CN114671789B - Method for continuously crystallizing mesotrione - Google Patents
Method for continuously crystallizing mesotrione Download PDFInfo
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- CN114671789B CN114671789B CN202111242116.2A CN202111242116A CN114671789B CN 114671789 B CN114671789 B CN 114671789B CN 202111242116 A CN202111242116 A CN 202111242116A CN 114671789 B CN114671789 B CN 114671789B
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- mesotrione
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- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000005578 Mesotrione Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 182
- 230000008025 crystallization Effects 0.000 claims abstract description 179
- 239000000243 solution Substances 0.000 claims abstract description 81
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 239000012452 mother liquor Substances 0.000 claims abstract description 36
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000007781 pre-processing Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000008346 aqueous phase Substances 0.000 claims description 15
- 239000011549 crystallization solution Substances 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011736 potassium bicarbonate Substances 0.000 claims description 10
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 10
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 10
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 230000032798 delamination Effects 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a mesotrione continuous crystallization method, and belongs to the technical field of pesticide crystallization. A method for continuously crystallizing mesotrione, which comprises the following steps of: respectively adding mesotrione solution, which is a mixed solution of dichloroethane solvent and mesotrione, into the three crystallization kettles; step 2: respectively preprocessing mesotrione solutions in the three crystallization kettles to separate out partial crystals from the mesotrione solutions in the three crystallization kettles; the three crystallization kettles are respectively a first crystallization kettle, a second crystallization kettle and a third crystallization kettle. The method can realize continuous crystallization of mesotrione without screening seed crystals or seeding, obtain stable mesotrione crystal form 1 product, has simple and convenient operation, is suitable for industrial production, and can recycle dichloroethane solvent and mesotrione in mother liquor.
Description
Technical Field
The invention relates to the technical field of pesticide crystallization, in particular to a mesotrione continuous crystallization method.
Background
The general route for mesotrione is as follows:
CN 1680102 (first positive in 2004), basic conditions (ph=9.5) were mentioned, and enolization precipitated the product in water, an early literature for the purification of mesotrione.
CN 101384547 (first arrival in 2007) provided the XRD pattern of form 1, and the form 1 polymorph was considered to have good thermal stability and more useful value. The patent also discloses a method for preparing the 1 type polymorph, but the preparation process requires precipitation in water, the alkalinity is kept before adding into a crystallization kettle, the acidity is kept in the kettle by adding hydrochloric acid and the like, the operation is complex, and more waste water and waste salt can be generated.
The publication number is CN111909066A, which discloses a crystallization treatment method for improving the quality of mesotrione products, mainly comprising two steps of seed crystal preparation process and crystallization process strengthening. The seed crystal preparation process comprises the following steps: recrystallizing mesotrione solid powder by using a dichloroethane solvent system, and carrying out constant-temperature crystal growing, filtering and drying to obtain mesotrione seed crystals; strengthening the crystallization process: and (3) performing program cooling on the mesotrione organic mother liquor decolorized by the active carbon to a metastable zone, adding the prepared screened seed crystal, and performing crystal growing, program cooling, crystal growing, filtering, leaching and drying to obtain mesotrione crystals.
Although the above patent can separate out the crystal product with better particles, the product quality is better after filtration. However, there are certain disadvantages: the seed crystal is added in each batch, the seed crystal dosage is large, strict requirements are also provided for the granularity of the seed crystal, the actual operation in production is complex, in addition, the mother solution after crystallization and filtration is not well utilized, the mesotrione content in the mother solution is high, and if the mesotrione is not recovered, the resources are not wasted, and the environment is polluted.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a mesotrione continuous crystallization method which can realize continuous crystallization of mesotrione without screening seed crystals and adding seed crystals, so as to obtain a stable mesotrione crystal form 1 product, has simple and convenient operation, is suitable for industrial production, and can recycle dichloroethane solvent and mesotrione in mother liquor.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A method for continuously crystallizing mesotrione,
step 1: respectively adding mesotrione solution, which is a mixed solution of dichloroethane solvent and mesotrione, into the three crystallization kettles;
step 2: respectively preprocessing mesotrione solutions in the three crystallization kettles to separate out partial crystals from the mesotrione solutions in the three crystallization kettles;
the three crystallization kettles are a first crystallization kettle, a second crystallization kettle and a third crystallization kettle respectively;
the discharge port of the first crystallization kettle is communicated with the feed port of the second crystallization kettle, and the discharge port of the second crystallization kettle is communicated with the feed port of the third crystallization kettle;
step 3: continuously feeding and crystallizing, namely continuously adding mesotrione solution into a first crystallization kettle through a feed inlet of the first crystallization kettle, enabling the first crystallization solution in the first crystallization kettle to enter a second crystallization kettle in a unidirectional way through a discharge hole, and enabling the second crystallization solution in the second crystallization kettle to enter a third crystallization kettle in a unidirectional way through the discharge hole;
step 4: and filtering the third crystallization solution flowing out of the discharge port of the third crystallization kettle to obtain a mesotrione crystal form 1 product and mother liquor.
