The top liquid is condensed and enters the distillate tank of the finished product tower 1, one way as reflux and the other way to the acetaldehyde oxime finished product tank 1; The bottom liquid of the first finished product tower is pumped to the acetaldehyde oxime second finished product tower by the first finished product tower bottom liquid pump, and is distilled and separated at an absolute pressure of 10-20KPa, a bottom temperature of 80-95°C, and a tower top temperature of 50-60°C. The top liquid enters the distillate tank of the second finished product tower after two-stage condensation, and is pressurized by the reflux pump of the second finished product tower and used as reflux all the way to the acetaldehyde oxime second finished product tank all the way; S10:2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 10-20 KPa and a bottom temperature of 80-95°C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device via the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime.

[0009] The mass concentration of the ammonia water is 24-26%.

[0010] The reaction temperature of S1 is 60-80°C and the pressure is 1.0-1.1 MPa.

[0011] The mass concentration of the hydrogen peroxide is 26-28%.

[0012] The acetaldehyde addition time is 150-180 minutes.

[0013] The temperature of the bottom of the tower S7 is 90-100°C, and the temperature of the top of the tower is 70-80°C.

[0014] The mass concentration of the Na2S2O3 aqueous solution is 5%.

[0015] The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 100-160 parts by mass of a strongly acidic ion exchange resin, 1000-1300 parts of ethylene dichloride, 10-20 parts of 4-isocyanatobenzoyl chloride, and 3-7 parts of aluminum trichloride to a reaction kettle, stir, and after the reaction is complete, filter and dry to obtain a 4-isocyanato strongly acidic ion exchange resin. A2: 100-150 parts of 4-isocyanate strong acid ion exchange resin, 20-30 parts of 2,5-dihydroxy-1,4-phenylenediphosphonic acid (CAS: 91633-16-8), 0.3-3 parts of 8-hydroxyquinoline-2-sulfonic acid (CAS: 20946-17-2), 1000-1300 parts of ethylene dichloride, and 2-5 parts of dibutyltin diacetate are stirred. After the reaction is complete, the mixture is filtered and dried to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and phenylenediphosphonic acid.

[0016] The reaction temperature of A1 is 10-20°C and the reaction time is 150-240 minutes.

[0017] The reaction temperature of A2 is 60-100°C and the reaction time is 150-240 minutes.

[0018] Reaction mechanism The 4-isocyanate strong acid ion exchange resin is subjected to a condensation reaction with 2,5-dihydroxy-1,4-phenylenediphosphonic acid, and the 4-isocyanate strong acid ion exchange resin is subjected to a condensation reaction with 8-hydroxyquinoline-2-sulfonic acid to obtain a quinoline-based strong acid ion exchange resin grafted with quinoline-2-sulfonic acid and phenylenediphosphonic acid.

[0019] Technical Effects The continuous production technology of butanone oxime and acetaldehyde oxime of the present invention has the following significant effects compared with the prior art: Compared with inorganic acids or unmodified strong acidic ion exchange resins, quinoline-2-sulfonic acid and phenylenediphosphonic acid as catalysts show the following significant advantages in the reaction of butanone oxime with acetaldehyde to prepare acetaldehyde oxime: 1. Higher selectivity: Quinoline-2-sulfonic acid and phenylenediphosphonic acid, as organic catalysts, can control the direction of the reaction through their specific structures and functional groups, thereby improving the selectivity of the target product; this means that they can more effectively promote the conversion of butanone oxime to acetaldehyde oxime and reduce the formation of by-products.

[0020] 2. Better solubility and compatibility: Compared with inorganic acids, organic catalysts such as quinoline-2-sulfonic acid and benzene diphosphonic acid have better solubility and compatibility in certain organic reactions; this helps to improve reaction efficiency because the catalyst can be more evenly distributed in the reaction system and fully contact with the reactants.

[0021] 3. Recyclability: Quinoline-2-sulfonic acid and benzene diphosphoric acid, as organic catalysts, can be recycled and reused through simple separation and purification steps after the reaction. This not only reduces production costs, but also reduces resource waste and environmental pollution.

[0022] 4. High catalytic efficiency: Because quinoline-2-sulfonic acid and benzene diphosphonic acid have specific structures and functional groups, they can interact with reactant molecules more effectively and improve catalytic efficiency; this means that under the same reaction conditions, higher reaction rates and yields can be achieved using these organic catalysts. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention object, the following is a detailed description in conjunction with examples and comparative examples: 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.

