CN105218450A - A kind of green production process of pyraclostrobin - Google Patents
A kind of green production process of pyraclostrobin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
Abstract
The invention provides a kind of green production process of pyraclostrobin.Described technological operation is simple, production process Green-pollution thing discharges, the recyclable recycling of solvent for use, product yield is high, effective reduction production cost, energy-saving and cost-reducing, gained pyraclostrobin content is high, crystal formation can be combined to form fungicidal composition with various sterilization agent well, and sterilization effect significantly and can not harm the crops.
Description
Technical field
The present invention relates to a kind of green production process of pyraclostrobin.
Background technology
Pyraclostrobin is a kind of methoxy acrylic new type bactericide, and be New-type wide-spectrum sterilant, the mechanism of action is mitochondrial respiratory inhibitor, makes plastosome can not produce and provide energy needed for cell eubolism, finally causes necrocytosis.
It can suppress fungus-caused most of diseases such as crop Ascomycetes, Basidiomycetes, deuteromycetes, Oomycete.There is very strong restraining effect to the growth of spore germination and mycelia, there is protection and therapeutic activity.Have perviousness and local systemic activity, the lasting period is long, resistance of rainwater washing against.Be widely used in preventing and treating the disease on wheat, paddy rice, peanut, grape, vegetables, potato, banana, lemon, coffee, fruit tree, walnut, tea tree, tobacco and ornamental plant, lawn and other field crop.
This sterilant not only toxicity is low, to non-target organism safety, and to user and environment all safety close friends, is classified as " Candidate Agents reducing risk " by U.S. EPA Environmental Protection Agency.
Pyraclostrobin can produce positive physiological regulatory action to crop, the generation of its energy ethene suppressing, crop can be helped like this to have longer time deposit bio-energy to guarantee ripening degree, can significantly improve the activity of the restore nitrification enzyme of crop.
Pyraclostrobin missible oil shows there is good prevention effect to powdery mildew of cucumber, oidium and banana freckle, leaf spot, sclerotium disease etc. through field control effectiveness test result.Prevent and treat powdery mildew of cucumber, the dosage of oidium is effective constituent 75 ~ 150g/hm
2(being converted into missible oil commodity amount is 20-40mL/667m
2).In their early stage even spraying after thin up. general spray medicine 3 ~ 4 times. interval 7d sprays 1 medicine.The effective constituent concentration of control banana freckle, leaf spot is 83.3-250mg/kg (extension rate is 1000-3000 times), starts spraying in their early stage. general spray medicine 3 times, interval 10d sprays 1 medicine.Spray medicine number of times is depending on the state of an illness.To cucumber, banana safety, have no poisoning and occur.
But, the production technique of current pyraclostrobin, production technology patent are mainly the large-size chemical companies such as America and Europe and hold, also Patents has been applied at home, define exclusive to the production and selling of domestic pyraclostrobin, for breaking the monopolization that American-European company produces domestic pyraclostrobin, also in the production technique of research and development pyraclostrobin, to this, mainly there is following patent documentation in current domestic manufacturer:
China Patent Publication No.: CN104592117A, a kind of synthetic method of pyraclostrobin is provided, the method is for raw material with p-Chlorobenzoic acid amide and Ortho Nitro Toluene, pyraclostrobin is prepared by synthesis, cyclization, oxidation, bromination, etherificate, reduction, the esterification of p-hydrochloride and the eight steps reactions that methylate, the purity of the pyraclostrobin of this method synthesis is more than 98.0%, and yield can reach 48%.Simultaneously to have production cost low for technique, grasps with easy and be easy to the features such as suitability for industrialized production.But this patent, in synthesizing pyrazole kresoxim-methyl process, have employed a large amount of additives, such as catalyzer, initiator, bromide reagent etc., these reagent not friendly to the environments, can bring pollution in the process of reproduction, therefore need a kind of green production process of pyrazoles Azoxystrobin.
