CN115626886A - Green thiodicarb synthesis process capable of reducing wastewater generation amount - Google Patents
Green thiodicarb synthesis process capable of reducing wastewater generation amount Download PDFInfo
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- CN115626886A CN115626886A CN202211373050.5A CN202211373050A CN115626886A CN 115626886 A CN115626886 A CN 115626886A CN 202211373050 A CN202211373050 A CN 202211373050A CN 115626886 A CN115626886 A CN 115626886A
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- pyridine
- methomyl
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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 80
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 79
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 60
- 230000008569 process Effects 0.000 title claims abstract description 51
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 312
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 264
- 238000005406 washing Methods 0.000 claims abstract description 134
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000005916 Methomyl Substances 0.000 claims abstract description 104
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 claims abstract description 103
- 239000000706 filtrate Substances 0.000 claims abstract description 66
- 239000003446 ligand Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000003825 pressing Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 67
- 239000000463 material Substances 0.000 claims description 61
- 239000012065 filter cake Substances 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 45
- 238000003860 storage Methods 0.000 description 16
- 239000000575 pesticide Substances 0.000 description 10
- 238000010008 shearing Methods 0.000 description 9
- 238000013112 stability test Methods 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000036632 reaction speed Effects 0.000 description 5
- 241000607479 Yersinia pestis Species 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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 2
- 230000009471 action Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 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
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 235000002789 Panax ginseng Nutrition 0.000 description 1
- 240000004371 Panax ginseng Species 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 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
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a thiodicarb green synthesis process for reducing the generation amount of wastewater, which comprises the following steps: taking a certain amount of pyridine, dividing the pyridine into two parts according to the proportion, adding one part of the pyridine and the methomyl into a ligand synthesis kettle, and adding the other part of the pyridine and the methomyl into a methomyl dissolution kettle to prepare a methomyl pyridine solution; when the temperature in the retainer synthesis kettle reaches the designated temperature, SCl is dripped 2 Simultaneously starting a circulating pump; to be SCl 2 After the dropwise adding, dropwise adding the methomyl pyridine solution into a ligand synthesis kettle for reaction; after the reaction is finished, sequentially carrying out 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 the occurrence of side reactions is reduced, the 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 washing filtrate and the methanol-containing filtrate generated in the process can be recycled, so that the process water amount added in the process is reduced, and the generation of waste water is reduced.
Description
[ technical field ] A
The invention belongs to the technical field of synthesis of pesticide compounds, and particularly relates to a green thiodicarb synthesis process for reducing the generation amount of wastewater.
[ background of the invention ]
As a dicarbamate pesticide with the characteristics of high efficiency, broad spectrum, low toxicity, systemic stomach toxicity and the like, the thiodicarb 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. The insecticidal composition can be used for preventing and treating lepidoptera, diptera and coleopteran pests on crops such as cotton, vegetables, fruit trees, tobacco and the like, has good prevention and treatment effects on pests with resistance to organophosphorus and pyrethrin insecticides, is safe for fish and birds, has no chronic poisoning, carcinogenesis, teratogenesis and mutagenesis effects, is safe for crops, and is one of key insecticides which have large dosage and are used for controlling agricultural pests in China and abroad in the last decade.
The existing synthesis method of thiodicarb is divided into the following steps according to the used raw material classification: (1) The hydrogen fluoride-methomyl oxime method has complex process flow and high cost, simultaneously uses gaseous hydrogen fluoride with high toxicity and strong corrosivity, has strict requirements on equipment materials, has large quantity of three wastes and large treatment difficulty, and has no industrial application value; (2) The synthesis process of the trimethylchlorosilane-methomyl has the advantages of complex production operation, high danger, low methomyl conversion rate and product yield, high cost and no industrial production significance; (3) The thiodicarb is synthesized by taking sulfur dichloride and methomyl as main raw materials, is the most researched synthesis method at present, and can be divided into the following parts according to the difference of used solvents and catalysts: (1) Carrying out the reaction by using one or more solvents without using a catalyst; (2) One or two catalysts are used, and more than two solvents are used simultaneously for reaction; (3) using a pipeline reactor for continuous production; (4) Thiodicarb is synthesized under low pressure (about 0.15MPa gauge pressure).
Despite the various synthetic methods of thiodicarb, the following problems still exist in the production process of thiodicarb:
(1) The amount of wastewater generated by producing each ton of thiodicarb exceeds 5 cubic meters or more, the wastewater contains various organic matters, the treatment difficulty is high, and the investment is large; (2) The thiodicarb synthesis reaction has more side reactions, high impurity content in the finished product and more impurity varieties (more compounds with different structures), and due to various factors such as raw materials, catalysts, process conditions, different equipment and the like, the thiodicarb generates other non-thiodicarb compounds with different structures during the reaction, and after the thiodicarb is brought into the finished product, the quality indexes such as yield, purity and the like of the thiodicarb are seriously influenced; (3) The heat storage stability is poor, so that the product cannot be sold and used, and great economic loss is caused to production enterprises; and (4) the thiodicarb is low in content and yield.
