CN110981766A - Method for treating waste sulfuric acid in mesotrione production - Google Patents
Method for treating waste sulfuric acid in mesotrione production Download PDFInfo
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- CN110981766A CN110981766A CN201911157551.8A CN201911157551A CN110981766A CN 110981766 A CN110981766 A CN 110981766A CN 201911157551 A CN201911157551 A CN 201911157551A CN 110981766 A CN110981766 A CN 110981766A
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- sulfuric acid
- mesotrione
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for treating waste sulfuric acid in mesotrione production, which comprises the following steps: carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonyl benzoic acid under the oxidation condition of 0.2-0.5A/cm3The oxidation time is 20-40 min; then a ceramic filter with the pore diameter less than or equal to 100nm is used for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid; adding white sugar into waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the sulfuric acid to the liquid surface by the foam, and filtering to remove the foam; the spent sulfuric acid is concentrated to the desired concentration. The method for treating the waste sulfuric acid has the advantages of mild condition, high speed and low cost, and the treated sulfuric acid can be recycledThe generation system not only saves the raw material cost, but also avoids the environmental pollution caused by the discharge of waste water.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a method for treating waste sulfuric acid in mesotrione production.
Background
Mesotrione is generally prepared by condensation rearrangement reaction of an intermediate 2-nitro-4-methylsulfonylbenzoyl chloride, and a large amount of concentrated sulfuric acid is required for nitration in a method for preparing 2-nitro-4-methylsulfonylbenzoyl chloride by chlorination of 2-nitro-4-methylsulfonylbenzoyl acid, so that a large amount of waste sulfuric acid containing 2-nitro-4-methylsulfonylbenzoic acid is generated, the concentration of the waste sulfuric acid is about 40%, the content of 2-nitro-4-methylsulfonylbenzoyl chloride is 0.5-1%, the corrosiveness is strong, and the direct discharge can cause serious environmental pollution.
At present, organic matters in waste sulfuric acid are usually removed by an extraction mode in the prior art, a large amount of organic solvent is needed in the method, the cost is high, and the extracted organic solvent is difficult to treat; the other treatment method is to use the waste sulfuric acid as a catalyst and hydrogen peroxide as an oxidant to self-catalytically oxidize organic matters in the waste sulfuric acid, and the method needs to heat the sulfuric acid to 100-180 ℃, has high energy consumption and higher requirement on the corrosion resistance of a container, and greatly increases the treatment cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for treating waste sulfuric acid in mesotrione production, so that the treated waste sulfuric acid can be recycled, and the method has the advantages of mild condition, high speed and low cost, not only saves the raw material cost, but also reduces the environmental pollution.
The technical scheme provided by the invention is as follows:
a process for treating waste sulfuric acid from mesotrione production, comprising the steps of:
(1) carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonyl benzoic acid under the oxidation condition of 0.2-0.5A/cm3The oxidation time is 20-40 min;
(2) then a ceramic filter with the pore diameter less than or equal to 100nm is used for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid;
(3) adding white sugar into waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the sulfuric acid to the liquid surface by the foam, and filtering to remove the foam;
(4) the spent sulfuric acid is concentrated to the desired concentration.
On the basis of the technical scheme, the adding amount of the white sugar is 5-10g of white sugar added to each liter of waste sulfuric acid.
On the basis of the technical scheme, the three-dimensional electrolytic oxidation conditions are as follows: the current is 0.2-0.5A/cm3And the electrolysis time is 20-40 min.
On the basis of the technical scheme, the pore diameter of the ceramic filter is not more than 50 nm.
On the basis of the technical scheme, the step (4) distills and concentrates the waste sulfuric acid to the required concentration at the temperature of more than 140 ℃.
On the basis of the technical scheme, the step (4) carries out falling film concentration on the waste sulfuric acid at 114-116 ℃ to obtain sulfuric acid with the concentration of 70 wt%, then concentrated sulfuric acid with the concentration of 98 wt% is added to adjust the concentration to 85 wt%, and then the mixture is frozen and crystallized at 5-7 ℃ to obtain refined sulfuric acid crystals with the concentration of 85 wt%.
