CN110981766B - 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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- CN110981766B CN110981766B CN201911157551.8A CN201911157551A CN110981766B CN 110981766 B CN110981766 B CN 110981766B CN 201911157551 A CN201911157551 A CN 201911157551A CN 110981766 B CN110981766 B CN 110981766B
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- sulfuric acid
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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
Abstract
The invention discloses a method for treating waste sulfuric acid in mesotrione production, which comprises the following steps: three-dimensional electrolytic oxidation is carried out on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonylbenzoic acid under the oxidation condition of 0.2-0.5A/cm 3 The oxidation time is 20-40min; then, a ceramic filter with the aperture less than or equal to 100nm is utilized for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid; adding white sugar into the waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping tiny impurities in the sulfuric acid to the liquid level 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 recycled to the generation system, so that the raw material cost is saved, and the environmental pollution caused by wastewater discharge is avoided.
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-methanesulfonyl benzoyl chloride, and in the method for preparing the 2-nitro-4-methanesulfonyl benzoyl chloride by acyl chlorination of 2-nitro-4-methanesulfonyl benzoyl chloride, a large amount of concentrated sulfuric acid is required for nitration, so that a large amount of waste sulfuric acid containing the 2-nitro-4-methanesulfonyl benzoyl acid is generated, the concentration of the waste sulfuric acid is about 40%, the content of the 2-nitro-4-methanesulfonyl benzoyl chloride is 0.5-1%, the corrosiveness is strong, and the direct discharge can cause serious environmental pollution.
At present, the prior art generally uses an extraction mode to remove organic matters in the waste sulfuric acid, and the method needs a large amount of organic solvents, has high cost and is difficult to treat the extracted organic solvents; the other treatment method is to use waste sulfuric acid as a catalyst and hydrogen peroxide as an oxidant to perform self-catalytic oxidation on organic matters in the waste sulfuric acid, and the method needs to heat the sulfuric acid to 100-180 ℃, has high energy consumption and high requirement on 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, which can achieve the aim of recycling the treated waste sulfuric acid.
The technical scheme provided by the invention is as follows:
a method for treating waste sulfuric acid in mesotrione production, comprising the following steps:
(1) Three-dimensional electrolytic oxidation is carried out on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonylbenzoic acid under the oxidation condition of 0.2-0.5A/cm 3 The oxidation time is 20-40min;
(2) Then, a ceramic filter with the aperture less than or equal to 100nm is utilized for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid;
(3) Adding white sugar into the waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping tiny impurities in the sulfuric acid to the liquid level 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 proposal, the addition amount of the white sugar is 5-10g of white sugar per liter of waste sulfuric acid.
Based on the technical scheme, the three-dimensional electrolytic oxidation conditions are as follows: the current is 0.2-0.5A/cm 3 The electrolysis time is 20-40min.
On the basis of the technical scheme, the pore diameter of the ceramic filter is not more than 50nm.
Based on the technical scheme, the step (4) is to distill and concentrate the waste sulfuric acid to the required concentration at the temperature of 140 ℃ or above.
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 70wt%, then adds concentrated sulfuric acid with the concentration of 98wt% to adjust the concentration to 85wt%, and then carries out freezing crystallization at 5-7 ℃ to obtain 85wt% refined sulfuric acid crystal.
Based on the technical proposal, copper cathode and titanium anode are adopted for three-dimensional electrolytic oxidation.
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 condition, high speed and low cost, and the treated sulfuric acid can be recycled to the generation system, so that the raw material cost is saved, and the environmental pollution caused by wastewater discharge is avoided.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. The reagents and starting materials used were purchased commercially, unless otherwise indicated. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1: the production process of mesotrione comprises the following steps:
(1) Adding 500 parts by weight of 98% concentrated sulfuric acid, 350 parts by weight of p-methylsulfonyl toluene and 1100 parts by weight of oxidized aqueous mother liquor into a nitration reaction kettle, uniformly dropwise adding 180 parts by weight of 98% nitric acid within 5 hours for nitration reaction, and preserving heat for 70 minutes after dropwise adding to obtain a nitration solution; introducing the nitrified liquid into an oxidation reaction kettle, and then adding 5 parts by weight of catalyst V 2 O 5 After the temperature is raised to 142 ℃, 890 parts by weight of 68% nitric acid are uniformly added dropwise within 19 hours, and the reaction temperature is controlled to be 146 ℃; then uniformly dripping 350 parts by weight of 50% nitric acid within 14.5 hours, and controlling the reaction temperature to be 144 ℃; the temperature was kept for 1 hour after the completion of the dropwise addition. Cooling the reaction liquid to 50 ℃, and then performing filter pressing to obtain an oxidation product and an oxidation aqueous mother liquid, and circularly rinsing the oxidation product by using 1100 parts by weight of water; adding NaOH solution to the oxidation product to adjust pH to 9.0 to dissolve the oxidation product, controlling temperature during the addition process60 ℃; then discharging and centrifuging while the mixture is hot, 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-methylsulfonyl benzoic acid; drying at 55 ℃ to obtain 2-nitro-4-methylsulfonyl benzoic acid; acid chlorination: adding thionyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonyl benzoic acid and DMF to perform heating reflux reaction, and distilling and separating the thionyl chloride after reacting for 11-12 hours to obtain 2-nitro-4-methylsulfonyl-benzoyl chloride.