[ summary of the invention ]
The invention aims to provide a thiodicarb green synthesis process for reducing the generation amount of wastewater, and mainly solves the problems of high wastewater amount, low product yield, low purity, more side reactions, more impurities, poor heat storage stability and the like.
Based on the purposes, the following technical scheme is adopted in the application: a green thiodicarb synthesis process for reducing wastewater generation comprises the following steps:
(1) Preparing materials: separately metering pyridine and SCl 2 And methomyl, pyridine is divided into two parts according to a proportion, wherein one part is added into a ligand synthesis kettle, chilled water is introduced into a jacket of the ligand synthesis kettle, the other part and the methomyl are added into a methomyl dissolution kettle to prepare a methomyl pyridine solution, and the methomyl pyridine solution is transferred to a methomyl head tank; SCl 2 Pressing in SCl 2 A head tank;
(2) When the temperature in the retainer synthesis kettle is not higher than-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump;
(3)SCl 2 after the dripping is finished, dripping the methomyl pyridine solution into a ligand synthesis kettle for reaction, and keeping a circulating pump to be always started in the process;
(4) After the reaction is finished, pressing the materials in the ligand synthesis kettle into a centrifuge by using nitrogen for solid-liquid separation to obtain a pyridine-containing centrifugate and a centrifugal filter cake, recovering the pyridine-containing centrifugate, and adding the pyridine-containing centrifugate into the methomyl dissolution kettle or the ligand synthesis kettle for recycling;
(5) Adding the centrifugal filter cake obtained in the step (4) into a washing kettle for washing, adding the washed material into a plate-and-frame filter press for filter pressing to obtain washing filtrate and washing filter cake, and recovering the washing filtrate;
(6) And (4) washing the water-washed filter cake obtained in the step (5) by methanol, centrifuging and drying to obtain the thiodicarb finished product.
Preferably, the molar ratio of each material is: methomyl pyridine SCl 2 The water is methanol =1, (5.795-6.016), (0.516-0.545), (16.133-20.266) and (8.886-9.035), and the mixture ratio of the materials is calculated according to the purity of 100 percent of the raw materials.
Preferably, the mass ratio of the pyridine used for dissolving methomyl in the step (1) to the methomyl is as follows: (1.5-1.6) is 1.
Preferably, SCl in step (2) 2 Dropping time of (2)Is 30 to 50min; the temperature at the time of dropping is not higher than 15 ℃.
Preferably, the dropping time of the methomyl pyridine solution in the step (3) is controlled to be 180-240 min, and the temperature is controlled to be not higher than 35 ℃ during dropping.
Preferably, the temperature in the washing kettle in the step (5) is not higher than 40 ℃, and the washing is carried out for 90-120 min by stirring.
Preferably, the washing filtrate recovered in the step (5) is sent to a filtrate metering tank, fresh softened water is added into a washing kettle after being replenished to a specified amount for washing, the washing filtrate after being used twice 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 dissolving kettle or a ligand synthesis kettle for recycling. The organic impurities dissolved in the filtrate of the washing after the first washing are less, the filtrate of the washing after the second washing can be washed for the second time by adding softened water, the organic impurities dissolved in the filtrate of the washing after the second washing are increased, the amount of pyridine in the filtrate of the washing after the second washing is greatly increased compared with that of the filtrate of the washing after the first washing, and if the softened water is added for continuing the washing, more organic impurities can be relatively dissolved, a certain amount of finished thiodicarb can be dissolved, and the indexes of the product, such as yield, quality, appearance and the like, are influenced.
Preferably, the methanol washing and centrifuging process in the step (6) specifically comprises the steps of adding the water-washed filter cake obtained in the step (5) into a methanol washing kettle, controlling the temperature in the methanol washing kettle to be not higher than 40 ℃, stirring and washing for 80-100 minutes to obtain a methanol-containing material, and feeding the methanol-containing material into a centrifuge for centrifuging to obtain a methanol-containing filtrate and a filter cake.
Preferably, the washing filter cake obtained in the step (6) can be washed continuously after fresh methanol is supplemented to the filtrate containing methanol obtained by centrifugation in the step (6), and the filtrate containing methanol can be sent to a methanol distillation device for recovering methanol after the filtrate containing methanol is used twice.
Preferably, the drying process in the step (6) is specifically to send the filter cake obtained after centrifugation into a double-cone dryer, and the drying is carried out at a temperature of not higher than 45 ℃ and a vacuum degree of not lower than 0.08 MPa.