[0024] 2. Acetaldehyde oxime is detected by gas chromatography.

[0025] Example 1 A continuous production technology for butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 25g of butanone, 40g of tert-butanol, 80g of water, 1g of TS-1 catalyst, and 40g of aqueous ammonia to the autoclave, stir, pressurize, and heat; S2: Slowly add 60g of hydrogen peroxide dropwise for 1.5h, and continue the reaction for 90min after the addition is complete; S3: After the reaction is completed, cool and filter; the filter cake is the catalyst, which is recovered for future use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 30 g of ether. The combined four extracts were washed with 20 g of Na2S2O3 aqueous solution and 30 g of water, respectively, and dried. S5: After drying, distill under normal pressure and reduced pressure, collect the fractions to obtain butanone oxime; S6: 160g of butanone oxime and 10g of catalyst were added to a reaction kettle, and 350g of acetaldehyde was slowly added dropwise at room temperature under stirring and reflux, and the mixture was reacted for 5h at normal pressure to generate a crude acetaldehyde oxime product, which was overflowed into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower via the acetaldehyde tower feed pump for distillation separation under normal pressure; the material is condensed in two stages and then enters the distillate tank. The distillate is divided into two paths, one as reflux liquid and the other returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, where it is distilled and separated at an absolute pressure of 50 kPa, a tower bottom temperature of 85°C, and a tower top temperature of 50°C. The tower top material is condensed in two stages and then sent to the butanone tank; S9: The bottom liquid of the butanone tower is pressurized by a pump and sent to the acetaldehyde oxime finished product tower 1, and is distilled and separated at an absolute pressure of 20 Pa, a bottom temperature of 75°C, and a top temperature of 50°C. The top liquid is condensed and enters the distillate tank of the finished product tower 1, one way as reflux and the other way to the acetaldehyde oxime finished product tank 1; The bottom liquid of the 1st finished product tower is pumped to the 2nd acetaldehyde oxime finished product tower by the 1st finished product tower bottom liquid pump, and is distilled and separated at an absolute pressure of 10KPa, a bottom temperature of 80°C, and a top temperature of 50°C. The top liquid enters the distillate tank of the 2nd finished product tower after two-stage condensation, and is pressurized by the 2nd finished product tower reflux pump and used as reflux all the way to the 2nd acetaldehyde oxime finished product tank all the way; S10:2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 10 KPa and a bottom temperature of 80°C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device via the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime.

[0026] The mass concentration of the ammonia water is 24%.

[0027] The reaction temperature of S1 is 60° C. and the pressure is 1.0 MPa.

[0028] The mass concentration of the hydrogen peroxide is 26%.

[0029] The acetaldehyde addition time is 150 minutes.

[0030] The bottom temperature of the S7 is 90°C and the top temperature is 70°C.

[0031] The mass concentration of the Na2S2O3 aqueous solution is 5%.

[0032] The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 100 g of strongly acidic ion exchange resin, 1000 g of dichloroethane, 10 g of 4-isocyanobenzoyl chloride, and 3 g of aluminum trichloride to a reaction kettle and stir. After the reaction is complete, filter and dry to obtain 4-isocyano strongly acidic ion exchange resin; A2: 100g of 4-isocyanate strong acid ion exchange resin, 20g of 2,5-dihydroxy-1,4-phenylenediphosphate (CAS: 91633-16-8), 0.3g of 8-hydroxyquinoline-2-sulfonic acid (CAS: 20946-17-2), 1000g of ethylene dichloride, and 2g of dibutyltin diacetate were stirred. After the reaction, the mixture was filtered and dried to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and phenylenediphosphate.

[0033] The reaction temperature of A1 is 10°C and the reaction time is 150 minutes.

[0034] The reaction temperature of A2 is 60°C and the reaction time is 150 minutes.

