Method for enhancing production efficiency of diacetylmonoxime through cross-flow filtration

Abstract

The invention relates to a method for enhancing the production efficiency of diacetylmonoxime through cross-flow filtration, and belongs to the technical field of diacetylmonoxime. The method comprises the following steps: adding a catalyst, butanone, ammonia water, hydrogen peroxide and tert-butyl alcohol into an ammoximation reactor, and cooling to room temperature after the reaction is finished; after cooling, standing for layering, carrying out cross-flow filtration on an upper-layer oil phase by virtue of a filter membrane with the pore diameter of 0.1 micron, carrying out reduced-pressure rectification on filtrate, and collecting fractions, so as to obtain high-purity diacetylmonoxime; the preparation method comprises the following steps: stirring a TS-1 titanium silicalite molecular sieve, 3-isocyanate propyl trimethoxy silane and a solvent to react; and adding a 1-hydroxyethylidene-1, 1-diphosphonic acid / tungsten complex, bis (2-hydracrylic acid) titanium dihydroxide and stannous octoate, carrying out a stirring reaction, filtering, and drying to obtain the product. The diacetylmonoxime prepared by the method has high yield, and the purity of the diacetylmonoxime is as high as 99.95%.

Description

Technical Field

[0001] The invention relates to the technical field of butanone oxime, in particular to a method for enhancing the production efficiency of butanone oxime by cross-flow filtration. Background Art

[0002] Butanone oxime is an important chemical product that can be used as a boiler deoxidizer, an anti-skinning agent for paints, and can be used to synthesize a cross-linking agent for construction. Among the synthesis methods of butanone oxime, the ammoxidation of butanone oxime is a clean, environmentally friendly and economical process. Research on the efficient and low-cost ammoxidation reaction of butanone oxime has become a hot topic in recent years.

[0003] Chinese patent CN1556096A relates to a process for producing acetone oxime or butanone oxime by oxidation of acetone or butanone. It belongs to the production technology of acetone oxime and butanone oxime. In this process, acetone or butanone is dissolved in isopropanol or tert-butanol at a dosage of 100-200g solvent / mol ketone, TS-1 catalyst is added at a dosage of 3-10g catalyst / mol ketone and ammonia is added at a dosage of 1.2-2mol ammonia / mol ketone to prepare a reaction solution, and then hydrogen peroxide is slowly added dropwise at a dosage of 1.0-1.3mol hydrogen peroxide / mol ketone to the reaction solution at 50℃-120℃ and 0.1MPa-1.0MPa pressure for 0.25-12 hours to obtain acetone oxime or butanone oxime product.

[0004] Chinese patent CN1651405A discloses a method for synthesizing butanone oxime, and proposes a new method for directly synthesizing butanone oxime by ammoxidizing butanone in an oxidation system composed of titanium silicon molecular sieve and hydrogen peroxide solution. The method is to directly synthesize butanone oxime by reacting butanone with 25% ammonia solution in a catalytic oxidation system composed of titanium silicon molecular sieve and 30% hydrogen peroxide solution in an appropriate solvent at normal pressure.

[0005] Chinese patent CN104610094A discloses a method for preparing butanone oxime, which mainly includes the following five steps: a raw material step, a reaction step, a membrane filtration step, an oxime-water separation step, and a refining step. The raw material step mainly stores raw materials and transports raw materials that meet the production process requirements to the reaction step, wherein the raw materials are mainly butanone, liquid ammonia and hydrogen peroxide, wherein the purity of butanone is ≥99.5wt%, the purity of liquid ammonia is ≥99.5wt%, and the purity of hydrogen peroxide is ≥27.5wt%.

[0006] The butanone oxime prepared by the above patents and prior art has a complex process and high production cost, and the purity of butanone oxime needs to be further improved. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for enhancing the production efficiency of butanone oxime by cross-flow filtration, and the operating steps are as follows: S1 Ammoximation reaction: According to weight, 1-3 parts of catalyst, 52-64 parts of butanone, 64-78 parts of ammonia water, 88-100 parts of hydrogen peroxide, and 100-150 parts of tert-butyl alcohol 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The mass concentration of the ammonia water is 25-28%.