Preferably, the ligand synthesis kettle is a reaction kettle with a high-speed shearing and grinding function.
The invention has the beneficial effects that:
the invention uses pyridine as a solvent and an organic base, and other solvents are not introduced in the preparation process, so that the centrifuged centrifugate can be directly returned to the methomyl reaction kettle for recycling pyridine, and the addition of pyridine in the process is reduced;
because a single solvent is used, the process requirements can be met only by washing once, and the washing filtrate after filter pressing can continuously participate in washing work after softened water is supplemented, so that the process water amount added in the process is reduced, and the waste water amount generated in the process is greatly reduced; the water washing filtrate after twice use can be sent to a pyridine recovery device for recovering pyridine, and due to the absence of other solvents, the phenomena of multi-component azeotrope, material entrainment and the like formed by pyridine, water and other solvents do not exist, and the pyridine yield is improved by 20 percent compared with the pyridine yield obtained by using a mixed solvent;
the methanol-containing filtrate after methanol washing and centrifugation is recycled, so that the using amount of methanol is reduced;
because only one solvent is used, the occurrence of side reactions in the process is reduced, the impurity types and contents in the finished product are reduced, and the purity and the thermal stability of the thiodicarb are improved;
dissolving methomyl in pyridine to prepare methomyl pyridine solution, adding the methomyl into a ligand synthesis kettle in the mode of the methomyl pyridine solution, wherein the reaction process belongs to liquid-solid reaction, the contact chance of reaction materials is more, and the reaction speed is high;
in the invention, SCl is added dropwise 2 In the process of mixing the methomyl pyridine solution, a circulating pump is used for circulation all the time, so that the mass transfer is strengthened, the dropwise added methomyl pyridine solution is added from the upper part of the reaction kettle, the main area of the reaction is also at the upper part of the reaction kettle, in the circulation process, the materials at the bottom of the reaction kettle also reach the upper part of the reaction kettle, the materials at the upper part of the reaction kettle gradually reach the bottom of the reaction kettle, and the reaction is simultaneously carried out in the reaction kettle, so that the materials are forced to be mixed, the contact and collision chances of the ligand of the main reaction materials and the 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, solid materials are sheared and become thin particles in the kettle, the number of the reactant particles in unit volume is increased, the collision and reaction probability is increased, and the reaction speed is further accelerated.
[ detailed description ] A
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described by the following embodiments, but is by no means limited thereto. The following is a description of the preferred embodiments of the present invention, and should not be taken as limiting the invention, but rather as embodying the invention in its broadest form and as indicating any variations, equivalents and modifications within the spirit and scope of the present invention.
The ligand synthesis kettle provided by the invention is a reaction kettle with a high-speed shearing and grinding function, and specifically, the ligand synthesis kettle used in the following examples is a high-shear emulsification reaction kettle of Shanghai Hongshen mechanoelectronic Co., ltd., the model of the ligand synthesis kettle is HRHF-18.5.
The raw materials used in the examples of the present invention are as follows:
the content of methomyl is not lower than 97.0 percent;
SCl 2 the content is not lower than 97.0 percent;
the content of pyridine is not lower than 99.0 percent;
the mass content of the methanol is 99.0 percent.
Example 1
(1) 468Kg of pyridine is taken and sucked into a methomyl dissolving kettle by vacuum, stirring is started, 300Kg of methomyl is added, the pyridine is dissolved to obtain a methomyl pyridine solution, and the methomyl pyridine solution is sucked into a methomyl solution head tank by vacuum;
(2) Taking 369Kg of pyridine, sucking the pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the ligand synthesis kettle; at the same time, 101KgSCl is mixed with nitrogen 2 Pressing in SCl 2 A head tank;
(3) When the temperature in the retainer synthesis kettle reaches-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 40 minutes, and controlling the dripping time to be SCl 2 The temperature is 10 ℃ when dripping; SCl 2 After the addition was complete, stirring was continued for 20 minutes, during which time the stirring was continuedThe ring pump is continuously started, and the materials are continuously circulated;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 180 minutes, controlling the reaction temperature to be 25 ℃ during dropwise adding, continuously operating the circulating pump in the operation process, continuously circulating the materials, continuously stirring for 20 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) Adding 528Kg of softened water into the washing kettle, starting stirring, adding the centrifugal filter cake prepared in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to be 30 ℃, and stirring for 90 minutes; then, pumping the materials in the washing kettle into a plate-and-frame filter press by a mud pump for filter pressing to obtain washing filtrate and washing filter cakes, and recovering the washing filtrate to a 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 be 30 ℃, and stirring for 80 minutes;
