CN117362244A - Method and system for continuously producing prothioconazole - Google Patents
Method and system for continuously producing prothioconazole Download PDFInfo
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- CN117362244A CN117362244A CN202311294054.9A CN202311294054A CN117362244A CN 117362244 A CN117362244 A CN 117362244A CN 202311294054 A CN202311294054 A CN 202311294054A CN 117362244 A CN117362244 A CN 117362244A
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- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000005825 Prothioconazole Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000002425 crystallisation Methods 0.000 claims abstract description 121
- 230000008025 crystallization Effects 0.000 claims abstract description 121
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 52
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 47
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 46
- -1 1-chloro-cyclopropan-1-yl Chemical group 0.000 claims abstract description 18
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 239000001294 propane Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 87
- 238000007670 refining Methods 0.000 claims description 77
- 239000002904 solvent Substances 0.000 claims description 68
- 230000003068 static effect Effects 0.000 claims description 66
- 239000007788 liquid Substances 0.000 claims description 56
- 239000012295 chemical reaction liquid Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 39
- 239000012452 mother liquor Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 34
- 238000006722 reduction reaction Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010924 continuous production Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 description 36
- 239000002002 slurry Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PCARSQBZDYOIPU-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2,4-triazolidine-3-thione Chemical compound C=1C=CC=C(Cl)C=1CC(C1(Cl)CC1)(O)CN1NCNC1=S PCARSQBZDYOIPU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QPDUQKTYZRXRBC-UHFFFAOYSA-N triazole-4-thione Chemical compound S=C1C=NN=N1 QPDUQKTYZRXRBC-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of prothioconazole production, and particularly discloses a method and a system for continuously producing prothioconazole. The prothioconazole is prepared by reacting raw material 2- (1-chloro-cyclopropan-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane in the presence of oxidant ferric chloride, wherein the oxidation reaction and crystallization and purification are both carried out in a tubular reactor. The invention adopts the tubular reactor to carry out continuous flow oxidation reaction and continuous crystallization operation, the prepared product crystal is cube-shaped grain, the granularity of the product is 100-200 mu m, the stability and the production efficiency of the product quality are improved, meanwhile, ferric chloride can be recycled, almost no three wastes are generated, the method is clean and environment-friendly, the product purity reaches more than 99%, the conversion rate is 100%, the yield is more than 99%, and the method is suitable for industrial production and has good economic and social benefits.
Description
Technical Field
The invention relates to the technical field of prothioconazole production, in particular to a method and a system for continuously producing prothioconazole.
Background
The prothioconazole is a low-toxicity, high-efficiency and broad-spectrum triazolethione bactericide developed by Bayer company, and is mainly used for preventing and treating various diseases of crops such as grains, wheat, beans and the like. Methods for preparing prothioconazole by oxidation of 2- (1-chloro-cyclopropan-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazol-in-5-thione-1-yl) -propane have been reported. The method requires air or catalytic amount of sulfur powder or excessive sulfur powder as a reaction reagent to perform oxidation reaction at a higher temperature, which can generate byproducts with peculiar smell, and the yield of the product is not high. In addition, the method has been reported in the literature to produce a large amount of solid waste by using excessive ferric trichloride as a reactant, and requires deep harmless treatment. In addition, most of the methods are intermittent production, the unstable fluctuation of product quality is large, the granularity of the product is also uneven, the yield is small, and the method is not beneficial to realizing industrial production.
At present, a series of continuous production methods appear in China, and a tubular reactor is used as a reaction vessel, 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane is dissolved in a solvent, an oxidant is added into the solvent for uniform mixing, then the uniform mixture and oxygen are simultaneously introduced into the tubular reactor for reaction, and after the reaction is finished, the reaction liquid discharged from a discharge port of the tubular reactor is subjected to purification crystallization treatment, so that a high-purity prothioconazole product is obtained. The process uses oxygen as an oxidant, and a large amount of excessive oxidation products can be generated by the product due to the excessively strong oxidation capability of the oxygen, so that the quality of the product is influenced, and the yield of the product is also influenced.
In addition, the presently disclosed continuous technological methods of prothioconazole are all oxidation reaction steps using a tubular reactor or a micro-channel reactor, a large amount of solvent is needed to be added into a reaction system to homogenize the system, and a traditional intermittent method is needed to carry out post-treatment after oxidation, so that the technology is still in intermittent fluctuation, the reaction efficiency is lower, the product quality is difficult to ensure, and the problem of uneven granularity of the product still exists. Therefore, it is necessary to find a process for producing prothioconazole in a full-process continuous manner, so as to improve the uniformity of prothioconazole product quality and improve the reaction efficiency.
Disclosure of Invention
Aiming at the problems of low production efficiency and unstable product quality of the existing industrial prothioconazole production process, the invention provides a method and a system for continuously producing prothioconazole.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for continuously producing prothioconazole, which comprises the following steps:
step a, respectively adding a raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane and ferric chloride into a reaction solvent, and uniformly mixing to obtain a raw material liquid and a ferric chloride solution;
Step b, continuously introducing the raw material liquid and the ferric chloride solution into a static mixer I respectively, uniformly mixing, and continuously introducing the mixed material into a tubular reactor I for oxidation reaction to obtain an oxidation reaction liquid;
step c, cooling the oxidation reaction liquid to 30-40 ℃, continuously introducing the cooled oxidation reaction liquid and a crystallization solvent into a static mixer II together, uniformly mixing, continuously introducing the mixed material into a tubular reactor II for crystallization, performing solid-liquid separation on the crystallized material liquid at the crystallization temperature of 20-30 ℃, and washing to obtain a prothioconazole crude product;
step d, adding part of refining solvent into a refining system, and then continuously adding the crude prothioconazole and the rest of refining solvent into the refining system at the same time for refining reaction to obtain refined reaction liquid;
step e, continuously introducing the refined reaction solution and the crystallization solvent into a static mixer III, uniformly mixing, continuously introducing the mixed material into a tubular reactor III, performing crystallization reaction, performing solid-liquid separation on the crystallized material solution at a crystallization temperature of 0-30 ℃, washing and drying to obtain a prothioconazole product;
in the step b, the tubular reactor I is a multi-stage reactor and comprises a low-temperature reaction section, a heating reaction section and a high-temperature reaction section; the temperature of the low-temperature reaction section is 20-30 ℃, the temperature of the heating reaction section is raised from 20-30 ℃ to 50-70 ℃, and the temperature of the high-temperature reaction section is 50-70 ℃.
