CN109833916B - Composite catalyst for propiconazole cyclization reaction and preparation method thereof - Google Patents
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Abstract
The invention relates to a composite catalyst for propiconazole cyclization reaction and a preparation method thereof, wherein the composite catalyst for propiconazole cyclization reaction comprises the following raw materials in parts by weight: 1.5 to 3.5 parts of zinc trifluoromethanesulfonate, 0.8 to 2.2 parts of trinitrobenzene sodium sulfonate, 0.6 to 1.4 parts of sodium dichromate and 9.5 to 10.6 parts of catalyst carrier; in the preparation process, zinc trifluoromethanesulfonate, sodium trinitrobenzene sulfonate and sodium dichromate are prepared into the composite catalyst through a catalyst carrier, so that the composite catalyst has good stability and excellent performance, can improve the reaction medium environment of the propiconazole cyclization reaction, improve the propiconazole cyclization reaction rate and the yield of cyclized products, is convenient and thorough to recover, does not bring impurities into the subsequent bromination reaction, does not influence the bromination reaction yield, and improves the yield and the purity of the final propiconazole technical product.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite catalyst for a propiconazole cyclization reaction and a preparation method thereof.
Background
The chemical structural formula of propiconazole is as follows:
the propiconazole raw drug is light yellow thick silk liquid, the boiling point (13.3Pa) is 180 ℃, the vapor pressure (20 ℃) is 0.133mPa, the refractive index is 1.5468, and the specific gravity (20 ℃) is 1.27g/cm3. The solubility in water is 110mg/L, and the product is easily dissolved in organic solvents. Stable at 320 deg.c, stable to light and no obvious hydrolysis. It is stable in acid and alkali medium and has no corrosion to metal. Storage stability was 3 years.
Propiconazole belongs to a low-toxicity bactericide, and has no teratogenesis, carcinogenesis and mutagenicity under test conditions. The crude drug is used for rat acute oral LD50>1517mg/kg, and acute transdermal LD50>4000 mg/kg.
Propiconazole has the characteristics of wide bactericidal spectrum, high activity, high bactericidal speed, long lasting period, strong systemic conductivity and the like, and has become a representative variety of large-tonnage triazole novel broad-spectrum bactericides in the world. Propiconazole is a systemic triazole novel broad-spectrum bactericide with dual functions of treatment and protection, can be absorbed by roots, stems and leaves, can be quickly conducted upwards in plant bodies, has special effects on diseases caused by ascomycetes, basidiomycetes and imperfect fungi, particularly wheat take-all, powdery mildew, rust disease, root rot, rice bakanae disease, sheath blight, banana leaf spot and the like, can effectively control most of diseases caused by higher fungi, but is ineffective on oomycete diseases. The residual effective period of the propiconazole is about 1 month.
In the existing propiconazole technical product production process, the production raw material cost is high, the cyclization reaction product yield is low, the quality is poor, and a catalyst is generally added to promote the reaction, so that the reaction rate is improved, and the product yield and quality are improved.
Chinese patent CN102225935B discloses a method for producing a propiconazole technical product, which comprises the steps of cyclizing 2, 4-dichloroacetophenone and 1, 2-pentanediol, brominating the cyclized product with bromine to generate 2-bromomethyl- (2, 4-dichlorophenyl) -4-propyl-1, 3-dioxolane, adding a solid heteropolyacid catalyst during the cyclization reaction, filtering and recovering the catalyst after the cyclization reaction is finished, then carrying out bromination reaction, carrying out condensation reaction on the 2-bromomethyl- (2, 4-dichlorophenyl) -4-propyl-1, 3-dioxolane, 1,2, 4-triazole and potassium carbonate after the bromination reaction is finished to prepare the propiconazole technical product, and reducing the introduction of new impurities due to the catalyst participating in the bromination reaction, during the condensation reaction, the method of preparing triazole potassium, performing the condensation reaction and removing the solvent simultaneously solves the problems of long reaction time and kettle sticking of triazole potassium, shortens the reaction time and effectively reduces the production cost, but the solid heteropoly acid catalyst has a common catalytic action and has small change to the reaction environment.