[0035] Example 2 A continuous production technology for butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 26g of butanone, 45g of tert-butanol, 90g of water, 2g of TS-1 catalyst, and 45g of aqueous ammonia to the autoclave, stir, pressurize, and heat; S2: Slowly add 63g of hydrogen peroxide dropwise for 2.5h, and continue the reaction for 100min after the addition is complete; S3: After the reaction is completed, cool and filter; the filter cake is the catalyst, which is recovered for future use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 33 g of ether. The combined four extracts were washed with 23 g of Na2S2O3 aqueous solution and 33 g of water, respectively, and dried. S5: After drying, distill under normal pressure and reduced pressure, collect the fractions to obtain butanone oxime; S6: 170g of butanone oxime and 13g of catalyst were added to a reaction kettle, and 360g of acetaldehyde was slowly added dropwise at room temperature under stirring and reflux. The mixture was reacted for 5.5h at normal pressure to generate a crude acetaldehyde oxime product, which overflowed into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower via the acetaldehyde tower feed pump for distillation separation under normal pressure; the material is condensed in two stages and then enters the distillate tank. The distillate is divided into two paths, one as reflux liquid and the other returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, where it is distilled at an absolute pressure of 55 kPa, a tower bottom temperature of 88°C, and a tower top temperature of 55°C. The tower top material is condensed in two stages and then sent to the butanone tank; S9: The bottom liquid of the butanone tower is pressurized by a pump and sent to the acetaldehyde oxime 1 finished product tower. At an absolute pressure of 25 Pa, the bottom temperature of the tower is 78°C and the top temperature of the tower is 55°C, and distillation separation is performed. The top liquid is condensed and enters the distillate tank of the 1 finished product tower, one way is used as reflux, and the other way is sent to the acetaldehyde oxime 1 finished product tank; The bottom liquid of the first finished product tower is pumped to the acetaldehyde oxime second finished product tower by the first finished product tower bottom liquid pump, and is distilled and separated at an absolute pressure of 15KPa, a bottom temperature of 85°C, and a tower top temperature of 55°C. The top liquid enters the distillate tank of the second finished product tower after two-stage condensation, and is pressurized by the reflux pump of the second finished product tower as reflux all the way and goes to the acetaldehyde oxime second finished product tank all the way; S10:2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 15 KPa and a bottom temperature of 85°C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device via the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime.

[0036] The mass concentration of the ammonia water is 25%.

[0037] The reaction temperature of S1 is 65° C. and the pressure is 1.05 MPa.

[0038] The mass concentration of the hydrogen peroxide is 27%.

[0039] The acetaldehyde addition time is 160 minutes.

[0040] The bottom temperature of the S7 is 95°C and the top temperature is 75°C.

[0041] The mass concentration of the Na2S2O3 aqueous solution is 5%.

[0042] The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 120 g of strongly acidic ion exchange resin, 1100 g of ethylene dichloride, 13 g of 4-isocyanatobenzoyl chloride, and 4 g of aluminum trichloride to a reaction kettle and stir. After the reaction is complete, filter and dry to obtain 4-isocyanato strongly acidic ion exchange resin; A2: 110g of 4-isocyanate strong acid ion exchange resin, 23g of 2,5-dihydroxy-1,4-phenylenediphosphate (CAS: 91633-16-8), 1g of 8-hydroxyquinoline-2-sulfonic acid (CAS No.: 20946-17-2), 1100g of ethylene dichloride, and 3g of dibutyltin diacetate were stirred. After the reaction, the mixture was filtered and dried to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and phenylenediphosphate.

[0043] The reaction temperature of A1 is 15°C and the reaction time is 170 minutes.

[0044] The reaction temperature of A2 is 70°C and the reaction time is 170 minutes.

