Method for producing diacetylmonoxime with high selectivity

Abstract

The invention relates to a method for producing diacetylmonoxime with high selectivity. The method comprises the following steps: by taking a catalyst, a solvent, butanone, ammonia water and a hydrogen peroxide aqueous solution as raw materials, carrying out ammoximation reaction, tert-butyl alcohol rectification, oxime-water separation and diacetylmonoxime rectification to obtain diacetylmonoxime; the catalyst is a boron-nickel-doped titanium silicalite molecular sieve, and the titanium silicalite molecular sieve, sulfydryl siloxane and ethanol are mixed to react, filtered and dried to obtain the sulfydryl titanium silicalite molecular sieve; the preparation method comprises the following steps: heating and reacting a mercapto titanium silicalite molecular sieve, allyl (cyclopentadienyl) nickel and sodium ethoxide; and finally adding (+)-IPC2B (allyl) borane, continuously reacting, and distilling to remove ethanol, thereby obtaining the product. The diacetylmonoxime prepared by the method disclosed by the invention has relatively 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 mainly used in the anti-skinning of alkyd resin coatings and epoxy resin coatings, industrial curing of silicone, anti-oxidation of instrument oil, and as a new deoxidizer to replace hydrazine as boiler feed water. At present, the industry mainly uses the hydroxylamine method for production, which has a complicated 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 solvent water, ammonia, butanone and hydrogen peroxide are used as raw materials, and heteropoly acid or heteropoly acid salt is used as catalyst to catalyze the synthesis of butanone oxime.

[0004] Chinese patent CN113230986B: Provides an industrial preparation device for butanone oxime, and a method for preparing butanone oxime using the device, the device comprises a butanone ammoximation reactor, a feeding system, a product separation system and a tail gas absorption system, the feeding system is used to input 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; the tail gas absorption system is used to absorb and separate the gaseous product 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: S1 Ammoximation reaction: According to weight, 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 aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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-butyl alcohol 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-butyl alcohol produced by the tower top condenser enters the distillation tank of the tert-butyl alcohol distillation tower, a part of it is refluxed to the tert-butyl alcohol 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 treatment before being discharged; S3 oxime water separation: A mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 130-140°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 70-80°C, and the pressure in the tower is maintained at -0.095MPa by a vacuum pump. Water and part of butanone oxime are obtained from the top of the tower and enter the distillate tank of the first distillation tower, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to be 80-90°C and the pressure to be -0.095MPa, and high-purity butanone oxime is obtained from the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of which is refluxed and part of which 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; The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0008] The mass concentration of the ammonia water is 20-25%.

[0009] The mass concentration of the hydrogen peroxide aqueous solution is 20-30%.

[0010] The solvent is one of water, tert-butyl alcohol and isopropyl alcohol.

[0011] 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.

[0012] The method for preparing 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 evenly, 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 (CAS No.: 12107-46-9) and 2-6 parts of sodium ethoxide to the above mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, add 0.02-0.2 parts of (+)-IPC2B (allyl) borane CAS: 106356-53-0 to the reaction system and continue the reaction. After the reaction is completed, remove ethanol by distillation to obtain boron-nickel doped titanium silicon molecular sieve.

[0013] The mercaptosiloxane is γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane.

[0014] The reaction temperature of K1 is 40-50°C and the reaction time is 100-150 minutes.

[0015] The reaction temperature of K2 is 60-70°C and the reaction time is 100-150 minutes.

[0016] The reaction temperature of K3 is 60-70°C and the reaction time is 120-180 minutes.

[0017] Reaction mechanism Catalyst preparation reaction mechanism The mercapto titanium silicalite undergoes an addition reaction with allyl (cyclopentadienyl) nickel, and then undergoes an addition reaction with 1(+)-IPC2B (allyl) borane, and finally obtains a titanium silicalite loaded with functional groups such as (cyclopentadienyl) nickel and borane. The reaction mechanism of this process is as follows: 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.

[0018] 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 to introduce borane functional groups by coordination or covalent bonding, thereby enhancing the catalytic activity and selectivity of the molecular sieve.