Summary of the invention
For solving above-mentioned Problems existing, the object of the present invention is to provide a kind of green production process of pyraclostrobin, described technological operation is simple, production process green non-pollution thing discharges, the recyclable recycling of solvent for use, and product yield is high, effective reduction production cost, energy-saving and cost-reducing, gained pyraclostrobin content is high, crystal formation can be combined to form fungicidal composition with various sterilization agent well, and sterilization effect significantly and can not harm the crops.
For achieving the above object, technical scheme of the present invention is:
A green production process for pyraclostrobin, comprises the steps:
1) 1200 ~ 1250kg tetrahydrofuran solution is added in reactor, stir 10 ~ 20 minutes, sampling detects the content of tetrahydrofuran (THF) in solution, content >=95% is qualified, after qualified, 3-(2-oil of mirbane methoxyl group is added while stirring in reactor)-1-(4-chloro-phenyl-)-1H-pyrazoles 300 ~ 400kg, add hydrazine hydrate 15 ~ 20kg simultaneously, reactor temperature drops to less than 0 DEG C, in reactor, slowly, at the uniform velocity add Raney's nickel 10 ~ 20kg, now reactor temperature rises to 5 DEG C automatically;
2) cool to 0 DEG C, slowly, at the uniform velocity drip hydrazine hydrate 145 ~ 150kg, drip and terminate rear insulation, keep reactor temperature≤5 DEG C, in question response still material molten clear after, middle control sampling analysis, middle control content >=95%, raw material≤0.5% is qualified;
3) step 2) after sampling analysis is qualified, at the temperature of≤2 DEG C, drip the vitriol oil 20 ~ 30kg, adjust ph, to slightly acidic, at the uniform velocity adds sodium bicarbonate 170 ~ 180kg;
4)-5 ~ 5 DEG C are cooled to, methyl-chloroformate 130 ~ 140kg is dripped in reactor, dropwise rear insulation 1.5 ~ 2.5 hours, sampling analysis, raw material peak area is less than 0.5% for qualified, and qualified rear suction filtration, obtains filter residue and filtrate, filter residue 200 ~ 300kg tetrahydrofuran (THF) divides secondary washing by soaking, filters to get filtrate; Filter residue is next after drying to feed intake as sodium bicarbonate;
5) merge suction filtration gained filtrate and tetrahydrofuran (THF) immersion filtration gained filtrate, carry out negative pressure and stir distillation, add toluene 850 ~ 950kg after steaming tetrahydrofuran (THF), be warming up to 90 ~ 100 DEG C, all dissolve to toluene, stir insulation 0.5 ~ 1.5 hour;
6) proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, use chilled brine crystallisation by cooling, when crystallization temperature in the kettle is down to 0 ~ 5 DEG C, be incubated 8 ~ 10 hours, suction filtration, centrifugal, dry intermediate siccative 300 ~ 350kg, control dry weight in wet base≤0.5%;
7) toluenic mother liquor after centrifugal proceeds to precipitation still, negative pressure boils off the solvent of 60 ~ 70%, distillation adopts twin-stage refrigated cooling, cooling fluid adopts the chilled brine at 20 DEG C, family, guarantee that the rate of recovery of solvent reaches 100%, crystallisation by cooling is centrifugal obtains crude intermediate, is seconds, by this crude intermediate and step 6) middle gained intermediate siccative merging, purify;
8) ethylene dichloride 2200 ~ 2300kg is dropped in reactor, drop into step 7) purify after intermediate 250 ~ 350kg, stir, steam heats up, carry out a point water when temperature reaches 75 ~ 83 DEG C, ethylene dichloride is back in reactor, and water separates from upper strata, till the ethylene dichloride of backflow becomes clearly by muddiness, moisture content≤0.2% in still is surveyed in sampling;