In order to solve the technical problems of unstable product quality, uneven product granularity and the like caused by non-whole-process continuity in the existing prothioconazole intermittent production process, particularly intermittent production of crystallization operation, the invention carries out intensive research on the prothioconazole production process, particularly the technical problem of intermittent process continuity of crystallization reaction.
The intermittent crystallization process is simple to operate, but the granularity of the product is uneven and the quality of the product is unstable, while the continuous crystallization needs to solve the problems of accurate control of crystallization initial crystallization time, crystallization speed and crystallization granularity, and avoids the phenomenon of crystal explosion, so that the granularity of the product is different; meanwhile, the technical problems of feeding sequence, material concentration, reaction temperature, reaction selectivity and the like of the oxidation reaction are required to be controlled, and side reactions are avoided as much as possible, so that the influence on the crystallization process is reduced.
Compared with the prior art, the continuous production method of prothioconazole provided by the invention has the advantages that the continuous oxidation reaction is carried out by adopting the multi-section tubular reactor, the reaction temperature of each section is controlled, the full progress of the oxidation reaction is ensured, and the occurrence of side reactions is reduced; and the tubular reactor is selected, the specific crystallization temperature is controlled, continuous crystallization is carried out, and a refining system is matched, so that the crystal form of the prepared prothioconazole product is uniform cube crystal grains, the granularity of the product is 100-200 mu m, the particle size distribution is centralized, the quality and the particle size uniformity of the prothioconazole product are effectively improved, the product purity can reach more than 99%, the raw material conversion rate can reach more than 100%, the product yield is more than 99%, the production efficiency is obviously improved, the personnel cost is reduced, the industrial scale production is facilitated, and the popularization and application value is higher.
The structural formulas of the 2- (1-chloro-cyclopropan-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolan-5-thione-1-yl) -propane and prothioconazole are shown as follows:
further, in the step a, the reaction solvent is one or more of acetonitrile, tetrahydrofuran, acetone, methanol, ethanol, n-butanol, isopropanol or water.
Further, in the step a, the mass concentration of the raw material liquid is 30% -40%, and the mass concentration of the ferric chloride solution is 40% -75%.
The preferable concentration of the reaction solvent and the materials is favorable for promoting the full progress of the oxidation reaction, improving the selectivity of the reaction and reducing the occurrence of side reactions.
Further, in the step b, the residence time of the low-temperature reaction section is 0.5-20 min, the heating time of the heating reaction section is 0.2-2 min, and the residence time of the high-temperature reaction section is 0.5-5 min.
Further, in the step b, the pressure of the oxidation reaction is 0.4MPa to 1.0MPa.
The invention avoids the generation of polymeric impurities by selecting the multistage oxidation reaction and controlling the temperature and time of each stage of reaction on the premise of ensuring full reaction, thereby improving the product quality and effectively reducing the influence of side reaction impurities on the crystallization process.
In the step b, firstly, introducing ferric chloride solution into a static mixer I, and then introducing the raw material liquid after 0.5-1 min.
Further, in the step b, the molar ratio of the 2- (1-chloro-cyclopropan-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane raw material to ferric chloride is 1:2-3.
Further, in the step b, the feeding speed of the ferric chloride solution is 0.5T/h-3T/h, and the feeding speed of the raw material liquid is 1T/h-5T/h.
The optimized material feeding sequence, feeding speed and material molar ratio are favorable for fully carrying out the oxidation reaction and reducing the generation of polymerization impurities.
Further, in the step c, the crystallization solvent is water.
Further, in the step c, the mass ratio of the crystallization solvent to the raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane is 2-4:1.
Further, in the step c, the residence time of the mixed material in the tubular reactor II is 0.5-2 min.
Further, in the step c, the feeding speed of the crystallization solvent is 2T/h-10T/h.
In the step c, the crystallization solvent is firstly introduced into a static mixer II, and the oxidation reaction liquid is then introduced after the oxidation reaction liquid is cooled to 30-40 ℃.
By controlling the feeding proportion, feeding speed and crystallization temperature of the materials in the crystallization process, the crystallization can be continuously and stably carried out, and the growth process of the prothioconazole crystals can be regulated and controlled, so that the uniform cubic prothioconazole is obtained, the quality of continuous crystallization products is ensured, and the particle size uniformity of the continuous crystallization products is improved.
Further, in the step d, the refining solvent is one or more of acetonitrile, tetrahydrofuran, acetone, methanol, ethanol, n-butanol, isopropanol, toluene, xylene or chlorobenzene.
Further, in the step d, the part of the refining solvent is 5% -20% of the total amount of the refining solvent.
Further, in the step d, the total amount of the refining solvent is 1 to 4 times of the mass of the raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane.
Further, in the step d, the residence time of the mixed material in the tubular reactor III is 0.5-2 min.
Further, in the step d, the refining reaction comprises a reduction reaction and an adsorption impurity removal process, and the temperature of the refining reaction is 20-30 ℃.
In combination with the above, the reducing agent used in the reduction reaction may be a substance having a reducing effect, which is conventional in the art, such as hydrogen, thiosulfate, hydrogenate, aluminum hydride, sulfite, borohydride, and the like.