(8) Feeding the material containing the methanol in the methanol washing kettle in the step (7) into a centrifuge, centrifuging to obtain filtrate containing the methanol and a filter cake, feeding the filtrate containing the methanol into a methanol metering tank for later use, feeding the filter cake into a double-cone dryer, and drying at a temperature lower than 45 ℃ and a vacuum degree not lower than 0.08MPa in the dryer to obtain 311.9Kg of finished thiodicarb product and 318Kg of generated process wastewater;
the content of thiodicarb is analyzed to be 98.31%, and the yield of thiodicarb is 96.44%;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 2.5 percent and is 5 percent lower than the national standard requirement, 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 embodiment 1 into a pyridine metering tank, supplementing fresh pyridine to 474Kg, sucking the pyridine into a methomyl dissolving 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 head tank by using vacuum;
(2) Measuring 378Kg of fresh pyridine, sucking the fresh pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the ligand synthesis kettle; at the same time, 103Kg of SCl was purged with nitrogen 2 Pressing in SCl 2 A head tank;
(3) When the temperature in the retainer synthesis kettle reaches-5 ℃, SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 30 minutes at SCl 2 The temperature is 8 ℃ when dripping; SCl 2 After the dropwise addition is finished, stirring is continuously carried out for 15 minutes, the circulating pump is continuously started during the stirring, and the materials are continuously circulated;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 200 minutes, controlling the reaction temperature to be 30 ℃ during dropwise adding, continuously operating the circulating pump in the operation process, continuously circulating the materials, continuously stirring for 30 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) Adding the washing filtrate obtained in the step (6) in the embodiment 1 into a washing filtrate metering tank, supplementing fresh softened water to 600Kg, adding the washing filtrate into a washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to 25 ℃, stirring for 100 minutes, pumping the materials in the washing kettle into a plate-and-frame filter press by a slurry pump, performing filter pressing to obtain washing filtrate and washing filter cake, and recovering the washing filtrate to a pyridine recovery device to recover pyridine;
(7) Feeding the methanol-containing filtrate obtained by centrifugation in the step (8) in the example 1 into a methanol metering tank, adding fresh methanol to 522Kg, adding the fresh methanol into a methanol washing kettle, starting stirring, adding the water-washed 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 carrying out centrifugation;
(8) Feeding the material containing the methanol obtained in the step (7) into a centrifuge, centrifuging to obtain filtrate containing the methanol and a filter cake, feeding the filtrate containing the methanol into a methanol distillation device to recover the methanol, feeding the filter cake into a double-cone dryer, and drying at a temperature lower than 45 ℃ and a vacuum degree not lower than 0.08MPa in the dryer to obtain 311.6Kg of a thiodicarb finished product and 390Kg of generated process wastewater;
analyzing the content of the thiodicarb to be 98.18 percent, and calculating the yield of the thiodicarb to be 96.22 percent;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 3.1 percent and is 5 percent lower than the national standard requirement, and other indexes are analyzed to meet the national standard requirement.
Example 3
(1) Adding the pyridine-containing centrifugate obtained by centrifuging the filter press in the step (5) in a pyridine metering tank, supplementing fresh pyridine to 468Kg, sucking the pyridine into a methomyl dissolving kettle by using vacuum, starting stirring, adding 300Kg of methomyl, obtaining a methomyl pyridine solution after the methomyl is completely dissolved, and sucking the methomyl pyridine solution into a methomyl solution head tank by using vacuum;
(2) Adding the pyridine recovered by the pyridine recovery device in the step (6) in the example 2 into a pyridine metering tank, supplementing fresh pyridine to 390Kg, sucking the pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the synthesis kettle; at the same time, 103Kg of SCl was purged with nitrogen 2 Pressing into SCl 2 A head tank;
(3) When the temperature in the ligand synthesis kettle reaches-6 ℃, the SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 45 minutes, SCl 2 The temperature during dripping is 5 ℃, SCl 2 After the dropwise addition is finished, stirring is continuously carried out for 30 minutes, the circulating pump is continuously started during the stirring, and the materials are continuously circulated;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 190 minutes, controlling the reaction temperature to be 20 ℃ during dropwise adding, continuously operating the circulating pump in the operation process, continuously circulating the materials, continuously stirring for 25 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) Adding softened water to 570Kg into a washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to be 30 ℃, stirring for 110 minutes, pumping the materials in the washing kettle into a plate-and-frame filter press by a mud pump, and press-filtering to obtain washing filtrate and washing filter cake, and recovering the washing filtrate;
(7) Metering 522Kg of fresh methanol, adding the fresh 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 be 30 ℃, stirring for 100 minutes, and centrifuging;