9) cool to 40 ~ 50 DEG C, add powder salt of wormwood 100 ~ 200kg, stir 25 ~ 35 minutes, drip methyl-sulfate 110 ~ 115kg, time for adding 0.5 ~ 1 hour, dropwises and is warming up to 55 ~ 60 DEG C, be incubated after 2 ~ 4 hours and sample, sample intermediate peak area is less than 0.5% for qualified;
10) add water after qualified 700 ~ 800kg, is warming up to 70 ~ 75 DEG C of insulation backflows 0.5 ~ 1.5 hour, is cooled to 40 ~ 50 DEG C, leave standstill 20 ~ 40 minutes, layering, branch vibration layer, oil reservoir continues the 700 ~ 800kg that adds water, and stirs 20 ~ 40 minutes, leaves standstill 20 ~ 40 minutes, branch vibration layer, now water layer pH value is neutral, and merge the absorption water of secondary water layer as tail gas absorber, oil reservoir proceeds to precipitation still and carries out negative pressure precipitation, steam is warming up to≤and 80 DEG C, continue to vacuumize 1 hour without during backflow at 80 DEG C;
11) steam off stops after 10 ~ 20 minutes vacuumizing, and adds Virahol 500 ~ 600kg, be stirred to entirely molten after proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, cool to 5 ~ 10 DEG C, stir 1 hour, blowing suction filtration, centrifugal, dry, control dry weight in wet base≤0.5%, after pulverizing, packaging, obtains described pyraclostrobin 270 ~ 280kg;
12) suction filtration gained filtrate proceeds in freezing kettle and continues deep cooling and fold part pyraclostrobin, and solvent carries out precipitation recovery.
Further, step 1) described in Raney's nickel added in 25 ~ 35 minutes.
Separately, step 2) described in hydrazine hydrate within 4.5 ~ 5.5 hours, drip off.
Separately have, step 3) in add adjust ph to 6 ~ 7 after the vitriol oil, and stir pH value after 1 hour and remain unchanged.
Again, step 4) described in the dropping temperature of methyl-chloroformate be-2 ~ 2 DEG C, time for adding 1 ~ 3 hour.
Further, step 4) in after sampling analysis, as defective, and after 1 hour, sampling analysis is still defective, adds the methyl-chloroformate of 1 ~ 1.5kg, until sampling analysis is qualified.
And, step 5) middle distillation employing twin-stage refrigated cooling, cooling fluid adopts the chilled brine at-20 DEG C, family, guarantees that the rate of recovery of solvent reaches 100%.
Separately, step 6) and step 11) described in drying course all dry in air draft baking oven, air draft oven temperature≤70 DEG C, air draft baking oven uses negative pressure recycling design, guarantees that whole solvent recuperation uses.
Beneficial effect of the present invention is:
Raney's nickel consumption is only 15 ~ 20kg, far below Raney's nickel consumption in existing technique, effectively reduces process costs; Step 6) and step 11) described in process of cooling all adopt level Four to cool, be incubated respectively at various level temperature, guarantee that the crystal formation of product is 4# crystal formation, meet the needs of downstream preparation processing; Described technological operation is simple, production process green non-pollution, the recyclable recycling of solvent for use, effective reduction production cost, energy-saving and cost-reducing, gained pyraclostrobin can be combined to form fungicidal composition with various sterilization agent, and sterilization effect significantly and can not harm the crops.Gained pyraclostrobin purity is more than 98%, and yield is up to 60 ~ 70%.
Embodiment
Following examples for illustration of the present invention, but can not be used for limiting the scope of the invention.The implementation condition adopted in embodiment can be for further adjustments according to the condition of producer, and unaccounted implementation condition is generally conventional laboratory conditions.