[0008] The mass concentration of the hydrogen peroxide is 25-30%.

[0009] The reaction temperature of S1 is 60-80°C, the pressure is 1.0-1.1 MPa, and the time is 3-4 hours.

[0010] The kettle temperature of the first vacuum distillation tower is 70-80°C, and the kettle temperature of the second vacuum distillation tower is 80-90°C.

[0011] The vacuum degree of the vacuum distillation tower is -0.09~-0.095Mpa.

[0012] The catalyst preparation method is: T1: 100-150 parts by weight of TS-1 titanium silicalite, 5-8 parts of 3-isocyanate propyltrimethoxysilane, and 1000-1400 parts of solvent are stirred at 40-50°C for 1-3h; T2: Add 5-10 parts of hydroxyethylidene diphosphonic acid / tungsten complex, 0.06-0.4 parts of di(2-hydroxypropionic acid) diammonium dihydroxide titanium, and 0.3-2 parts of stannous octoate, stir at 80-90°C for 1-3h, filter, and dry to obtain a catalyst.

[0013] The solvent is DMF.

[0014] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: According to weight, 20.5-41 parts of hydroxyethylidene diphosphonic acid, 29-58 parts of sodium tungstate dihydrate, and 400-500 parts of water are stirred at 50-60° C. for 40-80 minutes, and the water is distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.

[0015] Reaction mechanism The preparation of butanone oxime usually involves the reaction of butanone with hydroxylamine (or its derivatives). Under acidic conditions, the nitrogen atom of hydroxylamine attacks the carbonyl carbon of butanone nucleophilically to form an intermediate, which then loses a molecule of water to generate butanone oxime. This reaction can be expressed as: Under the catalysis of TS-1 titanium silicalite, hydrogen peroxide (hydrogen peroxide) can participate in the oxidation process, promote the formation of hydroxylamine or directly participate in the oxidation of butanone, thereby indirectly promoting the formation of butanone oxime; TS-1 titanium silicalite, as a solid acid catalyst, can provide acidic sites to accelerate the reaction.

[0016] Technical Effects The invention discloses a method for enhancing the production efficiency of butanone oxime by cross-flow filtration. Compared with the prior art, the invention has the following significant effects: 1. Isocyanate-based TS-1 titanium silicalite molecular sieve: By introducing isocyanate groups into the TS-1 titanium silicalite molecular sieve, its surface chemical properties can be changed, thereby affecting its catalytic performance; the isocyanate group has a high reactivity and can react with a variety of functional groups, so this modified molecular sieve can have a wider range of catalytic applications.

[0017] 2. Condensation reaction with hydroxyethylidene diphosphonic acid / tungsten complex: This complex may contain multiple active sites, which can react with isocyanate groups to form a cross-linked network structure; this structure has higher stability and catalytic activity, and can maintain catalytic performance under more stringent reaction conditions. At the same time, the introduction of tungsten can also enhance the redox performance of the catalyst.

[0018] 3. Condensation reaction with diammonium titanium dihydroxide (2-hydroxypropionic acid): This reaction may further change the surface properties of the catalyst and the distribution of active sites; as a transition metal complex, diammonium titanium dihydroxide has strong redox ability, and its introduction can improve the activity and selectivity of the catalyst in redox reactions. DETAILED DESCRIPTION

[0019] 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: Determination of butanone oxime content: The sample is vaporized and passed through a chromatographic column to separate butanone oxime from other components. It is monitored by a flame ionization detector and the mass fraction of butanone oxime is calculated by the area normalization method.

[0020] Example 1 A method for enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 Ammoximation reaction: 1g of catalyst, 52g of butanone, 64g of ammonia water, 88g of hydrogen peroxide, and 100g of tert-butanol are metered and fed 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 fed into 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The mass concentration of the ammonia water is 25%.

[0021] The mass concentration of the hydrogen peroxide is 25%.

[0022] The reaction temperature of S1 is 60°C, the pressure is 1.0 MPa, and the time is 3 hours.

[0023] The kettle temperature of the first vacuum distillation tower is 70°C, and the kettle temperature of the second vacuum distillation tower is 80°C.

[0024] The vacuum degree of the vacuum distillation tower is -0.09Mpa.