(8) Feeding the methanol-containing material obtained in the step (7) into a centrifuge, centrifuging to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for later use, feeding the filter cake into a double-cone dryer, and drying at a temperature of lower than 45 ℃ and a vacuum degree of not lower than 0.08MPa in the dryer to obtain 311.4Kg of thiodicarb finished product and 388Kg of generated process wastewater;
analyzing the thiodicarb content to be 98.03 percent, and calculating the yield of the thiodicarb to be 96.01 percent;
the thiodicarb is subjected to a thermal storage stability test according to the GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 3.1 percent and is lower than the national standard requirement by 5 percent, and 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 embodiment 3 into a pyridine metering tank, supplementing fresh pyridine to 445Kg, sucking the pyridine into a methomyl dissolving 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 head tank by using vacuum;
(2) Measuring 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; at the same time, 103KgSCl is mixed with nitrogen 2 Pressing in SCl 2 A head tank;
(3) When the temperature in the ligand synthesis kettle reaches-6 ℃, the SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 50 minutes and SCl 2 The temperature is 14 ℃ when dripping; SCl 2 After the dropwise addition is finished, continuously stirring for 25 minutes, continuously starting a circulating pump during the stirring, and continuously circulating the materials;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 240 minutes, controlling the reaction temperature to be 34 ℃ during dropwise adding, continuously operating the circulating pump in the operation process, continuously circulating the materials, continuously stirring for 25 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) Adding the washing filtrate obtained in the step (6) in the embodiment 3 into a washing filtrate metering tank, supplementing fresh softened water to 540Kg, then adding the washing filtrate into a washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to 35 ℃, stirring for 120 minutes, then pumping the materials in the washing kettle into a plate-and-frame filter press by a mud pump, carrying out filter pressing to obtain washing filtrate and washing filter cake, and recovering the washing filtrate to a pyridine recovery device to recover pyridine;
(7) Feeding the methanol-containing filtrate obtained by centrifuging in the step (8) in the embodiment 3 into a methanol metering tank, adding fresh methanol to 519Kg, adding the methanol into a methanol washing kettle, starting stirring, adding the water-washed 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 centrifuging;
(8) Feeding the material containing the methanol obtained in the step (7) into a centrifuge, centrifuging to obtain filtrate containing the methanol and a filter cake, feeding the filtrate containing the methanol into a methanol distillation device to recover the methanol, feeding the filter cake into a double-cone dryer, and drying at a temperature of lower than 45 ℃ and a vacuum degree of not lower than 0.08MPa in the dryer to obtain 310.6Kg of finished thiodicarb, and generating 333Kg of process wastewater;
analyzing the content of the thiodicarb to be 98.28 percent, and calculating the yield of the thiodicarb to be 96.01 percent;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 2.9 percent and is lower than the national standard requirement by 5 percent, and other indexes are analyzed to meet the national standard requirement.
Example 5
(1) Adding the pyridine-containing centrifugate obtained by centrifuging the filter press in the step (5) in the embodiment 4 into a pyridine metering tank, supplementing 465Kg of pyridine, sucking the pyridine into a methomyl dissolving kettle by using vacuum, starting stirring, adding 300Kg of methomyl, obtaining a methomyl pyridine solution after the methomyl is completely dissolved, and sucking the methomyl pyridine solution into a methomyl solution head tank by using vacuum;
(2) Adding the pyridine recovered by the pyridine recovery device in the step (6) in the example 4 into a pyridine metering tank, supplementing fresh pyridine to 381Kg, sucking the pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen saline into a jacket of the synthesis kettle; at the same time, 102KgSCl is mixed with nitrogen 2 Pressing in SCl 2 A head tank;
(3) When the temperature in the retainer synthesis kettle reaches-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 35 minutes, SCl 2 The temperature during dripping is 6 ℃, SCl 2 After the dropwise addition is finished, stirring is continuously carried out for 30 minutes, the circulating pump is continuously started during the stirring, and the materials are continuously circulated;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 210 minutes, controlling the reaction temperature to be 30 ℃ during dropwise adding, continuously operating the circulating pump in the process, continuously circulating the materials, continuously stirring for 30 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) Adding 630Kg of softened water into the washing kettle, starting stirring, adding the centrifugal filter cake obtained in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to be 38 ℃, stirring for 120 minutes, and then starting filter pressing; pumping the materials in the washing kettle into a plate-and-frame filter press by a mud pump for filter pressing to obtain washing filtrate and washing filter cake, and recovering the washing filtrate;
(7) Adding the methanol recovered by the methanol distillation device in the step (8) in the embodiment 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 sending to centrifugation;
(8) Feeding the methanol-containing material obtained in the step (7) into a centrifuge, centrifuging to obtain methanol-containing filtrate and a filter cake, feeding the methanol-containing filtrate into a methanol metering tank for recycling, feeding the filter cake into a double-cone dryer, and drying at a temperature of lower than 45 ℃ and a vacuum degree of not lower than 0.08MPa in the dryer to obtain 311.3Kg of thiodicarb finished product and 420Kg of generated process wastewater;
