Method for efficiently oxidizing butanone by using pressurized nanobubble fluidized bed

Abstract

The invention relates to a method for efficiently oxidizing butanone by using a pressurized nanobubble fluidized bed, and belongs to the technical field of diacetylmonoxime. The method comprises the following steps: adding a catalyst, butanone, tert-butyl alcohol and distilled water into a pressurized nano-bubble fluidized bed reactor, and heating; slowly dropwise adding ammonia water and hydrogen peroxide, cooling to room temperature after the reaction is finished, and filtering to obtain diacetylmonoxime; the catalyst disclosed by the invention is prepared from tetraethyl orthosilicate, a tetrapropylammonium hydroxide aqueous solution, deionized water, tetrabutyl titanate, an isopropanol solution, allyl silane, 2-trifluoromethylpyrimidine-4, 5-diamine, allylidene triphenylphosphine, ethanol and sodium ethoxide. The preparation method comprises the following steps: preparing tetraethyl orthosilicate, a tetrapropylammonium hydroxide aqueous solution, deionized water, tetrabutyl titanate, an isopropanol solution, allyl silane, 2-trifluoromethylpyrimidine-4, 5-diamine, allylidene triphenylphosphine, ethanol and sodium ethoxide; the diacetylmonoxime prepared by the method has high conversion rate and high selectivity.

Description

Technical Field

[0001] The invention relates to the technical field of butanone oxime, in particular to a method for using a pressurized nano bubble fluidized bed for efficient oxidation of butanone. Background Art

[0002] Butanone oxime, also known as methyl ethyl ketone oxime, is a colorless or light yellow transparent oily liquid. It is soluble in water and miscible with organic solvents such as methanol and ethanol. It has a strong ability to complex with metal ions and is easily volatile in the air. It reacts with sulfuric acid, hydrochloric acid, etc. to form hydroxylamine salts and release butanone at the same time.

[0003] Chinese patent CN101058550A: discloses a method for preparing butanone oxime, which adopts a two-stage countercurrent oximation process, each stage consisting of an oximation reactor, an oximation separator, and an oximation circulation pump. # There is an excess of butanone in the oximation reactor, and the hydroxylamine sulfate reacts completely. # There is an excess of hydroxylamine sulfate in the oximation reactor, and the butanone reacts completely. The feed molar ratio of butanone to hydroxylamine sulfate in the whole process is 1:1.

[0004] Chinese patent CN104610094B: A method for preparing butanone oxime, the method 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.

[0005] The above patents and prior art methods for preparing butanone oxime have long production process flows, complex processes, low conversion rates, and low selectivity. They also produce a large amount of inorganic salts and waste gases such as nitrogen oxides and sulfur dioxide that pollute the atmosphere, causing serious environmental pollution and equipment corrosion. They are not green synthesis methods. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a method for efficient oxidation of butanone in a pressurized nanobubble fluidized bed, the operating steps of which are as follows: S1: Weigh 5-10 parts of catalyst, 17-33 parts of butanone, 40-50 parts of tert-butanol, and 5-10 parts of distilled water by weight, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 12-17 parts of ammonia water and 54-62 parts of hydrogen peroxide. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The mass concentration of the ammonia water is 20-25%.

[0007] The mass concentration of the hydrogen peroxide is 25-30%.

[0008] The model of the pressurized nano bubble fluidized bed reactor is NBPFR-500, the reaction temperature is 70-80° C., and the reaction pressure is 0.4-0.5 MPa.

[0009] The ammonia water and hydrogen peroxide solution of S2 are added dropwise for 120-180 minutes respectively.

[0010] The reaction time of S2 is 40-60 min.

[0011] The preparation method of the catalyst is: A1: 7-12 parts of tetraethyl orthosilicate are dropped into a mixed solution of 3-7 parts of a 20-25% mass concentration of tetrapropylammonium hydroxide aqueous solution and 10-20 parts of deionized water, and then 0.1-0.5 parts of tetrabutyl titanate and 5-10 parts of isopropanol solution are slowly dropped under vigorous stirring, stirred at room temperature for 3-5 hours, transferred to a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: According to the mass ratio, 120-170 parts of the precursor and 10-15 parts of acryl silane are added to 1000-1200 parts of water, and then stirred at 30-40°C for 1-3 hours, filtered, and dried to obtain an acryl precursor; A3: Add 3-6 parts of 2-trifluoromethylpyrimidine-4,5-diamine (CAS No.: 1023817-05-1), 0.03-0.3 parts of allyl triphenylphosphine (CAS No.: 15935-94-1), 100-120 parts of propylene precursor, 1000-1500 parts of ethanol, and 1-3 parts of sodium ethoxide into a stirring kettle, heat and stir to react, filter, and dry to obtain a catalyst.

