Method for degrading traditional Chinese medicine residues in macrolide antibiotic wastewater

Abstract

The invention relates to a method for degrading traditional Chinese medicine residues in macrolide antibiotic wastewater, which comprises the following steps: carrying out alkalization treatment on macrolide antibiotic production wastewater, carrying out oxidation treatment, carrying out acidification treatment, and carrying out flocculation treatment in combination with high-temperature sterilization treatment to obtain dischargeable wastewater. The method effectively destroys the functional group structure of the macrolide antibiotics, reduces the content of traditional Chinese medicine residues in the wastewater, relieves the wastewater treatment pressure, reduces the pollution of the medicine residues to the environment, and has a good application prospect in treatment of the antibiotic pharmaceutical wastewater, and the clearance rate of the medicine residues reaches 98% or above.

Description

Technical Field

[0001] The present invention belongs to the field of fermentation pharmaceutical wastewater treatment, and specifically relates to a method for degrading drug residues in macrolide antibiotic wastewater. Background Art

[0002] Antibiotics such as avermectin, tylosin, erythromycin, and tacrolimus all belong to macrolide antibiotics. These antibiotics are currently produced in large quantities by fermentation extraction in the fields of pesticides, veterinary drugs, and human drugs, and are widely used globally. During the production process, a large amount of wastewater is generated, and there are obvious antibiotic residues in the wastewater, which cause great pressure on the subsequent sewage treatment. The discharge of untreated antibiotic wastewater also pollutes the environment.

[0003] Currently, the degradation of drug residues in antibiotic wastewater is mainly through the treatment with Fenton reagent composed of hydrogen peroxide and ferrous sulfate solution, and further treatment of the wastewater using aerobic or anaerobic systems. However, the antibiotic drug residues in the wastewater treated by the current method are still 200 μg / L. This residual amount is significantly higher than the drug residue concentration that can be tolerated by the anaerobic system treatment. In addition, the effluent COD value and amino nitrogen are still relatively high, and low-emission treatment has not been achieved.

[0004] Therefore, it is urgent to develop a method for degrading drug residues in antibiotic wastewater, which is of great significance for antibiotic production and subsequent wastewater treatment, and plays a key role in environmental protection. Summary of the Invention

[0005] The present invention provides a method for degrading drug residues in macrolide antibiotic wastewater. By first alkalizing, then oxidizing, and finally acidifying the antibiotic production wastewater, and combining with the treatment step of a modified polycationic inorganic flocculant and high-pressure steam disinfection treatment, the technical problem of high drug residue content in antibiotic production wastewater polluting the environment is solved, and the degradation rate of antibiotic drug residues is significantly increased while the effluent COD and amino nitrogen are also significantly reduced.

[0006] The technical solutions adopted to achieve the above invention objectives are as follows:

[0007] A method for degrading drug residues in macrolide antibiotic wastewater, comprising the following steps:

[0008] S1: Adding an alkalizing agent to the production wastewater of macrolide antibiotics for alkalization treatment to obtain an alkalized solution;

[0009] S2: Adding an oxidizing agent to the alkalized solution obtained in step S1 for oxidation treatment to obtain an oxidized solution;

[0010] S3: Adding an acidifying agent to the oxidized solution obtained in step S2 for acidification treatment to obtain an acidified solution;

[0011] S4: Add the acidified liquid obtained in step S3 to a modified polycationic inorganic flocculant for flocculation treatment, and separate the solid from the liquid to obtain the flocculation-treated wastewater;

[0012] S5: Subject the flocculation-treated wastewater obtained in step S4 to high-pressure steam disinfection treatment, and adjust the pH to 6 - 9 to obtain the dischargeable effluent.

[0013] Among them, the macrolide antibiotic wastewater is the fermentation antibiotic production wastewater.

[0014] Among them, the fermentation antibiotic production wastewater is the production wastewater of erythromycin, tylosin, avermectin or tacrolimus.

[0015] Among them, the fermentation antibiotic production wastewater is the organic wastewater generated by producing antibiotics through fermentation and then through separation, extraction, refining and purification processes.

[0016] Among them, the alkalizing agent in step S1 is calcium hydroxide.

[0017] Among them, the concentration of the alkalizing agent in step S1 is 3 - 5 mol / L, and the alkalizing pH is 12 - 13.

[0018] Among them, the oxidizing agent in step S2 is potassium permanganate solution.