analyzing the content of the thiodicarb to be 98.14 percent, and calculating the yield of the thiodicarb to be 96.09 percent;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 3.7 percent and is lower than the national standard requirement by 5 percent, and 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 jacket of the ligand synthesis kettle; simultaneously using nitrogen to react 101KgsCl 2 Pressing in SCl 2 A head tank;
(2) When the temperature in the retainer synthesis kettle reaches-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 40 minutes, and controlling the dripping time to be SCl 2 The temperature is 10 ℃ when dripping; SCl 2 After the dropwise addition is finished, stirring is continuously carried out for 20 minutes, the circulating pump is continuously started during the stirring, and the materials are continuously circulated;
(3) Adding 300Kg of methomyl into a ligand synthesis kettle, continuously operating a circulating pump in the operation process, continuously circulating the materials, continuously stirring for 180 minutes, and stopping the circulating pump after the reaction is finished;
(4) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(5) Adding 528Kg of softened water into the washing kettle, starting stirring, adding the centrifugal filter cake prepared in the step (5) into the washing kettle, adjusting the temperature in the washing kettle to be 30 ℃, and stirring for 90 minutes; then, pumping the materials in the washing kettle into a plate-and-frame filter press by a mud pump for filter pressing to obtain washing filtrate and washing filter cakes;
(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 be 30 ℃, and stirring for 80 minutes;
(7) Feeding the material containing methanol in the methanol washing kettle in the step (6) into a centrifuge, centrifuging to obtain filtrate containing methanol and a filter cake, feeding the filtrate containing methanol into a methanol metering tank for later use, feeding the filter cake into a double-cone dryer, and drying at a temperature of lower than 45 ℃ and a vacuum degree of not lower than 0.08MPa in the dryer to obtain 305.6Kg of finished thiodicarb product and 322Kg of generated process wastewater;
the content of thiodicarb is analyzed to be 96.54%, and the yield of thiodicarb is 92.79%;
the thiodicarb is subjected to a thermal storage stability test according to the GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 5.2 percent, which is 5 percent higher than the national standard requirement, and the product is unqualified.
Reason analysis: first step reaction, pyridine with SCl 2 The ligand obtained by the reaction is solid fine particles which are dispersed in a system, after the solid methomyl is added, the solid methomyl and the ligand solid have very low reaction speed and can react with each other to generate the thiodicarb by dissolving the solid methomyl in pyridine solvent; therefore, after the solid methomyl is added, the two materials do not react sufficiently within the specified reaction time, although the content of the thiodicarb reaches 96.54 percent, the yield of the thiodicarb is 92.79 percent, and the product is judged to be unqualified because the thiodicarb contains other impurities to cause the unqualified heat storage stability test.
Comparative example 2
The same as example 1 except that the ligand synthesis vessel used in this comparative example was a conventional enamel reactor, and SCl was added dropwise 2 And methomyl pyridine solutionIn the process, a circulating pump is not used for circulation, and 305.2Kg of thiodicarb finished product is finally obtained, and 320Kg of process wastewater is generated;
the content of thiodicarb is analyzed to be 96.11%, and the yield of thiodicarb is 92.26%;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 4.3 percent and is 5 percent lower than the national standard requirement, and other indexes are analyzed to meet the national standard requirement.
Reason analysis: comparative example 2 the ligand synthesis reactor used was a conventional enamel reactor having a structure and a quality in accordance with the standards promulgated by the ministry of the original chemical industry, wherein the type of the stirrer was a major factor affecting heat and mass transfer. Although the impeller type stirrer can form a main body circulation which is much larger than that of an anchor type stirrer and a paddle type stirrer and has strong stirring effect, when the same main body circulation amount 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 impeller type stirrer has the defects that the distribution of the provided shearing in the reaction kettle is not uniform, 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 the impeller, the integral mixing of the materials in the reaction kettle is influenced, and the purity and the yield of the finished thiodicarb are influenced.
The reaction kettle used in the application is a reaction kettle with a high-speed shearing and grinding function, and generates great shearing, friction, impact and mutual collision and friction among materials under the action of mechanical force and fluid mechanics effect to break dispersed phase particles or liquid drops, the linear velocity of the rotating teeth is gradually increased from the inner ring to the outer ring, the crushing environment is continuously improved, the materials are crushed to be finer and finer under the action of increasingly strong shearing, friction, impact, collision and the like in the moving process of the outer ring, the large-amplitude mixing of the ligand and the methomyl is increased, the reaction speed is increased, and the purity and the yield of the finished thiodicarb are increased.