[0045] Example 3 A continuous production technology for butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 28g butanone, 55g tert-butanol, 110g water, 2g TS-1 catalyst, and 55g ammonia water to the autoclave, stir, pressurize, and heat; S2: Slowly add 68g of hydrogen peroxide dropwise for 3.5h, and continue the reaction for 110min after the addition is complete; S3: After the reaction is completed, cool and filter; the filter cake is the catalyst, which is recovered for future use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 38 g of ether. The combined four extracts were washed with 28 g of Na2S2O3 aqueous solution and 38 g of water, respectively, and dried. S5: After drying, distill under normal pressure and reduced pressure, collect the fractions to obtain butanone oxime; S6: 190g of butanone oxime and 18g of catalyst were added to a reaction kettle, and 390g of acetaldehyde was slowly added dropwise at room temperature under stirring and reflux. The mixture was reacted for 6.5h at normal pressure to generate a crude acetaldehyde oxime product, which overflowed into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower via the acetaldehyde tower feed pump for distillation separation under normal pressure; the material is condensed in two stages and then enters the distillate tank. The distillate is divided into two paths, one as reflux liquid and the other returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, where it is distilled and separated at an absolute pressure of 55 kPa, a tower bottom temperature of 90°C, and a tower top temperature of 55°C. The tower top material is condensed in two stages and then sent to the butanone tank; S9: The bottom liquid of the butanone tower is pressurized by a pump and sent to the acetaldehyde oxime 1 finished product tower. At an absolute pressure of 25 Pa, the bottom temperature of the tower is 83°C and the top temperature of the tower is 55°C, and distillation separation is performed. The top liquid is condensed and enters the distillate tank of the 1 finished product tower, one way is used as reflux, and the other way is sent to the acetaldehyde oxime 1 finished product tank; The bottom liquid of the first finished product tower is pumped to the acetaldehyde oxime second finished product tower by the first finished product tower bottom liquid pump, and is distilled and separated at an absolute pressure of 15KPa, a bottom temperature of 90°C, and a tower top temperature of 55°C. The top liquid enters the distillate tank of the second finished product tower after two-stage condensation, and is pressurized by the reflux pump of the second finished product tower as reflux all the way and goes to the acetaldehyde oxime second finished product tank all the way; S10:2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 15 KPa and a bottom temperature of 90°C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device via the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime.

[0046] The mass concentration of the ammonia water is 25%.

[0047] The reaction temperature of S1 is 75° C. and the pressure is 1.05 MPa.

[0048] The mass concentration of the hydrogen peroxide is 27%.

[0049] The acetaldehyde addition time is 170 minutes.

[0050] The bottom temperature of the S7 is 95°C and the top temperature is 75°C.

[0051] The mass concentration of the Na2S2O3 aqueous solution is 5%.

[0052] The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 150 g of strongly acidic ion exchange resin, 1200 g of dichloroethane, 18 g of 4-isocyanatobenzoyl chloride, and 6 g of aluminum trichloride to a reaction kettle and stir. After the reaction is complete, filter and dry to obtain 4-isocyanato strongly acidic ion exchange resin; A2: 140g of 4-isocyanate strong acid ion exchange resin, 28g of 2,5-dihydroxy-1,4-phenylenediphosphate (CAS: 91633-16-8), 2g of 8-hydroxyquinoline-2-sulfonic acid (CAS: 20946-17-2), 1200g of ethylene dichloride, and 4g of dibutyltin diacetate were stirred. After the reaction, the mixture was filtered and dried to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and phenylenediphosphate.

[0053] The reaction temperature of A1 is 15°C and the reaction time is 220 minutes.

[0054] The reaction temperature of A2 is 90°C and the reaction time is 220 minutes.

[0055] Example 4 A continuous production technology for butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 30g butanone, 60g tert-butanol, 120g water, 3g TS-1 catalyst, and 60g ammonia water to the autoclave, stir, pressurize, and heat; S2: Slowly add 70g of hydrogen peroxide dropwise for 4.5 hours, and continue the reaction for 120 minutes after the addition is complete; S3: After the reaction is completed, cool and filter; the filter cake is the catalyst, which is recovered for future use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 40 g of ether. The combined four extracts were washed with 30 g of Na2S2O3 aqueous solution and 40 g of water, respectively, and dried. S5: After drying, distill under normal pressure and reduced pressure, collect the fractions to obtain butanone oxime; S6: 200g of butanone oxime and 20g of catalyst were added to a reaction kettle, and 400g of acetaldehyde was slowly added dropwise at room temperature under stirring and reflux, and the mixture was reacted for 7h at normal pressure to generate a crude acetaldehyde oxime product, which overflowed into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower via the acetaldehyde tower feed pump for distillation separation under normal pressure; the material is condensed in two stages and then enters the distillate tank. The distillate is divided into two paths, one as reflux liquid and the other returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, where it is distilled and separated at an absolute pressure of 60 kPa, a tower bottom temperature of 95°C, and a tower top temperature of 60°C. The tower top material is condensed in two stages and then sent to the butanone tank; S9: The bottom liquid of the butanone tower is pressurized by a pump and sent to the acetaldehyde oxime finished product tower 1, and is distilled and separated at an absolute pressure of 30 Pa, a bottom temperature of 85°C, and a top temperature of 60°C. The top liquid is condensed and enters the distillate tank of the finished product tower 1, one way as reflux and the other way to the acetaldehyde oxime finished product tank 1; The bottom liquid of the first finished product tower is pumped to the acetaldehyde oxime second finished product tower by the first finished product tower bottom liquid pump, and is distilled and separated at an absolute pressure of 20KPa, a bottom temperature of 95°C, and a tower top temperature of 60°C. The top liquid enters the distillate tank of the second finished product tower after two-stage condensation, and is pressurized by the reflux pump of the second finished product tower as reflux all the way and goes to the acetaldehyde oxime second finished product tank all the way; S10:2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 20 KPa and a bottom temperature of 95°C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device via the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime.