Chinese patent CN102503939B discloses an industrial production process of a cis-form propiconazole technical product, which is characterized in that a peroxide catalyst is added into propiconazole, and then recrystallization, filtration and cold drying are carried out in a mixed solvent, thus obtaining the cis-form propiconazole technical product. The recrystallization temperature is-10 ℃, the recrystallization time is preferably 8-16 hours, and the mixed solvent is preferably a mixed solvent of isopropanol and cyclohexane.
Chinese patent CN101781290B discloses a novel method for producing a propiconazole technical product, which comprises the steps of cyclizing 2, 4-dichloroacetophenone and 1, 2-pentanediol, brominating the cyclized product and bromine to generate 2-bromomethyl- (2, 4-dichlorophenyl) -4-propyl-1, 3-dioxolane, carrying out condensation reaction on the 2-bromomethyl- (2, 4-dichlorophenyl) -4-propyl-1, 3-dioxolane and 1,2, 4-triazole sylvite to prepare a crude product, and carrying out desolventizing, washing and high-vacuum distillation on the crude product to obtain the propiconazole technical product. After the cyclization reaction is finished, bromine is added in two times during the bromination reaction, firstly, bromine accounting for 1-10% of the total mass of the bromine is added into a reaction system for bromination induction reaction, and then, the rest bromine is added. In the bromination reaction, bromine is added in two times, bromine accounting for 1-10% of the total amount of the bromine is added firstly, the bromination reaction direction is guided, monobromide and dibromide of ketone generated by the secondary decomposition of cyclized products are reduced, and the purpose of improving the yield of the bromination reaction is finally achieved, the conversion rate of the bromide is high and can reach more than 97%.
Disclosure of Invention
The invention aims to provide a composite catalyst for a propiconazole cyclization reaction, and solves the problem that the catalytic action of a catalyst for the cyclization reaction is general and the impurity influence is brought to a bromination reaction due to inconvenient recovery in the existing preparation process of propiconazole.
In order to solve the defects and find a better composite catalyst for the propiconazole cyclization reaction, the invention provides the following technical scheme:
the composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 1.5 to 3.5 parts of zinc trifluoromethanesulfonate, 0.8 to 2.2 parts of trinitrobenzene sodium sulfonate, 0.6 to 1.4 parts of sodium dichromate and 9.5 to 10.6 parts of catalyst carrier.
Further, the composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in parts by weight: 2.5 parts of zinc trifluoromethanesulfonate, 1.5 parts of sodium trinitrobenzene sulfonate, 1.1 parts of sodium dichromate and 10.1 parts of a catalyst carrier.
Furthermore, the raw materials of the catalyst carrier comprise activated carbon, diatomite, zeolite powder, ceramic micro powder and calcium carbonate according to a mass ratio of 1: 2.5-4: 3.0-6.5: 1.5-5.5: 0.8 to 1.6. The catalyst carrier prepared by taking the active carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate as raw materials has large hardness and rich specific surface area, is convenient for loading active components and can improve the catalytic activity of the catalyst.
Furthermore, the particle size of the zeolite powder is 80-140 meshes.
In another aspect, the present invention provides a preparation method of the composite catalyst for propiconazole cyclization reaction, including the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into a zinc trifluoromethanesulfonate aqueous solution with the mass fraction of 65-85%, a sodium trinitrobenzene sulfonate aqueous solution with the mass fraction of 75-95% and a sodium dichromate aqueous solution with the mass fraction of 78-88% respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 100-150 meshes, then mixing and ball-milling for 1.5-2.5 h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 15-30 min, and then carrying out extrusion forming under the pressure of 0.35-0.65 MPa to obtain a carrier primary product;
s30, sintering the S20 carrier primary product for 1.5 to 3.5 hours at the temperature of 650 to 850 ℃, sprinkling 1/3 volumes of sodium trinitrobenzene sulfonate aqueous solution obtained by S10 when cooling to 145 to 165 ℃, sintering for 1.0 to 3.0 hours again at the temperature of 620 to 800 ℃, cooling to room temperature, and crushing to 50 to 80 meshes to obtain a catalyst carrier A;
s40, soaking the catalyst carrier A obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 16-26 h, then ultrasonically dispersing for 30min, drying, then preserving heat for 5-8 h at the temperature of 550-650 ℃, then soaking in the trinitrobenzene sodium sulfonate aqueous solution obtained in the residual 2/3 volume of S10 for 15-20 h, then ultrasonically drying for 45min again at the temperature of 88-98 ℃, then cooling to room temperature after heat treatment to obtain the composite catalyst for propiconazole cyclization reaction.