The adsorption impurity removal can be one or more of activated carbon adsorption, chelating agent adsorption, resin adsorption or molecular sieve adsorption.
Further, in step e, the crystallization solvent is water.
Further, in the step e, the mass ratio of the crystallization solvent to the raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane is 2-4:1.
Further, in the step e, the residence time of the mixed material in the tubular reactor III is 0.5-2 min.
In step e, the crystallization solvent is introduced into the static mixer III, and then the refining reaction liquid is introduced.
The preferred refining and crystallization processes can further enhance the purity of the prothioconazole product.
Further, the method further comprises the following steps: and c, acidifying, oxidizing and extracting the crystallization mother liquor obtained by solid-liquid separation in the step c, filtering and concentrating the raffinate, and sleeving the obtained concentrated liquor back to the step a to be used as a raw material of the ferric chloride solution.
By combining the above, the filtrate is concentrated to the concentration of 30% -40% of ferric chloride, and the mixture is returned to serve as a raw material for synthesizing prothioconazole.
The ferric chloride is recycled, so that the production of dangerous waste is effectively reduced, the production cost of prothioconazole is effectively reduced, and the continuous prothioconazole production process provided by the invention is more in line with the development requirements of environmental protection, energy conservation and consumption reduction.
The present invention also provides a system for continuous production of prothioconazole, said system comprising: the system comprises a static mixer I, a tubular reactor I, a static mixer II, a tubular reactor II, a refining system, a static mixer III and a tubular reactor III which are connected in sequence;
wherein the static mixer I is provided with a feed inlet and a discharge outlet and is used for mixing 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
the tubular reactor I is a multi-stage tubular reactor and comprises a low-temperature reaction section, a heating reaction section and a high-temperature reaction section, and is used for carrying out oxidation reaction on 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
the static mixer II is provided with 2 feed inlets and is used for mixing the oxidation reaction liquid and the crystallization solvent;
the tubular reactor II is connected with the outlet material of the static mixer and is used for carrying out crystallization reaction on the oxidation reaction liquid to obtain a crude prothioconazole;
the refining system comprises a plurality of reaction tanks which are respectively used for sequentially carrying out dissolution, reduction reaction and adsorption impurity removal on crude prothioconazole obtained by crystallization in a tubular reactor II;
The static mixer III is provided with 2 feed inlets for mixing the refined reaction liquid and the crystallization solvent;
and the tubular reactor III is connected with a discharge port of the static mixer III and is used for carrying out crystallization reaction on the refined reaction liquid to obtain a prothioconazole product.
The system for continuously producing prothioconazole provided by the invention can effectively improve the yield and purity of prothioconazole products, and simultaneously greatly improve the purification efficiency and process safety, thereby having good economic benefits.
Further, a first centrifugal device, a crude product mother liquor tank and a crude product mother liquor refining system are arranged between the tubular reactor II and the refining system;
the first centrifugal device is used for carrying out solid-liquid separation on crystallization reaction liquid in the tubular reactor II to obtain crude prothioconazole and crude mother liquor;
the crude product mother liquor tank is connected with the outlet of the first centrifugal device and is used for storing crude product mother liquor;
the crude mother liquor refining system is connected with an outlet of the crude mother liquor tank and comprises an acidification tank, an oxidation tank and an extraction tank, and is used for refining the crude mother liquor to obtain refined mother liquor.
Further, a heat exchanger is arranged between the tubular reactor I and the static mixer II.
Further, the system also comprises a second centrifugal device, a refined mother liquid tank and a solvent recovery system which are sequentially connected with the tubular reactor III;
the second centrifugal device is used for carrying out solid-liquid separation on crystallization reaction liquid in the tubular reactor III to obtain prothioconazole products and refined mother liquor;
the refined mother liquor tank is connected with the outlet of the second centrifugal device and is used for storing refined mother liquor;
and the solvent recovery system is connected with the outlet of the refining mother liquor tank and is used for recovering the solvent in the refining mother liquor.
According to the method and the system for continuously producing the prothioconazole, provided by the invention, the tubular reactor is adopted for continuous oxidation and continuous crystallization operation, so that a cube-shaped prothioconazole product can be obtained, the purity of the product can be improved to more than 99%, the yield can be improved to more than 99%, the purity and the yield of the prothioconazole product are greatly improved, the quality stability of the product is higher, the particle size of the product is more uniform, and meanwhile, the process is high in automation degree, the labor intensity is reduced, and the influence of human factors such as the skill level of operators is reduced, so that the method and the system are suitable for large-scale production application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a process flow for continuously producing prothioconazole according to an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The following describes embodiments of the present invention in detail.
A method for continuously producing prothioconazole, which comprises the following steps:
step a, delivering the vinylene carbonate synthetic solution to a first scraper evaporator, heating and distilling to obtain a top material, and in the step a, respectively adding raw materials of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane and ferric chloride into a reaction solvent, and uniformly mixing to obtain raw material liquid and ferric chloride solution;
step b, continuously introducing the raw material liquid and the ferric chloride solution into a static mixer I respectively, uniformly mixing, and continuously introducing the mixed material into a tubular reactor I for oxidation reaction to obtain an oxidation reaction liquid;
step c, cooling the oxidation reaction liquid to 30-40 ℃, continuously introducing the cooled oxidation reaction liquid and a crystallization solvent into a static mixer II together, uniformly mixing, continuously introducing the mixed material into a tubular reactor II for crystallization, performing solid-liquid separation on the crystallized material liquid at the crystallization temperature of 20-30 ℃, and washing to obtain a prothioconazole crude product;
Step d, adding part of refining solvent into a refining system, and then continuously introducing the crude prothioconazole and the rest of refining solvent into the refining system at the same time for refining reaction to obtain refined reaction liquid;
and e, continuously introducing the refined reaction solution and the crystallization solvent into a static mixer III, uniformly mixing, continuously introducing the mixed material into a tubular reactor III, performing crystallization reaction, performing solid-liquid separation on the crystallized material solution at a crystallization temperature of 0-30 ℃, washing and drying to obtain the prothioconazole product.