On the basis of the technical scheme, the three-dimensional electrolytic oxidation adopts a copper cathode and a titanium anode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method for treating the waste sulfuric acid has the advantages of mild conditions, high speed and low cost, and the treated sulfuric acid can be recycled to a generation system, so that the raw material cost is saved, and the environmental pollution caused by wastewater discharge is avoided.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1: the production process of mesotrione comprises the following steps:
(1) adding 500 weight parts of 98% concentrated sulfuric acid, 350 weight parts of p-methylsulfonyl toluene and 1100 weight parts of oxidized aqueous mother liquor into a nitration reaction kettle, and then, 5 hoursUniformly dropwise adding 180 parts by weight of 98% nitric acid for nitration reaction, and keeping the temperature for 70min after dropwise adding to obtain nitrified liquid; introducing the nitrifying liquid into an oxidation reaction kettle, and then adding 5 parts by weight of catalyst V2O5After the temperature is raised to 142 ℃, 890 parts by weight of 68 percent nitric acid is uniformly dripped in the mixture within 19 hours, and the reaction temperature is controlled to be 146 ℃; uniformly dropwise adding 350 parts by weight of 50% nitric acid within 14.5 hours, and simultaneously controlling the reaction temperature to be 144 ℃; after the addition, the temperature was maintained for 1 hour. Cooling the reaction solution to 50 ℃, then carrying out filter pressing to obtain an oxidation product and an oxidation aqueous mother solution, and circularly rinsing the oxidation product by 1100 parts by weight of water; adding NaOH solution into the oxidation product to adjust the pH value to 9.0 so as to dissolve the oxidation product, and controlling the temperature to be 60 ℃ in the adding process; discharging the materials while the materials are hot, centrifuging, dropwise adding hydrochloric acid to adjust the pH value to 2, keeping the temperature at 60 ℃ for 30min, cooling to 35 ℃, centrifuging and rinsing to obtain refined 2-nitro-4-methylsulfonylbenzoic acid; drying at 55 deg.C to obtain 2-nitro-4-methylsulfonylbenzoic acid; acyl chlorination: adding thionyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonyl benzoic acid and DMF (dimethyl formamide) to perform heating reflux reaction, reacting for 11-12 hours, and distilling to separate the thionyl chloride to obtain 2-nitro-4-methylsulfonyl-benzoyl chloride.
(2) Condensation rearrangement: dissolving the obtained 2-nitro-4-methylsulfonylbenzoyl chloride with dichloromethane, cooling to 15 ℃, adding 165 parts by weight of 1, 3-cyclohexanedione, and uniformly dropwise adding 175 parts by weight of triethylamine within 80min to perform esterification condensation; adding 15 parts by weight of acetone cyanohydrin, dropwise adding 160 parts by weight of triethylamine for rearrangement reaction, adding hydrochloric acid to adjust the pH value to about 1.0, separating liquid, washing with water, adding water for distillation to recover dichloromethane, discharging, and performing suction filtration to obtain crude sulcotrione; and putting the pumped crude mesotrione into a refining reaction kettle while the mesotrione is hot, stirring for 40min at 55 ℃, discharging, pumping and filtering, feeding the mother liquor into a methanol distillation kettle, distilling and refining to recover methanol, and drying and carrying out jet milling on the solid product to obtain a mesotrione finished product.
A large amount of waste sulfuric acid is generated in the production process of the mesotrione, and H in the waste sulfuric acid is measured2SO4The concentration of (A) is 40 wt% to 50 wt%.
Example 2
Carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by using a copper cathode and a titanium anode, wherein the oxidation condition is controlled to be 0.2A/cm3Oxidizing for 30min to obtain great amount of carbide in waste sulfuric acid, and coarse filtering with 100nm ceramic filter to eliminate small molecular suspended matter;
adding 5g of white sugar into each liter of waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the waste sulfuric acid to the liquid surface by the foam, and filtering to remove the foam;
evaporating and concentrating the filtered sulfuric acid at 145 ℃ to H2SO4The concentration of (B) is 70 wt%.
Example 3
Carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by using a copper cathode and a titanium anode, wherein the oxidation condition is controlled to be 0.5A/cm3Oxidizing for 30min to obtain great amount of carbide in waste sulfuric acid, and coarse filtering with 100nm ceramic filter to eliminate small molecular suspended matter;
adding 7g of white sugar into each liter of waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the waste sulfuric acid to the liquid surface by the foam, and filtering to remove the foam;
evaporating and concentrating the filtered sulfuric acid at 145 ℃ to H2SO4The concentration of (B) was 85 wt%.
