CN114685447A - Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production - Google Patents
Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production Download PDFInfo
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- CN114685447A CN114685447A CN202210492232.8A CN202210492232A CN114685447A CN 114685447 A CN114685447 A CN 114685447A CN 202210492232 A CN202210492232 A CN 202210492232A CN 114685447 A CN114685447 A CN 114685447A
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- CN
- China
- Prior art keywords
- imidacloprid
- mother liquor
- concentrated mother
- production
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000005906 Imidacloprid Substances 0.000 title claims abstract description 53
- 229940056881 imidacloprid Drugs 0.000 title claims abstract description 53
- 239000012452 mother liquor Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract 2
- 230000008025 crystallization Effects 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 150000007522 mineralic acids Chemical class 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000011027 product recovery Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- -1 chloronicotinyl Chemical group 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a method for recovering imidacloprid from concentrated mother liquor residue in imidacloprid production. Under the condition of stirring, adding a non-polar solvent into the imidacloprid concentrated mother liquor residue at 0-35 ℃, dropwise adding an inorganic strong acid, and reacting the inorganic strong acid with the imidacloprid in the mother liquor residue at a molar ratio of 1.0-5.0: 1. Stirring for a certain time, standing to separate out an acid water layer, adding a non-polar solvent into the acid water layer, dropwise adding an alkali liquor while stirring to neutralize to the pH of 7-8, standing to separate out a solvent layer, cooling for crystallization, and filtering to obtain the imidacloprid product. After the imidacloprid product is recovered from the mother liquor concentrated slag, the three wastes are reduced, and the product synthesis yield is improved.
Description
Technical collar city
The invention relates to a method for recovering imidacloprid products from concentrated mother liquor residues in imidacloprid production.
Background
Imidacloprid (Imidacloprid), 1- (6-chloro-3-picolyl) -N-nitroimidazolidine-2-imine, is a chloronicotinyl insecticide that can be absorbed systemically and is used in soil, seeds and leaves to control piercing-sucking mouthparts pests, including rice lice (ricehopper), aphids, thrips, whiteflies, termites, turf pests, soil insects, and beetles. The pesticide is most commonly used on rice, cereals, corn, potatoes, vegetables, sugar beets, fruits, cotton, hops or turf. The pesticide may be absorbed systemically in particular when it is used for the treatment of seeds or soil.
In the production of imidacloprid, more concentrated mother liquor residues are generated after the centrifugal mother liquor of the product is distilled and the solvent is recovered for reuse, about 250kg of concentrated mother liquor residues are generated per ton of the product, wherein the quantitative content of imidacloprid is about 30 percent. Originally, when solid waste is treated, the treatment cost is increased, and the yield is low, the consumption is high, and the production cost is high.
Disclosure of Invention
The invention provides a method for recovering imidacloprid from concentrated mother liquor residue in imidacloprid production, which is convenient, low in recovery cost and high in yield.
The invention provides a method for recovering imidacloprid from concentrated mother liquor residue in imidacloprid production. Under the condition of stirring, adding a non-polar solvent into the imidacloprid concentrated mother liquor residue at 0-35 ℃, dropwise adding an inorganic strong acid, and reacting the inorganic strong acid with the imidacloprid in the mother liquor residue at a molar ratio of 1.0-5.0: 1. Stirring for a certain time, standing to separate an acid water layer, adding a nonpolar solvent into the acid water layer, dropwise adding an alkali liquor while stirring to neutralize the pH value to 7-8, standing to separate a solvent layer, cooling to crystallize, and filtering to obtain the imidacloprid product.
The alkali liquor is potassium hydroxide or sodium hydroxide, preferably sodium hydroxide.
The non-polar solvent is dichloromethane or dichloroethane, preferably dichloromethane.
Preferably, the acidification temperature is carried out at 25 ℃ to obtain high recovery of imidacloprid.
The concentration of the alkali liquor is preferably 30%.
The mol ratio of the inorganic strong acid to the imidacloprid in the mother liquor slag is preferably 2.0: 1.