[0025] The catalyst preparation method is: T1: 100g TS-1 titanium silicalite, 5g 3-isocyanate propyltrimethoxysilane (CAS No. 15396-00-6), and 1000g solvent were stirred at 40°C for 1h; T2: Add 5 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.06 g of di(2-hydroxypropionic acid)diammonium dihydroxide titanium complex CAS: 65104-06-5, and 0.3 g of stannous octoate, stir at 80°C for 1 h, filter, and dry to obtain a catalyst.

[0026] The solvent is DMF.

[0027] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: 20.5 g of hydroxyethylidene diphosphonic acid, 29 g of sodium tungstate dihydrate and 400 g of water were stirred at 50°C for 40 minutes, and the water was distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.

[0028] Example 2 A method for enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 Ammoximation reaction: 2g of catalyst, 56g of butanone, 68g of ammonia water, 92g of hydrogen peroxide, and 120g of tert-butanol are metered and fed 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The mass concentration of the ammonia water is 26%.

[0029] The mass concentration of the hydrogen peroxide is 26%.

[0030] The reaction temperature of S1 is 65°C, the pressure is 1.05MPa, and the time is 3.5h.

[0031] The kettle temperature of the first vacuum distillation tower is 75°C, and the kettle temperature of the second vacuum distillation tower is 85°C.

[0032] The vacuum degree of the vacuum distillation tower is -0.09Mpa.

[0033] The catalyst preparation method is: T1: 110 g TS-1 titanium silicalite, 6 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1100 g solvent were stirred at 45 °C for 2 h; T2: Add 6 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.2 g of di(2-hydroxypropionic acid)diammonium dihydroxide titanium complex CAS: 65104-06-5, and 1 g of stannous octoate, stir at 85° C. for 2 h, filter, and dry to obtain a catalyst.

[0034] The solvent is DMF.

[0035] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: 26 g of hydroxyethylidene diphosphonic acid, 38 g of sodium tungstate dihydrate and 440 g of water were stirred at 55°C for 50 minutes, and the water was distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.

[0036] Example 3 A method for enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 Ammoximation reaction: 2g of catalyst, 62g of butanone, 74g of ammonia water, 98g of hydrogen peroxide, and 140g of tert-butanol are metered and fed 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The mass concentration of the ammonia water is 27%.

[0037] The mass concentration of the hydrogen peroxide is 28%.

[0038] The reaction temperature of S1 is 75°C, the pressure is 1.05MPa, and the time is 3.5h.

[0039] The kettle temperature of the first vacuum distillation tower is 75°C, and the kettle temperature of the second vacuum distillation tower is 85°C.

[0040] The vacuum degree of the vacuum distillation tower is -0.095Mpa.

[0041] The catalyst preparation method is: T1: 140 g TS-1 titanium silicalite, 7 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1300 g solvent were stirred at 45 °C for 2 h; T2: Add 9 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.3 g of di(2-hydroxypropionic acid)diammonium dihydroxide titanium complex CAS: 65104-06-5, and 1.5 g of stannous octoate, stir at 85° C. for 2 h, filter, and dry to obtain a catalyst.

[0042] The solvent is DMF.

[0043] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: 38 g of hydroxyethylidene diphosphonic acid, 55 g of sodium tungstate dihydrate and 480 g of water were stirred at 55°C for 70 minutes, and the water was distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.

[0044] Example 4 A method for enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 Ammoximation reaction: 3g of catalyst, 64g of butanone, 78g of ammonia water, 100g of hydrogen peroxide, and 150g of tert-butanol are metered and fed 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 fed into 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The mass concentration of the ammonia water is 28%.

[0045] The mass concentration of the hydrogen peroxide is 30%.

[0046] The reaction temperature of S1 is 80°C, the pressure is 1.1 MPa, and the time is 4 hours.

[0047] The kettle temperature of the first vacuum distillation tower is 80°C, and the kettle temperature of the second vacuum distillation tower is 90°C.

[0048] The vacuum degree of the vacuum distillation tower is -0.095Mpa.