[0056] The mass concentration of the ammonia water is 26%.

[0057] The reaction temperature of S1 is 80° C. and the pressure is 1.1 MPa.

[0058] The mass concentration of the hydrogen peroxide is 28%.

[0059] The acetaldehyde addition time is 180 minutes.

[0060] The temperature of the bottom of the tower of S7 is 100°C, and the temperature of the top of the tower is 80°C.

[0061] The mass concentration of the Na2S2O3 aqueous solution is 5%.

[0062] The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 160 g of strongly acidic ion exchange resin, 1300 g of dichloroethane, 20 g of 4-isocyanobenzoyl chloride, and 7 g of aluminum trichloride to a reaction kettle and stir. After the reaction is complete, filter and dry to obtain 4-isocyano strongly acidic ion exchange resin; A2: 150g of 4-isocyanate strong acid ion exchange resin, 30g of 2,5-dihydroxy-1,4-phenylenediphosphate (CAS: 91633-16-8), 3g of 8-hydroxyquinoline-2-sulfonic acid (CAS: 20946-17-2), 1300g of ethylene dichloride, and 5g of dibutyltin diacetate were stirred. After the reaction, the mixture was filtered and dried to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and phenylenediphosphate.

[0063] The reaction temperature of A1 is 20°C and the reaction time is 240 minutes.

[0064] The reaction temperature of A2 is 100°C and the reaction time is 240 minutes.

[0065] Comparative Example 1 The strongly acidic ion exchange resin was not modified, and the other steps were the same as in Example 1.

[0066] Comparative Example 2 The other steps were the same as in Example 1 except that 2,5-dihydroxy-1,4-phenylenediphosphoric acid was not added.

[0067] Comparative Example 3 The other steps were the same as in Example 1 except that 8-hydroxyquinoline-2-sulfonic acid was not added.

[0068] The test data is shown in Table 1.

[0069] Table 1 Purity of butanone oxime / % Purity of acetaldehyde oxime / % Selectivity of acetaldehyde oxime / % Example 1 99.87 99.94 99.91 Example 2 99.90 99.96 99.92 Example 3 99.92 99.98 99.94 Example 4 99.94 99.99 99.95 Comparative Example 1 87.31 85.37 83.78 Comparative Example 2 95.33 94.33 93.66 Comparative Example 3 96.02 95.52 94.83 Through the data analysis of the above examples and comparative examples, it can be seen that the butanone oxime and acetaldehyde oxime prepared by the present invention have higher purity, and acetaldehyde oxime has higher selectivity.