Preferably, the pretreatment in step 2 is:
cooling the mesotrione solution placed in the first crystallization kettle until obvious crystals are separated out, and then heating to a first crystallization temperature for preserving heat and growing crystals;
cooling the mesotrione solution placed in the second crystallization kettle until obvious crystals are separated out, heating to a first crystallization temperature, preserving heat and growing crystals, and slowly cooling to a second crystallization temperature;
cooling the mesotrione solution placed in the third crystallization kettle until obvious crystals are separated out, heating to the first crystallization temperature, preserving heat and growing crystals, and slowly cooling to the third crystallization temperature;
the first crystallization temperature is higher than the second crystallization temperature, which is higher than the third crystallization temperature.
Preferably, the first crystallization temperature is 40-50 ℃, the second crystallization temperature is 30-38 ℃, and the third crystallization temperature is 5-10 ℃.
Preferably, the dichloroethane solvent and mesotrione in the mother liquor are recovered and configured as mesotrione recovery solution having the same mass concentration as the mesotrione solution in the initial first crystallization kettle;
the mesotrione recovery solution is added to the first crystallization kettle.
Preferably, the mother liquor is decolorized to remove some of the organic impurities prior to recovery of the mother liquor.
Preferably, the dichloroethane solvent and mesotrione in the mother liquor are recovered by adopting a route A or a route B;
the route a: partially removing the dichloroethane solvent in the mother solution to obtain a dichloroethane recovery solvent and a mesotrione recovery solution with the same mass concentration as the mesotrione solution in the initial first crystallization kettle, and recycling the mesotrione recovery solution into the first crystallization kettle;
the route B: adding alkali liquor into the mother liquor for extraction, separating to obtain a first aqueous phase and a first organic phase, adding acid into the first aqueous phase for acidification to obtain an acidified solution, adding dichloroethane solvent for mixing, standing for delamination, and separating to obtain a second aqueous phase and a second organic phase;
the first organic phase is dichloroethane solvent, and the second organic phase is mixed solution of dichloroethane solvent and mesotrione;
the second organic phase is recycled to the first crystallization kettle.
Preferably, the alkali used in the alkaline solution is one or more of sodium hydroxide, sodium bicarbonate, potassium hydroxide and potassium bicarbonate.
Preferably, the pH of the alkali liquor is 9-12, the alkali in the alkali liquor is formed by mixing sodium bicarbonate or potassium bicarbonate and sodium hydroxide or potassium hydroxide, and the molar ratio of the sodium bicarbonate or the potassium bicarbonate to the sodium hydroxide or the potassium hydroxide is 0.02-0.4:1.
Preferably, the mass concentration of the mesotrione solution is 14-20%, and the pH value is 2-6.
Preferably, the acidified solution is hydrochloric acid or sulfuric acid.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the mesotrione solution in the crystallization kettle is pretreated, so that the crystallization kettle forms crystals which are easy to crystallize the mesotrione solution, and meanwhile, the mesotrione solution sequentially passes through the first crystallization kettle, the second crystallization kettle and the third crystallization kettle, so that a stable mesotrione crystal form 1 product can be obtained at the discharge port of the third crystallization kettle, and the mesotrione crystal form 1 product processing method is simple and convenient to operate and suitable for industrial production.
(2) According to the invention, the mother liquor is recovered through the arrangement of the route A and the route B, so that the utilization rate of mesotrione is improved, and the situation that mesotrione in the mother liquor is not recovered, so that the environment is polluted and the resource is wasted is avoided.