Because the molecular structure of the imidacloprid contains a pyridine ring, an SP2 hybrid orbit on a nitrogen atom on the ring does not participate in bonding and is occupied by a pair of lone-pair electrons, so that the pyridine has alkalinity. Therefore, pyridine and strong acid can form stable salt, and the salt is dissolved in water, so that imidacloprid is separated from imidazolidine and other impurities without pyridine rings. The pyridinium is neutralized by adding alkali, and then extracted by adding a nonpolar solvent, and then cooled and crystallized to realize imidacloprid recovery, wherein the imidacloprid recovery purity is as high as more than 97%, the recovery rate is higher than 50%, and the recovery materials are only acid, a nonpolar solvent and alkali liquor, so the method has high economic value.
Detailed Description
The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
The imidacloprid production concentrated mother liquor (100g) is added into a four-neck flask, 100g of dichloroethane is added, 27.6g (0.2344 mol) of 31% hydrochloric acid is added dropwise under stirring, the reaction is exothermic, and the reaction temperature is kept below 35 ℃. After the completion of the dropwise addition, the mixture was stirred for 30 minutes and then allowed to stand for 1 hour. Separating the lower solvent layer, concentrating the solvent layer and removing slag. Adding 20g of dichloroethane into the water layer, dropwise adding 30% sodium hydroxide solution while stirring, neutralizing until the pH is 7-8, standing for layering, cooling and crystallizing the solvent layer, filtering at-5-0 ℃, and drying to obtain 18.9g of imidacloprid product with the purity of 97.12%. The product recovery rate is 61.18%. The filtrate is combined into the first solvent layer for desolventizing and deslagging.
Example 2
The imidacloprid production concentrated mother liquor (100g) is added into a four-neck flask, 100g of dichloroethane is added, 20.7g (0.1758 mol) of 31 percent hydrochloric acid is added dropwise under stirring, the reaction is exothermic, and the reaction temperature is kept below 35 ℃. After the completion of the dropwise addition, the mixture was stirred for 30 minutes and then allowed to stand for 1 hour. Separating the lower solvent layer, concentrating the solvent layer and removing slag. Adding 20g of dichloroethane into a water layer, dropwise adding 30% sodium hydroxide solution while stirring, neutralizing until the pH is 7-8, standing for layering, cooling and crystallizing a solvent layer, filtering at-5-0 ℃, and drying to obtain 17.04g of imidacloprid product with the purity of 97.03%. The product recovery rate is 55.12%. The filtrate is combined into the first solvent layer for desolventizing and deslagging.
Example 3
The imidacloprid production concentrated mother liquor (100g) is added into a four-neck flask, 100g of dichloromethane is added, 27.6g (0.2344 mol) of 31 percent hydrochloric acid is added dropwise under stirring, the reaction is exothermic, and the reaction temperature is kept below 35 ℃. After the completion of the dropwise addition, the mixture was stirred for 30 minutes and then allowed to stand for 1 hour. Separating the lower solvent layer, and concentrating the solvent layer to remove residue. And adding 20g of dichloromethane into the water layer, dropwise adding 30% sodium hydroxide solution while stirring, neutralizing until the pH is 7-8, standing for layering, cooling and crystallizing the solvent layer, filtering at-5-0 ℃, and drying to obtain 18.1g of imidacloprid product with the purity of 97.22%. The product recovery rate is 58.66%. The filtrate is combined into the first solvent layer for desolventizing and deslagging.
Example 4
The imidacloprid production concentrated mother liquor (100g) is added into a four-neck flask, 100g of dichloroethane is added, 27.6g (0.2344 mol) of 31 percent hydrochloric acid is added dropwise under stirring, the reaction is exothermic, and the reaction temperature is kept below 35 ℃. After the completion of the dropwise addition, the mixture was stirred for 30 minutes and then allowed to stand for 1 hour. Separating the lower solvent layer, concentrating the solvent layer and removing slag. Adding 20g of dichloroethane into the water layer, dropwise adding 30% potassium hydroxide solution while stirring, neutralizing until the pH is 7-8, standing for layering, cooling and crystallizing the solvent layer, filtering at-5-0 ℃, and drying to obtain 18.6g of imidacloprid product with the purity of 97.06%. The product recovery rate is 60.18%. The filtrate is combined into the first solvent layer for desolventizing and deslagging.
