CN113248066A - Method for treating waste water of kungfu acid - Google Patents
Method for treating waste water of kungfu acid Download PDFInfo
- Publication number
- CN113248066A CN113248066A CN202110540187.4A CN202110540187A CN113248066A CN 113248066 A CN113248066 A CN 113248066A CN 202110540187 A CN202110540187 A CN 202110540187A CN 113248066 A CN113248066 A CN 113248066A
- Authority
- CN
- China
- Prior art keywords
- waste water
- acid
- water
- kungfu
- wastewater
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
- C02F1/265—Desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Extraction Or Liquid Replacement (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The operations of water washing and acid washing in the saponification and acidification reactions of the cyhalothrin acid require the addition of a large amount of water or dilute acid to wash the reaction products, thereby generating a large amount of salt-containing organic wastewater. The waste water has complex components, high concentration and high chroma and is difficult to treat. Most of organic substances in water are unsaturated organic substances containing organic fluorine or organic chlorine, and the substances are difficult to be biochemically degraded and even belong to biological toxic substances. The characteristics of the waste water determine that the waste water can not be treated by traditional methods such as coagulating sedimentation, biochemistry and the like, so that the treatment difficulty is very high. The invention discloses a method for treating waste water of kongfu acid, which is characterized by comprising the following steps: adding an alcohol solvent into the waste water of the cyhalothrin acid for full extraction, standing for layering, adjusting a water layer to be neutral, dehydrating and desalting by adopting MVR, and distilling and recovering an organic layer under reduced pressure. The method is simple in treatment, is suitable for industrial production, can greatly reduce the generation of wastewater, and reduces the COD content of high-concentration wastewater, thereby reducing the production cost.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating waste water by using cyhalothrin acid.
Background
Cyhalothric acid is also called trifluoro-chloro-chrysanthemic acid, trifluoro-monochloro-chrysanthemic acid and cyhalothric acid, the chemical name of the cyhalothric acid is 3- (2-chloro-3, 3, 3-trifluoro-1-propylene-1-yl) -2, 2-dimethyl cyclopropane carboxylic acid, which is an important intermediate for synthesizing a pyrethroid insecticide and is widely applied to the synthesis of high-efficiency low-toxicity pesticide raw medicines such as cyhalothrin, bifenthrin, heptafluoropenthrin and the like.
The preparation method of the trifluorchloromycetic acid is mainly based on the process developed by the American Fumei company (FMC), for example, the method described in US 4263319A and US4332815A, and is improved to a certain extent, see CN105503582A and CN 106008210A.
The preparation method mainly comprises the steps of taking methyl cardianate and trichlorotrifluoroethane (F113a) as raw materials, and carrying out three-step reactions of addition, cyclization, hydrolysis, saponification and acidification. Finally, the product of the trifluor-chloro-chrysanthemic acid is produced. The wastewater treatment of the kungfu acid is always a troublesome problem.
Firstly, the operations of water washing and acid washing in the saponification and acidification reactions of the cyhalothrin acid require the addition of a large amount of water or dilute acid to wash the reaction products, thereby generating a large amount of salt-containing organic wastewater. According to the prior art, each ton of the gongfu acid is produced into about 20 tons of concentrated salt wastewater according to the process conditions, the wastewater amount is large, the treatment cost is high, and the effective utilization is difficult.
Secondly, the waste water has complex components, high concentration and high chroma and is difficult to treat. Most of organic substances in water are unsaturated organic substances containing organic fluorine or organic chlorine, and the substances are difficult to be biochemically degraded and even belong to biological toxic substances. In addition, acid-base regulation and other neutralization steps in the production process generate a large amount of sodium chloride or sodium sulfate, and the salt content is about 5-15%. The characteristics of the waste water determine that the waste water can not be treated by traditional methods such as coagulating sedimentation, biochemistry and the like, so that the treatment difficulty is very high.
In CN109896683A, concentrated salt wastewater generated in the production process (cyclization and saponification) of kungfu acid is subjected to oil separation and multiple-effect evaporation to obtain a byproduct sodium chloride salt. The oil removal equipment has large investment and high production cost. CN106186147A and CN110228867A perform complexing extraction on the waste water of kungfu acid production by using a specific complexing extraction agent under an acid environment, wherein the complexing extraction agent comprises a complexing agent, a cosolvent and a diluent. The preparation method is that under the laboratory condition, the industrialized and continuous production can not be realized, and a large amount of wastewater produced in the industry is difficult to treat.
Therefore, the development of a low-cost industrial treatment method of kungfu acid, which is easy for wastewater treatment, is needed.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for treating waste water of kongfu acid, which has the advantages of easily available reagent raw materials, simple reaction and post-treatment and suitability for industrial production, can greatly reduce the generation of waste water, reduce the COD content of high-concentration waste water and further reduce the production cost.