The method for continuously producing prothioconazole provided by the embodiment of the invention can effectively improve the purity and yield of the product, has stable product characteristics and uniform particle size distribution, simultaneously reduces equipment investment and labor cost, reduces production energy consumption, has low production cost, almost does not generate three wastes in the production process, does not cause secondary pollution to the environment, and can be widely applied to large-scale production of prothioconazole products.
The embodiment of the invention also provides a system for continuously producing prothioconazole, which comprises: the system comprises a static mixer I, a tubular reactor I, a static mixer II, a tubular reactor II, a refining system, a static mixer III and a tubular reactor III which are connected in sequence;
Wherein the static mixer I is provided with a feed inlet and a discharge outlet and is used for mixing 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
the tubular reactor I is a multi-stage tubular reactor and comprises a low-temperature reaction section, a heating reaction section and a high-temperature reaction section, and is used for carrying out oxidation reaction on 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
the static mixer II is provided with 2 feed inlets and is used for mixing the oxidation reaction liquid and the crystallization solvent;
the tubular reactor II is connected with the outlet material of the static mixer and is used for carrying out crystallization reaction on the oxidation reaction liquid to obtain a crude prothioconazole;
the refining system comprises a plurality of reaction tanks which are respectively used for sequentially carrying out dissolution, reduction reaction and oxidation reaction on crude prothioconazole obtained by crystallization in the tubular reactor II;
the static mixer III is provided with 2 feed inlets for mixing the refined reaction liquid and the crystallization solvent;
and the tubular reactor III is connected with a discharge port of the static mixer III and is used for carrying out crystallization reaction on the refined reaction liquid to obtain a prothioconazole product.
The system for continuously producing prothioconazole provided by the invention has the advantages of simple equipment structure, high stability, high purification efficiency and good process safety, and can be widely applied to the production of prothioconazole.
In order to better illustrate the present invention, the following examples are provided for further illustration.
In the following examples and comparative examples 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazol-idine-5-thione-1-yl) -propane is abbreviated as starting material I.
Examples
Referring to fig. 1, the system for continuously producing prothioconazole adopted in the embodiment is formed by connecting a raw material I compounding tank, an iron chloride compounding tank, a static mixer I, an oxidation tube reactor I, a heat exchanger, a crystallization solvent storage tank, a static mixer II, a crystallization tube reactor II, a centrifugal fusion tank I, a centrifuge I, a crude mother liquor tank, a refining system, a static mixer III, a crystallization tube reactor III, a centrifugal fusion tank II, a centrifuge II, a dryer, a temperature control display system, a feed metering control system and related matched conveying equipment by using pipelines;
the metering pumps of the ferric chloride and the raw material I are respectively connected with the corresponding batching tanks, the outlets of the metering pumps are respectively connected with two feed inlets of the static mixer I through the mass flow regulation control system, the discharge outlet of the static mixer I is connected with the inlet of the oxidation tube reactor I, the outlet of the oxidation tube reactor I is connected with the inlet of the heat exchanger, and the outlet of the heat exchanger is connected with 1 feed inlet of the static mixer II; the metering pump of the crystallization solvent is connected with the crystallization solvent storage tank, and the outlet of the metering pump is connected with the other 1 feed inlet of the static mixer II through the mass flow rate adjusting and controlling system respectively; the outlet of the static mixer II is connected with the inlet of the crystallization tube reactor II, the outlet of the crystallization tube reactor II is connected with the centrifugal fusion tank I, the outlet of the centrifugal fusion tank I is connected with the centrifugal machine I, the centrifugal machine I is respectively connected with the refining system and the crude product mother liquor tank, the mother liquor in the crude product mother liquor tank is connected with the ferric chloride batching tank after being refined, the outlet of the refining system is connected with 1 feed inlet of the static mixer III, the outlet of the metering pump of the crystallization solvent is connected with the other 1 feed inlet of the static mixer III through the mass flow regulating and controlling system, the outlet of the static mixer III is connected with the crystallization tube reactor III, the crystallization tube reactor III is connected with the centrifugal fusion tank II, the outlet of the centrifugal fusion tank II is connected with the centrifugal machine II, and wet products are dried by the dryer to obtain prothioconazole finished products.
The refining system comprises a dissolving tank, a reduction reaction tank, a charging pump, a filtering device and a receiving tank. And each process node is provided with a temperature and pressure display and automatic regulation system.
The continuous prothioconazole production system comprises a low-temperature reaction section, a temperature-rising reaction section and a high-temperature reaction section, wherein the temperature of each section is controlled to be different, the reaction temperature of the low-temperature reaction section is controlled to be 20-30 ℃, the temperature-rising reaction section is controlled to gradually rise from 20-30 ℃ to 50-70 ℃ for reaction, and the reaction temperature of the high-temperature reaction section is controlled to be 50-70 ℃ for reaction.