Details are as follows for the specific embodiment of the green production process of a kind of pyraclostrobin of the present invention:
1) 1220kg tetrahydrofuran solution is added in 3000L reactor, stir 15 minutes, sampling detects the content of tetrahydrofuran (THF) in solution, content >=95% is qualified, after qualified, 3-(2-oil of mirbane methoxyl group is added while stirring in reactor)-1-(4-chloro-phenyl-)-1H-pyrazoles 350kg, add hydrazine hydrate 16kg simultaneously, reactor temperature drops to less than 0 DEG C, slowly, at the uniform velocity Raney's nickel 16kg is added in reactor, 30min adds, and now reactor temperature rises to 5 DEG C automatically, heating-up time 30min;
2) cool to 0 DEG C, slowly, at the uniform velocity drip hydrazine hydrate 147kg, time for adding 5 hours, drip and terminate rear insulation, keep reactor temperature≤5 DEG C, in question response still material molten clear after, middle control sampling analysis, middle control content >=95%, raw material≤0.5% is qualified; As defective, then continue insulation;
3) step 2) after sampling analysis is qualified, at the temperature of≤2 DEG C, drip vitriol oil 25kg, adjust ph to 6 ~ 7, and stir pH value after 1 hour and remain unchanged, consumption is few, discharge reduction.At the uniform velocity add sodium bicarbonate 175kg;
4) 0 DEG C is cooled to, methyl-chloroformate 133kg is dripped in reactor, dropping temperature is-2 ~ 2 DEG C, time for adding 2 hours, dropwises rear insulation 2 hours, sampling analysis, raw material peak area is less than 0.5% for qualified, and as defective, and after 1 hour, sampling analysis is still defective, add the methyl-chloroformate of 1.5kg, until sampling analysis is qualified; Qualified rear suction filtration, obtains filter residue and filtrate, and filter residue 200 ~ 300kg tetrahydrofuran (THF) divides secondary washing by soaking, filters to get filtrate; Filter residue is next after drying to feed intake as sodium bicarbonate;
5) suction filtration gained filtrate and tetrahydrofuran (THF) immersion filtration gained filtrate is merged, carry out negative pressure and stir distillation, twin-stage refrigated cooling is adopted in still-process, cooling fluid adopts the chilled brine at-20 DEG C, family, guarantee that the rate of recovery of solvent reaches 100%, after steaming tetrahydrofuran (THF), add toluene 900kg, be warming up to 95 DEG C, all dissolve to toluene, stir insulation 1 hour;
6) proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, use chilled brine crystallisation by cooling, when crystallization temperature in the kettle is down to 0 ~ 5 DEG C, be incubated 8 ~ 10 hours, suction filtration, centrifugal, dry intermediate siccative 350kg, control dry weight in wet base 0.5%(drying course to dry in air draft baking oven, air draft oven temperature≤70 DEG C, air draft baking oven uses negative pressure recycling design, guarantees that whole solvent recuperation uses);
7) toluenic mother liquor after centrifugal proceeds to precipitation still, negative pressure boils off the solvent of 60 ~ 70%, distillation adopts twin-stage refrigated cooling, cooling fluid adopts the chilled brine at 20 DEG C, family, guarantee that the rate of recovery of solvent reaches 100%, crystallisation by cooling is centrifugal obtains crude intermediate, is seconds, by this crude intermediate and step 6) middle gained intermediate siccative merging, purify;
8) ethylene dichloride 2250kg is dropped in 3000L reactor, drop into step 7) purify after intermediate 300kg, stir, steam heats up, carry out a point water when temperature reaches 75 ~ 83 DEG C, ethylene dichloride is back in reactor, and water separates from upper strata, till the ethylene dichloride of backflow becomes clearly by muddiness, moisture content≤0.2% in still is surveyed in sampling;
