CN115626886B - Thiodicarb green synthesis process for reducing wastewater production - Google Patents
Thiodicarb green synthesis process for reducing wastewater production Download PDFInfo
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- CN115626886B CN115626886B CN202211373050.5A CN202211373050A CN115626886B CN 115626886 B CN115626886 B CN 115626886B CN 202211373050 A CN202211373050 A CN 202211373050A CN 115626886 B CN115626886 B CN 115626886B
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- BAKXBZPQTXCKRR-UHFFFAOYSA-N thiodicarb Chemical compound CSC(C)=NOC(=O)NSNC(=O)ON=C(C)SC BAKXBZPQTXCKRR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 78
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 61
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 300
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 258
- 238000005406 washing Methods 0.000 claims abstract description 131
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000005916 Methomyl Substances 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 99
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 claims abstract description 98
- 239000000706 filtrate Substances 0.000 claims abstract description 62
- 239000003446 ligand Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000005119 centrifugation Methods 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 61
- 239000012065 filter cake Substances 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 230000001502 supplementing effect Effects 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 45
- 230000001276 controlling effect Effects 0.000 description 34
- 238000013112 stability test Methods 0.000 description 13
- 238000010009 beating Methods 0.000 description 12
- 239000000575 pesticide Substances 0.000 description 12
- 238000010008 shearing Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 238000005338 heat storage Methods 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000856 effect on pests Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000004783 oxidative metabolism Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/06—Compounds containing sulfur atoms only bound to two nitrogen atoms
- C07C381/08—Compounds containing sulfur atoms only bound to two nitrogen atoms having at least one of the nitrogen atoms acylated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a thiodicarb green synthesis process for reducing the wastewater generation amount, which comprises the following steps: taking a certain amount of pyridine, dividing the pyridine into two parts according to a proportion, adding one part into a ligand synthesis kettle, and adding the other part and methomyl into a methomyl dissolution kettle to prepare a methomyl pyridine solution; when the temperature in the ligand synthesis kettle reaches the specified temperature, starting to dropwise add SCl 2, and starting a circulating pump at the same time; after the SCl 2 is added dropwise, dripping the methomyl pyridine solution into a ligand synthesis kettle for reaction; after the reaction is finished, sequentially performing centrifugation, water washing, filter pressing, methanol washing, centrifugation and drying to obtain a finished product; in the process, only pyridine is used as a solvent, so that side reactions are reduced, impurity types and contents in finished products are reduced, and the purity and the thermal stability of thiodicarb are improved; and the centrifugal filtrate, the water washing filtrate and the methanol-containing filtrate generated in the process can be recycled, so that the process water quantity added in the process is reduced, and the generation of wastewater is reduced.
Description
[ Field of technology ]
The invention belongs to the technical field of pesticide compound synthesis, and particularly relates to a thiodicarb green synthesis process for reducing wastewater production.
[ Background Art ]
The thiodicarb is used as a dicarbamate pesticide with the characteristics of high efficiency, broad spectrum, low toxicity, systemic stomach toxicity and the like, and has higher insecticidal activity on resistant pest strains taking oxidative metabolism as a detoxification mechanism due to the introduction of thioether bonds in the structure. Can be used for preventing and controlling lepidoptera, diptera and coleoptera pests on crops such as cotton, vegetables, fruit trees and tobacco, has good prevention and control effect on pests with resistance to organophosphorus and pyrethroid pesticides, is safe to fish and birds, has no chronic poisoning, cancerogenic, teratogenic and mutagenic effects, is safe to crops, and is one of key pesticides with large use amount and agricultural pest control in China and abroad in recent ten years.
The current thiodicarb synthesis method is classified into: (1) The hydrogen fluoride-methomyl oxime method has complex process flow, high cost, and simultaneously uses hydrogen fluoride gas with high toxicity and strong corrosiveness, has strict requirements on equipment materials, has large three wastes and high treatment difficulty, and has no industrial application value; (2) The trimethyl chlorosilane-methomyl synthesis process has the advantages of complex production operation, high risk, low methomyl conversion rate and low product yield, high cost and no industrial production significance; (3) The synthesis of thiodicarb by using sulfur dichloride and methomyl as main raw materials is the most studied synthesis method at present, and can be divided into the following steps according to the difference of solvents and catalysts: (1) The reaction is carried out without a catalyst and with one or more solvents; (2) Using one or two catalysts and simultaneously using more than two solvents for reaction; (3) continuous production using a pipeline reactor; (4) Thiodicarb is synthesized under low pressure (about 0.15MPa gauge pressure).
Although thiodicarb has a variety of synthetic methods, the following problems remain in the production process of thiodicarb:
(1) The wastewater produced by producing thiodicarb per ton exceeds 5 cubic meters or more, and the wastewater contains various organic matters, so that the treatment difficulty and the investment are high; (2) The method has the advantages that the secondary reaction is more in the thiodicarb synthesis reaction, the impurity content in the finished product is high, the impurity variety is more (the number of compounds with different structures is more), and due to various factors such as raw materials, catalysts, process conditions, different equipment and the like, other non-thiodicarb structural compounds with different structures are generated during the methomyl reaction, and the quality indexes such as the yield, the purity and the like of the thiodicarb are seriously influenced after the non-thiodicarb structural compounds are brought into the finished product thiodicarb; (3) The thermal storage stability is poor, so that the product cannot be sold and used, and great economic loss is caused for production enterprises; (4) low thiodicarb content and low yield.