Specifically, the method for continuously producing prothioconazole by adopting the system comprises the following steps:
step a, adding a reaction solvent into each group of proportioning tanks respectively for raw material I and ferric chloride, and uniformly mixing to obtain a raw material liquid with the mass concentration of 30-40% and a ferric chloride solution with the mass concentration of 40-75%;
step b, continuously introducing ferric chloride solution into a static mixer I by using a high-precision metering pump according to the feeding speed of 0.5-3T/h, feeding the ferric chloride solution for 0.5-1 min, then, driving raw material liquid into the static mixer I by using the high-precision metering pump according to the feeding speed of 1-5T/h, fully mixing, continuously introducing the mixed material into an oxidation tube reactor I for oxidation reaction, sampling and detecting that the raw material I is not detected, and obtaining an oxidation reaction liquid after reaching a reaction end point;
Wherein the temperature of the low-temperature reaction section of the tubular reactor is 20-30 ℃, the residence time is 0.5-20 min, the temperature of the heating reaction section is controlled to be increased from 20-30 ℃ to 50-70 ℃ within 0.2-2 min, the temperature of the high-temperature reaction section is controlled to be 50-70 ℃ and the residence time is 0.5-5 min;
continuously introducing crystallization solvent into a static mixer II by using a high-precision metering pump according to the feeding speed of 2T/h-10T/h, continuously introducing oxidation reaction liquid cooled to 30-40 ℃ into the static mixer II after the crystallization solvent is fed for 0.5-1 min, continuously introducing the mixed material into a tubular reactor II for crystallization after full mixing, maintaining the crystallization temperature at 20-30 ℃ and the retention time at 0.5-2 min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank I, continuously introducing the crystallized slurry in the centrifugal fusion tank I into a centrifuge I after the crystallized feed liquid in the centrifugal fusion tank I reaches a fixed volume, centrifugally filtering, washing, and obtaining a filter cake as a prothioconazole crude product;
step d, firstly adding 5% -20% of the total amount of refining solvents into a dissolving tank of a refining system, then continuously adding crude prothioconazole into the dissolving tank, simultaneously continuously adding the rest refining solvents, stirring to promote the dissolution of the crude prothioconazole, simultaneously continuously introducing the crude prothioconazole solution dissolved at the upper layer of the dissolving tank into a reduction reaction tank, continuously adding a reducing agent for reduction reaction, then introducing the reduction reaction solution at the upper layer of the reduction reaction tank into an adsorption impurity removal tank for continuous impurity removal, and maintaining the temperature of the refining reaction at 30-50 ℃ and the residence time at 5-30 min to obtain the refined reaction solution;
And e, continuously introducing the crystallization solvent and the refining reaction liquid into a static mixer III by using a high-precision metering pump, fully mixing, continuously introducing the mixed material into a tubular reactor III, performing crystallization reaction at a crystallization temperature of 0-30 ℃ for 0.5-20 min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank II, continuously introducing the crystallization slurry in the centrifugal fusion tank II into a centrifuge II after the crystallization slurry in the centrifugal fusion tank II reaches a fixed volume, centrifugally filtering, washing and drying to obtain the prothioconazole product.
The specific process conditions for examples 1-9 are shown in Table 1 below.
TABLE 1 Process conditions for examples 1-9
Comparative example 1
The comparative example provides a continuous production method of prothioconazole, comprising the following steps:
step a, adding a reaction solvent into each group of batching tanks respectively for raw material I and ferric chloride, and uniformly mixing to obtain raw material liquid with the mass concentration of 32.04% and ferric chloride solution with the mass concentration of 51.32%;
and b, continuously introducing ferric chloride solution into a static mixer by using a high-precision metering pump according to the feeding speed of 0.75T/h, feeding the ferric chloride solution into the static mixer for 0.5min, then introducing raw material liquid into the static mixer by using the high-precision metering pump according to the feeding speed of 2T/h, fully mixing, continuously introducing the mixed material into an oxidation tube reactor for oxidation reaction, wherein the oxidation tube reactor is a one-stage reactor, the temperature is kept at 25 ℃ in the reaction process, the residence time is 30min, the reaction pressure is 0.7MPa, the sampling and detection raw material I content is 1.36%, the prothioconazole content is 98.02%, and no reaction is completed, so that solid is separated out.
The subsequent steps c-e are the same as in example 4, and will not be described here again.
The content of the finally prepared prothioconazole product is 98.35%, the yield is 97.67%, and the particle size of the product is mainly 120-130 mu m.
Comparative example 2
The comparative example provides a continuous production method of prothioconazole, comprising the following steps:
step a, adding a reaction solvent into each group of proportioning tanks respectively for raw material I and ferric chloride, and uniformly mixing to obtain raw material liquid with the mass concentration of 32.06% and ferric chloride solution with the mass concentration of 50.41%;
and b, continuously introducing ferric chloride solution into a static mixer by using a high-precision metering pump according to the feeding speed of 0.75T/h, feeding the ferric chloride solution for 1min, then, introducing raw material liquid into the static mixer by using the high-precision metering pump according to the feeding speed of 2T/h, fully mixing, continuously introducing the mixed material into an oxidation tube reactor for oxidation reaction, wherein the oxidation tube reactor is a one-stage reactor, the constant temperature is 65 ℃ in the reaction process, the residence time is 10min, the reaction pressure is 0.7MPa, the sampling and detecting raw material I content is 0.031%, the prothioconazole content is 97.83%, the content of new impurities is 1.74%, the reaction is complete, no solid is separated out, and the color of the material liquid is slightly deep.
The subsequent steps c-e are the same as in example 4, and will not be described here again.
The content of the finally prepared prothioconazole product is 97.66%, the yield is 97.98%, the particle size of the product is mainly 150-170 mu m, but a small amount of small spherical solid is produced, the content of prothioconazole in the detected small spherical substance is 92.38%, and the content of polymeric impurities is 6.81%.