[0012] The crystallization temperature of A1 is 170-180°C and the crystallization time is 20-25h.

[0013] The acryl silane is one of methacryloxyaminotrimethylsilane, methacryloxypropyltri(trimethylsiloxy)silane and methacryloxymethyltrimethoxysilane.

[0014] The reaction temperature of A3 is 70-80°C and the reaction time is 100-180 minutes.

[0015] Reaction mechanism 1. Formation of active center: The tetracoordinated framework titanium "TiO4" in titanium silicalite is the active center for catalyzing the ammoximation reaction. After the introduction of trifluoromethyl, triphenylphosphine and pyrimidine groups, these functional groups may interact with the titanium center to change the electron density and spatial structure of the titanium center, thereby forming a new highly active catalytic center.

[0016] 2. Substrate activation: In the ammoximation reaction, ketone compounds and ammonia are first adsorbed on the catalyst surface and activated by the titanium active center. The introduced functional groups may promote the activation process of the substrate by providing additional electrons or steric hindrance effects.

[0017] 3. Intermediate formation and conversion: The activated substrate forms an intermediate on the catalyst surface and is converted into the target product through a series of reaction steps. The introduced functional groups may affect the stability and conversion rate of the intermediate, thereby affecting the progress of the entire reaction.

[0018] 4. Product desorption and regeneration: The target product is desorbed from the catalyst surface, and the catalyst returns to its initial state, ready for the next round of reaction. The introduced functional groups may affect the product desorption rate and the catalyst regeneration ability.

[0019] Technical Effects The method for efficiently oxidizing butanone using a pressurized nanobubble fluidized bed of the present invention has the following significant effects compared with the prior art: 1. Improve catalytic activity: The introduced trifluoromethyl, triphenylphosphine and pyrimidine groups can improve the activity of the catalytic active center by changing the electron density and spatial structure of the titanium center, thereby improving the catalytic efficiency of the ammoximation reaction.

[0020] 2. Enhanced stability: These functional groups can enhance the stability and service life of the catalyst by reducing the occurrence of side reactions and the rate of carbon deposit formation. By controlling the residual H2O2 in the system, the occurrence of side reactions and carbon deposit formation are further inhibited, thus extending the life of the catalyst.

[0021] 3. Broaden the scope of substrates: The introduced functional groups can make the catalyst more compatible with a wider range of substrates, including various mono-substituted, di-substituted, tri-substituted amides and amides with cyclic structures.

[0022] 4. Improve product selectivity: By optimizing the catalyst structure and reaction conditions, the selectivity of the target product can be further improved and the generation of by-products can be reduced. DETAILED DESCRIPTION

[0023] 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 content test: liquid chromatography was used for detection, and the test results are shown in Table 1.

[0024] Example 1 A method for high-efficiency oxidation of butanone using a pressurized nanobubble fluidized bed, the operating steps of which are as follows: S1: Weigh 5 g of catalyst, 17 g of butanone, 40 g of tert-butanol, and 5 g of distilled water, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 12 g of ammonia water and 54 g of hydrogen peroxide. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The mass concentration of the ammonia water is 20%.

[0025] The mass concentration of the hydrogen peroxide is 25%.

[0026] The model of the pressurized nanobubble fluidized bed reactor is NBPFR-500, the reaction temperature is 70° C., and the reaction pressure is 0.4 MPa.

[0027] The ammonia water and hydrogen peroxide solution of S2 were added dropwise for 120 min respectively.

[0028] The reaction time of S2 is 40 min.

[0029] The preparation method of the catalyst is: A1: 7g of tetraethyl orthosilicate was dropped into a mixed solution of 3g of 20% tetrapropylammonium hydroxide aqueous solution and 10g of deionized water, and then 0.1g of tetrabutyl titanate and 5g of isopropanol solution were slowly added under vigorous stirring. After stirring at room temperature for 3h, the mixture was transferred into a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: 120 g of the precursor and 10 g of acryl silane were added to 1000 g of water, and then stirred at 30°C for 1 hour, filtered, and dried to obtain an acryl precursor; A3: Add 3g 2-trifluoromethylpyrimidine-4,5-diamine (CAS No.: 1023817-05-1), 0.03g allyl triphenylphosphine (CAS No.: 15935-94-1), 100g propylene precursor, 1000g ethanol and 1g sodium ethoxide into a stirring kettle, heat and stir to react, filter and dry to obtain a catalyst.

[0030] The crystallization temperature of A1 is 170°C and the crystallization time is 20h.

[0031] The acryl silane is methacryloxyaminotrimethylsilane.

[0032] The reaction temperature of A3 is 70° C. and the reaction time is 100 minutes.

