A method for producing butanone oxime with high selectivity

Abstract

The invention relates to a method for producing butanone oxime with high selectivity. The method comprises the following steps: the raw materials are a catalyst, a solvent, butanone, aqueous ammonia and aqueous hydrogen peroxide solution, and the butanone oxime is obtained through ammoximation reaction, distillation of tert-butyl alcohol, separation of oxime water and distillation of butanone oxime; the catalyst is a boron nickel doped titanium silicate, which is mixed with titanium silicate, mercaptosiloxane and ethanol, filtered and dried to obtain the mercapto titanium silicate; the mercapto titanium silicate, allyl (cyclopentadienyl) nickel and sodium ethoxide are subjected to a temperature reaction; and finally (+)-IPC2B (allyl) borane is added, the reaction is continued and the ethanol is removed by distillation to obtain the butanone oxime; the butanone oxime prepared by the method has high conversion rate and selectivity.

Description

Technical Field

[0001] The invention relates to the technical field of butanone oxime production, in particular to a method for producing butanone oxime with high selectivity. Background Art

[0002] Butanone oxime, also known as methyl ethyl ketone oxime, is primarily used in anti-scaling applications for alkyd and epoxy resin coatings, industrial curing of silicones, anti-oxidation of instrument oils, and as a new deoxidizer to replace hydrazine in boiler feed water. Currently, industrial production primarily utilizes the hydroxylamine process, which is a complex process.

[0003] Chinese patent CN113072461B belongs to the field of organic synthesis technology and specifically relates to a method for preparing butanone oxime. In the presence of aqueous solvent, butanone oxime is synthesized using ammonia, butanone, and hydrogen peroxide as raw materials and a heteropoly acid or heteropoly acid salt as a catalyst.

[0004] 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.

[0005] Chinese patent CN111116410A: relates to the chemical industry, specifically to a method for preparing butanone oxime; provides a method for preparing butanone oxime from hydroxylamine phosphate, butanone and toluene, and the present invention uses a graphene ionic liquid extractant to extract the inorganic phase.

[0006] The selectivity of butanone oxime prepared by the above patents and prior art needs to be further improved. Summary of the Invention

[0007] In order to solve the above problems, the present invention provides a method for producing butanone oxime with high selectivity, and the operating steps are as follows:

[0008] S1 ammoximation reaction:

[0009] 0.5-1.5 parts of catalyst, 30-40 parts of solvent, 10-20 parts of butanone, 12-25 parts of ammonia water, and 20-30 parts of hydrogen peroxide solution are metered by weight and then introduced into an ammoximation reactor; the reaction heat generated in the ammoximation reactor is removed by a cooler; and the mixture after the reaction is completed is sent to a reaction liquid intermediate tank;

[0010] The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere.

[0011] S2 tert-Butanol distillation:

[0012] The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 100-110°C, the tower top temperature is controlled at 70-80°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, a part of which is refluxed to the tert-butanol distillation tower, and the other part is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and then discharged.

[0013] S3 oxime water separation:

[0014] A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower. This mixture is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butanol distillation tower. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower through the stripping tower feed pump. The bottom temperature is controlled at 130-140°C and the pressure is 0.15MPa. The wastewater from the bottom of the tower is sent to the sewage treatment plant for treatment.

[0015] S4 butanone oxime distillation:

[0016] The aqueous oxime phase from the crude oxime tank is pressurized and fed into the first distillation tower via a pump. The kettle temperature is controlled at 70-80°C, and the pressure in the tower is maintained at -0.095 MPa via a vacuum pump. Water and some butanone oxime are obtained from the top of the tower and enter the distillate tank of the first distillation tower. They are then pressurized and fed to the oxime-water separation tower via a pump. The bottom liquid of the first distillation tower is pressurized and fed into the second distillation tower. The kettle temperature of the second distillation tower is controlled at 80-90°C and the pressure is -0.095 MPa. High-purity butanone oxime is obtained from the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of it is refluxed, and part is fed to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower via the bottom liquid of the second distillation tower for further separation and purification.

[0017] The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0018] The mass concentration of the ammonia water is 20-25%.

[0019] The mass concentration of the hydrogen peroxide aqueous solution is 20-30%.

[0020] The solvent is one of water, tert-butyl alcohol and isopropyl alcohol.