Comparative example 3
The comparative example provides a continuous production method of prothioconazole, comprising the following steps:
step a, adding a reaction solvent into each group of batching tanks respectively for raw material I and ferric chloride, and uniformly mixing to obtain raw material liquid with the mass concentration of 32.04% and ferric chloride solution with the mass concentration of 50.75%;
step b, continuously introducing ferric chloride solution into a static mixer by using a high-precision metering pump at a feeding speed of 0.75T/h, feeding the ferric chloride solution for 0.5min, then introducing raw material liquid into the static mixer by using the high-precision metering pump at a feeding speed of 1T/h, fully mixing, continuously introducing the mixed material into an oxidation tube reactor for oxidation reaction, sampling and detecting that the raw material I is not detected, the prothioconazole content of 99.06% reaches a reaction end point, and no solid is separated out, thus obtaining pale yellow oxidation reaction liquid;
Wherein the temperature of the low-temperature reaction section of the tubular reactor is 20-25 ℃, the residence time is 5min, the temperature of the heating reaction section is controlled to be raised from 20-25 ℃ to 55-60 ℃ within 1min, the temperature of the high-temperature reaction section is controlled to be 55-60 ℃, and the residence time is 5min;
step c, continuously introducing the oxidation reaction liquid into a tubular reactor, directly cooling to 5-10 ℃ for deep crystallization, maintaining the temperature at 5-10 ℃ in the crystallization process, introducing the crystallization reaction liquid into a centrifugal fusion tank for 2min, continuously introducing the crystallization slurry in the centrifugal fusion tank into a centrifuge after the crystallization slurry in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, washing, and obtaining a filter cake which is a crude prothioconazole product, wherein the coarse prothioconazole product has uneven granularity and large centrifugal filtering difficulty;
step d, firstly adding 5% of the total amount of refining solvent into a dissolving tank of a refining system, then continuously adding crude prothioconazole into the dissolving tank, simultaneously continuously adding the rest refining solvent, wherein the total amount of the refining solvent is 2.2 times of the mass of the raw material I, stirring to dissolve the crude prothioconazole, simultaneously continuously introducing the solution of the crude prothioconazole dissolved at the upper layer of the dissolving tank into a reduction reaction tank, continuously adding a reducing agent for reduction reaction, then introducing the reduction reaction solution at the upper layer of the reduction reaction tank into an adsorption impurity removal tank for continuous impurity removal, and maintaining the temperature of the refining reaction at 35 ℃ for 20min to obtain refined reaction solution;
And e, continuously introducing the refined reaction liquid into a tubular reactor by using a high-precision metering pump, performing crystallization reaction, wherein the crystallization temperature is 5-10 ℃, the residence time is 2min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifuge after the crystallized slurry in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, washing and drying to obtain the prothioconazole product.
The prepared prothioconazole product has the content of 99.16 percent, the yield of 98.98 percent, the particle size of the product is 20-500 mu m, the product is nonuniform in size and has no obvious crystal form, the product is in a powder amorphous state, the centrifugation time is long, and the dry and wet contents in the product are large.
Comparative example 4
The comparative example provides a continuous production method of prothioconazole, comprising the following steps:
step a and step b are the same as in example 4;
continuously introducing primary water into a static mixer by using a high-precision metering pump at a feeding speed of 2T/h, wherein the adding amount of the primary water is 2 times of the mass of the raw material I, continuously introducing oxidation reaction liquid cooled to 45 ℃ into the static mixer after 0.5min of feeding crystallization solvent, continuously introducing the mixed material into a tubular reactor for crystallization after full mixing, maintaining the crystallization temperature at 35 ℃ and the retention time at 2min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifuge after the crystallized feed liquid in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, and washing to obtain a filter cake, namely a prothioconazole crude product; the crude prothioconazole is in a fine powder form, is amorphous, has large centrifugal filtration load, and has a wet product drying weight loss of more than 30 percent;
Step d, firstly adding 5% of the total amount of refining solvent into a dissolving tank of a refining system, then continuously adding crude prothioconazole into the dissolving tank, simultaneously continuously adding the rest refining solvent, wherein the total amount of the refining solvent is 2.2 times of the mass of the raw material I, stirring to dissolve the crude prothioconazole, simultaneously continuously introducing the solution of the crude prothioconazole dissolved at the upper layer of the dissolving tank into a reduction reaction tank, continuously adding a reducing agent for reduction reaction, then introducing the reduction reaction solution at the upper layer of the reduction reaction tank into an adsorption impurity removal tank for continuous impurity removal, and maintaining the temperature of the refining reaction at 35 ℃ for 20min to obtain the refined reaction solution;
and e, continuously introducing primary water and refined reaction liquid into a static mixer by using a high-precision metering pump, fully mixing, continuously introducing the mixed material into a tubular reactor for crystallization reaction, continuously introducing the crystallized feed liquid into a centrifugal fusion tank at a crystallization temperature of 35 ℃ for 2min, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifugal machine II after the crystallized slurry in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, washing and drying to obtain the prothioconazole product.
The content of the prothioconazole product is 98.76%, the yield is 97.83%, the particle size of the product is 5-100 mu m, the product is uneven in size, no obvious crystal form exists, the product is fine powder, the product is amorphous, the centrifugal filtration load is large, the centrifugal time is long, the dry and wet content in the product reaches 34.16%, and the drying energy consumption is high.