(3) The invention recovers the mother liquor through the route B, converts the mesotrione product into sodium salt or potassium salt metal salt to form in the presence of alkali, dissolves in water, acidizes the first water phase by adding acid, adds dichloroethane solvent, stands for layering, separates to obtain a second organic phase and a second water phase, and the process enables mesotrione in the mother liquor to be purified.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is an XRD pattern of mesotrione form 1 of the present invention.
Detailed Description
A method for continuously crystallizing mesotrione,
step 1: respectively adding mesotrione solution, which is a mixed solution of dichloroethane solvent and mesotrione, into the three crystallization kettles;
step 2: respectively preprocessing mesotrione solutions in the three crystallization kettles to separate out partial crystals from the mesotrione solutions in the three crystallization kettles;
the three crystallization kettles are a first crystallization kettle, a second crystallization kettle and a third crystallization kettle respectively;
the discharge port of the first crystallization kettle is communicated with the feed port of the second crystallization kettle, and the discharge port of the second crystallization kettle is communicated with the feed port of the third crystallization kettle;
step 3: continuously feeding and crystallizing, namely continuously adding mesotrione solution into a first crystallization kettle through a feed inlet of the first crystallization kettle, enabling the first crystallization solution in the first crystallization kettle to enter a second crystallization kettle in a unidirectional way through a discharge hole, and enabling the second crystallization solution in the second crystallization kettle to enter a third crystallization kettle in a unidirectional way through the discharge hole;
step 4: and filtering the third crystallization solution flowing out of the discharge port of the third crystallization kettle to obtain a mesotrione crystal form 1 product and mother liquor.
The pretreatment in the step 2 is as follows:
cooling the mesotrione solution placed in the first crystallization kettle until obvious crystals are separated out, and then heating to a first crystallization temperature for preserving heat and growing crystals;
cooling the mesotrione solution placed in the second crystallization kettle until obvious crystals are separated out, heating to a first crystallization temperature, preserving heat and growing crystals, and slowly cooling to a second crystallization temperature;
cooling the mesotrione solution placed in the third crystallization kettle until obvious crystals are separated out, heating to the first crystallization temperature, preserving heat and growing crystals, and slowly cooling to the third crystallization temperature;
the first crystallization temperature is higher than the second crystallization temperature, the second crystallization temperature is higher than the third crystallization temperature, and the heat preservation and crystal growth time is longer than 1h.
The temperature of the mesotrione solution added into the crystallization kettle is 50-55 ℃, the first crystallization temperature is 40-50 ℃, the second crystallization temperature is 30-38 ℃, and the third crystallization temperature is 5-10 ℃.
Recovering dichloroethane solvent and mesotrione in the mother liquor and preparing mesotrione recovery solution with the same mass concentration as the mesotrione solution in the initial first crystallization kettle;
the mesotrione recovery solution is added to the first crystallization kettle.
The mother liquor is decolorized to remove part of organic impurities before being recovered, activated carbon is used for decolorizing the mother liquor, and the consumption of the activated carbon is 2wt% of the mother liquor; or the mother liquor is decolorized with a resin.
Recovering dichloroethane solvent and mesotrione in the mother liquor by adopting a route A or a route B;
the route a: partially removing the dichloroethane solvent in the mother solution to obtain a dichloroethane recovery solvent and a mesotrione recovery solution with the same mass concentration as the mesotrione solution in the initial first crystallization kettle, and recycling the mesotrione recovery solution into the first crystallization kettle;
the route B: adding alkali liquor into the mother liquor for extraction, separating to obtain a first aqueous phase and a first organic phase, adding acid into the first aqueous phase for acidification to obtain an acidified solution, adding dichloroethane solvent for mixing, standing for delamination, and separating to obtain a second aqueous phase and a second organic phase;
the first aqueous phase is a mixed solution of dichloroethane solvent and other organic impurities.
The second organic phase is a mixed solution of dichloroethane solvent and mesotrione;
the second organic phase is recycled to the first crystallization kettle.
Detecting that the mass content of the mesotrione crystal form 1 product is higher than 97%, selecting a route A to recover the mother liquor, and adopting a route B to recover the mother liquor when the mass content of the mesotrione crystal form 1 product is lower than 97%;
the quality content of the mesotrione crystal form 1 product is detected to be lower than 97 percent for the first time, the mother liquor is recovered by selecting a route B, when the mother liquor is recovered by selecting the route B, the quality content of the mesotrione crystal is not lower than 98.2 percent, and then the mother liquor is recovered by adopting a route A.