[0019] Technical Effects The invention discloses a method for producing butanone oxime with high selectivity. The method can bring the following benefits to the production of butanone oxime by reducing the ammonia-ketone ratio: 1. Improve product quality: A too high ammonia-ketone ratio will increase the impurity content in the product, thus 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.

[0020] 2. Reduce costs: A too high ammonia-ketone ratio will increase energy consumption and raw material consumption in the production process, thereby leading to an increase in production costs; by reducing the ammonia-ketone ratio, energy consumption and raw material consumption can be reduced, thereby reducing production costs.

[0021] 3. Improve production efficiency: A too high ammonia-to-ketone ratio will affect the reaction rate and product selectivity, thereby reducing production efficiency; by reducing the ammonia-to-ketone ratio, the reaction rate and product selectivity can be increased, thereby improving production efficiency.

[0022] 4. Extend equipment life: A high ammonia-to-ketone ratio will cause corrosion and wear to equipment such as reactors, thereby shortening the service life of the equipment; by reducing the ammonia-to-ketone ratio, the corrosion and wear of the equipment can be reduced and the service life of the equipment can be extended.

[0023] In short, reducing the ammonia-to-ketone ratio can improve product quality, reduce costs, improve production efficiency and extend equipment life, among other benefits. DETAILED DESCRIPTION

[0024] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples: Butanone oxime was detected by liquid chromatography, and the test results are shown in Table 1.

[0025] Example 1 A method for producing butanone oxime with high selectivity, the operating steps are: S1 Ammoximation reaction: 0.5g of catalyst, 30g of solvent, 10g of butanone, 12g of ammonia water, and 20g of hydrogen peroxide aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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°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, 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 treatment before being discharged; S3 oxime water separation: A mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 130°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 70°C, and the pressure in the tower is maintained at -0.095MPa by 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, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to 80°C and the pressure to -0.095MPa, and high-purity butanone oxime is obtained at the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of which is refluxed and part of which 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; The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0026] The mass concentration of the ammonia water is 20%.

[0027] The mass concentration of the aqueous hydrogen peroxide solution is 20%.

[0028] The solvent is tert-butyl alcohol.

[0029] The ammoximation reaction temperature of S1 is 60°C, the pressure is 1.0 MPa, and the time is 4 hours.

[0030] The method for preparing the boron-nickel doped titanium-silicon molecular sieve comprises the following steps: K1: 100 g of titanium silicalite, 5 g of mercaptosiloxane and 1000 g of ethanol were mixed evenly, and the mixture was heated to react; the mixture was then filtered and dried to obtain the mercapto titanium silicalite; K2: Add 0.05 g of allyl (cyclopentadienyl) nickel (CAS No.: 12107-46-9) and 2 g of sodium ethoxide to the above mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, 0.02 g (+)-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.

[0031] The mercaptosiloxane is gamma-mercaptopropyltrimethoxysilane.

[0032] The reaction temperature of K1 is 40°C and the reaction time is 100 minutes.

[0033] The reaction temperature of K2 is 60°C and the reaction time is 100 minutes.

[0034] The reaction temperature of K3 is 60°C and the reaction time is 120 minutes.

[0035] Example 2 A method for producing butanone oxime with high selectivity, the operating steps are: S1 Ammoximation reaction: 0.8g of catalyst, 33g of solvent, 13g of butanone, 18g of ammonia water, and 23g of hydrogen peroxide aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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-butyl alcohol 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-butyl alcohol produced by the tower top condenser enters the distillation tank of the tert-butyl alcohol distillation tower, a part of which is refluxed to the tert-butyl alcohol 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 treatment before being discharged; S3 oxime water separation: A mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 135°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 75°C, and the pressure in the tower is maintained at -0.095MPa by a vacuum pump. Water and part of butanone oxime are obtained from the top of the tower and enter the distillate tank of the first distillation tower, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to be 85°C and the pressure to be -0.095MPa, and high-purity butanone oxime is obtained from the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of which is refluxed and part of which 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; The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0036] The mass concentration of the ammonia water is 22%.

[0037] The mass concentration of the aqueous hydrogen peroxide solution is 23%.