[0021] The ammoximation reaction temperature of S1 is 60-70°C, the pressure is 1.0-1.1 MPa, and the time is 4-6 hours.

[0022] The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps:

[0023] K1: 100-200 parts of titanium silicalite, 5-8 parts of mercaptosiloxane and 1000-1500 parts of ethanol are mixed uniformly, and the mixture is heated to react; the mixture is then filtered and dried to obtain the mercapto titanium silicalite;

[0024] K2: Add 0.05-0.5 parts of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 2-6 parts of sodium ethoxide to the above-mentioned mercaptotitanium silicate molecular sieve, and then heat the reaction;

[0025] K3: Finally, 0.02-0.2 parts of (+)-IPC2B (allyl) borane CAS: 106356-53-0 were added to the reaction system and the reaction was continued. After the reaction was completed, ethanol was removed by distillation to obtain boron nickel doped titanium silicon molecular sieve.

[0026] The mercaptosiloxane is γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane.

[0027] The reaction temperature of K1 is 40-50°C and the reaction time is 100-150 minutes.

[0028] The reaction temperature of K2 is 60-70°C and the reaction time is 100-150 minutes.

[0029] The reaction temperature of K3 is 60-70°C and the reaction time is 120-180 minutes.

[0030] Reaction mechanism

[0031] Catalyst preparation reaction mechanism

[0032] Mercapto titanium silicalite undergoes an addition reaction with allyl (cyclopentadienyl) nickel, and then undergoes an addition reaction with 1(+)-IPC2B (allyl) borane, ultimately obtaining a titanium silicalite loaded with functional groups such as (cyclopentadienyl) nickel and borane. The reaction mechanism of this process is as follows:

[0033] Addition reaction of mercaptotitanium silicate molecular sieve and allyl(cyclopentadienyl)nickel: mercapto (-SH) acts as a nucleophile to attack the double bond in allyl(cyclopentadienyl)nickel to form a sulfur-carbon bond. At the same time, the nickel atom is combined with the titanium atom on the molecular sieve through a coordination bond, thereby loading the nickel onto the molecular sieve.

[0034] Further addition reaction with 1(+)-IPC2B(allyl)borane: Based on the existing nickel loading, the nickel center on the molecular sieve further reacts with 1(+)-IPC2B(allyl)borane, introducing borane functional groups through coordination or covalent bonding to enhance the catalytic activity and selectivity of the molecular sieve.

[0035] Technical Effects

[0036] The present invention provides a method for producing butanone oxime with high selectivity. By reducing the ammonia to ketone ratio, the present invention can bring the following benefits to the production of butanone oxime:

[0037] 1. Improve product quality: A high ammonia-ketone ratio will increase the impurity content in the product, thereby affecting the purity and quality of the product; by reducing the ammonia-ketone ratio, the generation of impurities can be reduced and the purity and quality of the product can be improved.

[0038] 2. Reduce costs: A high ammonia-ketone ratio will increase energy consumption and raw material consumption in the production process, thereby leading to increased production costs; by reducing the ammonia-ketone ratio, energy consumption and raw material consumption can be reduced, thereby reducing production costs.

[0039] 3. Improve production efficiency: A high ammonia-ketone ratio will affect the reaction rate and product selectivity, thereby reducing production efficiency; by reducing the ammonia-ketone ratio, the reaction rate and product selectivity can be increased, thereby improving production efficiency.

[0040] 4. Extend equipment life: A high ammonia-ketone ratio will cause corrosion and wear to equipment such as reactors, thereby shortening the service life of the equipment; by reducing the ammonia-ketone ratio, the corrosion and wear of the equipment can be reduced, thereby extending the service life of the equipment.

[0041] In short, reducing the ammonia-to-ketone ratio can improve product quality, reduce costs, increase production efficiency and extend equipment life, among other benefits. DETAILED DESCRIPTION

[0042] 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:

[0043] Butanone oxime was detected by liquid chromatography, and the test results are shown in Table 1.

[0044] Example 1

[0045] A method for producing butanone oxime with high selectivity, comprising the following steps:

[0046] S1 ammoximation reaction:

[0047] 0.5 g of catalyst, 30 g of solvent, 10 g of butanone, 12 g of ammonia water, and 20 g of hydrogen peroxide solution were metered and fed into an ammoximation reactor. The reaction heat generated in the ammoximation reactor was removed by a cooler. After the reaction, the mixture was fed into a reaction liquid intermediate tank.

