A method for enhancing butanone oxime production efficiency by cross-flow filtration

Abstract

The present invention relates to a method for strengthening butanone oxime production efficiency by cross-flow filtration, and belongs to the technical field of butanone oxime. The present invention adds catalyst, butanone, ammonia, hydrogen peroxide, and tert-butyl alcohol to an ammoximation reactor, and after the reaction is completed, it is cooled to room temperature; after cooling, stratification is allowed to proceed, and after cross-flow filtration of the upper oil phase through a filter membrane pore size of 0.1 micron, the filtrate is subjected to vacuum distillation, and fractions are collected to obtain high-purity butanone oxime; the catalyst of the present invention is stirred by TS-1 titanium silicon molecular sieve, 3-isocyanate propyltrimethoxysilane, and a solvent; hydroxyethylidene diphosphonic acid / tungsten complex, di(2-hydroxypropionic acid) diammonium dihydroxide titanium, and stannous octoate are then added, the reaction is stirred, filtered, and dried to prepare; the butanone oxime prepared by the present invention has a higher yield, and the purity of butanone oxime is also 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 used as a boiler deoxidizer, an anti-skinning agent for paints, and a crosslinking agent for construction. Among the methods for synthesizing butanone oxime, the ammoxidation of butanone oxime is a clean, environmentally friendly, and highly economical process. Research on the efficient and low-cost ammoxidation of butanone oxime has become a research hotspot in recent years.

[0003] Chinese patent CN1556096A relates to a process for producing acetone oxime or butanone oxime by oxidizing acetone or butanone. This process involves dissolving acetone or butanone in isopropyl alcohol or tert-butyl alcohol at a rate of 100-200 g of solvent per mol of ketone. TS-1 catalyst at a rate of 3-10 g of catalyst per mol of ketone and ammonia at a rate of 1.2-2 mol of ammonia per mol of ketone are added to the acetone or butanone solution to prepare a reaction solution. Hydrogen peroxide at a rate of 1.0-1.3 mol of hydrogen peroxide per mol of ketone is then slowly added dropwise to the reaction solution at a temperature of 50-120°C and a pressure of 0.1-1.0 MPa for 0.25-12 hours to produce the acetone oxime or butanone oxime product.

[0004] Chinese patent CN1651405A discloses a method for synthesizing butanone oxime, proposing a novel method for directly synthesizing butanone oxime by ammoxidizing butanone in an oxidation system consisting of titanium silicalite and a 30% aqueous hydrogen peroxide solution. This method involves reacting butanone with a 25% aqueous ammonia solution in a suitable solvent at atmospheric pressure in a catalytic oxidation system consisting of titanium silicalite and a 30% aqueous hydrogen peroxide solution to directly synthesize butanone oxime.

[0005] Chinese patent CN104610094A discloses a method for preparing butanone oxime, which comprises five main 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 primarily stores raw materials and delivers raw materials that meet production process requirements to the reaction step. The raw materials primarily comprise butanone, liquid ammonia, and hydrogen peroxide. The butanone has a purity of ≥99.5wt%, the liquid ammonia has a purity of ≥99.5wt%, and the hydrogen peroxide has a purity of ≥27.5wt%.

[0006] The butanone oxime prepared by the above patents and prior art has complex processes and high production costs, 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, the operating steps of which are as follows:

[0008] S1 ammoximation reaction:

[0009] 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-butanol are metered by weight and 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 cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification.

[0017] The mass concentration of the ammonia water is 25-28%.

[0018] The mass concentration of the hydrogen peroxide is 25-30%.

[0019] The reaction temperature of S1 is 60-80°C, the pressure is 1.0-1.1 MPa, and the time is 3-4 hours.

[0020] The temperature of the kettle of the first vacuum distillation tower is 70-80°C, and the temperature of the kettle of the second vacuum distillation tower is 80-90°C.

[0021] The vacuum degree of the vacuum distillation tower is -0.09~-0.095Mpa.