[0019] Among them, the concentration of the oxidizing agent in step S2 is 1 - 2 mol / L, and the addition amount is 1 - 3% (v / v).

[0020] Among them, the acidifying agent in step S3 is sulfuric acid solution, the concentration of the acidifying agent is 3 - 5 mol / L, and the acidifying pH is 5 - 6.

[0021] Among them, the flocculant in step S4 is polyaluminum ferric chloride sulfate.

[0022] Among them, the addition ratio of the flocculant in step S4 is 3 - 5% (v / v).

[0023] Among them, for the high-pressure steam disinfection in step S5, the conditions are steam pressure 15 pounds (1.05 kg / cm 2 ), temperature 121 °C, and pressure holding for 30 min.

[0024] Among them, in the above degradation method, the residue of antibiotics in the dischargeable effluent is less than or equal to 10 ppm.

[0025] Among them, in the above degradation method, the COD value in the dischargeable effluent is below 90 mg / L.

[0026] Among them, in the above degradation method, the amino nitrogen value in the dischargeable effluent is below 20 mg / L.

[0027] The technical solution of the present invention has at least the following beneficial technical effects:

[0028] 1. In the method for degrading antibiotic production wastewater of the present invention, the antibiotic production wastewater is first alkalized and then oxidized by a strong oxidant, which can effectively and selectively destroy the pharmacodynamic functional groups of the residual antibiotics in the macrolide antibiotic pharmaceutical wastewater. The subsequent acidification step effectively prevents the reverse reaction, so that the degradation rate of the antibiotic drug residues is significantly improved, and the antibiotic residues are greatly reduced.

[0029] 2. Through the treatment step of the modified multi-cationic inorganic flocculant of the present invention, macromolecular compounds and fine particles can be sedimented from the water to achieve a separation effect. Combined with the high-pressure steam disinfection treatment, while further degrading the antibiotics, the effluent COD value and amino nitrogen are also significantly reduced.

[0030] 3. After treating the macrolide antibiotic production wastewater of the present invention, the clearance rate of drug residues reaches more than 98%; COD: below 90 mg / L; amino nitrogen: below 20 mg / L. Specific embodiments

[0031] The following further illustrates the present invention in conjunction with specific embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and not to limit the scope of the present invention.

[0032] The detection of drug residues in the wastewater is carried out by using a high-performance liquid detection method:

[0033] Tacrolimus: The chromatographic column is C8 (4.6 mm * 25 cm * 5 μm); the mobile phase is phosphoric acid solution: acetonitrile: methanol = 785:155:155; the detection wavelength is 210 nm; the flow rate is 1 ml / min; the column oven temperature is 45 °C; the injection volume is 10 μL.

[0034] Tylosin: The chromatographic column is C18 (250 mm * 4.6 mm, 5 μm), the detection wavelength is 290 nm, the flow rate is 1.0 ml / min, the column temperature is 35 °C, and the mobile phase is sodium perchlorate solution: acetonitrile = 6:4 (v:v).

[0035] Erythromycin: The chromatographic column is Waters XBridge-C18, (250 mm × 4.6 mm, 5 μm), the detection wavelength is 215 nm, the flow rate is 1.0 ml / min, the column temperature is 35 °C, the injection volume is 40 μL, and the mobile phase is 0.025 mol / L potassium dihydrogen phosphate buffer solution: acetonitrile = 550:400 (v:v).

[0036] Avermectin: The chromatographic column is C18, (250mm×4.6mm, 5μm), the detection wavelength is 245nm, the flow rate is 1.0ml / min, at room temperature, the injection volume is 20μL, and the mobile phase is methanol: water = 85:15 (v:v).

[0037] Example 1

[0038] Take 1L of the production wastewater of avermectin. After liquid-phase detection, the drug residue in the wastewater is 269ppm. Add 3mol / L Ca(OH)2 to adjust the pH of the wastewater to 12. Add 2mol / L potassium permanganate solution to the obtained alkalized liquid for oxidation, and the addition amount is 1% (v / v). The obtained oxidized liquid is acidified with 5mol / L sulfuric acid solution to a pH of 5 to obtain an acidified liquid;

[0039] Add 4% (v / v) polyaluminum ferric chloride sulfate flocculant to the obtained acidified liquid, stir for 30min, and then stand to obtain the wastewater after flocculation treatment;

[0040] The wastewater treated with the above flocculant is subjected to high-pressure steam disinfection treatment. The steam pressure is 15 pounds (1.05kg / cm 2 ), the temperature is 121°C, keep the pressure for 30min, and finally add Ca(OH)2 to adjust the pH to the range of 6 - 9 to obtain the wastewater that can be discharged.