[ Invention ]
The invention aims to provide a thiodicarb green synthesis process for reducing the wastewater yield, which mainly solves the problems of high wastewater yield, low purity, more side reactions, more impurities, poor thermal storage stability and the like.
Based on the above purpose, the application adopts the following technical scheme: a thiodicarb green synthesis process for reducing the generation amount of wastewater comprises the following steps:
(1) Preparing materials: respectively metering pyridine, SCl 2 and methomyl, dividing the pyridine into two parts according to a proportion, adding one part into a ligand synthesis kettle, simultaneously introducing chilled water into a jacket of the ligand synthesis kettle, adding the other part and the methomyl into a methomyl dissolution kettle, preparing a methomyl pyridine solution, and transferring the solution to a methomyl overhead tank; pressing SCl 2 into an SCl 2 elevated tank;
(2) When the temperature in the ligand synthesis kettle is not higher than-4 ℃, starting to dropwise add SCl 2, and simultaneously starting a circulating pump;
(3) After SCl 2 is added, dripping methomyl pyridine solution into a ligand synthesis kettle for reaction, and keeping a circulating pump on all the time in the process;
(4) After the reaction is finished, pressing materials in the ligand synthesis kettle into a centrifuge by using nitrogen to perform solid-liquid separation to obtain pyridine-containing centrifugate and a centrifugal filter cake, and recycling the pyridine-containing centrifugate to be added into a methomyl dissolution kettle or a ligand synthesis kettle for recycling;
(5) Adding the centrifugal filter cake obtained in the step (4) into a water washing kettle for water washing, adding the washed material into a plate-and-frame filter press for filter pressing to obtain water washing filtrate and a water washing filter cake, and recovering the water washing filtrate;
(6) And (3) washing the water-washed filter cake obtained in the step (5) by methanol, and centrifuging and drying to obtain a thiodicarb finished product.
Preferably, the molar ratio of the materials is as follows: the methomyl is pyridine, SCl 2, water, methanol=1, (5.795-6.016), (0.516-0.545), (16.133-20.266) and (8.886-9.035), and the material proportion is calculated according to the purity of 100% of the raw material.
Preferably, the mass ratio of pyridine to methomyl for dissolving methomyl in step (1) is: (1.5-1.6): 1.
Preferably, the drop time of the SCl 2 in the step (2) is 30-50 min; the temperature at the time of dripping is not higher than 15 ℃.
Preferably, the dripping time of the methomyl pyridine solution in the step (3) is controlled to be 180-240 min, and the dripping temperature is controlled to be not higher than 35 ℃.
Preferably, the temperature in the water washing kettle in the step (5) is not higher than 40 ℃, and the stirring water washing is carried out for 90-120 min.
Preferably, the water washing filtrate recovered in the step (5) is sent to a filtrate metering tank, fresh softened water is added to a prescribed amount and then added into a water washing kettle for reference water washing, the water washing filtrate used for two times is sent to a pyridine recovery device for recovering pyridine, and the recovered pyridine can be metered together with fresh pyridine and then added into a methomyl dissolution kettle or a ligand synthesis kettle for recycling. The organic impurities dissolved in the water washing filtrate after the first water washing are less, the softened water is added to carry out the second water washing, the organic impurities dissolved in the filtrate after the second water washing are increased, the pyridine amount in the filtrate after the second water washing is greatly increased compared with the first time, if the softened water is added again to continue the water washing, more organic impurities can be relatively dissolved, a certain amount of finished thiodicarb is dissolved, and indexes such as the yield, the quality and the appearance of the product are affected.
Preferably, in the step (6), the methanol washing and centrifuging process is specifically that the water washing filter cake obtained in the step (5) is added into a methanol washing kettle, the temperature in the methanol washing kettle is controlled to be not higher than 40 ℃, the methanol washing kettle is stirred and washed for 80-100 minutes to obtain a methanol-containing material, and the methanol-containing material is sent into a centrifuge for centrifuging to obtain a methanol-containing filtrate and a filter cake.
Preferably, after supplementing fresh methanol to the methanol-containing filtrate obtained by centrifugation in the step (6), washing the water-washed filter cake obtained in the step (6), wherein the methanol-containing filtrate is used twice and then can be sent to a methanol distillation device for recovering methanol.
Preferably, in the drying process in the step (6), the filter cake obtained after centrifugation is sent to a double cone dryer, and the temperature is controlled to be not higher than 45 ℃ and the vacuum degree is controlled to be not lower than 0.08MPa for drying.
Preferably, the ligand synthesis kettle is a reaction kettle with a high-speed shearing and grinding function.