Comparative example 5
The comparative example provides a batch production method of prothioconazole, comprising the following steps:
step a and step b are the same as in example 4;
step c, directly adding primary water into a crystallization kettle, wherein the adding amount of the primary water is 2 times of the mass of the raw material I, adding an oxidation reaction liquid cooled to 35 ℃ into the crystallization kettle, maintaining the temperature of the crystallization kettle at 25 ℃, crystallizing for 30min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifuge after the crystallized feed liquid in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, and washing to obtain a filter cake, namely a prothioconazole crude product; the crude prothioconazole has uneven granularity and agglomeration phenomenon;
step d, adding a refining solvent into a dissolving tank of a refining system, continuously adding a crude prothioconazole product into the dissolving tank, wherein the total amount of the refining solvent is 2.2 times of the mass of the raw material I, stirring to dissolve the crude prothioconazole product, continuously introducing a solution of the crude prothioconazole product dissolved in the upper layer of the dissolving tank into a reduction reaction tank, continuously adding a reducing agent for reduction reaction, and then introducing a reduction reaction solution in the upper layer of the reduction reaction tank into an adsorption impurity removal tank for continuous impurity removal, wherein the temperature of the refining reaction is maintained at 35 ℃, and the retention time is 20min to obtain a refined reaction solution;
And e, directly adding primary water into a crystallization kettle, wherein the adding amount of the primary water is 2 times of the mass of the raw material I, then adding refined reaction liquid into the crystallization kettle, controlling the temperature of the crystallization kettle to be 25 ℃, keeping the temperature for 30min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifugal machine II after the crystallized slurry in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, washing and drying to obtain the prothioconazole product.
The content of the prothioconazole product prepared is 99.34%, the yield is 97.59%, the particle size of the product is 50-2400 mu m, the product is uneven in size and has the agglomeration phenomenon, the product is in an irregular cubic crystal form, the dry and wet contents of the product are uneven, the dry and wet contents of the product are low and can reach 18.14%.
Comparative example 6
The comparative example provides a batch production method of prothioconazole, comprising the following steps:
step a and step b are the same as in example 4;
step c, directly adding oxidation reaction liquid into a crystallization kettle, adding primary water into the crystallization kettle, wherein the adding amount of the primary water is 2 times of the mass of the raw material I, maintaining the temperature of the crystallization kettle at 25 ℃, maintaining the crystallization heat preservation time at 30min, continuously introducing the crystallized liquid into a centrifugal fusion tank, continuously introducing crystallization slurry in the centrifugal fusion tank into a centrifuge after the crystallized liquid in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, and washing to obtain a filter cake which is a prothioconazole crude product; the crude prothioconazole has the advantages of uneasy crystallization, particles, powder, uneven particle size and partial adhesion and balling;
Step d, adding a refining solvent into a dissolving tank of a refining system, continuously adding a crude prothioconazole product into the dissolving tank, wherein the total amount of the refining solvent is 2.2 times of the mass of the raw material I, stirring to dissolve the crude prothioconazole product, continuously introducing a solution of the crude prothioconazole product dissolved in the upper layer of the dissolving tank into a reduction reaction tank, continuously adding a reducing agent for reduction reaction, and then introducing a reduction reaction solution in the upper layer of the reduction reaction tank into an adsorption impurity removal tank for continuous impurity removal, wherein the temperature of the refining reaction is maintained at 35 ℃, and the retention time is 20min to obtain a refined reaction solution;
and e, directly adding refined reaction liquid into a crystallization kettle, adding primary water into the crystallization kettle, controlling the temperature of the crystallization kettle to be 25 ℃ and the heat preservation crystallization time to be 30min, continuously introducing the crystallized feed liquid into a centrifugal fusion tank, continuously introducing the crystallized slurry in the centrifugal fusion tank into a centrifugal machine II after the crystallized slurry in the centrifugal fusion tank reaches a fixed volume, centrifugally filtering, washing and drying to obtain the prothioconazole product.
The content of the prepared prothioconazole product is 98.42%, the yield is 98.47%, the particle size of the product is 20-2400 mu m, the size is uneven, the crystal forms are different, the crystal forms are small spheres, the crystal forms are irregular cubes, the crystal forms are also powdery, the product is uneven in dry and wet, the dry and wet content in the product is low and can reach 20.32%.
In conclusion, the method for continuously producing prothioconazole provided by the invention has the advantages of less equipment investment, high production efficiency, high purity of the produced prothioconazole product up to more than 99%, high yield up to more than 99%, stable product quality, uniform product particle size, suitability for industrial and continuous production, capability of remarkably improving the market competitiveness of enterprises and wide application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A method for continuously producing prothioconazole, which is characterized in that the method comprises the following steps:
step a, respectively adding a raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane and ferric chloride into a reaction solvent, and uniformly mixing to obtain a raw material liquid and a ferric chloride solution;
step b, continuously introducing the raw material liquid and the ferric chloride solution into a static mixer I respectively, uniformly mixing, and continuously introducing the mixed material into a tubular reactor I for oxidation reaction to obtain an oxidation reaction liquid;
Step c, cooling the oxidation reaction liquid to 30-40 ℃, continuously introducing the cooled oxidation reaction liquid and a crystallization solvent into a static mixer II together, uniformly mixing, continuously introducing the mixed material into a tubular reactor II for crystallization, performing solid-liquid separation on the crystallized material liquid at the crystallization temperature of 20-30 ℃, and washing to obtain a prothioconazole crude product;
step d, adding part of refining solvent into a refining system, and then continuously adding the crude prothioconazole and the rest of refining solvent into the refining system at the same time for refining reaction to obtain refined reaction liquid;
step e, continuously introducing the refined reaction solution and the crystallization solvent into a static mixer III, uniformly mixing, continuously introducing the mixed material into a tubular reactor III, performing crystallization reaction, performing solid-liquid separation on the crystallized material solution at a crystallization temperature of 0-30 ℃, washing and drying to obtain a prothioconazole product;
in the step b, the tubular reactor I is a multi-stage reactor and comprises a low-temperature reaction section, a heating reaction section and a high-temperature reaction section; the temperature of the low-temperature reaction section is 20-30 ℃, the temperature of the heating reaction section is raised from 20-30 ℃ to 50-70 ℃, and the temperature of the high-temperature reaction section is 50-70 ℃.
2. The method for continuously producing prothioconazole according to claim 1, wherein in step a, said reaction solvent is one or more of acetonitrile, tetrahydrofuran, acetone, methanol, ethanol, n-butanol, isopropanol, and water; and/or
In the step a, the mass concentration of the raw material liquid is 30% -40%, and the mass concentration of the ferric chloride solution is 40% -75%.