[0048] The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere.

[0049] S2 tert-Butanol distillation:

[0050] The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 100°C, the tower top temperature is controlled at 70°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, part of which is refluxed to the tert-butanol distillation tower, and the other part is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and then discharged.

[0051] S3 oxime water separation:

[0052] A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower and is pumped to the oxime-water separation tower for separation. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower via the stripping tower feed pump. The tower bottom temperature is controlled at 130°C and the pressure is 0.15MPa. The tower bottom wastewater is sent to the sewage treatment plant for treatment.

[0053] S4 butanone oxime distillation:

[0054] The aqueous oxime phase from the crude oxime tank is pumped into the first distillation tower under pressure, the kettle temperature is controlled at 70°C, and the pressure in the tower is maintained at -0.095 MPa by a vacuum pump. Water and some butanone oxime are obtained at the top of the tower and enter the distillate tank of the first distillation tower. They are then pumped to the oxime-water separation tower under pressure. The bottom liquid of the first distillation tower is pumped to the second distillation tower under pressure. The second distillation tower controls the kettle temperature at 80°C and the pressure at -0.095 MPa. High-purity butanone oxime is obtained at the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of it is refluxed, and part is sent to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower through the bottom liquid of the second distillation tower for further separation and purification.

[0055] The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0056] The mass concentration of the ammonia water is 20%.

[0057] The mass concentration of the hydrogen peroxide aqueous solution is 20%.

[0058] The solvent is tert-butanol.

[0059] The ammoximation reaction temperature of S1 is 60° C., the pressure is 1.0 MPa, and the time is 4 h.

[0060] The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps:

[0061] K1: 100 g of titanium silicate molecular sieve, 5 g of mercaptosiloxane and 1000 g of ethanol were mixed uniformly, and the mixture was heated to react; the mixture was then filtered and dried to obtain mercapto titanium silicate molecular sieve;

[0062] K2: Add 0.05g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 2g of sodium ethoxide to the above-mentioned mercaptotitanium silicate molecular sieve, and then heat the reaction;

[0063] K3: Finally, 0.02 g of (+)-IPC2B (allyl) borane CAS: 106356-53-0 was added to the reaction system and the reaction was continued. After the reaction was completed, ethanol was removed by distillation to obtain boron nickel doped titanium silicon molecular sieve.

[0064] The mercaptosiloxane is gamma-mercaptopropyltrimethoxysilane.

[0065] The reaction temperature of K1 is 40° C. and the reaction time is 100 minutes.

[0066] The reaction temperature of K2 is 60°C and the reaction time is 100 minutes.

[0067] The reaction temperature of K3 is 60°C and the reaction time is 120 minutes.

[0068] Example 2

[0069] A method for producing butanone oxime with high selectivity, comprising the following steps:

[0070] S1 ammoximation reaction:

[0071] 0.8g of catalyst, 33g of solvent, 13g of butanone, 18g of ammonia water, and 23g of hydrogen peroxide solution were metered and fed into an ammoximation reactor; the reaction heat generated in the ammoximation reactor was removed by a cooler; and the mixture after the reaction was completed was fed into a reaction liquid intermediate tank;

[0072] The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere.

[0073] S2 tert-Butanol distillation:

[0074] The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 105°C, the tower top temperature is controlled at 75°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, a portion of which is refluxed to the tert-butanol distillation tower, and the other portion is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and discharge.

[0075] S3 oxime water separation:

[0076] A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower and is pumped to the oxime-water separation tower for separation. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower via the stripping tower feed pump. The tower bottom temperature is controlled at 135°C and the pressure is 0.15MPa. The tower bottom wastewater is sent to the sewage treatment plant for treatment.

[0077] S4 butanone oxime distillation:

[0078] The aqueous oxime phase from the crude oxime tank is pumped into the first distillation tower under pressure, the kettle temperature is controlled at 75°C, and the pressure in the tower is maintained at -0.095 MPa by a vacuum pump. Water and some butanone oxime are obtained at the top of the tower and enter the distillate tank of the first distillation tower. They are pumped under pressure to the oxime-water separation tower. The bottom liquid of the first distillation tower is pumped under pressure and then sent to the second distillation tower. The second distillation tower controls the kettle temperature at 85°C and the pressure at -0.095 MPa. High-purity butanone oxime is obtained at the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of it is refluxed and part is sent to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower through the bottom liquid of the second distillation tower for further separation and purification.