[0041] The treated wastewater is detected by HPLC. The degradation rates of antibiotic residues, drug residues, COD values, and amino nitrogen values are shown in Table 1 below.

[0042] Table 1 Determination results of wastewater in each process of the degradation method of avermectin production wastewater

[0043]

[0044] Example 2:

[0045] Take 1L of the production wastewater of tylosin. After liquid-phase detection, the drug residue in the wastewater is 291ppm. Add 4mol / L Ca(OH)2 to adjust the pH of the wastewater to 12.6. Add 1.4mol / L potassium permanganate solution to the obtained alkalized liquid for oxidation, and the addition amount is 2% (v / v). The obtained oxidized liquid is acidified with 4mol / L sulfuric acid solution to a pH of 5.5 to obtain an acidified liquid;

[0046] Add 5% (v / v) polyaluminum ferric chloride sulfate flocculant to the obtained acidified liquid, stir for 30min, and then stand to obtain the wastewater after flocculation treatment;

[0047] The wastewater treated with the flocculant is subjected to high-pressure steam disinfection treatment. The steam pressure is 15 pounds (1.05kg / cm 2) At a temperature of 121 °C, keep the pressure for 30 min, and finally add Ca(OH)2 to adjust the pH to the range of 6 - 9 to obtain the wastewater that can be discharged.

[0048] The treated wastewater above was detected by HPLC, and the degradation rates of antibiotic residues, drug residues, COD values, and amino nitrogen values are shown in Table 2 below.

[0049] Table 2 Determination results of wastewater in each process of the degradation method for avermectin production wastewater

[0050]

[0051] Example 3:

[0052] Take 1 L of erythromycin production wastewater. After liquid phase detection, the drug residue in the wastewater is 342 ppm. Add 5 mol / L of Ca(OH)2 to adjust the pH of the wastewater to 13. Add 1 mol / L of potassium permanganate solution to the obtained alkalized solution for oxidation, and the addition amount is 3% (v / v). Acidify the obtained oxidized solution with 4 mol / L sulfuric acid solution to a pH of 6 to obtain an acidified solution.

[0053] Add 4% (v / v) of polyaluminum ferric chloride sulfate flocculant to the obtained acidified solution, stir for 30 min, and then let it stand to obtain the wastewater after flocculation treatment.

[0054] The wastewater after being treated with the flocculant is subjected to high-pressure steam disinfection treatment. The steam pressure is 15 pounds (1.05 kg / cm 2 ) At a temperature of 121 °C, keep the pressure for 30 min, and finally add Ca(OH)2 to adjust the pH to the range of 6 - 9 to obtain the wastewater that can be discharged.

[0055] The treated wastewater above was detected by HPLC, and the degradation rates of antibiotic residues, drug residues, COD values, and amino nitrogen values are shown in Table 3 below.

[0056] Table 3 Determination results of wastewater in each process of the degradation method for avermectin production wastewater

[0057]

[0058] Example 4:

[0059] Take 1 L of tacrolimus production wastewater. After liquid phase detection, the drug residue in the wastewater is 368 ppm. Add 4.5 mol / L of Ca(OH)2 to adjust the pH of the wastewater to 13. Add 1 mol / L of potassium permanganate solution to the obtained alkalized solution for oxidation, and the addition amount is 3% (v / v). Acidify the obtained oxidized solution with 3 mol / L sulfuric acid solution to a pH of 6 to obtain an acidified solution.

[0060] 3% (v / v) of polyaluminum ferric chloride sulfate flocculant was added to the obtained acidified solution, stirred for 30 min, and then left to stand to obtain the wastewater after flocculation treatment.

[0061] The wastewater treated with the flocculant was disinfected by high-pressure steam. The steam pressure was 15 pounds (1.05 kg / cm 2 ), the temperature was 121 °C, and the pressure was maintained for 30 min. Finally, Ca(OH)2 was added to adjust the pH to the range of 6 - 9 to obtain the wastewater that could be discharged.

[0062] The above-treated wastewater was detected by HPLC. The degradation rates of antibiotic residues, drug residues, COD value, and amino nitrogen value are shown in Table 4 below.