The invention has the beneficial effects that:
According to the invention, pyridine is used as a solvent and also as an organic base, and other solvents are not introduced in the preparation process, so that the centrifugate after centrifugation can be directly returned to the methomyl reaction kettle for recycling pyridine, and the addition amount of pyridine in the process is reduced;
Because a single solvent is used, the invention can meet the process requirement only by washing once, and the filter-pressed washing filtrate can continue to participate in the washing work after being supplemented with softened water, so that the process water quantity added in the process is reduced, and the wastewater quantity generated in the process is greatly reduced; the water washing filtrate after the two times of use can be sent to a pyridine recovery device to recover pyridine, and as other solvents are not present, the phenomena of multielement azeotrope, material entrainment and the like formed by pyridine, water and other solvents are not present, and the pyridine yield is improved by 20% compared with the use of mixed solvents;
according to the invention, the methanol-containing filtrate after washing and centrifugation of the methanol is recycled, so that the use amount of the methanol is reduced;
Because only one solvent is used, the occurrence of side reaction in the process is reduced, the impurity types and the impurity content in the finished product are reduced, and the purity and the thermal stability of thiodicarb are improved;
The invention firstly dissolves the methomyl in pyridine to prepare the methomyl pyridine solution, and the methomyl is added into a ligand synthesis kettle in the mode of the methomyl pyridine solution, the reaction process belongs to liquid-solid reaction, the contact opportunities of reaction materials are more, and the reaction speed is high;
According to the invention, a circulating pump is always used for circulating in the process of dropwise adding SCl 2 and the methomyl pyridine solution, so that mass transfer is enhanced, as the dropwise adding methomyl pyridine solution is added from the upper part of the reaction kettle, the main reaction area is also arranged at the upper part of the reaction kettle, and materials at the bottom of the reaction kettle also reach the upper part of the reaction kettle in the circulating process, and the materials at the upper part of the reaction kettle gradually reach the bottom of the reaction kettle and react at the same time in the kettle, so that the materials are forcedly mixed, the contact and collision opportunities of main reaction material ligands and methomyl are increased, and the reaction speed is further accelerated;
The ligand synthesis kettle used in the invention is a reaction kettle with a high-speed shearing and grinding function, in the kettle, solid materials are sheared and particles are thinned, the number of reactant particles in unit volume is increased, the probability of collision and reaction is increased, and the reaction speed is further accelerated.
[ Detailed description ] of the invention
The invention is illustrated by the following specific examples, but is in no way limited thereto, in order to make the objects, technical solutions and advantages of the invention more apparent. The following description of the preferred embodiments of the invention is merely illustrative of the invention and should not be taken as limiting the invention, it being understood that any modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
The ligand synthesis kettle is a reaction kettle with a high-speed shearing and grinding function, and concretely, the ligand synthesis kettle used in the following embodiment is a high-shearing emulsification reaction kettle of Shanghai Hongshan electromechanical Co., ltd, and the model is HRHF-18.5.
The raw materials used in the embodiment of the invention are as follows:
the content of methomyl is not less than 97.0%;
the content of SCl 2 is not less than 97.0%;
the pyridine content is not less than 99.0%;
The mass content of the methanol is 99.0 percent.
Example 1
(1) Taking 468Kg of pyridine, sucking the pyridine into a methomyl dissolution kettle by vacuum, starting stirring, adding 300Kg of methomyl, dissolving the pyridine by using the pyridine to obtain a methomyl pyridine solution, and sucking the solution into a methomyl solution overhead tank by vacuum;
(2) Taking 369Kg of pyridine, sucking the pyridine into a ligand synthesis kettle by vacuum, starting stirring, and introducing frozen brine into a ligand synthesis kettle jacket; simultaneously, using nitrogen to press 101KgSCl 2 into an SCl 2 overhead tank;
(3) When the temperature in the ligand synthesis kettle reaches-4 ℃, starting to dropwise add SCl 2, simultaneously starting a circulating pump, controlling the dropwise adding time to be 40 minutes, and controlling the dropwise adding temperature of SCl 2 to be 10 ℃; after the completion of the drop of SCl 2, continuously stirring for 20 minutes, and continuously starting a circulating pump during the period, and continuously beating and circulating the materials;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 180 minutes, controlling the reaction temperature to be 25 ℃ during dripping, continuously running a circulating pump in the operation process, continuously beating and circulating materials, continuously stirring for 20 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal press filter by using nitrogen to perform solid-liquid separation to obtain pyridine-containing centrifugate and a centrifugal filter cake, and recovering the pyridine-containing centrifugate;
(6) Adding 528Kg of softened water into a water washing kettle, starting stirring, adding the centrifugal filter cake prepared in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to 30 ℃, and stirring for 90 minutes; pumping the materials in the water washing kettle into a plate-and-frame filter press for filter pressing by using a slurry pump to obtain water washing filtrate and a water washing filter cake, and recycling the water washing filtrate to a water washing filtrate metering tank;
(7) Adding 519Kg of methanol into the methanol washing kettle, starting stirring, adding the filter cake obtained in the step (6) into the methanol washing kettle, adjusting the temperature in the kettle to 30 ℃, and stirring for 80 minutes;
(8) Feeding the methanol-containing material in the methanol washing kettle in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for standby, feeding the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 311.9Kg of thiodicarb finished product, and generating 318Kg of process wastewater;
the thiodicarb content was analyzed to be 98.31% and the thiodicarb yield was 96.44%;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability test method, the decomposition rate of the thiodicarb is 2.5% and is lower than the national standard requirement by 5%, and other indexes are analyzed to meet the national standard requirement.
