CN111302984B - Method for recycling acid in synthesis of 2-nitro-4-methylsulfonylbenzoic acid - Google Patents
Method for recycling acid in synthesis of 2-nitro-4-methylsulfonylbenzoic acid Download PDFInfo
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- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Abstract
A method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid comprises the following steps: 1) taking 4-methylsulfonyl toluene as a raw material, after completing nitration reaction and oxidation reaction in a concentrated sulfuric acid medium, filtering dilute acid mother liquor after 2-nitro-4-methylsulfonyl benzoic acid crude product, and concentrating to obtain recovered acid; 2) recovering acid for cyclic use, and removing a reaction byproduct polynitro compound from the dilute acid mother liquor by a resin adsorption method to ensure that the content of the polynitro compound in the adsorbed dilute acid mother liquor is less than 200 ppm; 3) concentrating the adsorbed dilute acid mother liquor, then applying the concentrated dilute acid mother liquor to nitration reaction, and after the nitration reaction is finished, adding the required catalyst and continuously using the catalyst for oxidation reaction; 4) desorbing and regenerating the adsorbed resin by solvent analysis, and recovering reaction byproducts after concentration, filtration and washing. The method avoids the safety and environmental protection risks caused by the continuous accumulation of the concentration of byproducts in the synthesis process, is safe, practical, green and environment-friendly, and is suitable for industrial implementation.
Description
Technical Field
The invention relates to a method for synthesizing 2-nitro-4-methylsulfonylbenzoic acid, in particular to a method for recycling recovered acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid.
Background
2-Nitro-4-methylsulfonylbenzoic acid, also known as o-Nitro-p-methylsulfonylbenzoic acid, having the name 2-Nitro-4-methylsulfonylbenzoic acid in English and the CAS number of 110964-79-9. 2-nitro-4-methylsulfonylbenzoic acid is an important intermediate for producing the herbicide mesotrione, and is widely used for producing dyes, medicines and pesticides. In the industrial production, 4-methylsulfonyl toluene is mainly used as a raw material, 2-nitro-4-methylsulfonyl toluene is obtained through nitration reaction in a concentrated sulfuric acid medium, then a 2-nitro-4-methylsulfonyl benzoic acid crude product is obtained through oxidation reaction of 2-nitro-4-methylsulfonyl toluene, and a 2-nitro-4-methylsulfonyl benzoic acid finished product is obtained through refining. Because the 2-nitro-4-methylsulfonyl toluene containing the electron-withdrawing group is difficult to oxidize, the oxidation reaction can be carried out in the presence of a catalyst.
A large amount of waste acid solution is generated in the synthesis process of the 2-nitro-4-methylsulfonylbenzoic acid, the waste acid solution is difficult to treat, and a side reaction can occur in the nitration reaction to generate 2, 6-dinitro-4-methylsulfonyltoluene and even polynitro side products. In the process of recycling the acid solution, the polynitro byproduct is accumulated continuously, when the concentration of the polynitro byproduct is high, the content and the yield of the product are affected, and meanwhile, the safety and environmental protection risks exist, so that the safe and stable implementation of industrial production is not facilitated, and the economic development of enterprises and society is restricted.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for recycling recovered acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid, wherein the recovered acid in the synthesis process is recycled for a certain period, and the polynitro byproduct is removed for recycling again.
In order to realize the purpose, the method for recycling the acid in the synthesis of the 2-nitro-4-methylsulfonylbenzoic acid comprises the following steps:
1) taking 4-methylsulfonyl toluene as a raw material, after completing nitration reaction and oxidation reaction in a concentrated sulfuric acid medium, filtering dilute acid mother liquor after 2-nitro-4-methylsulfonyl benzoic acid crude product, and concentrating to obtain recovered acid;
2) recovering acid for cyclic use, and removing a reaction byproduct polynitro compound from the dilute acid mother liquor by a resin adsorption method to ensure that the content of the polynitro compound in the adsorbed dilute acid mother liquor is less than 200 ppm;
3) concentrating the adsorbed dilute acid mother liquor, then applying the concentrated dilute acid mother liquor to nitration reaction, and after the nitration reaction is finished, adding the required catalyst and continuously using the catalyst for oxidation reaction;
4) desorbing and regenerating the adsorbed resin by solvent desorption to obtain resin desorption solution, and recovering reaction byproducts after concentration, filtration and washing.
