CN111909066A - Crystallization treatment method for improving quality of mesotrione product - Google Patents
Crystallization treatment method for improving quality of mesotrione product Download PDFInfo
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Abstract
The invention provides a crystallization treatment method for improving the quality of a mesotrione product, which mainly comprises two steps of a seed crystal preparation process and a crystallization process reinforcement. The seed crystal preparation process comprises the following steps: recrystallizing the mesotrione solid powder by using a dichloroethane solvent system, and obtaining mesotrione seed crystals by constant-temperature crystal growing, filtering and drying; strengthening the crystallization process: and (3) carrying out programmed cooling on the mesotrione organic mother liquor subjected to active carbon decoloration to a metastable zone, adding the prepared screened seed crystal, and carrying out crystal growing, programmed cooling, crystal growing, filtering, leaching and drying to obtain mesotrione crystals. By the crystallization method, the moisture content of the mesotrione is reduced to 3-6%, and the bulk density of the product reaches 0.75g/cm3～0.85g/cm3The product quantitative content is improved to more than 98.0 percent, the main granularity can reach 300-500 mu m, and the product has good fluidity.
Description
Technical Field
The invention belongs to the technical field of pesticide crystallization, and particularly relates to a crystallization treatment method for improving the quality of a mesotrione product.
Background
Mesotrione, also known as mesotrione, is a pre-emergent and post-emergent broad-spectrum selective herbicide capable of inhibiting hydroxyphenylpyruvate dioxygenase (HPPD) and can effectively control main broad-leaved weeds and some gramineous weeds. Molecular formula C14H13NO7S, molecular weight 339.32, chemical name 2- (4-methylsulfonyl) -2-nitrobenzoyl-cyclohexane-1, 3-dione. The chemical structural formula is as follows:
mesotrione was first developed as a triketone herbicide by the firm of mr. It was marketed in europe in 2001 under the trade name Callisto (milston). The synthesis reaction of mesotrione is mature, and the synthesis route is as follows: using 4-methylsulfonyl-2-nitrobenzoic acid as a raw material, dichloroethane as a solvent, acylating with thionyl chloride, using triethylamine as an acid-binding agent, esterifying with cyclohexanedione, and finally performing transposition rearrangement by using acetone cyanohydrin as a catalyst to obtain mesotrione:
currently, 3 crystal forms of mesotrione are reported, wherein the crystal form 1 belongs to a stable crystal form, and the crystal forms 2 and 3 are metastable crystal forms, so that the crystal form 1 product is often taken as a production target in industrial production. Stephen Dawson et al, in patent US2008O194880a1, propose a process for preparing mesotrione crystal form 1 product by adjusting the pH in an aqueous solution, and a process for converting a metastable crystal form 2 product to a stable crystal form 1 product; julie Marie wicher et al in patent USOO8063253B2 propose a process for purifying mesotrione, comprising filtration, adsorption, organic phase extraction of a mesotrione aqueous solution to reduce the impurity content of the mesotrione product; arthur Binder et al in patent USOO8063253B2 propose a process for obtaining pure mesotrione form 1 by pH adjustment separation and purification in aqueous solution and a process for converting metastable crystal form 2 to stable crystal form 1 by pH adjustment and addition of crystal form 1 seed; carmen Cohen et al, in US20120165197A1, disclose a process for obtaining crystalline form 3 of mesotrione from aqueous solutions of dimethyl sulfoxide, N-dimethylformamide and N-methyl-2-pyrrolidone, and mixtures thereof, by an acidification treatment; james Timothy Bristow et al in patent US20160355472A1 propose a process for the preparation of mesotrione by reaction in an organic solvent of petroleum ether, aqueous extraction with a weak base, acidified aqueous extraction.