Example 2
(1) Adding the pyridine-containing centrifugate obtained in the step (5) in the example 1 into a pyridine metering tank, supplementing fresh pyridine to 474Kg, sucking the pyridine into a methomyl dissolution kettle by using vacuum, starting stirring, adding 300Kg of methomyl, obtaining a methomyl pyridine solution after the methomyl is completely dissolved, and sucking the solution into a methomyl solution overhead tank by using vacuum;
(2) Measuring 378Kg of fresh pyridine, sucking the fresh pyridine into the ligand synthesis kettle by vacuum, starting stirring, and introducing frozen brine into a jacket of the ligand synthesis kettle; simultaneously, 103Kg of SCl 2 is pressed into an SCl 2 overhead tank by nitrogen;
(3) When the temperature in the ligand synthesis kettle reaches-5 ℃, starting to dropwise add SCl 2, simultaneously starting a circulating pump, controlling the dropwise adding time to be 30 minutes, and controlling the dropwise adding temperature of SCl 2 to be 8 ℃; after the completion of the drop of SCl 2, stirring is continued for 15 minutes, and a circulating pump is continuously started during the period, so that the materials are continuously circulated;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 200 minutes, controlling the reaction temperature to be 30 ℃ during dripping, continuously running a circulating pump in the operation process, continuously beating and circulating materials, continuously stirring for 30 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) The materials in the ligand synthesis kettle are pressed into a centrifugal press filter by nitrogen for solid-liquid separation, so as to obtain pyridine-containing centrifugate and a centrifugal filter cake, and the pyridine-containing centrifugate is recovered;
(6) Adding the water washing filtrate obtained in the step (6) in the example 1 into a water washing filtrate metering tank, supplementing fresh softened water to 600Kg, adding into a water washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to 25 ℃, stirring for 100 minutes, pumping the material in the water washing kettle into a plate-and-frame filter press by using a slurry pump for filter pressing to obtain water washing filtrate and a water washing filter cake, and recycling the water washing filtrate to a pyridine recycling device to recycle pyridine;
(7) Feeding the filtrate containing methanol obtained by centrifugation in the step (8) in the example 1 into a methanol metering tank, adding fresh methanol to 522Kg, adding the filtrate into a methanol washing kettle, starting stirring, adding the water washing filter cake obtained in the step (6) into the methanol washing kettle, adjusting the temperature in the methanol washing kettle to 25 ℃, stirring for 90 minutes, and feeding the filtrate into the centrifugation;
(8) Feeding the methanol-containing material obtained in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol distillation device for recovering methanol, feeding the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 311.6Kg of thiodicarb finished product, and generating 390Kg of process wastewater;
Analyzing the thiodicarb content to 98.18 percent, and calculating the thiodicarb yield to 96.22 percent;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability test method, the decomposition rate of the thiodicarb is 3.1% and is lower than the national standard requirement by 5%, and meanwhile, other indexes are analyzed to meet the national standard requirement.
Example 3
(1) Adding the pyridine-containing centrifugate obtained in the step (5) of the centrifugal press filter into a pyridine metering tank, supplementing fresh pyridine to 468Kg, sucking the pyridine into a methomyl dissolution tank by using vacuum, starting stirring, adding 300Kg of methomyl, obtaining a methomyl pyridine solution after the methomyl is completely dissolved, and pumping the methomyl pyridine solution into a methomyl solution overhead tank by using vacuum;
(2) Adding pyridine recovered by the pyridine recovery unit in the step (6) in the example 2 into a pyridine metering tank, replenishing fresh pyridine to 390Kg, sucking the fresh pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the synthesis kettle; simultaneously, 103Kg of SCl 2 is pressed into an SCl 2 overhead tank by nitrogen;
(3) When the temperature in the ligand synthesis kettle reaches minus 6 ℃, starting to dropwise add SCl 2, starting a circulating pump, controlling the dropwise adding time to be 45 minutes, controlling the dropwise adding temperature of SCl 2 to be 5 ℃, continuously stirring for 30 minutes after the dropwise adding of SCl 2 is finished, and continuously starting the circulating pump during the period, and continuously beating and circulating materials;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 190 minutes, controlling the reaction temperature to be 20 ℃ during dripping, continuously running a circulating pump in the operation process, continuously beating and circulating materials, continuously stirring for 25 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) The materials in the ligand synthesis kettle are pressed into a centrifugal press filter by nitrogen for solid-liquid separation, so as to obtain pyridine-containing centrifugate and a centrifugal filter cake, and the pyridine-containing centrifugate is recovered;
(6) Adding softened water to 570Kg into a water washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to be 30 ℃, stirring for 110 minutes, pumping materials in the water washing kettle into a plate-and-frame filter press by using a slurry pump for filter pressing to obtain water washing filtrate and a water washing filter cake, and recycling the water washing filtrate;
(7) 522Kg of fresh methanol is metered and added into a methanol washing kettle, stirring is started, then the water washing filter cake obtained in the step (6) is added into the methanol washing kettle, the temperature in the methanol washing kettle is regulated to 30 ℃, stirring is carried out for 100 minutes, and the water washing filter cake is sent to centrifugation;
(8) Feeding the methanol-containing material obtained in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for standby, feeding the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 311.4Kg of thiodicarb finished product, and generating 388Kg of process wastewater;
Analyzing the thiodicarb content to 98.03%, and calculating the thiodicarb yield 96.01%;
the thiodicarb is subjected to a heat storage stability test according to the standard GB/T19136-2003 method for measuring the heat storage stability of pesticides, the decomposition rate of the thiodicarb is 3.1 percent and is lower than the national standard requirement by 5 percent, and meanwhile, other indexes are analyzed to meet the national standard requirement.