[0038] The solvent is tert-butyl alcohol.

[0039] The ammoximation reaction temperature of S1 is 65° C., the pressure is 1.05 MPa, and the time is 5 h.

[0040] The method for preparing the boron-nickel doped titanium-silicon molecular sieve comprises the following steps: K1: 130 g of titanium silicalite, 6 g of mercaptosiloxane and 1100 g of ethanol were mixed evenly, and the mixture was heated to react; the mixture was then filtered and dried to obtain the mercapto titanium silicalite; K2: Add 0.2 g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 3 g of sodium ethoxide to the above mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, 0.1 g (+)-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.

[0041] The mercaptosiloxane is gamma-mercaptopropyltrimethoxysilane.

[0042] The reaction temperature of K1 is 45°C and the reaction time is 110 minutes.

[0043] The reaction temperature of K2 is 65°C and the reaction time is 110 minutes.

[0044] The reaction temperature of K3 is 65°C and the reaction time is 140 minutes.

[0045] Example 3 A method for producing butanone oxime with high selectivity, the operating steps are: S1 Ammoximation reaction: 1.3g of catalyst, 38g of solvent, 18g of butanone, 23g of ammonia water, and 28g of hydrogen peroxide aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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-butyl alcohol 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-butyl alcohol produced by the tower top condenser enters the distillation tank of the tert-butyl alcohol distillation tower, a part of which is refluxed to the tert-butyl alcohol 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 treatment before being discharged; S3 oxime water separation: A mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 135°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 75°C, and the pressure in the tower is maintained at -0.095MPa by a vacuum pump. Water and part of butanone oxime are obtained from the top of the tower and enter the distillate tank of the first distillation tower, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to be 85°C and the pressure to be -0.095MPa, and high-purity butanone oxime is obtained from the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of which is refluxed and part of which 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; The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0046] The mass concentration of the ammonia water is 24%.

[0047] The mass concentration of the aqueous hydrogen peroxide solution is 28%.

[0048] The solvent is tert-butyl alcohol.

[0049] The ammoximation reaction temperature of S1 is 65° C., the pressure is 1.05 MPa, and the time is 5 h.

[0050] The method for preparing the boron-nickel doped titanium-silicon molecular sieve comprises the following steps: K1: 180 g of titanium silicalite, 7 g of mercaptosiloxane and 1400 g of ethanol were mixed evenly, and the mixture was heated to react; the mixture was then filtered and dried to obtain the mercapto titanium silicalite; K2: Add 0.4 g of allyl (cyclopentadienyl) nickel (CAS No.: 12107-46-9) and 5 g of sodium ethoxide to the above mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, 0.15 g (+)-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.

[0051] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0052] The reaction temperature of K1 is 45°C and the reaction time is 140 minutes.

[0053] The reaction temperature of K2 is 65°C and the reaction time is 140 minutes.

[0054] The reaction temperature of K3 is 65°C and the reaction time is 160 minutes.

[0055] Example 4 A method for producing butanone oxime with high selectivity, the operating steps are: S1 Ammoximation reaction: 1.5g of catalyst, 40g of solvent, 20g of butanone, 25g of ammonia water, and 30g of hydrogen peroxide aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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 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, 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 treatment before being discharged; S3 oxime water separation: The mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 140°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 80°C, and the pressure in the tower is maintained at -0.095MPa by 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, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to 90°C and the pressure to -0.095MPa, and high-purity butanone oxime is obtained at the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of which is refluxed and part of which 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; The catalyst is boron-nickel doped titanium silicon molecular sieve.

[0056] The mass concentration of the ammonia water is 25%.

[0057] The mass concentration of the aqueous hydrogen peroxide solution is 30%.

[0058] The solvent is tert-butyl alcohol.

[0059] The ammoximation reaction temperature of S1 is 70°C, the pressure is 1.1 MPa, and the time is 6 hours.