The post-treatment method for mesotrione transposition rearrangement mainly comprises the following steps: in patent nos. CN85109771A and CN1860102A, methods of alkali extraction, acidification and recrystallization with organic solvent are adopted, and the acidified products obtained by these methods have relatively fine particle size and much tar, and are easily wrapped by tar, and the alkaline solution is strong alkali, which also easily causes instability of the product and generates tar. The method for obtaining the crude product by desolventizing is adopted in patents with patent numbers CN18530325A and CN105254543A, and then a method for recrystallizing by an alcohol solvent is adopted, wherein the recrystallization easily causes product dissolution loss, the yield is reduced, and a solvent different from a reaction system is additionally introduced, so that the system environment is interfered, in the patent with patent number WO2018178860A1, the crude product is dissolved by dichloroethane, part of the product is desolventized, the product is extracted to a water phase by potassium bicarbonate, and then the product is obtained by acidification, the method firstly obtains the crude product and then performs crystallization, the operation is complicated, in addition, the tar obtained by acidification is more, and the product is easily wrapped by the tar. Wangtao et al have proposed a method of carrying out secondary acidification on the mesotrione reaction solution, separating the organic phase and crystallizing to obtain a mesotrione product. The method is innovative in that a secondary acidification technology is used, so that the yield is improved, the three wastes are reduced, and the method is energy-saving and environment-friendly.
The evaluation indexes of the product quality of mesotrione mainly comprise: crystal habit, particle size, moisture content, quantitative content and the like. The mass fraction (namely the quantitative content) of the mesotrione product is more than or equal to 95% as specified in GB29382-2012, the requirement of export first-grade products is more than or equal to 98%, and poor crystal habit, granularity and the like can cause a large amount of solvent residues, thereby seriously influencing the determination of the mass fraction and reducing the product quality. The existing patent mainly provides an innovative scheme aiming at the aspects of separating and converting different crystal forms of mesotrione, improving the purity of reaction products, optimizing a post-treatment method of transposition rearrangement and the like, but the work of strengthening the crystallization process to obtain products with uniform particle size, good fluidity and low moisture content is not taken attention.
Patent CN110078647A, adding a hydrochloric acid aqueous solution into a mesotrione reaction product solution for primary acidification, separating to obtain a mesotrione organic phase, adding a potassium bicarbonate aqueous solution into the organic phase for extraction to obtain a mesotrione aqueous phase, adding a hydrochloric acid aqueous solution into the aqueous phase for secondary acidification, standing for layering to obtain an organic phase to be crystallized, wherein the concentration of the organic phase product is 0.10g/g solvent to 0.11g/g solvent, and the concentration of a filtered organic phase after crystallization is 0.06g/g solvent to 0.07g/g solvent; adding potassium bicarbonate water solution into the filtered organic phase for extraction to improve yield and reduce lossMixing the water phase with the water phase to be secondarily acidified, simultaneously carrying out secondary acidification, standing and layering to obtain the final organic phase to be crystallized, wherein the organic phase is matched into organic mother liquor. After carrying out crystallization treatment to organic mother liquor, the mesotrione product that obtains is mostly powdered, as shown in fig. 4, and the granularity is less, easy caking, and then lead to the product to be difficult for drying, and the moisture content is higher, dissolve incomplete higher, and the product parameter is: the moisture content is 13.7 percent, and the bulk density of the product is 0.61g/cm after drying3The quantitative content was 97.73% and Dv (50)53 μm. The quantitative content data is lower than 98%, so that the product needs to be pulverized and dried (pulverized into flour) in subsequent operations, and the parameters of the pulverized and dried product are as follows: bulk density 0.31g/cm3The quantitative content was 98.15%. Although powdering and then drying can increase the basis weight of the product, this not only increases the cost of production, but also increases the cost of transportation of the product due to the lower flowability and bulk density of the powdered product. Therefore, a crystallization treatment method is needed, which not only can ensure that the quantitative content of the mesotrione product reaches more than 98%, but also can improve the bulk density and the fluidity of the product so as to reduce the production and transportation cost of the mesotrione. The invention aims to provide a crystallization method capable of improving the quality of mesotrione products, so as to improve the crystal habit and granularity of the products, reduce the moisture content of the products, effectively shorten the drying time of the products, improve the quantitative content, the fluidity, the bulk density and the like of the products, and lay a foundation for realizing the continuity of industrial production.