Furthermore, in S20, the rotation speed of the mixing ball mill is 750r/min to 1250 r/min.
Further, in S30, the carrier is pre-sintered for 0.5 to 1.0 hour at a temperature of 250 to 350 ℃ before the primary carrier is sintered. The presintering can ensure the stable performance of the primary carrier, and the phenomena of cracking, breaking and the like can not occur due to too high temperature in the subsequent sintering, thereby improving the quality of the catalyst.
Further, in S40, the drying temperature is 95-105 ℃.
Further, in S40, the heat treatment is carried out for 3 to 5 hours at a temperature of 450 to 580 ℃.
Further, in S40, the cooling rate is 1 ℃/min to 3 ℃/min.
According to the technical scheme, the invention has the following beneficial effects:
(1) in the preparation process, zinc trifluoromethanesulfonate, sodium trinitrobenzene sulfonate and sodium dichromate are prepared into the composite catalyst together through a catalyst carrier, so that the composite catalyst has good stability and excellent performance, can improve the reaction medium environment of the propiconazole cyclization reaction, improve the propiconazole cyclization reaction rate and the yield of cyclized products, is convenient and thorough to recover, does not bring impurities into the subsequent bromination reaction, does not influence the bromination reaction yield, and improves the yield and the purity of the final propiconazole raw medicine;
(2) the composite catalyst for the propiconazole cyclization reaction prepared by the invention has better catalytic action, maintains an acid reaction environment, and can obviously improve the utilization rate of 1, 2-pentanediol and the yield of cyclized products by being supplemented with sodium dichromate, thereby reducing the production cost;
(3) the composite catalyst for the propiconazole cyclization reaction has the advantages of strong stability, simple preparation process and low energy consumption, so the composite catalyst has good economic benefit and is suitable for wide popularization.
The present invention will be described in further detail with reference to the following embodiments.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well known in the art, unless otherwise specified.
Example 1
Composite catalyst for propiconazole cyclization reaction
The composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 1.5kg of zinc trifluoromethanesulfonate, 0.8kg of sodium trinitrobenzene sulfonate, 0.6kg of sodium dichromate and 9.5kg of a catalyst carrier; the catalyst carrier is prepared from the following raw materials in percentage by mass of activated carbon, diatomite, zeolite powder, ceramic micropowder and calcium carbonate: 2.5: 3.0: 1.5: 0.8; the particle size of the zeolite powder is 80 meshes.
The preparation method comprises the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into a zinc trifluoromethanesulfonate aqueous solution with the mass fraction of 65%, a sodium trinitrobenzene sulfonate aqueous solution with the mass fraction of 75% and a sodium dichromate aqueous solution with the mass fraction of 78% respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 100 meshes, then mixing and ball-milling at the speed of 750r/min for 1.5h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 15min, and then carrying out extrusion forming under the pressure of 0.35MPa to obtain a primary carrier product;
s30, pre-burning the S20 carrier primary product at 250 ℃ for 0.5h, then sintering at 650 ℃ for 1.5h, when cooling to 145 ℃, sprinkling 1/3 volumes of aqueous solution of trinitrobenzene sodium sulfonate obtained from S10, sintering at 620 ℃ for 1.0h again, cooling to room temperature, and then crushing to 50 meshes to obtain the catalyst carrier;
s40, soaking the catalyst carrier obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 16h, then ultrasonically dispersing for 30min, drying at the temperature of 95 ℃, then preserving heat for 5h at the temperature of 550 ℃, then soaking in the residual 2/3 volume of the trinitrobenzene sodium sulfonate aqueous solution obtained in S10 for 15h, then ultrasonically treating for 45min, drying again at the temperature of 88 ℃, then preserving heat for 3h at the temperature of 450 ℃, and cooling to room temperature at the speed of 1 ℃/min to obtain the composite catalyst for the propiconazole cyclization reaction.
The composite catalyst prepared in the example is tested to be used in the propiconazole cyclization reaction, and the yield of cyclized products is 93.1%.