[0022] The catalyst preparation method is:

[0023] T1: By weight, 100-150 parts of TS-1 titanium silicalite, 5-8 parts of 3-isocyanatepropyltrimethoxysilane, and 1000-1400 parts of solvent are stirred at 40-50°C for 1-3 hours;

[0024] 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 1-3 hours, filter, and dry to obtain a catalyst.

[0025] The solvent is DMF.

[0026] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows:

[0027] By 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.

[0028] Reaction mechanism

[0029] The preparation of butanone oxime typically involves the reaction of butanone with hydroxylamine (or its derivatives). Under acidic conditions, the nitrogen atom of hydroxylamine nucleophilically attacks the carbonyl carbon of butanone, forming an intermediate that subsequently loses a molecule of water to produce butanone oxime. This reaction can be represented as:

[0030] 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 and accelerate the reaction.

[0031] Technical Effects

[0032] The present invention provides a method for enhancing the production efficiency of butanone oxime by cross-flow filtration. Compared with the prior art, the present invention has the following significant effects:

[0033] 1. Isocyanate-based TS-1 titanium silicalite molecular sieve: By introducing isocyanate groups into TS-1 titanium silicalite, its surface chemical properties can be changed, thereby affecting its catalytic performance; isocyanate groups have high reactivity and can react with a variety of functional groups, so this modified molecular sieve can have a wider range of catalytic applications.

[0034] 2. Condensation reaction with hydroxyethylidene diphosphonic acid / tungsten complexes: This complex may contain multiple active sites that 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. Furthermore, the introduction of tungsten can enhance the redox performance of the catalyst.

[0035] 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. Its introduction can improve the activity and selectivity of the catalyst in redox reactions. DETAILED DESCRIPTION

[0036] 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:

[0037] Determination of butanone oxime content: The sample is vaporized and passed through a chromatographic column to separate butanone oxime from other components. The sample is monitored by a flame ionization detector and the mass fraction of butanone oxime is calculated by the area normalization method.

[0038] Example 1

[0039] A method for enhancing butanone oxime production efficiency by cross-flow filtration, the operating steps of which are as follows:

[0040] S1 ammoximation reaction:

[0041] 1g of catalyst, 52g of butanone, 64g of ammonia water, 88g of hydrogen peroxide, and 100g of tert-butanol were metered and fed into an ammoximation reactor. The heat of reaction generated in the ammoximation reactor was removed by a cooler. After the reaction, the mixture was fed into a reaction liquid intermediate tank.

[0042] 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.

[0043] S2 tert-Butanol distillation:

[0044] 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.

[0045] S3 oxime water separation:

[0046] 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.

[0047] S4 butanone oxime distillation:

[0048] The aqueous oxime phase from the crude oxime tank is cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification.

[0049] The mass concentration of the ammonia water is 25%.

[0050] The mass concentration of the hydrogen peroxide is 25%.

[0051] The reaction temperature of S1 is 60°C, the pressure is 1.0 MPa, and the time is 3 hours.

[0052] The temperature of the kettle of the first vacuum distillation tower is 70°C, and the temperature of the kettle of the second vacuum distillation tower is 80°C.

[0053] The vacuum degree of the vacuum distillation tower is -0.09Mpa.

[0054] The catalyst preparation method is:

[0055] T1: 100 g TS-1 titanium silicate molecular sieve, 5 g 3-isocyanate propyltrimethoxysilane (CAS No. 15396-00-6), and 1000 g solvent were stirred at 40 °C for 1 h;

[0056] T2: 5 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.06 g of di(2-hydroxypropionic acid)diammonium titanium dihydroxide CAS: 65104-06-5, and 0.3 g of stannous octoate were added, and the mixture was stirred at 80° C. for 1 h. The mixture was filtered and dried to obtain a catalyst.

[0057] The solvent is DMF.

[0058] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows:

[0059] 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.