Disclosure of Invention
The invention aims to provide a crystallization treatment method for improving the quality of a mesotrione product, which improves the crystal habit and granularity of the product, improves the bulk density, the fluidity and the quantitative content of the product, and reduces the process operation difficulties of product coalescence, too difficult drying, inconvenient transportation and the like caused by too high moisture content.
On the basis of the organic mother liquor prepared by the method disclosed in the patent CN110078647A, the crystallization process of the organic mother liquor is subjected to enhanced control. Of course, the organic mother liquor of the present invention is not limited to the organic mother liquor prepared by the process of CN110078647A, and the organic mother liquor required to provide product quality and prepared correspondingly to mesotrione product is suitable for use in the present invention.
The technical scheme adopted by the invention for solving the technical problem mainly comprises two steps, as shown in figure 1, step 1 is a seed crystal preparation process, step 2 is a crystallization process strengthening stage, and the seed crystal preparation process and the crystallization strengthening stage can be sequentially carried out, can be carried out simultaneously or can be carried out independently.
The technical scheme of the invention is as follows:
a crystallization treatment method for improving the quality of mesotrione products is characterized by comprising the following steps of a crystal seed preparation process and a crystallization process strengthening stage:
wherein:
the preparation process of the seed crystal comprises the following steps: dissolving a mesotrione powder raw material in a dichloroethane solvent; stirring and dissolving at 50-55 ℃; then cooling to 10-15 ℃ within 120-240 min by adopting a cooling crystallization method, growing crystals, filtering and drying to obtain mesotrione seed crystals which are seed crystals with different particle sizes as shown in figures 2a,2b and 2 c;
in the seed crystal preparation process, the mesotrione powder raw material is dissolved in dichloroethane solvent in a mass ratio of 0.14-0.16: 1.
In the preparation process of the seed crystal, the seed crystal is stirred and dissolved at 50-55 ℃, and the stirring speed is 200-250 rpm.
The crystal growing time in the crystal seed preparation process is 3-5 h.
The strengthening stage of the crystallization process comprises the following steps:
1) adding acidic activated carbon powder accounting for 1-1.5% of the mass of the organic mother liquor to stir and decolor the organic mother liquor at 50-55 ℃;
2) after the decolorization is finished, carrying out hot filtration on the organic mother liquor, and carrying out programmed cooling to 40-45 ℃ within 20-60 min;
3) adding seed crystal with the mass of 3-5% of the organic mother liquor;
4) growing the crystal for 30-180 min under the constant temperature condition of 40-45 ℃;
5) after the crystallization is finished, the temperature is reduced to 10-15 ℃ within 60-180 min, and a primary crystal product is separated out from the crystallization kettle;
6) continuously keeping the obtained primary crystal product in a crystallization kettle for suspension, keeping the end temperature unchanged at 10-15 ℃, and growing crystals at constant temperature for 30-300 min;
7) and after the crystal growth is finished, filtering, leaching and drying to obtain a mesotrione product.
And in the strengthening stage of the crystallization process, the step 1) is stirred and decolored, the decoloring time is 20-60 min, and the stirring speed is 200-250 rpm.
And (3) in the strengthening stage of the crystallization process, the temperature is reduced in the step 2), and the temperature reduction rate is 10-45 ℃/h.
And in the strengthening stage of the crystallization process, seed crystals are added in the step 3), and the particle size range of the seed crystals is 150-450 mu m.
And (3) in the strengthening stage of the crystallization process, the temperature is reduced in the step 5), and the temperature reduction rate is 8-35 ℃/h.