Example 4
(1) Adding the pyridine-containing centrifugate obtained in the step (5) in the example 3 into a pyridine metering tank, supplementing fresh pyridine to 445Kg, sucking the pyridine into a methomyl dissolution kettle by using vacuum, starting stirring, adding 300Kg of methomyl, obtaining a methomyl pyridine solution after the methomyl is completely dissolved, and sucking the solution into a methomyl solution overhead tank by using vacuum;
(2) Metering 415Kg of pyridine, sucking the pyridine into a ligand synthesis kettle by vacuum, starting stirring, and introducing frozen brine into a jacket of the synthesis kettle; simultaneously, 103KgSCl 2 is pressed into the SCl 2 overhead tank by nitrogen;
(3) When the temperature in the ligand synthesis kettle reaches minus 6 ℃, starting to dropwise add SCl 2, simultaneously starting a circulating pump, controlling the dropwise adding time to be 50 minutes, and controlling the dropwise adding temperature of SCl 2 to be 14 ℃; after the completion of the drop of the SCl 2, continuously stirring for 25 minutes, and continuously starting a circulating pump during the period, and continuously beating and circulating the materials;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 240 minutes, controlling the reaction temperature to be 34 ℃ during dripping, continuously running a circulating pump in the operation process, continuously beating and circulating materials, continuously stirring for 25 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) The materials in the ligand synthesis kettle are pressed into a centrifugal press filter by nitrogen for solid-liquid separation, so as to obtain pyridine-containing centrifugate and a centrifugal filter cake, and the pyridine-containing centrifugate is recovered;
(6) Adding the water washing filtrate obtained in the step (6) in the embodiment 3 into a water washing filtrate metering tank, supplementing fresh softened water to 540Kg, adding into a water washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to 35 ℃, stirring for 120 minutes, pumping the material in the water washing kettle into a plate-and-frame filter press by using a slurry pump for filter pressing to obtain water washing filtrate and the water washing filter cake, and recycling the water washing filtrate to a pyridine recycling device to recycle pyridine;
(7) Feeding the filtrate containing methanol obtained by centrifugation in the step (8) in the embodiment 3 into a methanol metering tank, adding fresh methanol to 519Kg, adding into a methanol washing kettle, starting stirring, adding the water washing filter cake obtained in the step (6) into the methanol washing kettle, adjusting the temperature in the methanol washing kettle to 35 ℃, stirring for 85 minutes, and feeding into centrifugation;
(8) Delivering the methanol-containing material obtained in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, delivering the methanol-containing filtrate into a methanol distillation device for recovering methanol, delivering the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 310.6Kg of thiodicarb finished product, and generating 333Kg of process wastewater;
Analyzing the thiodicarb content to 98.28%, and calculating the thiodicarb yield 96.01%;
The thiodicarb is subjected to a heat storage stability test according to the standard GB/T19136-2003 method for measuring the heat storage stability of pesticides, the decomposition rate of the thiodicarb is 2.9 percent and is lower than the national standard requirement by 5 percent, and meanwhile, other indexes are analyzed to meet the national standard requirement.