[0079] The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0080] The mass concentration of the ammonia water is 22%.

[0081] The mass concentration of the hydrogen peroxide aqueous solution is 23%.

[0082] The solvent is tert-butanol.

[0083] The ammoximation reaction temperature of S1 is 65° C., the pressure is 1.05 MPa, and the time is 5 h.

[0084] The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps:

[0085] K1: 130 g of titanium silicalite, 6 g of mercaptosiloxane, and 1100 g of ethanol were mixed uniformly, and the mixture was heated for reaction; the mixture was then filtered and dried to obtain mercapto titanium silicalite;

[0086] K2: Add 0.2g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 3g of sodium ethoxide to the above-mentioned mercaptotitanium silicate molecular sieve, and then heat the reaction;

[0087] K3: Finally, 0.1 g of (+)-IPC2B (allyl) borane CAS: 106356-53-0 was added to the reaction system and the reaction was continued. After the reaction was completed, ethanol was removed by distillation to obtain boron-nickel doped titanium silicalite.

[0088] The mercaptosiloxane is gamma-mercaptopropyltrimethoxysilane.

[0089] The reaction temperature of K1 is 45° C. and the reaction time is 110 minutes.

[0090] The reaction temperature of K2 is 65°C and the reaction time is 110 minutes.

[0091] The reaction temperature of K3 is 65° C. and the reaction time is 140 minutes.

[0092] Example 3

[0093] A method for producing butanone oxime with high selectivity, comprising the following steps:

[0094] S1 ammoximation reaction:

[0095] 1.3 g of catalyst, 38 g of solvent, 18 g of butanone, 23 g of ammonia water, and 28 g of hydrogen peroxide solution were metered and fed into an ammoximation reactor. The reaction heat generated in the ammoximation reactor was removed by a cooler. After the reaction, the mixture was fed into a reaction liquid intermediate tank.

[0096] The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere.

[0097] S2 tert-Butanol distillation:

[0098] The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 105°C, the tower top temperature is controlled at 75°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, a portion of which is refluxed to the tert-butanol distillation tower, and the other portion is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and discharge.

[0099] S3 oxime water separation:

[0100] A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower and is pumped to the oxime-water separation tower for separation. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower via the stripping tower feed pump. The tower bottom temperature is controlled at 135°C and the pressure is 0.15MPa. The tower bottom wastewater is sent to the sewage treatment plant for treatment.

[0101] S4 butanone oxime distillation:

[0102] The aqueous oxime phase from the crude oxime tank is pumped into the first distillation tower under pressure, the kettle temperature is controlled at 75°C, and the pressure in the tower is maintained at -0.095 MPa by a vacuum pump. Water and some butanone oxime are obtained at the top of the tower and enter the distillate tank of the first distillation tower. They are pumped under pressure to the oxime-water separation tower. The bottom liquid of the first distillation tower is pumped under pressure and then sent to the second distillation tower. The second distillation tower controls the kettle temperature at 85°C and the pressure at -0.095 MPa. High-purity butanone oxime is obtained at the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of it is refluxed and part is sent to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower through the bottom liquid of the second distillation tower for further separation and purification.

[0103] The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0104] The mass concentration of the ammonia water is 24%.

[0105] The mass concentration of the hydrogen peroxide aqueous solution is 28%.

[0106] The solvent is tert-butanol.

[0107] The ammoximation reaction temperature of S1 is 65° C., the pressure is 1.05 MPa, and the time is 5 h.

[0108] The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps:

[0109] K1: 180 g of titanium silicalite, 7 g of mercaptosiloxane, and 1400 g of ethanol were mixed uniformly, and the mixture was heated for reaction; the mixture was then filtered and dried to obtain the mercapto titanium silicalite;

[0110] K2: Add 0.4 g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 5 g of sodium ethoxide to the above mercaptotitanium silicate molecular sieve, and then heat the reaction;

[0111] K3: Finally, 0.15 g of (+)-IPC2B (allyl) borane CAS: 106356-53-0 was added to the reaction system and the reaction was continued. After the reaction was completed, ethanol was removed by distillation to obtain boron-nickel doped titanium silicalite.