And (3) leaching the product in the step 7) in the strengthening stage of the crystallization process, and leaching by using dichloroethane at 0-10 ℃.
All reported patents on mesotrione products aim to improve the purity of the mesotrione products from the viewpoints of removing impurities and controlling reaction conditions, but the reported patents are used as important parameters for evaluating the quality of the mesotrione products: the crystal habit and the particle size are not regarded as sufficient. The product obtained by the method in patent CN110078647A is taken as an example, because no attention is paid to crystallization process and control on organic mother liquor, most of the product is in a slag form, as shown in fig. 4, the particle size is small, the product is easy to coalesce and has no crystal luster, and further the dissolution residue is difficult to reduce in the subsequent drying process, the dissolution residue can be reduced by powdering and re-evaporating, but certain difficulty exists in the transportation process of flour powder, and the production cost and the transportation cost are increased.
The invention has the beneficial effects that: obtaining a single crystal of mesotrione crystals in different organic solvents by a slow evaporation method, analyzing and simulating mesotrione single crystal data by Materials Studio software, and finding that the crystal habit of mesotrione in vacuum is a symmetrical polyhedral structure as shown in figure 7b, if the mesotrione can be successfully prepared, the method has important significance for actual production and transportation; FIG. 7a is a scanning electron microscope image of an actual product. This methodThe method is based on material Studio crystal habit simulation and prediction, a first batch of crystal seeds with better crystal quality are obtained through recrystallization process optimization, crystal seed optimization and screening, and a proper amount of crystal seeds are added in an organic mother liquor nucleation induction period, so that the stable 1 crystal form product obtained by the cooling crystallization method has better crystal habit and larger granularity, the moisture content and the quantitative content of the product are reduced, the bulk density, the flowability and the like of the product are improved, and the production and transportation cost of the mesotrione product is effectively reduced. By the crystallization method, the moisture content of the mesotrione is reduced to 3-6%, and the bulk density of the product reaches 0.75g/cm3～0.85g/cm3The product quantitative content is improved to more than 98.0 percent, the main granularity can reach 300-500 mu m, and the product has good fluidity.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
FIG. 2a is an SEM image of the seed crystal obtained in example 1 with the particle size of 150-200 μm after sieving;
FIG. 2b is an SEM image of the seed crystal obtained in example 1 with a particle size of 200-300 μm after sieving;
FIG. 2c is an SEM image of the seed crystal obtained in example 1 with a particle size of 300-450 μm after sieving;
FIG. 3 is a SEM photograph of a product obtained in example 1;
FIG. 4 is an SEM photograph of a product obtained in example 7;
FIG. 5 is the XRD powder diffractogram obtained for example 1;
FIG. 6 is a graph showing the particle size distribution obtained in example 1;
FIG. 7a SEM photograph of a single product obtained in example 1;
FIG. 7b shows a vacuum simulated crystal habit.
Detailed description of the invention
The above-described aspects of the present invention will be described in further detail with reference to the following examples. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
1) taking 16g of powder raw material product, and adding the powder raw material product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 55 ℃ for dissolving and clearing, wherein the stirring speed is 250 rpm;
3) cooling to 15 deg.C within 120 min;
4) growing the crystal for 5 hours at the constant temperature of 15 ℃, filtering and drying to obtain 9.8g of crystal seeds;
1) taking 340gm of organic mother liquor (the mass concentration is about 0.16), adding 5.1g of acidic activated carbon powder, and stirring for 60min in an oil bath kettle at 55 ℃ at the stirring speed of 250 rpm;
2) filtering the decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in a crystallizer of an ice maker with the temperature controlled at 55 ℃, and carrying out program cooling to 45 ℃ within 60 min;
3) adding 3.0g of prepared seed crystal;
4) growing crystal at 45 deg.C for 180 min;
5) after the crystal growth is finished at the temperature of 45 ℃, the temperature is reduced to 10 ℃ within 180 min;
6) growing the crystal for 300min at 10 ℃, and consuming the residual supersaturation degree;
7) and filtering partial slurry after crystal growth is finished at 10 ℃, leaching for 2-3 times by using glacial dichloroethane (0 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 22.00g, and weighing 20.70g after drying.