Example 5
(1) Adding the pyridine-containing centrifugate obtained in the step (5) of the centrifugal press filter in the example 4 into a pyridine metering tank, supplementing pyridine to 465Kg, sucking the pyridine-containing centrifugate into a methomyl dissolution tank by vacuum, starting stirring, adding 300Kg of methomyl, and pumping the methomyl pyridine solution into a methomyl solution overhead tank by vacuum after the methomyl is completely dissolved;
(2) Adding pyridine recovered by the pyridine recovery unit in the step (6) of the example 4 into a pyridine metering tank, supplementing fresh pyridine to 381Kg, sucking the fresh pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the synthesis kettle; simultaneously, 102KgSCl 2 is pressed into an SCl 2 overhead tank by nitrogen;
(3) When the temperature in the ligand synthesis kettle reaches-4 ℃, starting to dropwise add SCl 2, starting a circulating pump at the same time, controlling the dropwise adding time to be 35 minutes, controlling the temperature at 6 ℃ when SCl 2 is dropwise added, continuously stirring for 30 minutes after SCl 2 is dropwise added, and continuously starting the circulating pump during the period, and continuously beating and circulating materials;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 210 minutes, controlling the reaction temperature to be 30 ℃ during dripping, continuously running a circulating pump in the process, continuously beating and circulating materials, continuously stirring for 30 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) The materials in the ligand synthesis kettle are pressed into a centrifugal press filter by nitrogen for solid-liquid separation, so as to obtain pyridine-containing centrifugate and a centrifugal filter cake, and the pyridine-containing centrifugate is recovered;
(6) Adding 630Kg of softened water into a water-washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the water-washing kettle, adjusting the temperature in the water-washing kettle to 38 ℃, stirring for 120 minutes, and starting filter pressing; pumping the materials in the water washing kettle into a plate-and-frame filter press for filter pressing by using a slurry pump to obtain water washing filtrate and a water washing filter cake, and recycling the water washing filtrate;
(7) Adding the methanol recovered from the methanol distillation device in the step (8) in the example 4 into a methanol metering tank, supplementing fresh methanol to 522Kg, adding the methanol into a methanol washing kettle, starting stirring, adding the water washing filter cake obtained in the step (6) into the methanol washing kettle, adjusting the temperature in the methanol washing kettle to 38 ℃, stirring for 95 minutes, and centrifuging;
(8) Delivering the methanol-containing material obtained in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, delivering the methanol-containing filtrate into a methanol metering tank for recycling, delivering the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 311.3Kg of thiodicarb finished product, and generating 420Kg of process wastewater;
analyzing thiodicarb content 98.14%, and calculating thiodicarb yield 96.09%;
The thiodicarb is subjected to a heat storage stability test according to the standard GB/T19136-2003 method for measuring the heat storage stability of pesticides, the decomposition rate of the thiodicarb is 3.7 percent and is lower than the national standard requirement by 5 percent, and meanwhile, other indexes are analyzed to meet the national standard requirement.
Comparative example 1
(1) Taking 837Kg of pyridine, sucking the pyridine into a ligand synthesis kettle by vacuum, starting stirring, and introducing frozen brine into a ligand synthesis kettle jacket; simultaneously, using nitrogen to press 101KgSCl 2 into an SCl 2 overhead tank;
(2) When the temperature in the ligand synthesis kettle reaches-4 ℃, starting to dropwise add SCl 2, simultaneously starting a circulating pump, controlling the dropwise adding time to be 40 minutes, and controlling the dropwise adding temperature of SCl 2 to be 10 ℃; after the completion of the drop of SCl 2, continuously stirring for 20 minutes, and continuously starting a circulating pump during the period, and continuously beating and circulating the materials;
(3) 300Kg of methomyl is metered and added into a ligand synthesis kettle, a circulating pump continuously runs in the operation process, materials are continuously circulated, stirring is continuously carried out for 180 minutes, the reaction is finished, and the circulating pump is stopped;
(4) Pressing the materials in the ligand synthesis kettle into a centrifugal press filter by using nitrogen to perform solid-liquid separation to obtain pyridine-containing centrifugate and a centrifugal filter cake, and recovering the pyridine-containing centrifugate;
(5) Adding 528Kg of softened water into a water washing kettle, starting stirring, adding the centrifugal filter cake prepared in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to 30 ℃, and stirring for 90 minutes; then pumping the materials in the washing kettle into a plate-and-frame filter press for filter pressing by using a slurry pump to obtain washing filtrate and a washing filter cake;
(6) Adding 519Kg of methanol into the methanol washing kettle, starting stirring, adding the filter cake obtained in the step (5) into the methanol washing kettle, adjusting the temperature in the kettle to 30 ℃, and stirring for 80 minutes;
(7) Feeding the methanol-containing material in the methanol washing kettle in the step (6) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for standby, feeding the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 305.6Kg of thiodicarb finished product, and generating 322Kg of process wastewater;
the thiodicarb content was analyzed to be 96.54% and the thiodicarb yield was 92.79%;
the thiodicarb is subjected to a heat storage stability test according to the standard GB/T19136-2003 method for measuring the heat storage stability of pesticides, the decomposition rate of the thiodicarb is 5.2 percent, which is higher than the national standard requirement by 5 percent, and the product is unqualified.