Further, concentrating the dilute acid mother liquor obtained in the step 1) under the conditions that the vacuum degree is 0.095-0.1 Mpa and the temperature is 100-200 ℃ to obtain recovered acid containing 70-98% of sulfuric acid by mass percent.
Further, the cycle of recycling the recovered acid in the step 2) is 1-10 cycles.
Further, in the step 2), the resin adsorption method is adopted to remove the polynitro byproducts, and a nonpolar macroporous adsorption resin dual-column series adsorption column filled with styrene and divinylbenzene polymers as basic frameworks is adopted.
Further, step 2) the resin is selected from: one or more of HP20, HP20SS, HP21, SP70, SP700, SP825L, SP850, CHP20, CHP55, SP 207.
Further, the step 2) of removing the polynitro byproduct by using a resin adsorption method further comprises the following steps: and (2) under the condition that the temperature is 5-60 ℃, enabling the dilute acid mother liquor to pass through a double-column series adsorption column filled with resin at the flow rate of 0.5-4 times of the resin filling volume per hour, and then washing the adsorption column with 2-3 BV of water, so that the content of polynitro compounds in the adsorbed dilute acid mother liquor is less than 200 ppm.
Further, the molar equivalent of the sulfuric acid lost during the concentration in the step 1) is determined by an acid-base titration method after the concentration is finished, wherein the amount of the catalyst required for supplementing in the step 3) is 0-4%.
Further, the solvent used for desorption and regeneration of the resin in the step 4) through solvent analysis is one or more of acetone, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-butanol, isobutanol, isopropanol, methanol, ethanol and water.
Further, the resin in the step 4) is desorbed and regenerated by solvent desorption to obtain: and (3) at the temperature of 10-60 ℃, using 2-8 BV of the solvent to perform solvent analysis on the adsorption column at the flow rate of 0.5-8 BV/h for the next adsorption period.
Further, the step of concentrating, filtering and washing in step 4) and then recovering the reaction by-product comprises the steps of evaporating the solvent from the resin analysis solution obtained by desorption and regeneration through solvent analysis under the condition of negative pressure, precipitating the solid in a water phase, filtering, washing and drying to obtain the polynitro compound which is the nitration by-product.
Due to the implementation of the technical scheme, the invention not only realizes the safe recycling of the recovered acid for synthesizing the 2-nitro-4-methylsulfonylbenzoic acid, reduces the unit consumption of raw materials, solves the problem that a large amount of waste acid is difficult to treat, but also solves the safety and environmental protection risks generated by long-term accumulation of reaction by-products, namely polynitro compounds, and the yield and the content of the product both meet the target requirements. The method has the advantages of simple process, high safety, less three-waste pollution, environmental protection and suitability for industrial application.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and that the present invention is not limited by the following examples, and that the conditions employed in the examples may be further modified according to specific requirements, and that the conditions not specified are generally conditions in routine experimentation.