9) cool to 40 ~ 50 DEG C, add powder salt of wormwood 150kg, stir 30 minutes, drip methyl-sulfate 112.5kg, time for adding 0.5 ~ 1 hour, dropwises and is warming up to 55 ~ 60 DEG C, be incubated after 3 hours and sample, sample intermediate peak area is less than 0.5% for qualified; Defective continuation insulation, until qualified;
10) add water after qualified 750kg, is warming up to 70 ~ 75 DEG C of insulation backflows 1 hour, is cooled to 45 DEG C, leave standstill 30 minutes, layering, branch vibration layer, oil reservoir continues the 750kg that adds water, and stirs 30 minutes, leaves standstill 30 minutes, branch vibration layer, now water layer pH value is neutral, and merge the absorption water of secondary water layer as tail gas absorber, oil reservoir proceeds to precipitation still and carries out negative pressure precipitation, steam is warming up to≤and 80 DEG C, continue to vacuumize 1 hour without during backflow at 80 DEG C;
11) steam off stops after 15 minutes vacuumizing, and adds Virahol 550kg, be stirred to entirely molten after proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, cool to 5 ~ 10 DEG C, stir 1 hour, blowing suction filtration, centrifugal, dry, control dry weight in wet base≤0.5% drying course to dry in air draft baking oven, air draft oven temperature≤70 DEG C, air draft baking oven uses negative pressure recycling design, guarantees that whole solvent recuperation uses), after pulverizing, packaging, obtains described pyraclostrobin 270 ~ 280kg;
Suction filtration gained filtrate proceeds in freezing kettle continues deep cooling and folds part pyraclostrobin, and solvent carries out precipitation recovery.
The pyraclostrobin that the present invention produces and antimicrobial combination form fungicidal composition, form synergy, be applicable to the crop pest of preventing and treating Cereal, various melon and fruit, vegetables, particularly prevent and treat the crop pests such as paddy rice, wheat, barley, capsicum, banana, mango, pineapple, cucumber, tomato, as wheat rust, wheat powdery mildew, large wheat rust, wheat net blotch, capsicum epidemic disease, wheat leaf blight, leaf spot of peanut etc.Fungicidal composition of the present invention has good prevention effect to ascomycetes, basidiomycetes, imperfect fungi and Oomycete fungal disease; Significant effect is all had in the application of control rust, Powdery Mildew, leaf spot, net blotch, reticulate pattern disease, glume blight, leaf blight, black spot, epidemic disease.Above-mentioned fungicidal composition can produce higher synergistic function, and activity is greater than the activity of independent component.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (8)
1. a green production process for pyraclostrobin, is characterized in that, comprises the steps:
1200 ~ 1250kg tetrahydrofuran solution is added in reactor, stir 10 ~ 20 minutes, sampling detects the content of tetrahydrofuran (THF) in solution, content >=95% is qualified, after qualified, adds 3-(2-oil of mirbane methoxyl group while stirring in reactor)-1-(4-chloro-phenyl-)-1H-pyrazoles 300 ~ 400kg, add hydrazine hydrate 15 ~ 20kg simultaneously, reactor temperature drops to less than 0 DEG C, in reactor, slowly, at the uniform velocity add Raney's nickel 10 ~ 20kg, and now reactor temperature rises to 5 DEG C automatically;
Cool to 0 DEG C, slowly, at the uniform velocity drip hydrazine hydrate 145 ~ 150kg, drip and terminate rear insulation, keep reactor temperature≤5 DEG C, in question response still material molten clear after, middle control sampling analysis, middle control content >=95%, raw material≤0.5% is qualified;
Step 2) after sampling analysis is qualified, at the temperature of≤2 DEG C, drip the vitriol oil 20 ~ 30kg, adjust ph, to slightly acidic, at the uniform velocity adds sodium bicarbonate 170 ~ 180kg;