And (3) reason analysis: the first step of reaction, namely, the ligand obtained by the reaction of pyridine and SCl 2 is solid fine particles dispersed in a system, and after solid methomyl is added, the solid methomyl and ligand solid react slowly, and the solid methomyl and ligand can react with each other to generate thiodicarb only by dissolving in the solvent pyridine; therefore, after solid methomyl is added, the two materials react insufficiently within a prescribed reaction time, and the thiodicarb content reaches 96.54 percent, but the thiodicarb yield is 92.79 percent, and the heat storage stability test is failed due to the fact that other impurities are contained in the thiodicarb, so that the product is judged to be failed.
Comparative example 2
The difference with example 1 is that the ligand synthesis kettle used in this comparative example is a common enamel reaction kettle, and no circulating pump is used for circulating in the process of dropwise adding SCl 2 and methomyl pyridine solution, so as to finally obtain 305.2Kg of thiodicarb finished product and generate 320Kg of process wastewater;
the analysis of thiodicarb content is 96.11 percent, and the thiodicarb yield is 92.26 percent;
The thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability test method, the decomposition rate of the thiodicarb is 4.3 percent and is lower than the national standard requirement by 5 percent, and meanwhile, other indexes are analyzed to meet the national standard requirement.
And (3) reason analysis: the ligand synthesis kettle used in comparative example 2 is a common enamel reaction kettle, and the structure and the quality of the reaction kettle accord with the standards issued by the ministry of standardization, wherein the type of stirrer is a main factor influencing heat and mass transfer. Although the impeller type stirrer can form a main body circulation which is much larger than an anchor type stirrer and a paddle type stirrer and has strong shearing action, when the same main body circulation quantity is achieved, the consumed power is smaller than that of the anchor type glass lining stirrer and the paddle type glass lining stirrer, but the disadvantage is that the shearing provided is unevenly distributed in the reaction kettle, bubbles or liquid drops are very fine in a high shearing area near the impeller, and the bubbles or liquid drops are condensed into large bubbles or large liquid drops in a low shearing area far away from the impeller, so that the materials in the glass lining reaction kettle are divided into two circulation areas up and down by the impeller, and the integral mixing of the materials in the reaction kettle is influenced, thereby influencing the purity and the yield of the finished thiodicarb.
The reaction kettle used in the application is a reaction kettle with a high-speed shearing and grinding function, and generates great shearing, friction and impact and mutual collision and friction action among materials under the action of mechanical force and hydrodynamic effect to crush dispersed phase particles or liquid drops, the crushing environment is continuously improved along with the gradual increase of the linear speed of rotating teeth from an inner ring to an outer ring, the materials are crushed to be finer and finer under the action of stronger shearing, friction, impact, collision and the like in the process of moving towards the outer ring, the large-scale mixing of ligands and methomyl is increased, the reaction speed is increased, and the purity and the yield of finished thiodicarb are increased.
Comparative example 3
The difference from example 1 is that the molar ratio of the materials in this comparative example is: methomyl: pyridine: SCl 2: water: methanol=1:6.1:0.55:15.7:9.22, specifically as follows:
(1) Taking 470Kg of pyridine, sucking the pyridine into a methomyl dissolution kettle by vacuum, starting stirring, adding 300Kg of methomyl, dissolving the pyridine by using the pyridine to obtain a methomyl pyridine solution, and sucking the solution into a methomyl solution overhead tank by vacuum;
(2) Taking 404Kg of pyridine, sucking the pyridine into a ligand synthesis kettle by vacuum, starting stirring, and introducing frozen brine into a ligand synthesis kettle jacket; simultaneously, 105KgSCl 2 is pressed into the SCl 2 overhead tank by nitrogen;
(3) When the temperature in the ligand synthesis kettle reaches-4 ℃, starting to dropwise add SCl 2, simultaneously starting a circulating pump, controlling the dropwise adding time to be 40 minutes, and controlling the dropwise adding temperature of SCl 2 to be 10 ℃; after the completion of the drop of SCl 2, continuously stirring for 20 minutes, and continuously starting a circulating pump during the period, and continuously beating and circulating the materials;
(4) Dripping the methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution overhead tank, controlling the dripping time to be 180 minutes, controlling the reaction temperature to be 25 ℃ during dripping, continuously running a circulating pump in the operation process, continuously beating and circulating materials, continuously stirring for 20 minutes after the dripping of the methomyl pyridine solution is finished, stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal press filter by using nitrogen to perform solid-liquid separation to obtain pyridine-containing centrifugate and a centrifugal filter cake, and recovering the pyridine-containing centrifugate;
(6) Adding 507Kg of softened water into a water washing kettle, starting stirring, adding the centrifugal filter cake prepared in the step (5) into the water washing kettle, adjusting the temperature in the water washing kettle to 30 ℃, and stirring for 90 minutes; pumping the materials in the water washing kettle into a plate-and-frame filter press for filter pressing by using a slurry pump to obtain water washing filtrate and a water washing filter cake, and recycling the water washing filtrate to a water washing filtrate metering tank;
(7) Adding 518Kg of methanol into a methanol washing kettle, starting stirring, adding the filter cake obtained in the step (6) into the methanol washing kettle, adjusting the temperature in the kettle to 30 ℃, and stirring for 80 minutes;
(8) Feeding the methanol-containing material in the methanol washing kettle in the step (7) into a centrifuge for centrifugation to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for standby, feeding the filter cake into a biconical dryer, controlling the temperature in the dryer to be lower than 45 ℃ and the vacuum degree to be not lower than 0.08MPa for drying to obtain 303.7Kg of thiodicarb finished product, and generating 320Kg of process wastewater;
the thiodicarb content was analyzed to be 96.12% and the thiodicarb yield was 91.81%;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability test method, the decomposition rate of the thiodicarb is 4.5% and is lower than the national standard requirement by 5%, and meanwhile, other indexes are analyzed to meet the national standard requirement.