In the embodiment of the invention, the technical route of the recycling method for acid in the synthesis of 2-nitro-4-methylsulfonyl comprises the following steps:
1) 4-methylsulfonyl toluene is used as a raw material, after nitration reaction and oxidation reaction in a concentrated sulfuric acid medium are completed, dilute acid mother liquor after filtering a 2-nitro-4-methylsulfonylbenzoic acid crude product is concentrated under the conditions of a certain vacuum degree and a certain temperature to obtain a recovered acid with a certain concentration for the next batch of reaction;
2) after the recovered acid is circularly applied for a certain period, removing a reaction byproduct polynitro compound from the dilute acid mother liquor by adopting a resin adsorption method, so that the content of the polynitro compound in the adsorbed dilute acid mother liquor is less than 200 ppm;
3) concentrating the adsorbed dilute acid mother liquor from which the reaction by-products are removed in the step 2), applying the concentrated dilute acid mother liquor to the nitration reaction, and adding a catalyst after the nitration reaction is finished for continuing the oxidation reaction;
4) desorbing and regenerating the resin adsorbed in the step 2) by solvent analysis, and applying the resin to the next adsorption period;
5) and 4) concentrating, filtering, washing and drying the resin analysis liquid obtained in the step 4), and recovering reaction byproducts.
Example 1
Concentrating the dilute acid mother liquor obtained after filtering the 2-nitro-4-methylsulfonylbenzoic acid crude product to 170-180 ℃ under the condition of the vacuum degree of 0.095-0.1 MPa to obtain recovered acid with the concentration of 90-98%, continuously and circularly applying the recovered acid to the 4 th cycle, and taking 600g of the dilute acid mother liquor obtained after filtering, wherein the content of polynitro substituent is 6012ppm by analysis. Measuring 40ml of SP700 adsorption resin by using a measuring cylinder, respectively moving the SP700 adsorption resin into two adsorption columns, compacting the SP700 adsorption resin, and keeping the upper layer of the resin to have a water layer of 3-5 cm. Connecting the mother liquid of the diluted acid to be adsorbed, a peristaltic pump and two adsorption columns by using a rubber tube. Controlling the flow rate to be 0.5-1 BV/h by a peristaltic pump at the temperature of 5-10 ℃, enabling the dilute acid mother liquor to pass through an adsorption column, then washing the adsorption column by 80ml of water, merging effluent and the adsorbed dilute acid mother liquor, and analyzing to obtain 59ppm of polynitro substitutes in the adsorbed dilute acid mother liquor and more than 99% of polynitro substitutes.
And concentrating the adsorbed dilute acid under the condition that the vacuum degree is 0.095-0.1 MPa, and finishing when the temperature of the kettle reaches 170 ℃. And (5) cooling, sampling and analyzing, wherein the acid content of the concentrated recovered acid is 90.8%. After the nitration reaction is finished, when the catalyst is applied to the oxidation reaction step, 0.2g of catalyst (0.7% of molar equivalent of the lost sulfuric acid) needs to be supplemented by calculation, and the catalyst and the recovered acid are mixed and used for the next batch of reaction. After nitration reaction, oxidation reaction and product refining, white crystalline solid is obtained with the yield of 86.0 percent and the content of 98.5 percent.
And (3) carrying out solvent desorption on the adsorption column at 40 ℃ by using 160ml of isopropanol at a flow rate of 0.5-0.6 BV/h, and then washing the adsorption column at a flow rate of 1BV/h by using 120ml of soft water at 40 ℃ for the next adsorption period.
280ml of resin analysis solution is evaporated at the temperature of not more than 60 ℃ under the condition that the vacuum degree is 0.095-0.1 MPa, isopropanol and a small amount of water are evaporated, then the temperature is reduced to below 25 ℃, and the water phase is filtered, washed and dried in vacuum at low temperature to obtain 2.1g of polynitro by-product.
Example 2
Concentrating the dilute acid mother liquor after filtering the 2-nitro-4-methylsulfonylbenzoic acid crude product to 170-180 ℃ under the condition of the vacuum degree of 0.095-0.1 MPa to obtain recovered acid with the concentration of 90-98%, continuously and circularly applying the recovered acid to the 6 th cycle, taking 600g of the dilute acid mother liquor after filtering, and analyzing the content of nitro substitutes in the dilute acid mother liquor to be 7203 ppm. Measuring 40ml of SP825L adsorption resin by using a measuring cylinder, respectively moving into two adsorption columns, compacting, and keeping the upper layer of the resin to have a water layer of 3-5 cm. The diluted acid to be adsorbed, the peristaltic pump and the two adsorption columns are connected by a rubber tube. Controlling the flow rate to be 2-2.5 BV/h by a peristaltic pump at the temperature of 20-30 ℃, enabling the diluted acid mother liquor to pass through an adsorption column, then washing the adsorption column by 120ml of water, combining effluent with the adsorbed diluted acid mother liquor, and analyzing to obtain 50ppm of nitro substitutes in the adsorbed diluted acid and more than 99% of nitro substitute adsorption rate.
And concentrating the adsorbed dilute acid under the condition that the vacuum degree is 0.095-0.1 MPa, and finishing when the temperature of the kettle reaches 180 ℃. And (5) cooling, sampling and analyzing, wherein the acid content of the concentrated recovered acid is 93.5%. After the nitration reaction is finished, when the catalyst is applied to the oxidation reaction step, 0.45g of the catalyst (1.5% of the molar equivalent of the lost sulfuric acid) needs to be added by calculation, and the catalyst is applied to the next batch of reaction. After nitration reaction, oxidation reaction and product refining, white crystalline solid is obtained with the yield of 86.7 percent and the content of 98.2 percent.
And (3) carrying out solvent desorption on the adsorption column at 50 ℃ by using 200ml of ethanol at a flow rate of 1-1.2 BV/h, and then washing the adsorption column at a flow rate of 2BV/h by using 160ml of soft water at 50 ℃ for the next adsorption period.
And (3) steaming out ethanol and a small amount of water at the temperature of not more than 60 ℃ under the condition that the vacuum degree is 0.095-0.1 MPa, then cooling to below 25 ℃, filtering and washing the water phase, and drying in vacuum at low temperature to obtain a byproduct of 2.5 g.
Example 3
Concentrating the dilute acid mother liquor after filtering the 2-nitro-4-methylsulfonylbenzoic acid crude product to 170-180 ℃ under the condition of the vacuum degree of 0.095-0.1 MPa to obtain recovered acid with the concentration of 90-98%, continuously recycling until the 5 th cycle, taking 600g of the dilute acid mother liquor after filtering, and analyzing the content of nitro substitutes to be 6872 ppm. Measuring 40ml of SP207 adsorption resin by using a measuring cylinder, respectively moving the SP207 adsorption resin into two adsorption columns, compacting the SP207 adsorption resin, and keeping the upper layer of the resin to have a water layer of 3-5 cm. The diluted acid to be adsorbed, the peristaltic pump and the two adsorption columns are connected by a rubber tube. Controlling the flow rate to be 3-4 BV/h by a peristaltic pump at 55-60 ℃, enabling the dilute acid mother liquor to pass through an adsorption column, then washing the adsorption column by 100ml of water, combining effluent with the adsorbed dilute acid mother liquor, and analyzing to obtain 115ppm of nitro substitutes in the adsorbed dilute acid, wherein the adsorption rate of the nitro substitutes is more than 98%.
And concentrating the adsorbed dilute acid under the condition that the vacuum degree is 0.095-0.1 MPa, and finishing when the temperature of the kettle reaches 180 ℃. And (5) cooling, sampling and analyzing, wherein the acid content of the concentrated recovered acid is 92.8%. After the nitration reaction is finished, when the catalyst is applied to the oxidation reaction step, 0.25g of the catalyst (0.8% of the molar equivalent of the lost sulfuric acid) needs to be supplemented by calculation and is applied to the next batch of reaction. After nitration reaction, oxidation reaction and product refining, white crystalline solid is obtained with yield of 85.9 percent and content of 98.1 percent.
And (3) carrying out solvent desorption on the adsorption column at 50 ℃ by using 160ml of ethanol at a flow rate of 1.5-2 BV/h, and then washing the adsorption column at a flow rate of 3BV/h by using 160ml of soft water at 40 ℃ for the next adsorption period.
And (3) distilling 320ml of resin analysis solution at the temperature of not more than 60 ℃ under the condition that the vacuum degree is 0.095-0.1 MPa, then cooling to below 25 ℃, filtering and washing a water phase, and drying in vacuum at low temperature to obtain 2.2g of a byproduct.
Example 4
Concentrating the dilute acid mother liquor after filtering the 2-nitro-4-methylsulfonylbenzoic acid crude product to 170-180 ℃ under the condition of the vacuum degree of 0.095-0.1 MPa to obtain recovered acid with the concentration of 90-98%, continuously and circularly applying the recovered acid to the 12 th cycle, taking 600g of the dilute acid mother liquor after filtering, and analyzing the content of nitro substitutes in the dilute acid mother liquor to be 6098 ppm. Controlling the flow rate to be 1-1.3 BV/h by a peristaltic pump at the temperature of 20-30 ℃, enabling the diluted acid mother liquor to pass through an SP850 adsorption column after desorption and regeneration of isopropanol and soft water, then washing the adsorption column by 80ml of water, combining the discharged water with the adsorbed diluted acid mother liquor, and analyzing to obtain 121ppm of nitro substitutes in the adsorbed diluted acid and more than 98% of nitro substitute adsorption rate.
And concentrating the adsorbed dilute acid under the condition that the vacuum degree is 0.095-0.1 MPa, and finishing when the temperature of the kettle reaches 175 ℃. And (5) cooling, sampling and analyzing, wherein the acid content of the concentrated recovered acid is 91.9%. After the nitration reaction is finished, when the catalyst is applied to the oxidation reaction step, 0.3g of catalyst (0.9% of the molar equivalent of the lost sulfuric acid) needs to be supplemented by calculation and is applied to the next batch of reaction. After nitration reaction, oxidation reaction and product refining, white crystalline solid is obtained with the yield of 86.4 percent and the content of 98.3 percent.
The adsorption column was subjected to solvent desorption at 30 ℃ using 200ml of isopropanol at a flow rate of 1BV/h, and then washed with 30 ℃ 120ml of soft water at a flow rate of 2BV/h for the next adsorption cycle.
And (3) distilling 320ml of resin analysis solution at the vacuum degree of 0.095-0.1 MPa and the temperature of no more than 60 ℃ to remove isopropanol and a small amount of water, then cooling to below 25 ℃, filtering and washing the water phase, and drying in vacuum at low temperature to obtain 2.2g of a byproduct.
Example 5
Concentrating the dilute acid mother liquor after filtering the 2-nitro-4-methylsulfonylbenzoic acid crude product to 170-180 ℃ under the condition of the vacuum degree of 0.095-0.1 MPa to obtain recovered acid with the concentration of 90-98%, continuously and circularly applying the recovered acid to the 18 th cycle, taking 600g of the filtered dilute acid mother liquor, and analyzing the content of nitro substitutes to be 8098 ppm. Controlling the flow rate to be 2-3 BV/h by a peristaltic pump at 45-50 ℃, enabling the diluted acid mother liquor to pass through an SP207 adsorption column after desorption and regeneration of ethanol and soft water, then washing the adsorption column by 100ml of water, combining effluent with the adsorbed diluted acid mother liquor, and analyzing to obtain 160ppm of nitro substitutes in the adsorbed diluted acid and the adsorption rate of the nitro substitutes is more than 98%.
And concentrating the adsorbed dilute acid under the condition that the vacuum degree is 0.095-0.1 MPa, and finishing when the temperature of the kettle reaches 180 ℃. And (5) cooling, sampling and analyzing, wherein the acid content of the concentrated recovered acid is 94.6%. After the nitration reaction is finished, when the catalyst is applied to the oxidation reaction step, 0.4g of catalyst (1% of the molar equivalent of the lost sulfuric acid) needs to be supplemented by calculation and is applied to the next batch of reaction. After nitration reaction, oxidation reaction and product refining, white crystalline solid is obtained with the yield of 86.2 percent and the content of 98.8 percent.