Example 2
Composite catalyst for propiconazole cyclization reaction
The composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 3.5kg of zinc trifluoromethanesulfonate, 2.2kg of sodium trinitrobenzene sulfonate, 1.4kg of sodium dichromate and 10.6kg of a catalyst carrier; the catalyst carrier is prepared from the following raw materials in percentage by mass of activated carbon, diatomite, zeolite powder, ceramic micropowder and calcium carbonate: 4: 6.5: 5.5: 1.6; the particle size of the zeolite powder is 140 meshes.
The preparation method comprises the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into 85% zinc trifluoromethanesulfonate aqueous solution, 95% sodium trinitrobenzene sulfonate aqueous solution and 88% sodium dichromate aqueous solution respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 150 meshes, then mixing and ball-milling at a speed of 1250r/min for 2.5h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 30min, and then carrying out extrusion forming under the pressure of 0.65MPa to obtain a primary carrier product;
s30, pre-burning the S20 carrier primary product at 350 ℃ for 1.0h, then sintering at 850 ℃ for 3.5h, sprinkling 1/3 volumes of aqueous solution of trinitrobenzene sodium sulfonate obtained from S10 when cooling to 165 ℃, sintering at 800 ℃ for 3.0h again, cooling to room temperature, and then crushing to 80 meshes to obtain the catalyst carrier;
s40, soaking the catalyst carrier obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 26h, then ultrasonically dispersing for 30min, drying at 105 ℃, then preserving heat for 8h at 650 ℃, then soaking in the residual 2/3 volume of the trinitrobenzene sodium sulfonate aqueous solution obtained in S10 for 20h, then ultrasonically treating for 45min, drying again at 98 ℃, then preserving heat for 5h at 580 ℃, and cooling to room temperature at the rate of 3 ℃/min to obtain the composite catalyst for propiconazole cyclization reaction.
The composite catalyst prepared in the embodiment is tested to be used in the propiconazole cyclization reaction, and the yield of cyclized products is 92.5%.
Example 3
Composite catalyst for propiconazole cyclization reaction
The composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 1.9kg of zinc trifluoromethanesulfonate, 1.0kg of sodium trinitrobenzene sulfonate, 0.8kg of sodium dichromate and 9.7kg of a catalyst carrier; the catalyst carrier is prepared from the following raw materials in percentage by mass of activated carbon, diatomite, zeolite powder, ceramic micropowder and calcium carbonate: 3.0: 3.5: 2.5: 1.0; the particle size of the zeolite powder is 100 meshes.
The preparation method comprises the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into 67% zinc trifluoromethanesulfonate aqueous solution, 77% sodium trinitrobenzene sulfonate aqueous solution and 80% sodium dichromate aqueous solution respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 110 meshes, then mixing and ball-milling at the speed of 850r/min for 2.5h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 19min, and then carrying out extrusion forming under the pressure of 0.40MPa to obtain a primary carrier product;
s30, pre-burning the S20 carrier primary product at 280 ℃ for 1.0h, then sintering at 700 ℃ for 2.0h, sprinkling 1/3 volumes of aqueous solution of trinitrobenzene sodium sulfonate obtained from S10 when cooling to 150 ℃, sintering at 660 ℃ for 1.5h again, cooling to room temperature, and then crushing to 60 meshes to obtain the catalyst carrier;
s40, soaking the catalyst carrier obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 18h, then ultrasonically dispersing for 30min, drying at 98 ℃, then preserving heat for 6h at 570 ℃, then soaking in the residual 2/3 volume of the trinitrobenzene sodium sulfonate aqueous solution obtained in S10 for 16h, then ultrasonically treating for 45min, drying again at 90 ℃, then preserving heat for 3.5h at 480 ℃, and cooling to room temperature at the rate of 3 ℃/min to obtain the composite catalyst for the propiconazole cyclization reaction.
Through tests, the composite catalyst prepared in the embodiment is used for the propiconazole cyclization reaction, and the yield of cyclized products is 91.9%.
Example 4
Composite catalyst for propiconazole cyclization reaction
The composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 3.3kg of zinc trifluoromethanesulfonate, 2.0kg of sodium trinitrobenzene sulfonate, 1.2kg of sodium dichromate and 10.2kg of a catalyst carrier; the catalyst carrier is prepared from the following raw materials in percentage by mass of activated carbon, diatomite, zeolite powder, ceramic micropowder and calcium carbonate: 3.5: 5.5: 4.5: 1.4; the particle size of the zeolite powder is 120 meshes.