[0060] The method for preparing the boron-nickel doped titanium-silicon molecular sieve comprises the following steps: K1: 200 g of titanium silicalite, 8 g of mercaptosiloxane and 1500 g of ethanol were mixed evenly, and the mixture was heated to react; the mixture was then filtered and dried to obtain the mercapto titanium silicalite; K2: Add 0.5 g of allyl(cyclopentadienyl)nickel (CAS No.: 12107-46-9) and 6 g of sodium ethoxide to the above mercaptotitanium silicon molecular sieve, and then heat the reaction; K3: Finally, 0.2 g (+)-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.

[0061] The mercaptosiloxane is gamma-mercaptopropyltriethoxysilane.

[0062] The reaction temperature of K1 is 50°C and the reaction time is 150 minutes.

[0063] The reaction temperature of K2 is 70°C and the reaction time is 150 minutes.

[0064] The reaction temperature of K3 is 70°C and the reaction time is 180 minutes.

[0065] Comparative Example 1 Instead of adding boron-nickel doped titanium silicon molecular sieve, titanium silicon molecular sieve is directly added, and the rest is the same as in Example 1.

[0066] Comparative Example 2 Allyl(cyclopentadienyl)nickel was not added, and the rest was the same as in Example 1.

[0067] Comparative Example 3 The other steps were the same as in Example 1 except that (+)-IPC2B (allyl) borane was not added.

[0068] Table 1 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 Through the data analysis of the above examples and comparative examples, the butanone oxime prepared by the present invention has a higher conversion rate and selectivity.

[0069] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for producing butanone oxime with high selectivity, the operating steps of which are: S1 Ammoximation reaction: According to weight, 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 aqueous solution are metered and then introduced into an ammoximation reactor; the reaction heat generated by the ammoximation reactor is taken away by a cooler; the mixture after the reaction is completed is sent to a reaction liquid intermediate tank; The tail gas from the reactor is cooled by a tail gas cooler, and the condensate is returned to the ammoximation reactor. The non-condensable gas passes through a 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-butyl alcohol 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-butyl alcohol produced by the tower top condenser enters the distillation tank of the tert-butyl alcohol distillation tower, a part of it is refluxed to the tert-butyl alcohol 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 treatment before being discharged; S3 oxime water separation: A mixed liquid of butanone oxime and water is obtained at the bottom of the tert-butyl alcohol distillation tower, which is pumped to the oxime-water separation tower for separation through the bottom liquid pump of the tert-butyl alcohol distillation tower. The upper layer of the oxime-water separation tower overflows to the crude oxime tank and is then sent to the distillation process; the lower layer is sent to the wastewater stripping tower through the stripping tower feed pump, and the tower bottom temperature is controlled to be 130-140°C and the pressure is 0.15MPa; the tower bottom wastewater 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 sent to the first distillation tower by a pump, the kettle temperature is controlled to be 70-80°C, and the pressure in the tower is maintained at -0.095MPa by 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, and are pressurized by a pump and sent to the oxime-water separation tower. The bottom liquid of the first distillation tower is pressurized by a pump and sent to the second distillation tower; the second distillation tower controls the kettle temperature to be 80-90°C and the pressure to be -0.095MPa, and high-purity butanone oxime is obtained at the top of the tower. After condensation, it enters the distillation tank of the second distillation tower, part of it is refluxed, and part of it 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; The catalyst is boron-nickel doped titanium silicon molecular sieve, which is prepared by the reaction of mercapto titanium silicon molecular sieve, allyl (cyclopentadienyl) nickel and (+)-IPC2B (allyl) borane.

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

3. The method for producing butanone oxime with high selectivity according to claim 1, characterized in that: 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, characterized in that: 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, characterized in that: 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.

6. The method for producing butanone oxime with high selectivity according to claim 1, characterized in that: The method for preparing 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 evenly, 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 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.

7. The method for producing butanone oxime with high selectivity according to claim 6, characterized in that: The mercaptosiloxane is γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane.

8. The method for producing butanone oxime with high selectivity according to claim 6, characterized in that: The reaction temperature of K1 is 40-50°C and the reaction time is 100-150 minutes.

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

10. The method for producing butanone oxime with high selectivity according to claim 6, characterized in that: The reaction temperature of K3 is 60-70°C and the reaction time is 120-180 minutes.