[0112] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0113] The reaction temperature of K1 is 45° C. and the reaction time is 140 minutes.

[0114] The reaction temperature of K2 is 65°C and the reaction time is 140 minutes.

[0115] The reaction temperature of K3 is 65° C. and the reaction time is 160 minutes.

[0116] Example 4

[0117] A method for producing butanone oxime with high selectivity, comprising the following steps:

[0118] S1 ammoximation reaction:

[0119] 1.5g of catalyst, 40g of solvent, 20g of butanone, 25g of ammonia water, and 30g of hydrogen peroxide solution were metered and fed into an ammoximation reactor. The reaction heat generated in the ammoximation reactor was removed by a cooler. After the reaction, the mixture was fed into a reaction liquid intermediate tank.

[0120] The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere.

[0121] S2 tert-Butanol distillation:

[0122] The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 110°C, the tower top temperature is controlled at 80°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, part of which is refluxed to the tert-butanol distillation tower, and the other part is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and then discharged.

[0123] S3 oxime water separation:

[0124] A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower and is pumped to the oxime-water separation tower for separation. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower via the stripping tower feed pump. The tower bottom temperature is controlled at 140°C and the pressure is 0.15 MPa. The tower bottom wastewater is sent to the sewage treatment plant for treatment.

[0125] S4 butanone oxime distillation:

[0126] The aqueous oxime phase from the crude oxime tank is pumped into the first distillation tower under pressure, the kettle temperature is controlled at 80°C, and the pressure in the tower is maintained at -0.095 MPa by a vacuum pump. Water and some butanone oxime are obtained at the top of the tower and enter the distillate tank of the first distillation tower. They are then pumped to the oxime-water separation tower under pressure. The bottom liquid of the first distillation tower is pumped to the second distillation tower under pressure. The second distillation tower controls the kettle temperature at 90°C and the pressure at -0.095 MPa. High-purity butanone oxime is obtained at the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of it is refluxed, and part is sent to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower through the bottom liquid of the second distillation tower for further separation and purification.

[0127] The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0128] The mass concentration of the ammonia water is 25%.

[0129] The mass concentration of the hydrogen peroxide aqueous solution is 30%.

[0130] The solvent is tert-butanol.

[0131] The ammoximation reaction temperature of S1 is 70° C., the pressure is 1.1 MPa, and the time is 6 h.

[0132] The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps:

[0133] K1: 200 g of titanium silicalite, 8 g of mercaptosiloxane, and 1500 g of ethanol were mixed uniformly, and the mixture was heated to react; the mixture was then filtered and dried to obtain the mercapto titanium silicalite;

[0134] K2: Add 0.5 g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 6 g of sodium ethoxide to the above mercaptotitanium silicate molecular sieve, and then heat the reaction;

[0135] K3: Finally, 0.2 g of (+)-IPC2B (allyl) borane CAS: 106356-53-0 was added to the reaction system and the reaction was continued. After the reaction was completed, ethanol was removed by distillation to obtain boron-nickel doped titanium silicalite.

[0136] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0137] The reaction temperature of K1 is 50° C. and the reaction time is 150 minutes.

[0138] The reaction temperature of K2 is 70°C and the reaction time is 150 minutes.

[0139] The reaction temperature of K3 is 70°C and the reaction time is 180 minutes.

[0140] Comparative Example 1

[0141] Instead of adding boron-nickel doped titanium silicon molecular sieve, titanium silicon molecular sieve was directly added, and the rest was the same as in Example 1.

[0142] Comparative Example 2

[0143] Allyl(cyclopentadienyl)nickel was not added, and the other steps were the same as in Example 1.

[0144] Comparative Example 3

[0145] The other steps were the same as in Example 1 except that (+)-IPC2B (allyl) borane was not added.

[0146] Table 1

[0147] Conversion rate / % Selectivity / % Example 1 99.93 100 Example 2 99.95 100 Example 3 99.97 100 Example 4 99.99 100 Comparative Example 1 93.53 95.39 Comparative Example 2 97.88 98.69 Comparative Example 3 98.36 99.22

[0148] Through the data analysis of the above examples and comparative examples, the butanone oxime prepared by the present invention has a high conversion rate and selectivity.