Claims (6)
1. A method for recovering imidacloprid from concentrated mother liquor slag in imidacloprid production is characterized by comprising the following steps: under the condition of stirring, adding a non-polar solvent into the imidacloprid concentrated mother liquor residue at 0-35 ℃, dropwise adding an inorganic strong acid, reacting the inorganic strong acid with the imidacloprid in the mother liquor residue, stirring, standing to separate an acid water layer, adding the non-polar solvent into the acid water layer, dropwise adding an alkali liquor under stirring to neutralize to the pH of 7-8, standing to separate a solvent layer, cooling for crystallization, and filtering to obtain the imidacloprid product.
2. The method for recovering imidacloprid from the concentrated mother liquor residue in imidacloprid production as claimed in claim 1, which is characterized in that: the strong inorganic acid and the imidacloprid in the mother liquor slag react at a molar ratio of 1.0-5.0: 1.
3. The method for recovering imidacloprid from the concentrated mother liquor residue in imidacloprid production as claimed in claim 1, characterized in that: the strong inorganic acid is hydrochloric acid or sulfuric acid.
4. The method for recovering imidacloprid from the concentrated mother liquor residue in imidacloprid production as claimed in claim 1, which is characterized in that: the non-polar solvent is dichloromethane or dichloroethane.
5. The method for recovering imidacloprid from the concentrated mother liquor residue in imidacloprid production as claimed in claim 1, which is characterized in that: the reaction of the concentrated mother liquor and the inorganic strong acid is carried out at 0-35 ℃.
6. The method for recovering imidacloprid from the concentrated mother liquor residue in imidacloprid production as claimed in claim 1, which is characterized in that: the alkali liquor is sodium hydroxide or potassium hydroxide solution, and the concentration of the alkali liquor is 10-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210492232.8A CN114685447A (en) | 2022-05-07 | 2022-05-07 | Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210492232.8A CN114685447A (en) | 2022-05-07 | 2022-05-07 | Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114685447A true CN114685447A (en) | 2022-07-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210492232.8A Pending CN114685447A (en) | 2022-05-07 | 2022-05-07 | Method for recycling imidacloprid from concentrated mother liquor residue in imidacloprid production |
Country Status (1)
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040210054A1 (en) * | 2003-04-17 | 2004-10-21 | Bor-Kuan Chen | Process for the preparation of diamine single-sided condensation products |
| CN1847241A (en) * | 2006-04-17 | 2006-10-18 | 江苏长青农化股份有限公司 | Synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine |
| CN1860884A (en) * | 2005-05-12 | 2006-11-15 | 青岛科技大学 | Admire and monoformamidine hydrochloride aqueous agent and its prodn. method |
| CN101434597A (en) * | 2008-12-15 | 2009-05-20 | 沙隆达集团公司 | Method for recycling imidacloprid from imidacloprid production mother liquor |
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN107540657A (en) * | 2017-10-25 | 2018-01-05 | 湖北沙隆达股份有限公司 | Mother liquor processing method caused by one kind 98% imidacloprid original powder of production |
-
2022
- 2022-05-07 CN CN202210492232.8A patent/CN114685447A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040210054A1 (en) * | 2003-04-17 | 2004-10-21 | Bor-Kuan Chen | Process for the preparation of diamine single-sided condensation products |
| CN1860884A (en) * | 2005-05-12 | 2006-11-15 | 青岛科技大学 | Admire and monoformamidine hydrochloride aqueous agent and its prodn. method |
| CN1847241A (en) * | 2006-04-17 | 2006-10-18 | 江苏长青农化股份有限公司 | Synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine |
| CN101434597A (en) * | 2008-12-15 | 2009-05-20 | 沙隆达集团公司 | Method for recycling imidacloprid from imidacloprid production mother liquor |
| CN101921261A (en) * | 2010-08-25 | 2010-12-22 | 青岛海利尔药业有限公司 | Process for separating and recovering behind a kind of imidacloprid synthesis |
| CN107540657A (en) * | 2017-10-25 | 2018-01-05 | 湖北沙隆达股份有限公司 | Mother liquor processing method caused by one kind 98% imidacloprid original powder of production |
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