The above description is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (9)
1. The thiodicarb synthesis process for reducing the wastewater production is characterized by comprising the following steps of:
(1) Preparing materials: respectively metering pyridine, SCl 2 and methomyl, dividing the pyridine into two parts according to a proportion, adding one part into a ligand synthesis kettle, simultaneously introducing chilled water into a jacket of the ligand synthesis kettle, adding the other part and the methomyl into a methomyl dissolution kettle, dissolving the methomyl to prepare a methomyl pyridine solution, and transferring the methomyl pyridine solution to a methomyl overhead tank; pressing SCl 2 into an SCl 2 elevated tank;
(2) When the temperature in the ligand synthesis kettle is not higher than-4 ℃, starting to dropwise add SCl 2, and simultaneously starting a circulating pump;
(3) After the SCl 2 is added dropwise, dripping the methomyl pyridine solution in the methomyl overhead tank into a ligand synthesis kettle for reaction, and keeping a circulating pump open all the time in the process;
(4) After the reaction is finished, pressing materials in the ligand synthesis kettle into a centrifuge by using nitrogen to perform solid-liquid separation to obtain pyridine-containing centrifugate and a centrifugal filter cake, and recycling the pyridine-containing centrifugate to be added into a methomyl dissolution kettle or a ligand synthesis kettle for recycling;
(5) Adding the centrifugal filter cake obtained in the step (4) into a water washing kettle for water washing, adding the washed material into a plate-and-frame filter press for filter pressing to obtain water washing filtrate and a water washing filter cake, and recovering the water washing filtrate;
(6) Washing the water-washed filter cake obtained in the step (5) by methanol, and centrifuging and drying to obtain a thiodicarb finished product;
The molar ratio of the materials is as follows: methomyl pyridine SCl 2 water methanol=1 (5.795-6.016) (0.516-0.545) (16.133-20.266) (8.886-9.035).
2. The thiodicarb synthesis process for reducing wastewater production according to claim 1, wherein the mass ratio of pyridine to methomyl for dissolving methomyl in step (1) is: (1.5 to 1.6): 1.
3. The thiodicarb synthesis process for reducing the wastewater production according to claim 1, wherein the drop time of the SCl 2 in the step (2) is 30-50 min; the temperature at the time of dripping is not higher than 15 ℃.
4. The thiodicarb synthesis process for reducing wastewater production according to claim 1, wherein the dripping time of the methomyl pyridine solution in the step (3) is controlled to be 180-240 min, and the dripping temperature is controlled to be not higher than 35 ℃.
5. The thiodicarb synthesis process for reducing wastewater production according to claim 1, wherein the temperature in the water-washing kettle is controlled to be not higher than 40 ℃ in the water-washing process of the step (5), and the water-washing is performed for 90-120 min under stirring.
6. The thiodicarb synthesis process for reducing the wastewater production according to claim 1, wherein the washing filtrate recovered in the step (5) is fed into a washing filtrate metering tank, fresh softened water is added into a washing kettle after being replenished to a prescribed amount, and the washing filtrate after two uses is fed into a pyridine recovery device to recover pyridine, and the recovered pyridine is added into a methomyl dissolution kettle or a ligand synthesis kettle for recycling.
7. The thiodicarb synthesis process for reducing the wastewater production according to claim 1, wherein the methanol washing and centrifuging process in the step (6) is specifically that the water washing filter cake obtained in the step (5) is added into a methanol washing kettle, the temperature in the methanol washing kettle is controlled to be not higher than 40 ℃, the mixture is stirred and washed for 80-100 minutes to obtain a methanol-containing material, and the methanol-containing material is sent into a centrifuge for centrifuging to obtain a methanol-containing filtrate and a filter cake.
8. The thiodicarb synthesis process for reducing wastewater production according to claim 7, wherein the methanol-containing filtrate obtained in the step (6) is added into a methanol washing kettle after supplementing fresh methanol, the washing filter cake obtained in the step (5) is continuously washed, and the methanol-containing filtrate obtained in the step (5) after two times is used is sent into a methanol distillation device for recovering methanol.
9. The thiodicarb synthesis process for reducing wastewater production according to claim 7, wherein the drying process in step (6) is specifically that a filter cake obtained after centrifugation is fed into a biconical dryer, and the temperature is controlled to be not higher than 45 ℃ and the vacuum degree is controlled to be not lower than 0.08MPa for drying.
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