The quality of the obtained product is characterized: moisture content was 3.1%; as shown in fig. 5, a stable crystalline form (1 form) solid product was obtained after drying; as shown in FIG. 6, the product Dv (50)499 μm; as shown in FIG. 3, the product has large and uniform particle size and a bulk density of 0.81g/cm3The quantitative content was 98.35%. The moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
Example 2
1) taking 14g of an original powder product, and adding the 14g of the original powder product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 50 ℃ to dissolve and clear, wherein the stirring speed is 200 rpm;
3) cooling to 10 deg.C within 240min at constant speed;
4) growing the crystal for 3 hours at the constant temperature of 10 ℃, filtering and drying to obtain 8.7g of crystal seeds;
1) taking 329gm of organic mother liquor (mass concentration is about 0.17), adding 3.3g of acidic activated carbon powder, and stirring for 20min in an oil bath kettle at 50 ℃ at the stirring speed of 200 rpm;
2) filtering the decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in an ice maker, controlling the temperature of the crystallizer to be 50 ℃, and carrying out program cooling to 40 ℃ within 20 min;
3) adding 1.7g of prepared seed crystal;
4) growing crystal at 40 deg.C for 30 min;
5) after the crystal growth is finished at 40 ℃, the temperature is reduced to 10 ℃ within 60 min;
6) growing the crystal for 30min at 10 ℃, and consuming the residual supersaturation degree;
7) and filtering partial slurry after crystal growth is finished at 10 ℃, leaching for 2-3 times by using glacial dichloroethane (10 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 17.40g, and weighing 16.68g after drying.
The quality of the obtained product is characterized: the moisture content is 3.1 percent, and the product is obtained after drying, and the bulk density is 0.78g/cm3Before powdering, the quantitative content is 98.20 percent, and the Dv (50) is 324 mu m; the moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
Example 3
1) taking 15g of an original powder product, and adding the 15g of the original powder product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 53 ℃ for dissolving and clearing, wherein the stirring speed is 230 rpm;
3) cooling to 13 deg.C at constant speed within 120 min;
4) growing the crystal for 4 hours at the constant temperature of 13 ℃, filtering and drying to obtain 9.1g of crystal seeds;
1) taking 247.4gm of organic mother liquor (mass concentration is about 0.17), adding 3.7g of acidic activated carbon powder, and stirring for 40min in an oil bath kettle at 53 ℃ and at the stirring speed of 230 rpm;
2) filtering the decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in an ice maker crystallizer with the temperature controlled at 53 ℃, and carrying out program cooling to 43 ℃ within 40 min;
3) adding 1.5g of prepared seed crystal;
4) growing the crystal at 43 ℃ for 100 min;
5) after the crystal growth is finished at 43 ℃, the temperature is reduced to 13 ℃ within 120 min;
6) growing crystal for 130min at 13 ℃, and consuming the residual supersaturation degree;
7) and filtering the slurry after the crystal growth is finished at the temperature of 13 ℃, leaching for 2-3 times by using glacial dichloroethane (8 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 32.8g, and weighing 30.9g after drying.