Comparative example 3
The difference from example 1 is that, in this case,the molar ratio of the materials in the comparative example is as follows: methomyl pyridine SCl 2 Methanol =1, 15.22, specifically as follows:
(1) Taking 470Kg of pyridine, sucking into a methomyl dissolution kettle by vacuum, starting stirring, adding 300Kg of methomyl, dissolving the methomyl by using the pyridine to obtain a methomyl pyridine solution, and sucking the methomyl pyridine solution into a methomyl solution head tank by vacuum;
(2) Sucking 404Kg of pyridine into a ligand synthesis kettle by using vacuum, starting stirring, and introducing frozen brine into a jacket of the ligand synthesis kettle; at the same time, nitrogen gas is used to react 105KgSCl 2 Pressing in SCl 2 A head tank;
(3) When the temperature in the retainer synthesis kettle reaches-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump, controlling the dripping time to be 40 minutes, and controlling the dripping time to be SCl 2 The temperature is 10 ℃ when dripping; SCl 2 After the dropwise addition is finished, continuously stirring for 20 minutes, continuously starting a circulating pump during the stirring, and continuously circulating the materials;
(4) Dropwise adding a methomyl pyridine solution into the ligand synthesis kettle from the methomyl solution head tank, controlling the dropwise adding time to be 180 minutes, controlling the reaction temperature to be 25 ℃ during dropwise adding, continuously operating the circulating pump in the operation process, continuously circulating the materials, continuously stirring for 20 minutes after the dropwise adding of the methomyl pyridine solution is finished, and stopping the circulating pump after the reaction is finished;
(5) Pressing the materials in the ligand synthesis kettle into a centrifugal filter press by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, and recovering the centrifugal liquid containing pyridine;
(6) 507Kg of softened water is added into the washing kettle, stirring is started, the centrifugal filter cake prepared in the step (5) is added into the washing kettle, the temperature in the washing kettle is adjusted to be 30 ℃, and stirring is carried out for 90 minutes; then, pumping the materials in the washing kettle into a plate-and-frame filter press by using a slurry pump for filter pressing to obtain washing filtrate and washing filter cakes, and recovering the washing filtrate to a washing filtrate metering tank;
(7) Adding 518Kg 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 be 30 ℃, and stirring for 80 minutes;
(8) Feeding the material containing methanol in the methanol washing kettle in the step (7) into a centrifuge, centrifuging to obtain filtrate containing methanol and a filter cake, feeding the filtrate containing methanol into a methanol metering tank for later use, feeding the filter cake into a double-cone dryer, and drying at a temperature of lower than 45 ℃ and a vacuum degree of not lower than 0.08MPa in the dryer to obtain 303.7Kg of finished thiodicarb product and generate 320Kg of process wastewater;
the content of thiodicarb is analyzed to be 96.12%, and the yield of thiodicarb is 91.81%;
the thiodicarb is subjected to a thermal storage stability test according to the standard GB/T19136-2003 pesticide thermal storage stability determination method, the decomposition rate of the thiodicarb is 4.5 percent and is 5 percent lower than the national standard requirement, and other indexes are analyzed to meet the national standard requirement.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The green thiodicarb synthesis process capable of reducing the generation amount of wastewater is characterized by comprising the following steps of:
(1) Preparing materials: separately metering pyridine and SCl 2 And methomyl, pyridine is divided into two parts according to the proportion, one part is added into a ligand synthesis kettle, chilled water is introduced into a jacket of the ligand synthesis kettle, the other part and the methomyl are added into a methomyl dissolution kettle, methomyl is dissolved to prepare methomyl pyridine solution, and the methomyl pyridine solution is transferred to a methomyl head tank; SCl 2 Pressing in SCl 2 A head tank;
(2) When the temperature in the retainer synthesis kettle is not higher than-4 ℃, SCl is dripped 2 Simultaneously starting a circulating pump;
(3) To be SCl 2 After the dropping, dropping the methomyl pyridine solution in the methomyl head tank into a ligand synthesis kettle for reaction, and keeping a circulating pump always on in the process;
(4) After the reaction is finished, pressing the materials in the ligand synthesis kettle into a centrifuge by using nitrogen for solid-liquid separation to obtain a centrifugal liquid containing pyridine and a centrifugal filter cake, recovering the centrifugal liquid containing pyridine, and adding the centrifugal liquid containing pyridine into a methomyl dissolution kettle or the ligand synthesis kettle for recycling;
(5) Adding the centrifugal filter cake obtained in the step (4) into a washing kettle for washing, adding the washed material into a plate-and-frame filter press for filter pressing to obtain washing filtrate and washing filter cake, and recovering the washing filtrate;
(6) Washing the water-washed filter cake obtained in the step (5) by methanol, centrifuging and drying to obtain the thiodicarb finished product.
2. The thiodicarb green synthesis process for reducing wastewater production according to claim 1, wherein the molar ratio of the materials is: methomyl pyridine SCl 2 The water comprises methanol (5.795-6.016), water (0.516-0.545), water (16.133-20.266) and water (8.886-9.035).