The preparation method comprises the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into 82% zinc trifluoromethanesulfonate aqueous solution, 93% sodium trinitrobenzene sulfonate aqueous solution and 86% sodium dichromate aqueous solution respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 140 meshes, then mixing and ball-milling at a speed of 1150r/min for 1.5h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 28min, and then carrying out extrusion forming under the pressure of 0.55MPa to obtain a primary carrier product;
s30, pre-burning the S20 carrier primary product at 330 ℃ for 0.5h, then sintering at 800 ℃ for 3.0h, sprinkling 1/3 volumes of aqueous solution of trinitrobenzene sodium sulfonate obtained from S10 when cooling to 160 ℃, sintering at 770 ℃ for 2.5h again, cooling to room temperature, and then crushing to 70 meshes to obtain the catalyst carrier;
s40, soaking the catalyst carrier obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 24 hours, then ultrasonically dispersing for 30 minutes, drying at the temperature of 102 ℃, then preserving heat for 7 hours at the temperature of 620 ℃, then soaking in the residual 2/3 volume of the trinitrobenzene sodium sulfonate aqueous solution obtained in S10 for 19 hours, then ultrasonically treating for 45 minutes, drying again at the temperature of 96 ℃, then preserving heat for 4.5 hours at the temperature of 560 ℃, and then cooling to room temperature at the speed of 1 ℃/min to obtain the composite catalyst for the propiconazole cyclization reaction.
Through tests, the composite catalyst prepared in the embodiment is used for the propiconazole cyclization reaction, and the yield of cyclized products is 92.6%.
Example 5
Composite catalyst for propiconazole cyclization reaction
The composite catalyst for the propiconazole cyclization reaction comprises the following raw materials in percentage by mass: 2.5kg of zinc trifluoromethanesulfonate, 1.5kg of sodium trinitrobenzene sulfonate, 1.1kg of sodium dichromate and 10.1kg of catalyst carrier; the catalyst carrier is prepared from the following raw materials in percentage by mass of activated carbon, diatomite, zeolite powder, ceramic micropowder and calcium carbonate: 3.2: 4.5: 3.2: 1.3; the particle size of the zeolite powder is 100 meshes.
The preparation method comprises the following steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into a zinc trifluoromethanesulfonate aqueous solution with the mass fraction of 75%, a sodium trinitrobenzene sulfonate aqueous solution with the mass fraction of 85% and a sodium dichromate aqueous solution with the mass fraction of 82% respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate in the mass ratio to 130 meshes, then mixing and ball-milling at a speed of 1050r/min for 2.0h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 22min, and then carrying out extrusion forming under the pressure of 0.50MPa to obtain a primary carrier product;
s30, pre-burning the S20 carrier primary product at the temperature of 300 ℃ for 0.5h, then sintering at the temperature of 750 ℃ for 2.5h, sprinkling 1/3 volumes of trinitrobenzene sodium sulfonate aqueous solution obtained by S10 when cooling to 155 ℃, sintering at the temperature of 740 ℃ for 2.0h again, cooling to room temperature, and then crushing to 60 meshes to obtain the catalyst carrier;
s40, soaking the catalyst carrier obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 22h, then ultrasonically dispersing for 30min, drying at 101 ℃, then preserving heat for 6.5h at 600 ℃, then soaking in the residual 2/3 volume of the trinitrobenzene sodium sulfonate aqueous solution obtained in S10 for 18h, then ultrasonically drying for 45min, drying again at 94 ℃, then preserving heat for 4h at 520 ℃, and cooling to room temperature at the speed of 2 ℃/min to obtain the composite catalyst for the propiconazole cyclization reaction.