The alkali used in the alkali liquor is one or more of sodium hydroxide, sodium bicarbonate, potassium hydroxide and potassium carbonate.
The pH of the alkali liquor is 9-12, the alkali in the alkali liquor is formed by mixing sodium bicarbonate or potassium bicarbonate and sodium hydroxide or potassium hydroxide, the molar ratio of the sodium bicarbonate or the potassium bicarbonate to the sodium hydroxide or the potassium hydroxide is 0.02-0.4:1, and the molar ratio of the sodium bicarbonate or the potassium bicarbonate to the sodium hydroxide or the potassium hydroxide is 0.1-0.2:1.
The mass concentration of mesotrione solution is 14-20%, and the pH value is 2-6.
The acidified solution is hydrochloric acid or sulfuric acid.
Different amounts and different types of alkali extraction effects are selected, and the extraction effect is good in a specific pH range. When the pH is too high, mesotrione is easy to form disodium salt or dipotassium salt, the solubility in water and an organic phase is poor, and when the dosage is insufficient, mesotrione cannot be completely extracted when the dichloroethane solution is extracted, and the recovery rate of mesotrione is easy to be reduced. If bicarbonate is adopted, the alkali dosage is increased, the mesotrione can not be completely extracted when the dichloroethane solution is extracted, and the concentration of the mesotrione in the mother solution is also changed, so that the alkali dosage is difficult to control, and the stability is poor when the alkali is extracted; in the research process, if bicarbonate is mixed with strong alkali, the problem of unstable alkali extraction effect can be well solved.
In the step 3, continuous feeding crystallization is carried out, mesotrione solution is continuously added into the first crystallization kettle through a feed inlet of the first crystallization kettle, the first crystallization solution in the first crystallization kettle is unidirectionally fed into the second crystallization kettle through a discharge hole, and the second crystallization solution in the second crystallization kettle is unidirectionally fed into the third crystallization kettle through the discharge hole; the residence time of mesotrione solution in the three crystallization kettles is not less than 2 hours, preferably 4-7 hours; ensuring that mesotrione solution is crystallized to obtain a mesotrione crystal form 1 product with higher purity, otherwise, the obtained mesotrione crystal form 1 product has fine particles, which can cause difficult filtration of a third crystallization solution when the third crystallization solution is filtered; the longer the mesotrione solution is crystallized in the crystallization kettle, the more uniform the mesotrione crystal form 1 product particles obtained by the mesotrione solution crystallization are, the higher the product content is, but the longer the equipment stay, the lower the productivity is, and the preferred the mesotrione solution stay time is 4-7h in consideration of the actual productivity requirement of the amplified production.
In the examples, a crystallization kettle with a laboratory capacity of 500ml was taken as an example.
And respectively adding mesotrione solution into the first crystallization kettle, the second crystallization kettle and the third crystallization kettle, wherein the liquid surfaces of the mesotrione solution in the first crystallization kettle, the second crystallization kettle and the third crystallization kettle reach the discharge port of the crystallization kettle, the mass concentration of the mesotrione solution is 18%, and the temperature of the mesotrione solution is 50-55 ℃.
After mesotrione solution is added into the first crystallization kettle, the mesotrione solution in the first crystallization kettle is cooled from 50-55 ℃ to 28 ℃ for 2 hours, when solid is obviously precipitated, the temperature is raised to 45 ℃ again, the temperature is kept for more than 1 hour, part of the precipitated crystals are dissolved, and the temperature is kept for waiting.
After mesotrione solution is added into the second crystallization kettle, slowly cooling the mesotrione solution in the second crystallization kettle to 25 ℃ from 50-55 ℃ for 2 hours, heating to 45 ℃ when obvious solids are separated out, preserving heat for more than 1 hour, slowly cooling the mesotrione solution in the second crystallization kettle to 35 ℃ for 4 hours, and preserving heat for later use.
After the mesotrione solution is added into the third crystallization kettle, slowly cooling the mesotrione solution in the second crystallization kettle to 25 ℃ from 50-55 ℃ for 2 hours, heating to 45 ℃ and preserving heat for more than 1 hour when obvious solid is separated out, and slowly cooling the mesotrione solution in the second crystallization kettle to 5-10 ℃ from 45 ℃ for 6 hours.