[0070] 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 continuous production technology of butanone oxime and acetaldehyde oxime, the operating steps of which are: S1: Add 25-30 parts of butanone, 40-60 parts of tert-butanol, 80-120 parts of water, 1-3 parts of TS-1 catalyst, and 40-60 parts of ammonia water into the autoclave, stir, pressurize, and heat; S2: Slowly add 60-70 parts of hydrogen peroxide solution dropwise for 1.5-4.5 hours, and continue the reaction for 90-120 minutes after the addition is completed; S3: After the reaction is completed, the mixture is cooled and filtered; the filter cake is the catalyst, which is recovered for later use; S4: The filtrate was adjusted to pH 7 with acetic acid, then extracted four times with 30-40 parts of ether, and the combined four extracts were respectively treated with 20-30 parts of Na 2 S 2 O 3 Aqueous solution, washed with 30-40 parts of water, and dried; S5: After drying, distill under normal pressure, distill under reduced pressure, collect fractions, and obtain butanone oxime; S6: 160-200 parts of butanone oxime and 10-20 parts of a catalyst are added to a reaction kettle, and 350-400 parts of acetaldehyde are slowly added dropwise at room temperature under stirring, condensing and reflux, and reacted for 5-7 hours under normal pressure to generate a crude acetaldehyde oxime product, and the crude product overflows into a crude acetaldehyde oxime tank; S7: The material in the crude acetaldehyde oxime tank is pumped to the acetaldehyde removal tower through the acetaldehyde tower feed pump, and distilled and separated under normal pressure; the material is condensed in two stages and then enters the distillate tank, and the distillate is divided into two paths, one as reflux liquid, and the other is returned to the reactor in S6; S8: The acetaldehyde tower bottom liquid is pumped to the butanone removal tower, and distillation separation is performed at an absolute pressure of 50-60KPa, a tower bottom temperature of 85-95°C, and a tower top temperature of 50-60°C. The tower top material is condensed in two stages and then goes to the butanone tank; S9: The butanone tower bottom liquid is pumped to the acetaldehyde oxime 1 finished product tower after being pressurized by a pump, and distilled and separated at an absolute pressure of 20-30Pa, a bottom temperature of 75-85°C, and a tower top temperature of 50-60°C. The top liquid is condensed and enters the 1 finished product tower distillate tank, one way is used as reflux, and the other way is used to go to the acetaldehyde oxime 1 finished product tank; The bottom liquid of the 1 finished product tower is pumped to the acetaldehyde oxime 2 finished product tower by the 1 finished product tower bottom liquid pump, and distilled and separated at an absolute pressure of 10-20KPa, a bottom temperature of 80-95°C, and a top temperature of 50-60°C. The top liquid enters the distillate tank of the 2 finished product tower after two-stage condensation, and is pressurized by the 2 finished product tower reflux pump as reflux all the way and goes to the acetaldehyde oxime 2 finished product tank all the way; S10: 2 The bottom liquid of the finished product tower is transported to the acetaldehyde oxime removal tower for distillation separation at an absolute pressure of 10-20 KPa and a bottom temperature of 80-95° C. Acetaldehyde oxime is recovered from the top of the tower, and the bottom material is transported to the butanone oxime device through the acetaldehyde oxime removal tower bottom liquid pump to recover butanone oxime; The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, which is obtained by reacting 4-isocyano-based strongly acidic ion exchange resin, 2,5-dihydroxy-1,4-benzenediphosphoric acid, 8-hydroxyquinoline-2-sulfonic acid, and dibutyltin diacetate to obtain a quinoline-based strongly acidic ion exchange resin containing quinoline-2-sulfonic acid and benzene diphosphoric acid.

2. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The mass concentration of the ammonia water is 24-26%.

3. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The reaction temperature of S1 is 60-80°C and the pressure is 1.0-1.1 MPa.

4. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The mass concentration of the hydrogen peroxide is 26-28%.

5. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The acetaldehyde dropping time is 150-180min.

6. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The bottom temperature of the S7 is 90-100°C, and the top temperature is 70-80°C.

7. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The Na 2 S 2 O 3 The mass concentration of the aqueous solution is 5%.

8. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 1, Features: The catalyst of S6 is a quinoline-based strongly acidic ion exchange resin, and its preparation method is as follows: A1: Add 100-160 parts of strongly acidic ion exchange resin, 1000-1300 parts of dichloroethane, 10-20 parts of 4-isocyanobenzoyl chloride, and 3-7 parts of aluminum chloride into a reaction kettle according to their mass proportions, stir, filter, and dry after the reaction to obtain 4-isocyano strongly acidic ion exchange resin; A2: 100-150 parts of 4-isocyanate strong acid ion exchange resin, 20-30 parts of 2,5-dihydroxy-1,4-benzenediphosphoric acid, 0.3-3 parts of 8-hydroxyquinoline-2-sulfonic acid, 1000-1300 parts of ethylene dichloride, 2-5 parts of dibutyltin diacetate, stir, filter and dry after the reaction is completed to obtain a quinoline-based strong acid ion exchange resin containing quinoline-2-sulfonic acid and benzene diphosphoric acid.

9. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 8, Features: The reaction temperature of A1 is 10-20°C and the reaction time is 150-240 minutes.

10. A continuous production technology of butanone oxime and acetaldehyde oxime according to claim 8, Features: The reaction temperature of A2 is 60-100°C and the reaction time is 150-240 minutes.