Method for recovering fluoride in cephalosporin medicine waste liquid

Abstract

The invention discloses a method for recovering fluoride in cephalosporin medicine waste liquid, which belongs to the technical field of medicine, the fluoride is recovered by adopting precipitation reaction, the waste liquid is subjected to potassium hydroxide reaction, fluoboric acid is enabled to react to generate potassium fluoborate, and the potassium fluoborate is separated out and recovered. The method is high in treatment recovery rate, good in purity, simple in process route and suitable for large-scale production and utilization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of drug synthesis, and particularly relates to a method for recovering fluorides in cefalosporin waste liquid. BACKGROUND

[0002] Fluorine is one of the essential trace elements for human beings, animals and plants. Trace amounts of fluorine can promote the growth and development of children and prevent tooth decay. However, excessive fluorine intake into the body not only causes damage to the skeletal system, but also causes damage to the digestive, respiratory and nervous systems, leading to systemic diseases such as cardiovascular and central nervous system diseases; in addition, excessive fluorine also causes certain damage to animals and plants.

[0003] The prior art CN105836937A reports a method for removing fluorides in wastewater, but the removal method needs to detect pH and perform electrolysis, which is relatively complex to operate.

[0004] At present, most of the cefalosporin drugs produced in China do not recover fluorides in waste liquid. Fluorides in cefalosporin waste liquid are derived from boron trifluoride dimethyl carbonate. In industrial production, boron trifluoride dimethyl carbonate is used as a catalyst for cefalosporin intermediates to accelerate the reaction. Since boron trifluoride dimethyl carbonate is used as a catalyst and does not participate in the reaction, boron trifluoride dimethyl carbonate will hydrolyze when it comes into contact with water, and a large amount of fluoroboric acid (HBF4) will exist in the waste liquid. Considering that fluorides can harm human health, in order to effectively recycle resources and reduce environmental governance costs, it is of great significance to study the recovery of fluorides before cefalosporin waste liquid treatment. SUMMARY

[0005] The application aims to provide a method for recovering fluorides in cefalosporin waste liquid, which has high recovery rate and good purity, and has the advantages of simple process route and suitability for large-scale production and utilization.

[0006] The technical solution provided by the application is as follows:

[0007] The application adopts a precipitation reaction to recover fluorides. The waste liquid is reacted with potassium hydroxide to make fluoroboric acid react to generate water-insoluble potassium fluoroborate, so as to recover potassium fluoroborate. The chemical reaction principle is as follows: HBF4+KOH=H2O+KBF4↓.

[0008] The specific fluorine recovery method steps are as follows:

[0009] (1) Put the waste liquid generated in the production of cefalosporin drugs into a reaction tank, start stirring and control the temperature of the liquid;

[0010] (2) Add a certain amount of potassium hydroxide to the reaction tank in step (1) to adjust the pH of the liquid, stir for a certain time, and then reduce the solution to a certain temperature to crystallize;

[0011] (3) The solid potassium fluoroborate in the centrifuge is washed with water. After the centrifuge is finished, the wet potassium fluoroborate is dried and finally the dry product is collected.

[0012] Preferably, the temperature of the liquid in step (1) is 10-20°C.

[0013] Preferably, the pH in step (2) is 6.0 to 8.0, and more preferably, the pH range is 6.0 to 7.6.

[0014] Preferably, the stirring time in step (2) is 20 to 60 minutes.

[0015] Preferably, the crystal growth temperature in step (2) is 0 to 10°C.

[0016] Preferably, the drying temperature in step (3) is 50-65℃ and the drying time is 2-10h.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: the fluoride recovery method provided by the present invention has a simple process, a high fluoride recovery rate, and is suitable for large-scale production; at the same time, it reduces the fluoride content in the waste liquid and reduces the waste liquid treatment cost. Detailed Implementation

[0018] The invention will be further described in detail below through specific embodiments, but this does not limit the scope of the invention.

[0019] Example 1

[0020] 450L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The reaction vessel was stirred, and the temperature of the liquid was controlled between 10 and 20℃. 12kg of potassium hydroxide was added to the reaction vessel to adjust the pH of the liquid to 6.0, and stirring was performed for 30 minutes. After the time was up, the solution temperature was lowered to 0-10℃, and crystals were grown for 1 hour. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After the centrifuge was finished, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65℃ for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.0018kg / L, the potassium fluoroborate recovery rate was 98.2%, and the purity was 99.1%.