[0033] Example 2 A method for high-efficiency oxidation of butanone using a pressurized nanobubble fluidized bed, the operating steps of which are as follows: S1: Weigh 6 g of catalyst, 21 g of butanone, 43 g of tert-butanol, and 6 g of distilled water, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 14 g of ammonia water and 57 g of hydrogen peroxide. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The mass concentration of the ammonia water is 22%.

[0034] The mass concentration of the hydrogen peroxide is 26%.

[0035] The model of the pressurized nanobubble fluidized bed reactor is NBPFR-500, the reaction temperature is 75° C., and the reaction pressure is 0.45 MPa.

[0036] The ammonia water and hydrogen peroxide solution of S2 were added dropwise for 140 min respectively.

[0037] The reaction time of S2 is 45 min.

[0038] The preparation method of the catalyst is: A1: 9g of tetraethyl orthosilicate was dropped into a mixed solution of 5g of 22% tetrapropylammonium hydroxide aqueous solution and 13g of deionized water, and then 0.2g of tetrabutyl titanate and 6g of isopropanol solution were slowly added under vigorous stirring. After stirring at room temperature for 4h, the mixture was transferred into a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: 130 g of the precursor and 12 g of acryl silane were added to 1050 g of water, and then stirred at 35°C for 2 hours, filtered, and dried to obtain an acryl precursor; A3: Add 4g 2-trifluoromethylpyrimidine-4,5-diamine CAS No.: 1023817-05-1, 0.1g allyl triphenylphosphine CAS No.: 15935-94-1, 105g propylene precursor, 1100g ethanol, and 2g sodium ethoxide into a stirring kettle, heat and stir to react, filter, and dry to obtain a catalyst.

[0039] The crystallization temperature of A1 is 175°C and the crystallization time is 22h.

[0040] The acryl silane is methacryloxypropyl tris(trimethylsiloxy)silane.

[0041] The reaction temperature of A3 is 75° C. and the reaction time is 120 minutes.

[0042] Example 3 A method for high-efficiency oxidation of butanone using a pressurized nanobubble fluidized bed, the operating steps of which are as follows: S1: Weigh 8 g of catalyst, 30 g of butanone, 8 g of tert-butanol, and 8 g of distilled water, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 16 g of ammonia water and 60 g of hydrogen peroxide solution. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The mass concentration of the ammonia water is 24%.

[0043] The mass concentration of the hydrogen peroxide is 28%.

[0044] The model of the pressurized nanobubble fluidized bed reactor is NBPFR-500, the reaction temperature is 75° C., and the reaction pressure is 0.45 MPa.

[0045] The ammonia water and hydrogen peroxide solution of S2 were added dropwise for 160 min respectively.

[0046] The reaction time of S2 is 55 min.

[0047] The preparation method of the catalyst is: A1: 11g of tetraethyl orthosilicate was dropped into a mixed solution of 6g of 24% tetrapropylammonium hydroxide aqueous solution and 18g of deionized water, and then 0.4g of tetrabutyl titanate and 8g of isopropanol solution were slowly added under vigorous stirring. After stirring at room temperature for 4h, the mixture was transferred into a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: 160 g of the precursor and 14 g of acryl silane were added to 1150 g of water, and then stirred at 35°C for 2 hours, filtered, and dried to obtain an acryl precursor; A3: Add 5g 2-trifluoromethylpyrimidine-4,5-diamine CAS No.: 1023817-05-1, 0.2g allyl triphenylphosphine CAS No.: 15935-94-1, 115g propylene precursor, 1400g ethanol, and 2g sodium ethoxide into a stirring kettle, heat and stir to react, filter, and dry to obtain a catalyst.

[0048] The crystallization temperature of A1 is 175°C and the crystallization time is 24h.

[0049] The acryl silane is methacryloxypropyl tris(trimethylsiloxy)silane.

[0050] The reaction temperature of A3 is 75° C. and the reaction time is 160 minutes.

[0051] Example 4 A method for high-efficiency oxidation of butanone using a pressurized nanobubble fluidized bed, the operating steps of which are as follows: S1: Weigh 10 g of catalyst, 33 g of butanone, 50 g of tert-butanol, and 10 g of distilled water, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 17 g of ammonia water and 62 g of hydrogen peroxide. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The mass concentration of the ammonia water is 25%.

[0052] The mass concentration of the hydrogen peroxide is 30%.

[0053] The model of the pressurized nanobubble fluidized bed reactor is NBPFR-500, the reaction temperature is 80° C., and the reaction pressure is 0.5 MPa.

[0054] The ammonia water and hydrogen peroxide solution of S2 were added dropwise for 180 min respectively.

[0055] The reaction time of S2 is 60 min.