A method for treating waste water of kungfu acid is characterized by comprising the following steps: adding an alcohol solvent into the waste water of the cyhalothrin acid for full extraction, standing for layering, adjusting a water layer to be neutral, dehydrating and desalting by adopting MVR, and distilling and recovering an organic layer under reduced pressure.
Preferably, the solubility of the alcohol solvent in water is 0.05-8%, preferably 1-3%.
Preferably, the alcoholic solvent is a monohydric alcohol.
Preferably, the alcohol solvent is at least one of butanol, pentanol, hexanol, heptanol and octanol, and preferably at least one of pentanol, hexanol and heptanol.
Preferably, potassium chloride or sodium chloride is contained in the waste water of the kungfu acid.
Preferably, the mass ratio of the waste water of the cyhalothrin acid to the alcohol solvent is 1: 0.1 to 0.5.
Preferably, the extraction is one of single-stage extraction, multi-stage counter-current extraction and continuous counter-current extraction.
The applicant finds that because the salt content of the waste water of the kungfu acid is 160000PPm and the waste water amount is larger, the waste water is discharged after being dehydrated and desalted by MVR, and because the COD in the waste water is larger than 110000PPm, the rest is organic impurities except a small amount of methanol. Directly advance MVR after saponification transfers the alkali and can lead to organic impurity enrichment in the mother liquor, form the oiliness, can't filter salt, because the enrichment of organic impurity simultaneously, lead to waste water boiling point to rise higher, surpass MVR temperature rise, finally lead to the unable normal operating of MVR. Therefore, organic impurities in the wastewater need to be extracted firstly, then MVR is carried out, and the mother liquor is recycled after the wastewater is concentrated, so that the salt is filtered normally.
Theoretically, the extractant should be immiscible with the original solvent, however, after several attempts by the applicant to perform wastewater extraction tests using dichloroethane, ethyl acetate (or isopropyl acetate), n-amyl alcohol and other solvents, it was found that it was difficult to obtain the expected technical effect when using a water-immiscible solvent. When dichloroethane is used, extraction needs to be carried out for three times, organic matters are still mixed in the concentrated salt, although COD of distilled water is minimum, the extraction times are more, the operation is complex, and the extraction efficiency is too low. The solubility of the ethyl acetate in water is about 8 percent, the ethyl acetate is easy to decompose under the acidic condition of the wastewater, the COD of the water distilled out after the ethyl acetate extraction is about 80000, the COD is too high to enter a biochemical pool and still needs to be further treated, and when the wastewater is extracted by the alcohol which is difficult to dissolve in water, the unexpected treatment effect is achieved. And when and only when the solubility of the alcohol in water is 1-3%, the technical effect of treatment is best, when the n-amyl alcohol is adopted for extracting the wastewater, only one extraction is needed, the salt can be normally filtered, the mother liquor can be continuously used, and the COD of the distilled water is within an acceptable range and can be directly treated. If the solubility of the alcohol in water is too high or too low, the treatment effect is deteriorated.
Compared with the prior art, the invention has the following advantages:
1. the kungfu acid wastewater is extracted by the specific alcohol, so that organic impurities are removed, the generation of wastewater can be greatly reduced, the COD content of high-concentration wastewater is reduced, and the production cost is further reduced.
2. After toxic pollutants containing fluorine and chlorine in the unsaturated carboxylic acid in the wastewater are removed, the quality of the subsequent evaporation byproduct salt and the treatment effect of the evaporated water are improved.
3. The invention uses alcohol as extractant, which is cheap and easy to get, and can further reduce production cost by recycling.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
Taking 600g of the waste water of the cyhalothrin acid (the salt is potassium chloride or sodium chloride), adding 150g of n-amyl alcohol, stirring, standing for layering, adjusting the water layer to be neutral by using alkali, dehydrating under reduced pressure for desalting, and evaporating the organic layer under reduced pressure for recovering the solvent for reuse.
After extraction, the waste water COD31500 is evaporated out by decompression, and after filtration, the salt content is 98.2 percent.
Example 2
Taking 600g of the waste water of the kungfu acid (salt is potassium chloride or sodium chloride), adding 150g of n-butyl alcohol, stirring, standing for layering, adjusting the water layer to be neutral by using alkali, dehydrating under reduced pressure for desalting, and evaporating the organic layer under reduced pressure for recovering the solvent for reuse.
After extraction, the waste water COD is evaporated out by decompression, 56000, and after filtration, the salt content is 98.6%.