The quality of the obtained product is characterized: the moisture content is 5.8 percent, and the product is obtained after drying, and the bulk density is 0.85g/cm3Before powdering, the quantitative content is 98.11 percent, and the Dv (50) is 407 mu m; the moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
Example 4
1) taking 15g of an original powder product, and adding the 15g of the original powder product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 52 ℃ for dissolving and clearing, wherein the stirring speed is 210 rpm;
3) cooling to 10 deg.C within 200min at constant speed;
4) growing the crystal for 3 hours at the constant temperature of 10 ℃, filtering and drying to obtain 9.6g of crystal seeds;
1) collecting 353gm of organic mother liquor (mass concentration about 0.18), adding 3.5g of acidic activated carbon powder, and stirring for 40min in an oil bath kettle at 52 deg.C and at 220 rpm;
2) filtering decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in an ice maker, controlling the temperature of the crystallizer to be 52 ℃, and carrying out program cooling to 43 ℃ within 30 min;
3) adding 3.4g of prepared seed crystal;
4) growing the crystal for 110min at 43 ℃;
5) after the crystal growth is finished at 43 ℃, the temperature is reduced to 13 ℃ within 120 min;
6) growing the crystal for 200min at 13 ℃, and consuming the residual supersaturation degree;
7) and filtering partial slurry after crystal growth is finished at the temperature of 13 ℃, leaching for 2-3 times by using glacial dichloroethane (3 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 25.1g, and weighing 23.9g after drying.
The quality of the obtained product is characterized: the moisture content is 4.6 percent, and the product is obtained after drying, and the bulk density is 0.83g/cm3Before powdering, the quantitative content is 98.50%, Dv (50)426 μm; the moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
Example 5
1) taking 16g of an original powder product, and adding the original powder product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 54 ℃ for dissolving and clearing, wherein the stirring speed is 240 rpm;
3) cooling to 10 deg.C within 150min at constant speed;
4) growing the crystal for 4 hours at the constant temperature of 10 ℃, filtering and drying to obtain 10.3g of crystal seeds;
1) taking 262gm of organic mother liquor (the mass concentration is about 0.18), adding 2.6g of acid activated carbon powder, and stirring for 30min in an oil bath kettle at 53 ℃ at the stirring speed of 230 rpm;
2) filtering decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in a crystallizer of an ice maker with the temperature controlled at 53 ℃, and carrying out program cooling to 42 ℃ within 42 min;
3) adding 2.1g of prepared seed crystal;
4) growing crystal at 42 deg.C for 150 min;
5) after the crystal growth is finished at 42 ℃, the temperature is reduced to 10 ℃ within 120 min;
6) growing the crystal for 100min at 10 ℃, and consuming the residual supersaturation degree;
7) and filtering partial slurry after crystal growth is finished at 10 ℃, leaching for 2-3 times by using glacial dichloroethane (6 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 31.5g, and weighing 30.3g after drying.
The quality of the obtained product is characterized: the moisture content is 3.8 percent, and the product is obtained after drying, and the bulk density is 0.84g/cm3Before powdering, the quantitative content is 98.50 percent, and Dv (50)389 mu m; the moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
Example 6
1) taking 15g of an original powder product, and adding the 15g of the original powder product into a 250mL crystallizer filled with 100g of dichloroethane solvent;
2) heating to 53 ℃ for dissolving and clearing, wherein the stirring speed is 240 rpm;
3) cooling to 10 deg.C within 150min at constant speed;
4) growing crystal at constant temperature of 10 ℃ for 300min, filtering and drying to obtain 10.7g of seed crystal;
1) taking 305g of organic mother liquor (the mass concentration is about 0.16), adding 4g of acidic activated carbon powder, and stirring for 30min in an oil bath kettle at 53 ℃ at the stirring speed of 220 rpm;
2) filtering the decolorized mother liquor by using a preheated round-bottom flask and a preheated funnel, quickly placing the filtered mother liquor in an ice maker, controlling the temperature of the crystallizer to be 53 ℃, and carrying out program cooling to 43 ℃ within 50 min;
3) adding 2.5g of prepared seed crystal;
4) growing crystal at 43 deg.C for 60 min;
5) after the crystal growth is finished at 43 ℃, the temperature is reduced to 10 ℃ within 120 min;
6) growing the crystal for 120min at 10 ℃, and consuming the residual supersaturation degree;
7) and filtering partial slurry after crystal growth is finished at 10 ℃, leaching for 2-3 times by using glacial dichloroethane (2 ℃), filtering until no liquid drops fall, transferring the wet product to a watch glass, wherein the wet weight is 20.8g, and weighing 19.7g after drying.