[0063] Table 4 Determination results of wastewater in each process of the degradation method of avermectin production wastewater

[0064]

[0065] Comparative Example 1:

[0066] 1 L of avermectin production wastewater was taken. The drug residue in the wastewater was 328 ppm detected by liquid phase. 5 mol / L of Ca(OH)2 was added to adjust the pH of the wastewater to 12.5. 1 mol / L of potassium permanganate solution was added to the obtained alkalized solution for oxidation, and the addition amount was 3% (v / v). The obtained oxidized solution was acidified with 3 mol / L sulfuric acid solution, and the pH was 6. 3% (v / v) of polyaluminum ferric chloride sulfate flocculant was added to the obtained acidified solution, stirred for 30 min, and then left to stand. The wastewater treated with the flocculant was disinfected with sodium hypochlorite for 1 min. Finally, Ca(OH)2 was added to adjust the pH to the range of 6 - 9. The obtained treated wastewater was detected by HPLC. The antibiotic residue was 27 ppm, the degradation rate of drug residue was 91.77%, COD: 124 mg / L; amino nitrogen: 26 mg / L.

[0067] Comparative Example 2:

[0068] 1 L of tylosin production wastewater was taken. The drug residue in the wastewater was 367 ppm detected by liquid phase. 5 mol / L of Ca(OH)2 was added to adjust the pH of the wastewater to 13. Sulfuric acid solution was added to the obtained alkalized solution to adjust the pH to 6, and then Fenton reagents such as hydrogen peroxide and ferrous sulfate were added for treatment. The wastewater treated with Fenton reagents was disinfected by high-pressure steam. The steam pressure was 15 pounds (1.05 kg / cm 2 ), the temperature was 121 °C, and the pressure was maintained for 30 min. Finally, Ca(OH)2 was added to adjust the pH to the range of 6 - 9. The obtained treated wastewater was detected by HPLC. The antibiotic residue was 36 ppm, the degradation rate of drug residue was 90.19%, COD: 157 mg / L; amino nitrogen: 31 mg / L.

Claims

1. A method for degrading pharmaceutical residues in macrolide antibiotic wastewater, characterized in that It includes the following steps: S1: Adding an alkalizing agent to the production wastewater of macrolide antibiotics for alkalization treatment to obtain an alkalized solution; S2: Adding an oxidizing agent to the alkalized solution obtained in step S1 for oxidation treatment to obtain an oxidized solution; S3: Adding an acidifying agent to the oxidized solution obtained in step S2 for acidification treatment to obtain an acidified solution; S4: Adding a modified polycationic inorganic flocculant to the acidified solution obtained in step S3 for flocculation treatment, and separating the solid and liquid to obtain the flocculation-treated wastewater; S5: Performing high-pressure steam disinfection treatment on the flocculation-treated wastewater obtained in step S4, and adjusting the pH to 6 - 9 to obtain the dischargeable water.

2. The degradation method according to claim 1, characterized in that The macrolide antibiotic wastewater is the production wastewater of fermentation antibiotics.

3. The degradation method according to claim 2, characterized in that The production wastewater of fermentation antibiotics is erythromycin production wastewater, tylosin production wastewater, avermectin production wastewater or tacrolimus production wastewater.

4. The degradation method according to claim 1, characterized in that The alkalizing agent in step S1 is calcium hydroxide, the concentration of the alkalizing agent is 3 - 5 mol / L, and the alkalization pH is 12 - 13.

5. The degradation method according to claim 1, wherein The oxidizing agent in step S2 is potassium permanganate solution, the concentration of the oxidizing agent is 1 - 2 mol / L, and the addition amount is 1 - 3% (v / v).

6. The degradation method according to claim 1, wherein The acidifying agent in step S3 is sulfuric acid solution, the concentration of the acidifying agent is 3 - 5 mol / L, and the acidification pH is 5 - 6.

7. The degradation method according to claim 1, characterized in that The flocculant in step S4 is polyaluminum ferric chloride sulfate, and the addition ratio of the flocculant is 3 - 5% (v / v).

8. The degradation method according to claim 1, characterized in that The high-pressure steam sterilization described in step S5 is carried out under the conditions of a steam pressure of 15 pounds (1.05 kg / cm 2 ), a temperature of 121 °C, and a pressure holding time of 30 minutes.

9. The degradation method according to any one of claims 1-8, characterized in that The residue of antibiotics in the dischargeable water is less than or equal to 10 ppm.

10. The degradation method according to any one of claims 1-8, characterized in that The COD value in the dischargeable water is below 90 mg / L, and the amino nitrogen value is below 20 mg / L.

Images