Cool to-5 ~ 5 DEG C, methyl-chloroformate 130 ~ 140kg is dripped in reactor, dropwise rear insulation 1.5 ~ 2.5 hours, sampling analysis, raw material peak area is less than 0.5% for qualified, and qualified rear suction filtration, obtains filter residue and filtrate, filter residue 200 ~ 300kg tetrahydrofuran (THF) divides secondary washing by soaking, filters to get filtrate; Filter residue is next after drying to feed intake as sodium bicarbonate;
Merge suction filtration gained filtrate and tetrahydrofuran (THF) immersion filtration gained filtrate, carry out negative pressure and stir distillation, add toluene 850 ~ 950kg after steaming tetrahydrofuran (THF), be warming up to 90 ~ 100 DEG C, all dissolve to toluene, stir insulation 0.5 ~ 1.5 hour;
Proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, use chilled brine crystallisation by cooling, when crystallization temperature in the kettle is down to 0 ~ 5 DEG C, be incubated 8 ~ 10 hours, suction filtration, centrifugal, dry intermediate siccative 300 ~ 350kg, control dry weight in wet base≤0.5%;
Toluenic mother liquor after centrifugal proceeds to precipitation still, negative pressure boils off the solvent of 60 ~ 70%, distillation adopts twin-stage refrigated cooling, cooling fluid adopts the chilled brine at 20 DEG C, family, guarantee that the rate of recovery of solvent reaches 100%, crystallisation by cooling is centrifugal obtains crude intermediate, is seconds, by this crude intermediate and step 6) middle gained intermediate siccative merging, purify;
Ethylene dichloride 2200 ~ 2300kg is dropped in reactor, drop into step 7) purify after intermediate 250 ~ 350kg, stir, steam heats up, carry out a point water when temperature reaches 75 ~ 83 DEG C, ethylene dichloride is back in reactor, and water separates from upper strata, till the ethylene dichloride of backflow becomes clearly by muddiness, moisture content≤0.2% in still is surveyed in sampling;
Cool to 40 ~ 50 DEG C, add powder salt of wormwood 100 ~ 200kg, stir 25 ~ 35 minutes, drip methyl-sulfate 110 ~ 115kg, time for adding 0.5 ~ 1 hour, dropwises and is warming up to 55 ~ 60 DEG C, be incubated after 2 ~ 4 hours and sample, sample intermediate peak area is less than 0.5% for qualified;
Add water after qualified 700 ~ 800kg, is warming up to 70 ~ 75 DEG C of insulation backflows 0.5 ~ 1.5 hour, is cooled to 40 ~ 50 DEG C, leave standstill 20 ~ 40 minutes, layering, branch vibration layer, oil reservoir continues the 700 ~ 800kg that adds water, and stirs 20 ~ 40 minutes, leaves standstill 20 ~ 40 minutes, branch vibration layer, now water layer pH value is neutral, and merge the absorption water of secondary water layer as tail gas absorber, oil reservoir proceeds to precipitation still and carries out negative pressure precipitation, steam is warming up to≤and 80 DEG C, continue to vacuumize 1 hour without during backflow at 80 DEG C;
Steam off stops after 10 ~ 20 minutes vacuumizing, and adds Virahol 500 ~ 600kg, be stirred to entirely molten after proceed to the one-level cooling still circulating water cooling of 40 ~ 50 DEG C, be incubated 3 hours to 45 DEG C; After proceed to secondary cooling still, with the circulating water cooling of 25 ~ 35 DEG C, to 30 DEG C be incubated 2 hours; After proceed to three grades of cooling stills, with the circulating water cooling of 10 ~ 20 DEG C, to 15 DEG C insulation 2 hours; After proceed to crystallization kettle, cool to 5 ~ 10 DEG C, stir 1 hour, blowing suction filtration, centrifugal, dry, control dry weight in wet base≤0.5%, after pulverizing, packaging, obtains described pyraclostrobin 270 ~ 280kg;
Suction filtration gained filtrate proceeds in freezing kettle continues deep cooling and folds part pyraclostrobin, and solvent carries out precipitation recovery.
2. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 1) described in Raney's nickel added in 25 ~ 35 minutes.
3. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 2) described in hydrazine hydrate within 4.5 ~ 5.5 hours, drip off.
4. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 3) in add adjust ph to 6 ~ 7 after the vitriol oil, and stir pH value after 1 hour and remain unchanged.
5. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 4) described in the dropping temperature of methyl-chloroformate be-2 ~ 2 DEG C, time for adding 1 ~ 3 hour.
6. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 4) in after sampling analysis, as defective, and sampling analysis is still defective after 1 hour, add the methyl-chloroformate of 1 ~ 1.5kg, until sampling analysis is qualified.
7. the green production process of a kind of pyraclostrobin according to claim 1, is characterized in that, step 5) middle distillation employing twin-stage refrigated cooling, cooling fluid adopts the chilled brine at-20 DEG C, family, guarantees that the rate of recovery of solvent reaches 100%.
8. the green production process of a kind of pyraclostrobin according to claim 1, it is characterized in that, step 6) and step 11) described in drying course all dry in air draft baking oven, air draft oven temperature≤70 DEG C, air draft baking oven uses negative pressure recycling design, guarantees that whole solvent recuperation uses.
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| CN106008349A (en) * | 2016-07-02 | 2016-10-12 | 安徽广信农化股份有限公司 | Crystallization treating technology for pyraclostrobin |
| CN106243040A (en) * | 2016-07-28 | 2016-12-21 | 山东康乔生物科技有限公司 | A kind of pyraclostrobin novel crystal forms V and preparation method thereof |
| CN106543066A (en) * | 2016-11-11 | 2017-03-29 | 深圳市新阳唯康科技有限公司 | A kind of pyraclostrobin novel crystal forms and preparation method thereof |
| CN106631965A (en) * | 2016-12-21 | 2017-05-10 | 深圳市新阳唯康科技有限公司 | Novel pyraclostrobin crystal form and preparation method thereof |
| CN106749025A (en) * | 2016-11-14 | 2017-05-31 | 四川福思达生物技术开发有限责任公司 | A kind of method of succinct synthesizing pyrazole kresoxim-methyl |
| CN107021927A (en) * | 2017-03-28 | 2017-08-08 | 天津大学 | A kind of pyraclostrobin crystal formation and preparation method thereof |
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| CN110041258A (en) * | 2019-04-26 | 2019-07-23 | 永农生物科学有限公司 | A kind of mixing crystal form of pyraclostrobin and preparation method thereof |
| CN110092755A (en) * | 2018-01-31 | 2019-08-06 | 江苏优嘉植物保护有限公司 | A kind of production technology of pyraclostrobin safely cleaning |
| CN110494417A (en) * | 2017-02-01 | 2019-11-22 | 索尔维亚斯股份公司 | The production for the aromatic hydroxyamines that N- replaces |
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| CN106243040A (en) * | 2016-07-28 | 2016-12-21 | 山东康乔生物科技有限公司 | A kind of pyraclostrobin novel crystal forms V and preparation method thereof |
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| CN106631965A (en) * | 2016-12-21 | 2017-05-10 | 深圳市新阳唯康科技有限公司 | Novel pyraclostrobin crystal form and preparation method thereof |
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| CN107021927A (en) * | 2017-03-28 | 2017-08-08 | 天津大学 | A kind of pyraclostrobin crystal formation and preparation method thereof |
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| CN111655668A (en) * | 2018-01-17 | 2020-09-11 | Gsp作物科学有限公司 | Improved process for the preparation of pyraclostrobin |
| CN111655668B (en) * | 2018-01-17 | 2024-02-13 | Gsp作物科学有限公司 | Improved process for the preparation of pyraclostrobin |
| CN110092755A (en) * | 2018-01-31 | 2019-08-06 | 江苏优嘉植物保护有限公司 | A kind of production technology of pyraclostrobin safely cleaning |
| CN110092755B (en) * | 2018-01-31 | 2022-04-01 | 江苏优嘉植物保护有限公司 | Process for producing pyraclostrobin |
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