After the three crystallization kettles reach the designated temperature, the discharge port of the first crystallization kettle is communicated with the feed port of the second crystallization kettle, and the discharge port of the second crystallization kettle is communicated with the feed port of the third crystallization kettle.
Continuously feeding the materials into a feed inlet of a first crystallization kettle, wherein the feed rate is 5.0ml/min, collecting 600g of a third crystallization solution from a discharge outlet of a third crystallization kettle, filtering the collected third crystallization solution, and drying 108g of wet product and 492g of mother liquor to obtain 101.5g of mesotrione crystal form 1 product, wherein the detected quantitative content of the mesotrione crystal form 1 product is 98.5%.
When the content of the mesotrione crystal form 1 product is detected to be higher than 97% for the first time, the mother liquor is recovered by selecting a route A, the dichloroethane solvent in 492g of mother liquor is partially removed, the dichloroethane recovery solvent and the mesotrione recovery solution with the same mass concentration as the mesotrione solution added into the first crystallization kettle are obtained, finally, the mesotrione recovery solution and the mesotrione solution are continuously circulated into the first crystallization kettle in a ratio of 1:15 until the content of the mesotrione crystal form 1 product is lower than 97%, and the route B is adopted for post-treatment.
When the content of the mesotrione crystal form 1 product is detected to be lower than 97% for the first time, a route B is selected to recycle the mother liquor; adding aqueous solution of potassium bicarbonate and potassium hydride with pH of 10-11 into 492g of mother solution for extraction, separating to obtain a first aqueous phase and a first organic phase, adding hydrochloric acid into the first aqueous phase for acidification, adding 35g of dichloroethane solvent into the hydrochloric acid acidified solution, standing for layering, separating to obtain a second aqueous phase and a second organic phase, wherein the second aqueous phase is a salt-containing aqueous phase, the second organic phase is a mixed solution of mesotrione and dichloroethane solvent, the mass concentration of the mesotrione solution of the second organic phase is 18%, and finally continuously circulating the second organic phase and the mesotrione solution into a first crystallization kettle in a ratio of 1:15 until the content of mesotrione crystal form 1 products is higher than 98.2%, and performing post-treatment by adopting a method A.
Claims (9)
1. A method for continuously crystallizing mesotrione, which is characterized by comprising the following steps:
step 1: respectively adding mesotrione solution, which is a mixed solution of dichloroethane solvent and mesotrione, into the three crystallization kettles;
step 2: respectively preprocessing mesotrione solutions in the three crystallization kettles to separate out partial crystals from the mesotrione solutions in the three crystallization kettles;
the three crystallization kettles are a first crystallization kettle, a second crystallization kettle and a third crystallization kettle respectively;
the discharge port of the first crystallization kettle is communicated with the feed port of the second crystallization kettle, and the discharge port of the second crystallization kettle is communicated with the feed port of the third crystallization kettle;
step 3: continuously feeding and crystallizing, namely continuously adding mesotrione solution into a first crystallization kettle through a feed inlet of the first crystallization kettle, enabling the first crystallization solution in the first crystallization kettle to enter a second crystallization kettle in a unidirectional way through a discharge hole, and enabling the second crystallization solution in the second crystallization kettle to enter a third crystallization kettle in a unidirectional way through the discharge hole;
step 4: filtering the third crystallization solution flowing out of the discharge port of the third crystallization kettle to obtain a mesotrione crystal form 1 product and mother liquor;
the pretreatment in the step 2 is as follows:
cooling the mesotrione solution placed in the first crystallization kettle until obvious crystals are separated out, and then heating to a first crystallization temperature for preserving heat and growing crystals;
cooling the mesotrione solution placed in the second crystallization kettle until obvious crystals are separated out, heating to a first crystallization temperature, preserving heat and growing crystals, and slowly cooling to a second crystallization temperature;
cooling the mesotrione solution placed in the third crystallization kettle until obvious crystals are separated out, heating to the first crystallization temperature, preserving heat and growing crystals, and slowly cooling to the third crystallization temperature;
the first crystallization temperature is higher than the second crystallization temperature, which is higher than the third crystallization temperature.