3. The method for continuously producing prothioconazole according to claim 1, wherein in step b, the residence time of said low temperature reaction section is 0.5 min-20 min, the temperature rise time of said temperature rise reaction section is 0.2 min-2 min, and the residence time of said high temperature reaction section is 0.5 min-5 min; and/or
In the step b, firstly, introducing ferric chloride solution into a static mixer I, and then introducing the raw material liquid after 0.5-1 min; and/or
In the step b, the feeding speed of the ferric chloride solution is 0.5T/h-3T/h, and the feeding speed of the raw material liquid is 1T/h-5T/h.
4. The method for continuously producing prothioconazole according to claim 1, wherein in step c, said crystallization solvent is water; and/or
In the step c, the residence time of the mixed material in the tubular reactor II is 0.5-2 min; and/or
In the step c, the feeding speed of the crystallization solvent is 2T/h-10T/h; and/or
In the step c, the crystallization solvent is firstly introduced into a static mixer II, and the oxidation reaction liquid is then introduced after the oxidation reaction liquid is cooled to 30-40 ℃.
5. The method for continuously producing prothioconazole according to claim 1, wherein in step d, said refining solvent is one or more of acetonitrile, tetrahydrofuran, acetone, methanol, ethanol, n-butanol, isopropanol, toluene, xylene, and chlorobenzene; and/or
In the step d, the part of the refining solvent is 5% -20% of the total amount of the refining solvent; and/or
In the step d, the total amount of the refining solvent is 1 to 4 times of the mass of the raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thioketone-1-yl) -propane; and/or
In the step d, the residence time of the mixed material in the tubular reactor III is 0.5-2 min; and/or
In the step d, the refining reaction comprises a reduction reaction and an adsorption impurity removal process, and the temperature of the refining reaction is 20-30 ℃.
6. The method for continuously producing prothioconazole according to claim 1, wherein in step e, said crystallization solvent is water; and/or
In the step e, the mass ratio of the crystallization solvent to the raw material of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane is 2-4:1; and/or
In the step e, the residence time of the mixed material in the tubular reactor III is 0.5-2 min;
in the step e, the crystallization solvent is firstly introduced into a static mixer III, and then the refining reaction liquid is introduced.
7. The method for continuously producing prothioconazole according to claim 1, further comprising: and c, acidifying, oxidizing and extracting the crystallization mother liquor obtained by solid-liquid separation in the step c, filtering and concentrating the raffinate, and sleeving the obtained concentrated liquor back to the step a to be used as a raw material of the ferric chloride solution.
8. A system for a process for the continuous production of prothioconazole according to any one of claims 1 to 7, wherein said system comprises a static mixer i, a tubular reactor i, a static mixer ii, a tubular reactor ii, a refining system, a static mixer iii and a tubular reactor iii, which are connected in sequence;
wherein the static mixer I is provided with a feed inlet and a discharge outlet and is used for mixing 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
The tubular reactor I is a multi-stage tubular reactor and comprises a low-temperature reaction section, a heating reaction section and a high-temperature reaction section, and is used for carrying out oxidation reaction on 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolidine-5-thione-1-yl) -propane feed liquid and ferric chloride solution;
the static mixer II is provided with 2 feed inlets and is used for mixing the oxidation reaction liquid and the crystallization solvent;
the tubular reactor II is connected with the outlet material of the static mixer and is used for carrying out crystallization reaction on the oxidation reaction liquid to obtain a crude prothioconazole;
the refining system comprises a plurality of reaction tanks which are respectively used for sequentially carrying out dissolution, reduction reaction and oxidation reaction on crude prothioconazole obtained by crystallization in the tubular reactor II;
the static mixer III is provided with 2 feed inlets for mixing the refined reaction liquid and the crystallization solvent;
and the tubular reactor III is connected with a discharge port of the static mixer III and is used for carrying out crystallization reaction on the refined reaction liquid to obtain a prothioconazole product.
9. The system of claim 8, wherein a first centrifugal device, a crude mother liquor tank and a crude mother liquor refining system are arranged between the tubular reactor II and the refining system;
The first centrifugal device is used for carrying out solid-liquid separation on crystallization reaction liquid in the tubular reactor II to obtain crude prothioconazole and crude mother liquor;
the crude product mother liquor tank is connected with the outlet of the first centrifugal device and is used for storing crude product mother liquor;
the crude mother liquor refining system is connected with an outlet of the crude mother liquor tank and comprises an acidification tank, an oxidation tank and an extraction tank, and is used for refining the crude mother liquor to obtain refined mother liquor.
10. The system of claim 8, further comprising a second centrifuge, a refining mother liquor tank, and a solvent recovery system connected in sequence to the tubular reactor iii;
the second centrifugal device is used for carrying out solid-liquid separation on crystallization reaction liquid in the tubular reactor III to obtain prothioconazole products and refined mother liquor;
the refined mother liquor tank is connected with the outlet of the second centrifugal device and is used for storing refined mother liquor;
and the solvent recovery system is connected with the outlet of the refining mother liquor tank and is used for recovering the solvent in the refining mother liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311294054.9A CN117362244A (en) | 2023-10-08 | 2023-10-08 | Method and system for continuously producing prothioconazole |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311294054.9A CN117362244A (en) | 2023-10-08 | 2023-10-08 | Method and system for continuously producing prothioconazole |
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| Publication Number | Publication Date |
|---|---|
| CN117362244A true CN117362244A (en) | 2024-01-09 |
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| CN202311294054.9A Pending CN117362244A (en) | 2023-10-08 | 2023-10-08 | Method and system for continuously producing prothioconazole |
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| Country | Link |
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| CN (1) | CN117362244A (en) |
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