(2) Condensation rearrangement: after the obtained 2-nitro-4-methylsulfonyl benzoyl chloride is dissolved by methylene dichloride, the temperature is reduced to 15 ℃, 165 parts by weight of 1, 3-cyclohexanedione is added, and 175 parts by weight of triethylamine is uniformly added dropwise within 80 minutes for esterification condensation; then 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 to about 1.0, separating liquid, washing with water, adding water for distillation to recover dichloromethane, discharging and suction-filtering to obtain crude sulcotrione; and (3) putting the filtered crude sulcotrione into a refining reaction kettle while the sulcotrione is hot, stirring for 40min at 55 ℃, discharging, performing suction filtration, feeding the mother solution into a methanol distillation kettle, distilling and refining to recover methanol, and drying and jet-pulverizing a solid product to obtain a sulcotrione finished product.
A large amount of waste sulfuric acid is generated in the production process of mesotrione, and H in the waste sulfuric acid is measured 2 SO 4 The concentration of (2) is 40wt% to 50wt%.
Example 2
Three-dimensional electrolytic oxidation is carried out on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by utilizing a copper cathode and a titanium anode, and the oxidation condition is controlled to be 0.2A/cm 3 Oxidizing for 30min, wherein a large amount of carbide appears in the waste sulfuric acid, and coarse filtering to remove small molecular suspended matters by using a ceramic filter with the aperture of 100 nm;
adding 5g of white sugar into each liter of waste sulfuric acid, reacting sulfuric acid with white sugar to generate foam, wrapping tiny impurities in the waste sulfuric acid to the liquid level by the foam, and filtering to remove the foam;
evaporating and concentrating the filtered sulfuric acid to H at 145 DEG C 2 SO 4 The concentration of (2) was 70wt%.
Example 3
Three-dimensional electrolytic oxidation is carried out on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by utilizing a copper cathode and a titanium anode, and the oxidation condition is controlled to be 0.5A/cm 3 Oxidizing for 30min, wherein a large amount of carbide appears in the waste sulfuric acid, and coarse filtering to remove small molecular suspended matters by using a ceramic filter with the aperture of 100 nm;
adding 7g of white sugar into each liter of waste sulfuric acid, reacting sulfuric acid with white sugar to generate foam, wrapping tiny impurities in the waste sulfuric acid to the liquid level by the foam, and filtering to remove the foam;
evaporating and concentrating the filtered sulfuric acid to H at 145 DEG C 2 SO 4 The concentration of (2) was 85wt%.
Example 4
Three-dimensional electrolytic oxidation is carried out on waste sulfuric acid generated in the 2-nitro-4-methylsulfonyl benzoic acid synthesis process by utilizing a copper cathode and a titanium anode, and the oxidation condition is controlled to be 0.3A/cm 3 Oxidizing for 30min, wherein a large amount of carbide appears in the waste sulfuric acid, and coarse filtering to remove small molecular suspended matters by using a ceramic filter with the aperture of 100 nm;
adding 5g of white sugar into each liter of waste sulfuric acid, reacting sulfuric acid with white sugar to generate foam, wrapping tiny impurities in the waste sulfuric acid to the liquid level 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 70wt%, then adding concentrated sulfuric acid with the concentration of 98wt% to adjust the concentration to 85wt%, and then carrying out freeze crystallization at 5-7 ℃ to obtain 85wt% refined sulfuric acid crystals.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present invention is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, make improvements and modifications within the scope and spirit of the present invention.
Claims (2)
1. A method for treating waste sulfuric acid in mesotrione production, which is characterized by comprising the following steps:
(1) The method comprises the steps of carrying out three-dimensional electrolytic oxidation on waste sulfuric acid generated in the synthesis process of 2-nitro-4-methylsulfonylbenzoic acid, wherein the oxidation conditions are as follows: the current is 0.2-0.5A/cm 3 The oxidation time is 20-40min; the three-dimensional electrolytic oxidation adopts a copper cathode and a titanium anode;
(2) Then, a ceramic filter with the aperture less than or equal to 100nm is utilized for coarse filtration to remove small molecular suspended matters in the waste sulfuric acid;
(3) Adding white sugar into the waste sulfuric acid, reacting the sulfuric acid with the white sugar to generate foam, wrapping tiny impurities in the sulfuric acid to the liquid level by the foam, and filtering to remove the foam; the addition amount of the white sugar is 5-10g of white sugar added per liter of waste sulfuric acid;
(4) Concentrating the waste sulfuric acid to 70wt% or 85wt% at 140 deg.c; or alternatively
The waste sulfuric acid is subjected to falling film concentration at 114-116 ℃ to obtain sulfuric acid with the concentration of 70wt%, then concentrated sulfuric acid with the concentration of 98wt% is added to adjust the concentration to 85wt%, and then the sulfuric acid is subjected to freezing crystallization at 5-7 ℃ to obtain 85wt% refined sulfuric acid crystals.
2. The method for treating waste sulfuric acid in mesotrione production according to claim 1, wherein: the pore size of the ceramic filter is not more than 50nm.
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| US4406760A (en) * | 1981-11-25 | 1983-09-27 | Exxon Research & Engineering Co. | Electrolytic process for treating sulfuric acid streams |
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| 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 |
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2019
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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 |
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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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