2. A method for continuous crystallization of mesotrione according to claim 1, characterized in that: the first crystallization temperature is 40-50deg.C, the second crystallization temperature is 30-38deg.C, and the third crystallization temperature is 5-10deg.C.
3. A method for continuous crystallization of mesotrione according to claim 1, characterized in that:
recovering dichloroethane solvent and mesotrione in the mother liquor and preparing mesotrione recovery solution with the same mass concentration as the mesotrione solution in the initial first crystallization kettle;
the mesotrione recovery solution is added to the first crystallization kettle.
4. A method for continuous crystallization of mesotrione according to claim 3, characterized in that:
and (3) decoloring the mother liquor to remove part of organic impurities before recovering the mother liquor.
5. A method for continuous crystallization of mesotrione according to claim 3 or 4, characterized in that: recovering dichloroethane solvent and mesotrione in the mother liquor by adopting a route A or a route B;
the route a: partially removing the dichloroethane solvent in the mother solution to obtain a dichloroethane recovery solvent and a mesotrione recovery solution with the same mass concentration as the mesotrione solution in the initial first crystallization kettle, and recycling the mesotrione recovery solution into the first crystallization kettle;
the route B: adding alkali liquor into the mother liquor for extraction, separating to obtain a first aqueous phase and a first organic phase, adding acid into the first aqueous phase for acidification to obtain an acidified solution, adding dichloroethane solvent for mixing, standing for delamination, and separating to obtain a second aqueous phase and a second organic phase;
the second organic phase is a mixed solution of dichloroethane solvent and mesotrione;
the second organic phase is recycled to the first crystallization kettle.
6. A method for continuous crystallization of mesotrione according to claim 5, wherein: the alkali used in the alkali liquor is one or more of sodium hydroxide, sodium bicarbonate, potassium hydroxide and potassium bicarbonate.
7. A method for continuous crystallization of mesotrione according to claim 6, wherein: the pH value of the alkali liquor is 9-12, the alkali in the alkali liquor is formed by mixing sodium bicarbonate or potassium bicarbonate and sodium hydroxide or potassium hydroxide, and the molar ratio of the sodium bicarbonate or the potassium bicarbonate to the sodium hydroxide or the potassium hydroxide is 0.02-0.4:1.
8. A method for continuous crystallization of mesotrione according to claim 1, characterized in that: the mass concentration of mesotrione solution is 14-20%, and the pH value is 2-6.
9. A method for continuous crystallization of mesotrione according to claim 5, wherein: the acid is hydrochloric acid or sulfuric acid.
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| CN1860102A (en) * | 2003-10-02 | 2006-11-08 | 辛根塔参与股份公司 | Process for purifying mesotrione |
| CN101010292A (en) * | 2004-08-26 | 2007-08-01 | 辛根塔参与股份公司 | Process for the preparation of polymorphs of mesotrione |
| CN101384547A (en) * | 2006-01-18 | 2009-03-11 | 先正达参股股份有限公司 | Process for the crystallisation of mesotrione |
| CN103373946A (en) * | 2012-04-23 | 2013-10-30 | 中国中化股份有限公司 | Method for preparing mesotrione with stable crystal form |
| CN110078647A (en) * | 2019-05-15 | 2019-08-02 | 北京颖泰嘉和生物科技股份有限公司 | A kind of post-processing approach of mesotrione reaction product |
| CN111909066A (en) * | 2020-06-24 | 2020-11-10 | 天津大学 | Crystallization treatment method for improving quality of mesotrione product |
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| CN1860102A (en) * | 2003-10-02 | 2006-11-08 | 辛根塔参与股份公司 | Process for purifying mesotrione |
| CN101010292A (en) * | 2004-08-26 | 2007-08-01 | 辛根塔参与股份公司 | Process for the preparation of polymorphs of mesotrione |
| CN101384547A (en) * | 2006-01-18 | 2009-03-11 | 先正达参股股份有限公司 | Process for the crystallisation of mesotrione |
| CN103373946A (en) * | 2012-04-23 | 2013-10-30 | 中国中化股份有限公司 | Method for preparing mesotrione with stable crystal form |
| CN110078647A (en) * | 2019-05-15 | 2019-08-02 | 北京颖泰嘉和生物科技股份有限公司 | A kind of post-processing approach of mesotrione reaction product |
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