[0021] Example 2

[0022] 450L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The vessel was stirred, and the temperature of the liquid was controlled between 10 and 20℃. 15kg of potassium hydroxide was added to the reaction vessel to adjust the pH to 7.0, and stirring was continued for 60 minutes. After stirring, the solution temperature was lowered to 0-10℃, and crystals were grown for 1 hour. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After centrifugation, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65℃ for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.0013kg / L, the potassium fluoroborate recovery rate was 98.7%, and the purity was 99.7%.

[0023] Example 3

[0024] 470L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The vessel was stirred, and the liquid temperature was maintained between 10 and 20°C. 17kg of potassium hydroxide was added to the reaction vessel to adjust the pH to 7.6, and stirring was continued for 20 minutes. After stirring, the solution temperature was lowered to 0-10°C, and crystals were grown for 1 hour. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was then sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After centrifugation, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65°C for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.0009kg / L, the potassium fluoroborate recovery rate was 99.1%, and the purity was 99.2%.

[0025] Comparative Example 1

[0026] 450L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The reaction vessel was stirred, and the liquid temperature was maintained between 10 and 20℃. 10kg of potassium hydroxide was added to the reaction vessel to adjust the pH to 5.5, and stirring was continued for 30 minutes. After the time was up, the solution temperature was lowered to 0-10℃, and crystals were grown for 1 hour. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After the centrifuge was finished, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65℃ for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.018kg / L, the potassium fluoroborate recovery rate was 82.3%, and the purity was 99.0%.

[0027] Comparative Example 2

[0028] 450L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The reaction vessel was stirred, and the liquid temperature was maintained between 10 and 20°C. 12kg of potassium hydroxide was added to the reaction vessel to adjust the pH to 6.0, and the mixture was stirred for 30 minutes. After stirring, the solution temperature was kept at 10-20°C for 1 hour to allow crystal growth. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After centrifugation, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65°C for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.015kg / L, the potassium fluoroborate recovery rate was 85.2%, and the purity was 99.0%.

[0029] Comparative Example 3

[0030] 450L of cephalosporin-containing fluoride waste liquid (fluoride content 0.1kg / L) was added to the reaction vessel. The reaction vessel was stirred, and the liquid temperature was maintained between 10 and 20℃. 25kg of potassium hydroxide was added to the reaction vessel to adjust the pH to 8.5, and stirring was performed for 30 minutes. After the time was up, the solution temperature was lowered to 0-10℃, and crystals were grown for 1 hour. After crystal growth, solid-liquid separation was performed using a centrifuge. The separated waste liquid was sent to a distillation kettle for solvent recovery. 50kg of water was added to the reaction vessel to wash the solid potassium fluoroborate in the centrifuge. After the centrifuge finished spinning, the centrifuge was stopped, and the wet potassium fluoroborate was transferred to a dryer for drying. The dryer temperature was controlled at 60-65℃ for 5 hours. Finally, the dried product was collected. The fluoride content in the recovered cephalosporin waste liquid was determined to be 0.004kg / L, the potassium fluoroborate recovery rate was 96%, and the purity was 97.5%.

Claims

1. A method for recovering fluoride from cephalosporin drug waste liquid, characterized in that, The recycling method includes the following steps: (1) Place the waste liquid generated from the production of cephalosporin drugs into a reaction tank, turn on the agitator and control the temperature of the liquid. (2) Add a certain amount of potassium hydroxide to the reaction vessel in step (1), adjust the pH of the solution, stir for a time, and then lower the solution to a certain temperature to grow crystals. (3) The solid potassium fluoroborate in the centrifuge is washed with water. After the centrifuge is finished, the wet potassium fluoroborate is dried and finally the dry product is collected.

2. The method for recovering fluoride from cephalosporin drug waste liquid according to claim 1, characterized in that, The temperature of the liquid in step (1) is 10-20℃.

3. The method for recovering fluoride from cephalosporin drug waste liquid according to claim 1, characterized in that, The pH value mentioned in step (2) is 6.0 to 8.0, preferably in the range of 6.0 to 7.

6.

4. The method for recovering fluoride from cephalosporin drug waste liquid according to claim 1, characterized in that, The stirring time mentioned in step (2) is 20 to 60 minutes.

5. The method for recovering fluoride from cephalosporin drug waste liquid according to claim 1, characterized in that, The crystal growth temperature in step (2) is 0 to 10°C.

6. The method for recovering fluoride from cephalosporin drug waste liquid according to claim 1, characterized in that, The drying temperature in step (3) is 50-65℃, and the drying time is 2-10h.