[0049] The catalyst preparation method is: T1: 150 g TS-1 titanium silicalite, 8 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1400 g solvent were stirred at 50 ° C for 3 h; T2: Add 10 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.4 g of di(2-hydroxypropionic acid)diammonium dihydroxide titanium complex CAS: 65104-06-5, and 2 g of stannous octoate, stir at 90° C. for 3 h, filter, and dry to obtain a catalyst.

[0050] The solvent is DMF.

[0051] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: 41 g of hydroxyethylidene diphosphonic acid, 58 g of sodium tungstate dihydrate and 500 g of water were stirred at 60°C for 80 minutes, and the water was distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.

[0052] Comparative Example 1 The TS-1 titanium silicalite molecular sieve was not modified, and the other properties were the same as those in Example 1.

[0053] Comparative Example 2 The hydroxyethylidene diphosphonic acid / tungsten complex was not added, and the other steps were the same as in Example 1.

[0054] Comparative Example 3 The other steps were the same as in Example 1 except that no di(2-hydroxypropionic acid) diammonium dihydroxide titanium was added.

[0055] The test results are shown in Table 1.

[0056] Table 1 Yield / % purity / % Example 1 94.46 99.83 Example 2 94.88 99.87 Example 3 95.09 99.91 Example 4 95.32 99.95 Comparative Example 1 80.61 86.23 Comparative Example 2 87.79 93.17 Comparative Example 3 89.13 95.45 Through the data analysis of the above embodiments and comparative examples, the butanone oxime prepared by the present invention has a higher yield, and the purity of butanone oxime is as high as 99.95%.

[0057] 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 enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 Ammoximation reaction: According to weight, 1-3 parts of catalyst, 52-64 parts of butanone, 64-78 parts of ammonia water, 88-100 parts of hydrogen peroxide, and 100-150 parts of tert-butyl alcohol 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 cooled and then allowed to stand for stratification. The upper oil phase is filtered through a cross-flow filter with a pore size of 0.1 micron. The filtrate is then pressurized by a pump and sent to a vacuum distillation tower. Water and part of butanone oxime are obtained at the top of the vacuum distillation tower and enter the distillate tank of the vacuum distillation tower. The water is then pressurized by a pump and sent to an oxime-water separation tower. The bottom liquid of the vacuum distillation tower is then pressurized by a pump and sent to a vacuum distillation tower. High-purity butanone oxime is obtained at the top of the vacuum distillation tower. After condensation, the high-purity butanone oxime is entered into the distillate tank of the vacuum distillation tower. Part of the high-purity butanone oxime is refluxed and part of the high-purity ... The catalyst is prepared by reacting TS-1 titanium silicon molecular sieve, 3-isocyanate propyl trimethoxysilane, hydroxyethylidene diphosphonic acid / tungsten complex and di(2-hydroxypropionic acid) diammonium dihydroxide titanium.

2. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The mass concentration of the ammonia water is 25-28%.

3. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide is 25-30%.

4. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The reaction temperature of S1 is 60-80°C, the pressure is 1.0-1.1MPa, and the time is 3-4h.

5. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The kettle temperature of the first vacuum distillation tower is 70-80°C, and the kettle temperature of the second vacuum distillation tower is 80-90°C.

6. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The vacuum degree of the vacuum distillation tower is -0.09~-0.095Mpa.

7. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The catalyst preparation method is: T1: 100-150 parts by weight of TS-1 titanium silicalite, 5-8 parts of 3-isocyanate propyltrimethoxysilane, and 1000-1400 parts of solvent are stirred at 40-50°C for 1-3h; T2: Add 5-10 parts of hydroxyethylidene diphosphonic acid / tungsten complex, 0.06-0.4 parts of di(2-hydroxypropionic acid) diammonium dihydroxide titanium, and 0.3-2 parts of stannous octoate, stir at 80-90°C for 1-3h, filter, and dry to obtain a catalyst.

8. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 7, characterized in that: The solvent is DMF.

9. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 7, characterized in that: The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: According to weight, 20.5-41 parts of hydroxyethylidene diphosphonic acid, 29-58 parts of sodium tungstate dihydrate, and 400-500 parts of water are stirred at 50-60° C. for 40-80 minutes, and the water is distilled off to obtain a hydroxyethylidene diphosphonic acid / tungsten complex.