[0060] Example 2

[0061] A method for enhancing butanone oxime production efficiency by cross-flow filtration, the operating steps of which are as follows:

[0062] S1 ammoximation reaction:

[0063] 2g of catalyst, 56g of butanone, 68g of ammonia water, 92g of hydrogen peroxide, and 120g of tert-butanol were metered and fed into an ammoximation reactor. The heat of reaction generated in the ammoximation reactor was removed by a cooler. The mixture after the reaction was completed was fed into a reaction liquid intermediate tank.

[0064] 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.

[0065] S2 tert-Butanol distillation:

[0066] 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.

[0067] S3 oxime water separation:

[0068] 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.

[0069] S4 butanone oxime distillation:

[0070] The aqueous oxime phase from the crude oxime tank is cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification.

[0071] The mass concentration of the ammonia water is 26%.

[0072] The mass concentration of the hydrogen peroxide is 26%.

[0073] The reaction temperature of S1 is 65°C, the pressure is 1.05 MPa, and the time is 3.5 hours.

[0074] The temperature of the kettle of the first vacuum distillation tower is 75°C, and the temperature of the kettle of the second vacuum distillation tower is 85°C.

[0075] The vacuum degree of the vacuum distillation tower is -0.09Mpa.

[0076] The catalyst preparation method is:

[0077] T1: 110 g TS-1 titanium silicate molecular sieve, 6 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1100 g solvent were stirred at 45 ° C for 2 h;

[0078] T2: Add 6 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.2 g of di(2-hydroxypropionic acid)diammonium titanium dihydroxide CAS: 65104-06-5, and 1 g of stannous octoate, stir at 85°C for 2 h, filter, and dry to obtain a catalyst.

[0079] The solvent is DMF.

[0080] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows:

[0081] 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.

[0082] Example 3

[0083] A method for enhancing butanone oxime production efficiency by cross-flow filtration, the operating steps of which are as follows:

[0084] S1 ammoximation reaction:

[0085] 2g of catalyst, 62g of butanone, 74g of ammonia water, 98g of hydrogen peroxide, and 140g of tert-butanol 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.

[0086] 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.

[0087] S2 tert-Butanol distillation:

[0088] 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.

[0089] S3 oxime water separation:

[0090] 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.

[0091] S4 butanone oxime distillation:

[0092] The aqueous oxime phase from the crude oxime tank is cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification.

[0093] The mass concentration of the ammonia water is 27%.

[0094] The mass concentration of the hydrogen peroxide is 28%.

[0095] The reaction temperature of S1 is 75°C, the pressure is 1.05 MPa, and the time is 3.5 hours.

[0096] The temperature of the kettle of the first vacuum distillation tower is 75°C, and the temperature of the kettle of the second vacuum distillation tower is 85°C.

[0097] The vacuum degree of the vacuum distillation tower is -0.095Mpa.

[0098] The catalyst preparation method is:

[0099] T1: 140 g TS-1 titanium silicate molecular sieve, 7 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1300 g solvent were stirred at 45 ° C for 2 h;

[0100] T2: 9 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.3 g of di(2-hydroxypropionic acid)diammonium titanium dihydroxide CAS: 65104-06-5, and 1.5 g of stannous octoate were added, and the mixture was stirred at 85° C. for 2 h. The mixture was filtered and dried to obtain a catalyst.

[0101] The solvent is DMF.

[0102] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows:

[0103] 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.

[0104] Example 4

[0105] A method for enhancing butanone oxime production efficiency by cross-flow filtration, the operating steps of which are as follows:

[0106] S1 ammoximation reaction:

[0107] 3g of catalyst, 64g of butanone, 78g of ammonia water, 100g of hydrogen peroxide, and 150g of tert-butanol were metered and fed into an ammoximation reactor. The heat of reaction generated in the ammoximation reactor was removed by a cooler. After the reaction, the mixture was fed into a reaction liquid intermediate tank.

[0108] 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.

[0109] S2 tert-Butanol distillation:

[0110] 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.