Through tests, the composite catalyst prepared in the embodiment is used for the propiconazole cyclization reaction, and the yield of cyclized products is 92.7%.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The composite catalyst for the propiconazole cyclization reaction is characterized by comprising the following raw materials in parts by weight: 1.5 to 3.5 parts of zinc trifluoromethanesulfonate, 0.8 to 2.2 parts of trinitrobenzene sodium sulfonate, 0.6 to 1.4 parts of sodium dichromate and 9.5 to 10.6 parts of catalyst carrier; the catalyst carrier is prepared from the following raw materials in parts by mass: 2.5-4: 3.0-6.5: 1.5-5.5: 0.8 to 1.6; the preparation method of the composite catalyst for the propiconazole cyclization reaction comprises the following preparation steps:
s10, preparing the zinc trifluoromethanesulfonate, the sodium trinitrobenzene sulfonate and the sodium dichromate in parts by weight into a zinc trifluoromethanesulfonate aqueous solution with the mass fraction of 65-85%, a sodium trinitrobenzene sulfonate aqueous solution with the mass fraction of 75-95% and a sodium dichromate aqueous solution with the mass fraction of 78-88% respectively for later use;
s20, mixing and crushing the activated carbon, the diatomite, the zeolite powder, the ceramic micro powder and the calcium carbonate according to the mass ratio to 100-150 meshes, then mixing and ball-milling for 1.5-2.5 h, drying, adding into the zinc trifluoromethanesulfonate aqueous solution obtained in the step S10, stirring for 15-30 min, and then carrying out extrusion forming under the pressure of 0.35-0.65 MPa to obtain a carrier primary product;
s30, sintering the S20 carrier primary product for 1.5 to 3.5 hours at the temperature of 650 to 850 ℃, sprinkling 1/3 volumes of sodium trinitrobenzene sulfonate aqueous solution obtained by S10 when cooling to 145 to 165 ℃, sintering for 1.0 to 3.0 hours again at the temperature of 620 to 800 ℃, cooling to room temperature, and crushing to 50 to 80 meshes to obtain a catalyst carrier A;
s40, soaking the catalyst carrier A obtained in S30 in the sodium dichromate aqueous solution obtained in S10 for 16-26 h, then ultrasonically dispersing for 30min, drying, then preserving heat for 5-8 h at the temperature of 550-650 ℃, then soaking in the trinitrobenzene sodium sulfonate aqueous solution obtained in the residual 2/3 volume of S10 for 15-20 h, then ultrasonically drying for 45min again at the temperature of 88-98 ℃, then cooling to room temperature after heat treatment to obtain the composite catalyst for propiconazole cyclization reaction.
2. The composite catalyst for the propiconazole cyclization reaction as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 2.5 parts of zinc trifluoromethanesulfonate, 1.5 parts of sodium trinitrobenzene sulfonate, 1.1 parts of sodium dichromate and 10.1 parts of a catalyst carrier.
3. The composite catalyst for propiconazole cyclization reaction according to claim 1, wherein the zeolite powder has a particle size of 80-140 mesh.
4. The composite catalyst for the cyclization reaction of propiconazole according to claim 1, wherein in S20, the rotation speed of the mixing ball mill is 750r/min to 1250 r/min.
5. The composite catalyst for a propiconazole cyclization reaction according to claim 1, wherein in S30, the primary support is calcined at a temperature of 250 to 350 ℃ for 0.5 to 1.0 hour before sintering.
6. The composite catalyst for propiconazole cyclization reaction according to claim 1, wherein the drying temperature in S40 is 95 to 105 ℃.
7. The composite catalyst for propiconazole cyclization according to claim 1, wherein in S40, the heat treatment is performed by keeping the temperature at 450 to 580 ℃ for 3 to 5 hours.
8. The composite catalyst for propiconazole cyclization reaction according to claim 1, wherein the cooling rate is 1 ℃/min to 3 ℃/min in S40.
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| CN101862675B (en) * | 2009-04-17 | 2012-02-29 | 中国石油化工股份有限公司 | Catalyst loaded with zinc trifluoromethanesulfonate, preparation method and application |
| CN202621129U (en) * | 2012-03-29 | 2012-12-26 | 江苏泰仓农化有限公司 | Propiconazole bromination reaction automatic control system |
| CN105061406A (en) * | 2015-07-17 | 2015-11-18 | 江苏禾本生化有限公司 | Preparation technology of difenoconazole technical material |
| CN106349037A (en) * | 2016-08-26 | 2017-01-25 | 安徽金邦医药化工有限公司 | 3-methyl-2-cyclopentene-1-ketone catalytic preparation method |
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