Example 3
Taking 600g of the waste water of the cyhalothrin acid (the salt is potassium chloride or sodium chloride), adding 150g of n-octanol, stirring, standing for layering, adjusting the water layer to be neutral by alkali, decompressing, dehydrating and desalting, decompressing the organic layer, and evaporating the solvent back for reuse.
After extraction, the waste water COD28000 is evaporated out under reduced pressure, and after filtration, the salt content is 96.5 percent.
Example 4
Taking 600g of the waste water of the cyhalothrin acid (salt is potassium chloride or sodium chloride), adding 150g of mixed solution of n-amyl alcohol and n-butyl alcohol (the mass ratio of the n-amyl alcohol to the n-butyl alcohol is 1: 1), stirring, standing for layering, adjusting the water layer to be neutral by using alkali, performing reduced pressure dehydration for removing salt, and performing reduced pressure evaporation on the organic layer to recover the solvent for reuse.
After extraction, the waste water COD30500 is evaporated out by decompression, and after filtration, the salt content is 98.0 percent.
Comparative example 1
Taking 600g of the waste water of the cyhalothrin acid (the salt is potassium chloride or sodium chloride), directly dehydrating and desalting under reduced pressure without adding an extracting agent, distilling the waste water COD26500 under reduced pressure, and filtering to obtain the salt content of 94 percent. After the salt mother liquor is used for the second time, the organic impurities are enriched to form oily matters, so that the crystallized salt cannot be filtered.
Comparative example 2
Taking 600g of the waste water of the kungfu acid (salt is potassium chloride or sodium chloride), adding 150g of dichloroethane, stirring, standing for layering, adjusting the water layer to be neutral by using alkali, decompressing, dehydrating and desalting, decompressing the organic layer, and evaporating the solvent back for reuse. After extraction for three times, the standard is reached, the waste water COD21000 is evaporated out under reduced pressure, and the salt content is 96.1 percent after filtration.
Comparative example 3
Taking 600g of the waste water of the cyhalothrin acid (the salt is potassium chloride or sodium chloride), adding 150g of ethyl acetate, stirring, standing for layering, adjusting the water layer to be neutral by using alkali, dehydrating under reduced pressure for desalting, and evaporating the organic layer under reduced pressure for recovering the solvent for reuse. After extraction, the waste water COD80800 is evaporated out by decompression, and the salt content is 97.0 percent after filtration.
Comparative example 4
600g of the waste water of the kongfu acid (salt composition is potassium chloride or sodium chloride) is taken, 150g of propanol is added, and stirring is carried out. Since propanol is soluble in water, extraction cannot be achieved.
Comparative example 5
Taking 600g of the waste water of the kungfu acid (salt is potassium chloride or sodium chloride), adding 150g of decanol, stirring, standing for layering, adjusting the water layer to be neutral by alkali, decompressing, dehydrating and desalting, decompressing the organic layer, and evaporating the solvent back for reuse. After extraction, the waste water COD23800 is evaporated out under reduced pressure, and after filtration, the salt content is 94.5%.
The above examples and comparative examples are summarized as follows:
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for treating waste water of kungfu acid is characterized by comprising the following steps: adding an alcohol solvent into the waste water of the cyhalothrin acid for full extraction, standing for layering, adjusting a water layer to be neutral, dehydrating and desalting by adopting MVR, and distilling and recovering an organic layer under reduced pressure.
2. The method for treating the waste water of the kungfu acid as claimed in claim 1, wherein the solubility of the alcohol solvent in water is 0.05-8%, preferably 1-3%.
3. The method for treating waste water of kungfu acid as claimed in claim 1, wherein the alcohol solvent is monohydric alcohol.
4. The method for treating waste water of cyhalothrin acid as claimed in claim 1, wherein the alcohol solvent is at least one of butanol, pentanol, hexanol, heptanol and octanol, preferably at least one of pentanol, hexanol and heptanol.
5. The method according to claim 1, wherein potassium chloride or sodium chloride is contained in the waste water.
6. The method for treating waste water of kungfu acid as claimed in claim 1, wherein the mass ratio of the waste water of kungfu acid to the alcohol solvent is 1: 0.1 to 0.5.