3. The process for green synthesis of thiodicarb with reduced wastewater generation as claimed in claim 1, wherein the mass ratio of pyridine to methomyl used for dissolving methomyl in step (1) is: (1.5-1.6) is 1.
4. The process for green synthesis of thiodicarb with reduced wastewater production as claimed in claim 1, wherein SCl in step (2) 2 The dropping time of (3) is 30-50 min; the temperature at the time of dropping is not higher than 15 ℃.
5. The process for green synthesis of thiodicarb with reduced wastewater production as claimed in claim 1, wherein the dropping time of the methomyl pyridine solution in step (3) is controlled to be 180-240 min, and the temperature is controlled to be not higher than 35 ℃.
6. The green thiodicarb synthesis process capable of reducing wastewater production according to claim 1, wherein the temperature in the washing kettle is controlled to be not higher than 40 ℃ in the washing process in the step (5), and the washing is performed for 90-120 min under stirring.
7. The process for green synthesis of thiodicarb with reduced wastewater production as claimed in claim 1, wherein the washing filtrate recovered in step (5) is fed into a washing filtrate metering tank, fresh softened water is added to a predetermined amount, and then the washing filtrate is fed into a washing kettle for washing, the washing filtrate obtained after two times of use is fed into a pyridine recovery unit for recovering pyridine, and the recovered pyridine is fed into the methomyl dissolution kettle or the ligand synthesis kettle for recycling.
8. The green thiodicarb synthesis process capable of reducing the wastewater generation amount according to claim 1, wherein the methanol washing and centrifugation process in step (6) is specifically to add the water-washed filter cake obtained in step (5) into a methanol washing kettle, control the temperature in the methanol washing kettle to be not higher than 40 ℃, stir and wash for 80-100 minutes to obtain a methanol-containing material, and send the methanol-containing material into a centrifuge for centrifugation to obtain a methanol-containing filtrate and a filter cake.
9. The green thiodicarb synthesis process capable of reducing wastewater generation amount according to claim 8, wherein the methanol-containing filtrate obtained in step (6) is supplemented with fresh methanol, and then added into a methanol washing kettle to continuously wash the water-washed filter cake obtained in step (5), and the twice-processed methanol-containing filtrate is fed into a methanol distillation device to recover methanol.
10. The process for green synthesis of thiodicarb with reduced wastewater production as claimed in claim 8, wherein the drying step in step (6) is carried out by feeding the filter cake obtained after centrifugation into a double-cone dryer, and drying at a temperature of not higher than 45 ℃ and a vacuum of not lower than 0.08 MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047106A (en) * | 2017-12-26 | 2018-05-18 | 湖南海利常德农药化工有限公司 | The preparation method of sulphur sulfate |
| CN212284039U (en) * | 2019-12-02 | 2021-01-05 | 河南金鹏化工有限公司 | Continuous production device for thiodicarb salinization reaction |
| CN112479957A (en) * | 2021-01-22 | 2021-03-12 | 潍坊海邦化工有限公司 | Synthesis method of thiodicarb |
| CN112778179A (en) * | 2021-01-29 | 2021-05-11 | 湖南海利常德农药化工有限公司 | Synthesis method of thiodicarb |
| CN114031533A (en) * | 2021-11-15 | 2022-02-11 | 山东华阳农药化工集团有限公司 | Preparation method of high-content thiodicarb |
| CN114315672A (en) * | 2021-12-14 | 2022-04-12 | 山东第一医科大学(山东省医学科学院) | Thiodicarb synthesis method with high methomyl conversion rate |
-
2022
- 2022-11-02 CN CN202211373050.5A patent/CN115626886B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047106A (en) * | 2017-12-26 | 2018-05-18 | 湖南海利常德农药化工有限公司 | The preparation method of sulphur sulfate |
| CN212284039U (en) * | 2019-12-02 | 2021-01-05 | 河南金鹏化工有限公司 | Continuous production device for thiodicarb salinization reaction |
| CN112479957A (en) * | 2021-01-22 | 2021-03-12 | 潍坊海邦化工有限公司 | Synthesis method of thiodicarb |
| CN112778179A (en) * | 2021-01-29 | 2021-05-11 | 湖南海利常德农药化工有限公司 | Synthesis method of thiodicarb |
| CN114031533A (en) * | 2021-11-15 | 2022-02-11 | 山东华阳农药化工集团有限公司 | Preparation method of high-content thiodicarb |
| CN114315672A (en) * | 2021-12-14 | 2022-04-12 | 山东第一医科大学(山东省医学科学院) | Thiodicarb synthesis method with high methomyl conversion rate |
Non-Patent Citations (1)
| Title |
|---|
| 柴生勇等: "（硫双灭多威合成路线研究", 陕西化工, pages 23 - 25 * |
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