[0111] S3 oxime water separation:

[0112] 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.

[0113] S4 butanone oxime distillation:

[0114] The aqueous oxime phase from the crude oxime tank is cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification.

[0115] The mass concentration of the ammonia water is 28%.

[0116] The mass concentration of the hydrogen peroxide is 30%.

[0117] The reaction temperature of S1 is 80°C, the pressure is 1.1 MPa, and the time is 4 hours.

[0118] The temperature of the kettle of the first vacuum distillation tower is 80°C, and the temperature of the kettle of the second vacuum distillation tower is 90°C.

[0119] The vacuum degree of the vacuum distillation tower is -0.095Mpa.

[0120] The catalyst preparation method is:

[0121] T1: 150 g TS-1 titanium silicate molecular sieve, 8 g 3-isocyanate propyltrimethoxysilane CAS No. 15396-00-6, and 1400 g solvent were stirred at 50 ° C for 3 h;

[0122] T2: Add 10 g of hydroxyethylidene diphosphonic acid / tungsten complex, 0.4 g of di(2-hydroxypropionic acid)diammonium titanium dihydroxide CAS: 65104-06-5, and 2 g of stannous octoate, stir at 90° C. for 3 h, filter, and dry to obtain a catalyst.

[0123] The solvent is DMF.

[0124] The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows:

[0125] 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.

[0126] Comparative Example 1

[0127] The TS-1 titanium silicalite molecular sieve was not modified, and the other properties were the same as in Example 1.

[0128] Comparative Example 2

[0129] The hydroxyethylidene diphosphonic acid / tungsten complex was not added, and the other steps were the same as in Example 1.

[0130] Comparative Example 3

[0131] The same procedures as in Example 1 were followed except that titanium diammonium di(2-hydroxypropionic acid)dihydroxide was not added.

[0132] The test results are shown in Table 1.

[0133] Table 1

[0134] 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

[0135] Through the data analysis of the above examples and comparative examples, the butanone oxime prepared by the present invention has a high yield and the purity of butanone oxime is as high as 99.95%.

[0136] 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 enhancing the production efficiency of butanone oxime by cross-flow filtration, the operating steps of which are: S1 ammoximation reaction: 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-butanol are metered by weight and 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 cooled and 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 pumped under pressure into a first vacuum distillation tower. Water and a portion of butanone oxime are obtained at the top of the first vacuum distillation tower and enter the distillate tank of the first vacuum distillation tower. The pressurized liquid in the bottom of the first vacuum distillation tower is pumped to a second vacuum distillation tower. High-purity butanone oxime is obtained at the top of the second vacuum distillation tower and, after condensation, enters the distillate tank of the second vacuum distillation tower, where part of it is refluxed and part is sent to the finished oxime tank. The material in the bottom of the tower is pumped through the bottom of the second vacuum distillation tower to the oxime-water separation tower for further separation and purification. The catalyst is prepared by reacting TS-1 titanium silicalite, 3-isocyanate propyltrimethoxysilane, hydroxyethylidene diphosphonic acid / tungsten complex, and bis(2-hydroxypropionic acid) diammonium dihydroxide titanium; The catalyst preparation method is: T1: By weight, 100-150 parts of TS-1 titanium silicalite, 5-8 parts of 3-isocyanatepropyltrimethoxysilane, and 1000-1400 parts of solvent are stirred at 40-50°C for 1-3 hours; 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 1-3 hours, filter, and dry to obtain a catalyst; The preparation method of the hydroxyethylidene diphosphonic acid / tungsten complex is as follows: By 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 removed by distillation to obtain a hydroxyethylidene diphosphonic acid / tungsten complex; The reaction temperature of S1 is 60-80°C, the pressure is 1.0-1.1 MPa, and the time is 3-4 hours.

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

5. The method for enhancing the production efficiency of butanone oxime by cross-flow filtration according to claim 1, characterized in that: The solvent is DMF.