Example 4
Carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by using a copper cathode and a titanium anode, wherein the oxidation condition is controlled to be 0.3A/cm3Oxidizing for 30min to obtain great amount of carbide in waste sulfuric acid, and coarse filtering with 100nm ceramic filter to eliminate small molecular suspended matter;
adding 5g of white sugar into each liter of waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the waste sulfuric acid to the liquid surface by the foam, and filtering to remove the foam;
then carrying out falling film concentration at 114-116 ℃ to obtain sulfuric acid with the concentration of 70 wt%, then adding concentrated sulfuric acid with the concentration of 98 wt% to adjust the sulfuric acid to 85 wt%, and then carrying out freeze crystallization at 5-7 ℃ to obtain refined sulfuric acid crystals with the concentration of 85 wt%.
The embodiments described above are presented to enable those skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations can be made without departing from the scope and spirit of the invention as defined by the appended claims.
Claims (7)
1. A method for treating waste sulfuric acid in mesotrione production is characterized by comprising the following steps:
(1) carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonyl benzoic acid under the oxidation condition of 0.2-0.5A/cm3The oxidation time is 20-40 min;
(2) then a ceramic filter with the pore diameter less than or equal to 100nm is used for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid;
(3) adding white sugar into waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping micro impurities in the sulfuric acid to the liquid surface by the foam, and filtering to remove the foam;
(4) the spent sulfuric acid is concentrated to the desired concentration.
2. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: the addition amount of white sugar is 5-10g per liter of waste sulfuric acid.
3. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: the three-dimensional electrolytic oxidation conditions are as follows: the current is 0.2-0.5A/cm3And the electrolysis time is 20-40 min.
4. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: the pore size of the ceramic filter is not more than 50 nm.
5. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: in the step (4), the waste sulfuric acid is distilled and concentrated to the required concentration at the temperature of more than 140 ℃.
6. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: in the step (4), the waste sulfuric acid is subjected to falling film concentration at 114-116 ℃ to obtain sulfuric acid with the concentration of 70 wt%, then concentrated sulfuric acid with the concentration of 98 wt% is added to adjust the concentration to 85 wt%, and then the mixture is subjected to freeze crystallization at 5-7 ℃ to obtain refined sulfuric acid crystals with the concentration of 85 wt%.
7. The process of treating spent sulfuric acid from mesotrione production as claimed in claim 1, wherein: the three-dimensional electrolytic oxidation adopts a copper cathode and a titanium anode.
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Citations (8)
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|---|---|---|---|---|
| US4406760A (en) * | 1981-11-25 | 1983-09-27 | Exxon Research & Engineering Co. | Electrolytic process for treating sulfuric acid streams |
| US5523518A (en) * | 1992-12-16 | 1996-06-04 | Chlorine Engineers Corp., Ltd. | Recycling of waste sulfuric acid |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
| CN104030409A (en) * | 2014-06-12 | 2014-09-10 | 盐城工学院 | Method for electrochemical pretreatment on methyl sulcotrione pesticide wastewater |
| CN104086438A (en) * | 2014-06-30 | 2014-10-08 | 浙江中山化工集团股份有限公司 | Recycling process of methyl sulcotrione solvent |
| CN107673523A (en) * | 2017-11-17 | 2018-02-09 | 惠州市臻鼎环保科技有限公司 | A kind of recovery and treatment method of nitration mixture waste water |
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| US4406760A (en) * | 1981-11-25 | 1983-09-27 | Exxon Research & Engineering Co. | Electrolytic process for treating sulfuric acid streams |
| US5523518A (en) * | 1992-12-16 | 1996-06-04 | Chlorine Engineers Corp., Ltd. | Recycling of waste sulfuric acid |
| CN102219191A (en) * | 2011-04-20 | 2011-10-19 | 江苏亚邦染料股份有限公司 | Recycling method for waste sulfuric acid of dye intermediate product |
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| CN109052337A (en) * | 2018-08-27 | 2018-12-21 | 青岛惠城信德新材料研究院有限公司 | A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge |
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