7. The method of claim 1, wherein the extraction is one of single-stage extraction, multi-stage counter-current extraction, and continuous counter-current extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110540187.4A CN113248066B (en) | 2021-05-18 | 2021-05-18 | Cyhalous acid wastewater treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110540187.4A CN113248066B (en) | 2021-05-18 | 2021-05-18 | Cyhalous acid wastewater treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113248066A true CN113248066A (en) | 2021-08-13 |
| CN113248066B CN113248066B (en) | 2022-12-02 |
Family
ID=77182429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110540187.4A Active CN113248066B (en) | 2021-05-18 | 2021-05-18 | Cyhalous acid wastewater treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113248066B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB960936A (en) * | 1962-02-21 | 1964-06-17 | Gas Council | Improvements in and relating to the treatment of phenolic effluents |
| CN105384292A (en) * | 2015-11-13 | 2016-03-09 | 中蓝连海设计研究院 | H acid production industrial waste water treatment method |
| CN105906122A (en) * | 2016-05-23 | 2016-08-31 | 江苏瑞升华能源科技有限公司 | Treatment technology of high-organic matter high-salt wastewater and treatment device thereof |
| CN107686203A (en) * | 2017-09-27 | 2018-02-13 | 哈尔滨工业大学 | A kind of recycling treatment process using cross current solvent extraction method to H acid producing waste waters |
| CN110228867A (en) * | 2019-06-25 | 2019-09-13 | 北京惠宇乐邦环保科技有限公司 | A kind of preprocess method of time acid producing waste water |
| CN110627287A (en) * | 2019-10-24 | 2019-12-31 | 常州大学 | Device and method for treating high-concentration organic wastewater containing ammonium sulfate salt |
-
2021
- 2021-05-18 CN CN202110540187.4A patent/CN113248066B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB960936A (en) * | 1962-02-21 | 1964-06-17 | Gas Council | Improvements in and relating to the treatment of phenolic effluents |
| CN105384292A (en) * | 2015-11-13 | 2016-03-09 | 中蓝连海设计研究院 | H acid production industrial waste water treatment method |
| CN105906122A (en) * | 2016-05-23 | 2016-08-31 | 江苏瑞升华能源科技有限公司 | Treatment technology of high-organic matter high-salt wastewater and treatment device thereof |
| CN107686203A (en) * | 2017-09-27 | 2018-02-13 | 哈尔滨工业大学 | A kind of recycling treatment process using cross current solvent extraction method to H acid producing waste waters |
| CN110228867A (en) * | 2019-06-25 | 2019-09-13 | 北京惠宇乐邦环保科技有限公司 | A kind of preprocess method of time acid producing waste water |
| CN110627287A (en) * | 2019-10-24 | 2019-12-31 | 常州大学 | Device and method for treating high-concentration organic wastewater containing ammonium sulfate salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113248066B (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1620362B1 (en) | Process for producing 1, 3-propanediol | |
| CA2854114C (en) | A method and an arrangement for separating at least one carboxylic acid and furfural from a dilute aqueous mixture thereof | |
| CH678619A5 (en) | ||
| US20220259549A1 (en) | Method for Separating Biomass from Solid Fermentation Product | |
| CN113248066B (en) | Cyhalous acid wastewater treatment method | |
| CN1259310C (en) | Process for extracting and separating caprolactam from amide oil | |
| KR20120024771A (en) | Method for producing crystals of adipic acid | |
| CN107445349A (en) | A kind of recycling processing method of gallic acid production wastewater | |
| CN105152447B (en) | A kind of method administered acrylic acid wastewater and reclaim sodium acetate | |
| CN104276937A (en) | Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct | |
| CN1246234C (en) | Treatment of waste water in producing isophthalic acid dicarbomethoxy-5-sodium sulphonate and its resource utilization method | |
| JP3902069B2 (en) | Method for treating wastewater containing N, N-dimethylformamide | |
| WO2018229342A1 (en) | Extraction of furfural and optionally (an) organic acid(s) from their aqueous solution | |
| CN1126197A (en) | Removal of carbonyl impurities from alpha, beta-unsaturated carboxylic acids | |
| CN109368859B (en) | Zero-discharge treatment process for fluoride-applying wastewater in steroid drug production | |
| CN114436883A (en) | Method for recovering N, N-dimethylacetamide from multi-component solution system | |
| CN1317263C (en) | Process for producing SIPA using polyester dyeing modifier SIPM waste water as raw material | |
| CN117417247A (en) | Method for extracting lactic acid by using low-boiling point organic solvent | |
| KR20050037994A (en) | Application of scrubbing process for “method for treating of etching waste acid or waste acid” | |
| CN1300089C (en) | Method of preparing adipic acid by cyclohexane oxidation liquid pickling water HzO2 catalytic oxidation | |
| CN111704272B (en) | Method for treating hydroquinone-containing sewage and recovering resources | |
| CN113019355B (en) | Method for treating waste sulfuric acid in production of 2-nitro-4-methylsulfonyl benzoic acid | |
| CN111943297A (en) | Method for resourceful treatment of high-salinity high-organic wastewater | |
| CN107473291B (en) | Treatment method of high-salinity wastewater | |
| JP2024042251A (en) | How to obtain iodine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |