CN113562912A - Method for treating spironolactone intermediate production wastewater - Google Patents
Method for treating spironolactone intermediate production wastewater Download PDFInfo
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- CN113562912A CN113562912A CN202110717346.3A CN202110717346A CN113562912A CN 113562912 A CN113562912 A CN 113562912A CN 202110717346 A CN202110717346 A CN 202110717346A CN 113562912 A CN113562912 A CN 113562912A
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- wastewater
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- spironolactone
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- intermediate production
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- 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
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- 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
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
Abstract
The invention discloses a method for treating spironolactone intermediate production wastewater, which is characterized by comprising the following four steps: 1) carrying out neutralization reaction; 2) separating filtrate, solid and washing liquid by decompression, cooling, solvent adding, cooling, filter pressing and washing; 3) vacuum drying the solid to obtain sodium bromide; 4) the filtrate and the washing liquid are combined and the solvent is recovered for direct use, and the dimethyl sulfoxide is evaporated from the residual liquid. According to the invention, HBr aqueous solution is adopted to carry out neutralization reaction on wastewater generated by spironolactone intermediate, filtrate, solid and washing liquid are separated out by decompression, cooling, solvent adding, cooling, filter pressing and washing, and the solvent is recovered by utilizing pressure, so that the solvent can be changed into valuables, the difficulty and time of wastewater treatment are reduced, the efficiency of wastewater treatment is improved, the environmental pollution is avoided, and the pressure of environmental protection treatment is reduced.
Description
Technical Field
The invention belongs to the technical field of wastewater recovery treatment, and relates to a method for treating spironolactone intermediate production wastewater.
Background
Spironolactone (1), chemically known as (70 c, 170c) -7. (acetylthio) 17. hydroxy-3. oxopregna-4-ene-21. carboxylic acid 1L lactone, is a mineralocorticoid antagonist developed by the american pfeir company and is now marketed in many countries for clinical use as a diuretic. However, 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene is an important intermediate for synthesizing spironolactone, and the main preparation method is to take 4-AD as a raw material, protect the 3-carbonyl group with triethyl orthoformate, then take dimethyl sulfoxide as a solvent, perform epoxidation reaction with trimethyl sulfide bromide under the catalysis of sodium ethoxide, decompress and evaporate ethanol after the reaction is finished, then add water to separate out a product, and generate about 15 tons of wastewater every 1 ton of product is produced, and at the present stage, the wastewater directly enters a wastewater treatment system for treatment, so that the wastewater treatment difficulty is increased, the treatment time is longer, and even the environmental pollution is directly caused.
Through retrieval, chinese patent document No. CN104311460A, publication date 2015, 01, 28, discloses a method for recovering and treating waste salt of dimethyl sulfoxide, which proposes that "nitric acid is added into a waste salt solution of dimethyl sulfoxide to perform neutralization reaction and oxidation reaction, and then dimethyl sulfone, sodium nitrate and sodium methanesulfonate crystals are separated out", in the prior art, nitric acid oxidation has a huge potential safety hazard, nitrogen oxides generated in the oxidation process are not easy to recover, and environmental protection pressure is increased.
The invention discloses a method for preparing a low-residue flocculant in wastewater and a method for recycling wastewater, wherein the method is disclosed in Chinese patent document publication No. CN110372805A, published in 2019, 10 and 25, and the method for preparing the flocculant comprises the following steps: step a: synthesizing an environment-responsive flocculant intermediate; step b: synthesizing temperature stimulus response starch; step c: synthesizing temperature/pH stimuli-responsive starch ", which is still in the laboratory stage, and requires a long time for industrial application.
In summary, the spironolactone intermediate wastewater at the present stage has the problems of high treatment difficulty, long time and difficult recovery. For this reason, a new technical solution is needed to solve the above-mentioned technology.
Disclosure of Invention
The invention aims to provide a method for treating wastewater from spironolactone intermediate production, which solves the problems of high difficulty and long time for treating wastewater from spironolactone intermediate production at the present stage in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for treating spironolactone intermediate production wastewater is characterized by comprising the following specific steps:
1) adding wastewater generated by 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene into a reaction kettle, and dropwise adding 30-50% HBr aqueous solution into the reaction kettle to perform neutralization reaction until the pH is = 5-7;
2) evaporating water from the wastewater after the neutralization reaction under the conditions that the pressure is-0.095 Mpa and the temperature is controlled below 90 ℃ until no water flows out, then cooling the feed liquid without water to 25-35 ℃, adding a solvent with the weight ratio of 1-2 times, continuously cooling to-15-5 ℃, carrying out filter pressing to form a filtrate, and washing with the solvent with the weight ratio of 0.4-0.6 time to form a washing liquid and a solid;
3) vacuum drying the solid formed by washing in the step 2 at 35-45 ℃ for 3-5 hours to obtain sodium bromide;
4) and simultaneously combining the filtrate and the washing liquid in the step 2, recovering the solvent under normal pressure for direct application, and evaporating the dimethyl sulfoxide from the residual liquid under the conditions that the pressure is 0.098Mpa and the temperature is controlled below 90 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, HBr aqueous solution is adopted to carry out neutralization reaction on wastewater generated by spironolactone intermediate, filtrate, solid and washing liquid are separated out by decompression, cooling, solvent adding, cooling, filter pressing and washing, and the solvent is recovered by utilizing pressure, so that the solvent can be changed into valuables, the difficulty and time of wastewater treatment are reduced, the efficiency of wastewater treatment is improved, the environmental pollution is avoided, and the pressure of environmental protection treatment is reduced.
2. The invention utilizes the dimethyl sulfoxide, sodium bromide and sodium hydroxide in the wastewater as resources by controlling the pressure and the temperature, and eliminates the discharge of the wastewater.
3. The method has the characteristics of simple process, environment-friendly treatment process and high yield.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the application of the invention.
Example 1:
adding 2500kg of wastewater generated by synthesizing 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene into a reaction kettle, dropwise adding 40% HBr aqueous solution into the reaction kettle to perform neutralization reaction until the pH is =7, consuming 126kg of HBr aqueous solution, evaporating 1326kg of water under the condition that the pressure is-0.095 Mpa and the temperature is controlled at 70 ℃, directly recycling 1326kg of water as process water, cooling feed liquid without water outflow to 30 ℃, adding 1950kg of dichloromethane, continuously cooling to-15 ℃, performing heat preservation and crystallization for 5 hours, performing pressure filtration to form filtrate, washing with 130kg of dichloromethane to generate washing liquid, simultaneously generating 400kg of solid after washing, performing vacuum drying on the generated solid at 40 ℃ for 4 hours to obtain 340kg of sodium bromide (after analysis, 98.5 percent of the content, meeting the requirements of industrial products), simultaneously, after the formed filtrate and washing liquid are combined, 2000kg of dichloromethane is recovered under normal pressure and the internal temperature is ensured to be below 90 ℃, the dichloromethane is directly used, and then 950kg of dimethyl sulfoxide with the content of 99.5 percent is distilled out of the residual liquid under the conditions that the pressure is 0.098Mpa and the temperature is controlled to be 80 ℃ (GC.
Example 2:
adding 2500kg of wastewater generated by synthesizing 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene into a reaction kettle, dropwise adding 40% HBr aqueous solution into the reaction kettle, performing neutralization reaction until the pH is =7, consuming 126kg of HBr aqueous solution, evaporating 1350kg of water under the pressure of-0.095 Mpa and at the temperature of 50 ℃, directly recycling 1350kg of water as process water, cooling feed liquid flowing out of water to 30 ℃, adding 2552kg of chloroform, continuously cooling to-15 ℃, performing heat preservation and crystallization for 5 hours, performing pressure filtration to form filtrate, washing with 130kg of chloroform to generate washing liquid, simultaneously generating 410kg of solid after washing, performing vacuum drying on the generated solid at the temperature of 40 ℃ for 4 hours to obtain 350kg of sodium bromide (after analysis, content 98.7%, meeting industrial product requirements), simultaneously, combining the formed filtrate and washing liquid, recovering 2600kg of chloroform under normal pressure and ensuring the internal temperature to be below 90 ℃, directly applying the chloroform, and then steaming 930kg of dimethyl sulfoxide out of the residual liquid under the conditions that the pressure is 0.098Mpa and the temperature is controlled to be 60 ℃, wherein the content is 99.3% (GC.