The adsorption column was subjected to solvent desorption at 50 ℃ with 120ml of ethanol at a flow rate of 1BV/h, and then washed with 120ml of soft water at 60 ℃ at a flow rate of 3BV/h for the next adsorption cycle.
And (3) steaming out ethanol and a small amount of water at the temperature of not more than 60 ℃ under the condition that the vacuum degree is 0.095-0.1 MPa, then cooling to below 25 ℃, filtering and washing the water phase, and drying in vacuum at low temperature to obtain a byproduct of 2.8 g.
Those of ordinary skill in the art will understand that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that changes can be made in the embodiments of the invention without departing from the principles and spirit of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid comprises the following steps:
1) taking 4-methylsulfonyl toluene as a raw material, after completing nitration reaction and oxidation reaction in a concentrated sulfuric acid medium, filtering dilute acid mother liquor after 2-nitro-4-methylsulfonyl benzoic acid crude product, and concentrating to obtain recovered acid;
2) recovering acid for cyclic use, and removing a reaction byproduct polynitro compound from the dilute acid mother liquor by a resin adsorption method to ensure that the content of the polynitro compound in the adsorbed dilute acid mother liquor is less than 200 ppm;
3) concentrating the adsorbed dilute acid mother liquor, then applying the concentrated dilute acid mother liquor to nitration reaction, and after the nitration reaction is finished, adding the required catalyst and continuously using the catalyst for oxidation reaction;
4) desorbing and regenerating the adsorbed resin by solvent desorption to obtain resin desorption solution, and recovering reaction byproducts after concentration, filtration and washing.
2. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the dilute acid mother liquor in step 1) is concentrated under a vacuum degree of 0.095-0.1 Mpa and a temperature of 100-200 ℃ to obtain recycled acid with a sulfur acid content of 70-98% by mass.
3. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the recycling period of the recycled acid in step 2) is 1-10 periods.
4. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein in the step 2) of removing the polynitro byproduct by using the resin adsorption method, a nonpolar macroporous adsorption resin dual-column series adsorption column filled with styrene and divinylbenzene polymers as basic frameworks is adopted.
5. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the resin of step 2) is selected from the group consisting of: one or more of HP20, HP20SS, HP21, SP70, SP700, SP825L, SP850, CHP20, CHP55, SP 207.
6. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid as claimed in claim 1, wherein the step 2) of removing polynitro by-products by resin adsorption further comprises: and (2) under the condition that the temperature is 5-60 ℃, enabling the dilute acid mother liquor to pass through a double-column series adsorption column filled with resin at the flow rate of 0.5-4 times of the resin filling volume per hour, and then washing the adsorption column with 2-3 BV of water, so that the content of polynitro compounds in the adsorbed dilute acid mother liquor is less than 200 ppm.
7. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid as claimed in claim 1, wherein the amount of the catalyst required for the replenishment in step 3) is 0% to 4%, and the amount of sulfuric acid lost during the concentration in step 1) is determined by acid-base titration after the concentration is finished.
8. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the solvent used in the desorption and regeneration of the resin in step 4) by solvent desorption is one or more of acetone, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-butanol, isobutanol, isopropanol, methanol, ethanol, and water.
9. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the desorption regeneration of the resin in step 4) by solvent desorption is as follows: and (3) at the temperature of 10-60 ℃, using 2-8 BV of the solvent to perform solvent analysis on the adsorption column at the flow rate of 0.5-8 BV/h for the next adsorption period.
10. The method for recycling acid in the synthesis of 2-nitro-4-methylsulfonylbenzoic acid according to claim 1, wherein the operation method of step 4) for recycling reaction byproducts after concentration, filtration and washing comprises: and (3) evaporating the solvent from the resin analysis solution obtained by desorption and regeneration through solvent analysis under the condition of negative pressure, precipitating the solid in a water phase, filtering, washing and drying to obtain the nitration reaction byproduct polynitro compound.
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