[0056] The preparation method of the catalyst is: A1: 12g of tetraethyl orthosilicate was dropped into a mixed solution of 7g of 25% tetrapropylammonium hydroxide aqueous solution and 20g of deionized water, and then 0.5g of tetrabutyl titanate and 10g of isopropanol solution were slowly added under vigorous stirring. After stirring at room temperature for 5h, the mixture was transferred into a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: 170 g of the precursor and 15 g of acryl silane were added to 1200 g of water, and then stirred at 40° C. for 3 hours, filtered, and dried to obtain an acryl precursor; A3: Add 6g 2-trifluoromethylpyrimidine-4,5-diamine CAS No.: 1023817-05-1, 0.3g allyl triphenylphosphine CAS No.: 15935-94-1, 120g propylene precursor, 1500g ethanol, and 3g sodium ethoxide into a stirring kettle, heat and stir to react, filter, and dry to obtain a catalyst.

[0057] The crystallization temperature of A1 is 180°C and the crystallization time is 25h.

[0058] The acryl silane is methacryloxymethyltrimethoxysilane.

[0059] The reaction temperature of A3 is 80° C. and the reaction time is 180 minutes.

[0060] Comparative Example 1 The other steps were the same as in Example 1 except that 2-trifluoromethylpyrimidine-4,5-diamine and allyl triphenylphosphine were not added.

[0061] Comparative Example 2 The other steps were the same as in Example 1 except that 2-trifluoromethylpyrimidine-4,5-diamine was not added.

[0062] Comparative Example 3 Allylidene triphenylphosphine was not added, and the other steps were the same as in Example 1.

[0063] Table 1 Conversion rate / % Selectivity / % Example 1 100 99.86 Example 2 100 99.88 Example 3 100 99.91 Example 4 100 99.95 Comparative Example 1 87.29 85.63 Comparative Example 2 94.33 93.52 Comparative Example 3 95.12 94.89 Through the analysis of the above examples and comparative examples, the butanone oxime prepared by the present invention has high conversion rate and high selectivity.

[0064] 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 efficient oxidation of butanone using a pressurized nanobubble fluidized bed, the operating steps of which are: S1: Weigh 5-10 parts of catalyst, 17-33 parts of butanone, 40-50 parts of tert-butanol, and 5-10 parts of distilled water by weight, add them into a pressurized nanobubble fluidized bed reactor, and heat up; S2: Slowly drop 12-17 parts of ammonia water and 54-62 parts of hydrogen peroxide. After the reaction is completed, cool to room temperature and filter to obtain butanone oxime; The catalyst is prepared from tetraethyl orthosilicate, tetrapropylammonium hydroxide aqueous solution, tetrabutyl titanate, acrylsilane, 2-trifluoromethylpyrimidine-4,5-diamine, and allyl triphenylphosphine; The mass concentration of the ammonia water is 20-25%.

2. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide is 25-30%.

3. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 1, characterized in that: The model of the pressurized nano bubble fluidized bed reactor is NBPFR-500, the reaction temperature is 70-80° C., and the reaction pressure is 0.4-0.5 MPa.

4. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 1, characterized in that: The ammonia water and hydrogen peroxide solution of S2 are added dropwise for 120-180 minutes respectively.

5. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 1, characterized in that: The reaction time of S2 is 40-60 min.

6. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 1, characterized in that: The preparation method of the catalyst is: A1: 7-12 parts of tetraethyl orthosilicate are dropped into a mixed solution of 3-7 parts of a 20-25% mass concentration of tetrapropylammonium hydroxide aqueous solution and 10-20 parts of deionized water, and then 0.1-0.5 parts of tetrabutyl titanate and 5-10 parts of isopropanol solution are slowly dropped under vigorous stirring, stirred at room temperature for 3-5 hours, transferred to a high-pressure reactor for crystallization, filtered, washed, dried, and then calcined at high temperature in an air atmosphere to obtain a precursor; A2: According to the mass ratio, 120-170 parts of the precursor and 10-15 parts of acryl silane are added to 1000-1200 parts of water, and then stirred at 30-40°C for 1-3 hours, filtered, and dried to obtain an acryl precursor; A3: Add 3-6 parts of 2-trifluoromethylpyrimidine-4,5-diamine, 0.03-0.3 parts of allyl triphenylphosphine, 100-120 parts of propylene precursor, 1000-1500 parts of ethanol, and 1-3 parts of sodium ethoxide into a stirring kettle, heat and stir to react, filter, and dry to obtain a catalyst.

7. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 6, characterized in that: The crystallization temperature of A1 is 170-180°C and the crystallization time is 20-25h.

8. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 6, characterized in that: The acryl silane is one of methacryloxyaminotrimethylsilane, methacryloxypropyltri(trimethylsiloxy)silane and methacryloxymethyltrimethoxysilane.

9. The method for efficient oxidation of butanone using a pressurized nanobubble fluidized bed according to claim 6, characterized in that: The reaction temperature of A3 is 70-80°C and the reaction time is 100-180 minutes.