Example 3:
adding 2500kg of wastewater generated by synthesizing 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene into a reaction kettle, dropwise adding 40% HBr aqueous solution into the reaction kettle to perform neutralization reaction until the pH is =7, consuming 126kg of HBr aqueous solution, evaporating 1326kg of water under the condition that the pressure is-0.095 Mpa and the temperature is controlled at 60 ℃, directly recycling 1326kg of water as process water, cooling feed liquid without water outflow to 30 ℃, adding 1300kg of chloroform, continuously cooling to-15 ℃, performing heat preservation and crystallization for 5 hours, performing pressure filtration to form filtrate, washing with 130kg of chloroform to generate washing liquid, generating 380kg of solid after washing, performing vacuum drying on the generated solid at 40 ℃ for 4 hours to obtain 330kg of sodium bromide (after analysis, 98.3 percent of the content, meeting the requirements of industrial products), simultaneously, combining the formed filtrate and washing liquid, recovering 1350kg of chloroform for direct application under normal pressure and ensuring the internal temperature to be below 90 ℃, and then distilling 950kg of dimethyl sulfoxide out of the residual liquid under the conditions that the pressure is 0.098Mpa and the temperature is controlled to be 70 ℃, wherein the content is 99.6 percent (GC.
Claims (6)
1. A method for treating spironolactone intermediate production wastewater is characterized by comprising the following specific steps:
1) adding wastewater generated by the spironolactone intermediate into a reaction kettle, and dropwise adding 30-50% HBr aqueous solution into the reaction kettle for neutralization reaction;
2) evaporating water from the waste water after the neutralization reaction under reduced pressure until no water flows out, then cooling the feed liquid without water flowing out to 25-35 ℃, adding a solvent with the weight ratio of 1-2 times, continuously cooling to-15-5 ℃, carrying out filter pressing to form a filtrate, and washing with the solvent with the weight ratio of 0.4-0.6 to form a washing liquid and a solid;
3) vacuum drying the solid formed by washing in the step 2 at 35-45 ℃ for 3-5 hours to obtain sodium bromide;
4) and simultaneously combining the filtrate and the washing liquid in the step 2, recovering the solvent under normal pressure for direct application, and evaporating the residual liquid under reduced pressure to remove the dimethyl sulfoxide.
2. The method for treating wastewater from spironolactone intermediate production as described in claim 1, wherein said spironolactone intermediate in step 1 is 17b, 20 b-epoxy-3-ethoxy-17 a-pregna-3, 5-diene.
3. The method for treating wastewater from spironolactone intermediate production according to claim 1, wherein in step 1, the pH of the neutralization reaction is 5 to 7.
4. The method for treating wastewater from spironolactone intermediate production as described in claim 1, wherein in step 2, the pressure of the reduced pressure is controlled to-0.095 MPa, and the temperature is controlled to 90 ℃ or lower.
5. The method for treating wastewater from spironolactone intermediate production according to claim 1, wherein in step 2, the solvent is any one of methanol, ethanol, dichloromethane, tetrahydrofuran, acetonitrile and chloroform.
6. The method for treating wastewater from spironolactone intermediate production as described in claim 1, wherein in step 3, the pressure for decompression is controlled at-0.098 MPa and the temperature is controlled at 90 ℃ or lower.
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2021
- 2021-06-28 CN CN202110717346.3A patent/CN113562912B/en active Active
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| GB1544642A (en) * | 1976-06-04 | 1979-04-25 | Bristol Myers Co | 9,11-epoxy steroids and synthesis of corticosteroids therefrom |
| CN102249993A (en) * | 2011-05-10 | 2011-11-23 | 浙江爱迪亚营养科技开发有限公司 | Method for treating waste water generated from production of 3-cyanopyridine and recovering nicotinic acid |
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