[0149] 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 method for producing butanone oxime with high selectivity, comprising the following steps: S1 ammoximation reaction: 0.5-1.5 parts of catalyst, 30-40 parts of solvent, 10-20 parts of butanone, 12-25 parts of ammonia water, and 20-30 parts of hydrogen peroxide solution are metered by weight and then introduced into an ammoximation reactor; the reaction heat generated in the ammoximation reactor is removed by a cooler; and the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by the tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through the tail gas absorption tower and is washed with high-purity water. The tail gas after washing is discharged into the atmosphere. S2 tert-Butanol distillation: The reaction liquid in the reaction liquid intermediate tank is pumped to the tert-butanol distillation tower for distillation. The tower bottom temperature is controlled at 100-110°C, the tower top temperature is controlled at 70-80°C, and the tower bottom pressure is 0.05MPa. The tert-butanol produced by the tower top condenser enters the distillation tank of the tert-butanol distillation tower, a part of which is refluxed to the tert-butanol distillation tower, and the other part is returned to the ammoximation reactor. The non-condensable gas at the top of the tower is condensed by the tail gas condenser, and the non-condensable gas enters the tail gas absorption tower for washing and then discharged. S3 oxime water separation: A mixture of butanone oxime and water is obtained at the bottom of the tert-butanol distillation tower. This mixture is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butanol distillation tower. The upper layer of the oxime-water separation tower overflows into the crude oxime tank and is then sent to the distillation process. The lower layer is pumped into the wastewater stripping tower through the stripping tower feed pump. The bottom temperature is controlled at 130-140°C and the pressure is 0.15MPa. The wastewater from the bottom of the tower is sent to the sewage treatment plant for treatment. S4 butanone oxime distillation: The aqueous oxime phase from the crude oxime tank is pressurized and fed into the first distillation tower via a pump. The kettle temperature is controlled at 70-80°C, and the pressure in the tower is maintained at -0.095 MPa via a vacuum pump. Water and part of butanone oxime are obtained at the top of the tower and enter the distillate tank of the first distillation tower. They are then pressurized and fed to the oxime-water separation tower via a pump. The bottom liquid of the first distillation tower is pressurized and fed into the second distillation tower. The kettle temperature of the second distillation tower is controlled at 80-90°C and the pressure is -0.095 MPa. High-purity butanone oxime is obtained at the top of the tower and enters the distillate tank of the second distillation tower after condensation. Part of the butanone oxime is refluxed, and part is fed to the finished oxime tank. The materials in the bottom of the tower are pumped to the oxime-water separation tower via the bottom liquid of the second distillation tower for further separation and purification. The catalyst is a boron nickel doped titanium silicalite molecular sieve, which is prepared by the reaction of mercapto titanium silicalite, allyl (cyclopentadienyl) nickel, and (+)-IPC2B (allyl) borane; The preparation method of the boron-nickel doped titanium silicon molecular sieve comprises the following steps: K1: 100-200 parts of titanium silicalite, 5-8 parts of mercaptosiloxane and 1000-1500 parts of ethanol are mixed uniformly, and the mixture is heated to react; the mixture is then filtered and dried to obtain the mercapto titanium silicalite; K2: Add 0.05-0.5 parts of allyl (cyclopentadienyl) nickel and 2-6 parts of sodium ethoxide to the above-mentioned mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, 0.02-0.2 parts of (+)-IPC2B (allyl) borane is added to the reaction system and the reaction is continued. After the reaction is completed, ethanol is removed by distillation to obtain boron-nickel doped titanium silicon molecular sieve; The mercaptosiloxane is γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane; The ammoximation reaction temperature of S1 is 60-70°C, the pressure is 1.0-1.1 MPa, and the time is 4-6 hours.

2. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The mass concentration of the ammonia water is 20-25%.

3. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The mass concentration of the hydrogen peroxide aqueous solution is 20-30%.

4. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The solvent is one of water, tert-butyl alcohol and isopropyl alcohol.

5. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The reaction temperature of K1 is 40-50°C and the reaction time is 100-150 minutes.

6. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The reaction temperature of K2 is 60-70°C and the reaction time is 100-150 minutes.

7. The method for producing butanone oxime with high selectivity according to claim 1, wherein: The reaction temperature of K3 is 60-70°C and the reaction time is 120-180 minutes.