The quality of the obtained product is characterized: the moisture content is 5.2 percent, and the product is obtained after drying, and the bulk density is 0.75g/cm3Before powdering, the quantitative content is 98.06 percent, and Dv (50) is 392 mu m; the moisture content of mesotrione obtained by the crystallization process described in patent CN110078647A was 13.7%, and the bulk density of the product obtained after drying was 0.61g/cm3The quantitative content is 97.73 percent, and the Dv (50) is 53 mu m, so that the quality of the mesotrione product prepared by the method is obviously improved.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (9)
1. A crystallization treatment method for improving the quality of mesotrione products is characterized by comprising a crystal seed preparation process and a crystallization process strengthening stage;
the preparation process of the seed crystal comprises the following steps: dissolving a mesotrione powder raw material in a dichloroethane solvent; stirring and dissolving at 50-55 ℃; then cooling to 10-15 ℃ within 120-240 min by adopting a cooling crystallization method, growing crystals, filtering and drying to obtain mesotrione seed crystals;
the strengthening stage of the crystallization process comprises the following steps:
1) adding acidic activated carbon powder accounting for 1-1.5% of the mass of the organic mother liquor to stir and decolor the organic mother liquor at 50-55 ℃;
2) after the decolorization is finished, carrying out hot filtration on the organic mother liquor, and carrying out programmed cooling to 40-45 ℃ within 20-60 min;
3) adding screened seed crystal with the mass of 3-5% of the organic mother liquor;
4) growing the crystal for 30-180 min at 40-45 ℃;
5) after the crystallization is finished, the temperature is reduced to 10-15 ℃ within 60-180 min, and a primary crystal product is separated out from the crystallization kettle;
6) continuously keeping the obtained primary crystal product in a crystallization kettle for suspension, keeping the end temperature to be 10-15 ℃ unchanged, and growing crystals at constant temperature for a period of time, wherein the crystal growing time is 30-300 min;
7) and after the crystal growth is finished, filtering, leaching and drying to obtain a mesotrione product.
2. The method as set forth in claim 1, characterized in that the mesotrione powder raw material is dissolved in dichloroethane solvent in a mass ratio of 0.14-0.16: 1 during the seed crystal preparation process.
3. The method as set forth in claim 1, wherein the seed crystal is dissolved by stirring at a temperature of 50 ℃ to 55 ℃ at a stirring speed of 200rpm to 250 rpm.
4. The method of claim 1, wherein the time for growing the seed crystal in the process of preparing the seed crystal is 3-5 hours.
5. The method as set forth in claim 1, wherein the decoloring is performed by stirring in the step 1) of the strengthening stage of the crystallization process, the decoloring time is 20 to 60min, and the stirring speed is 200 to 250 rpm.
6. The method as set forth in claim 1, wherein the temperature of the crystallization process is reduced at a rate of 10 to 45 ℃/h in the strengthening stage step 2).
7. The method as set forth in claim 1, wherein the seed crystal is added in the step 3) of the strengthening stage of the crystallization process, and the particle size of the seed crystal is in the range of 150 to 450 μm.
8. The method as set forth in claim 1, wherein the temperature of the crystallization process is reduced at a rate of 8 to 35 ℃/hr in the strengthening stage of crystallization step 5).
9. The method as set forth in claim 1, wherein the product is rinsed in the strengthening stage of crystallization step 7) using dichloroethane of 0 to 10 ℃.
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| CN114671789A (en) * | 2021-10-25 | 2022-06-28 | 上虞颖泰精细化工有限公司 | Method for continuous crystallization of mesotrione |
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