Method for synchronously reducing biological inhibition of antibiotics and thiocyanate radicals in erythromycin wastewater

Abstract

The invention discloses a method for synchronously reducing biological inhibition of antibiotics and thiocyanate radicals in erythromycin wastewater, and relates to the technical field of industrial wastewater treatment. The specific treatment method comprises the following steps: regulating and controlling the water quality characteristics of the wastewater, adding a selective reaction reagent, and regulating and controlling the reaction temperature, time and stirring rate to realize synchronous microbial toxicity reduction of antibiotics and thiocyanate radicals in the erythromycin wastewater. According to the method, the reaction process is stable, the process conditions are easy to regulate and control, the consumed time is short, the selectivity of the removal process is high, and other substances in the wastewater do not need to be regulated and controlled or removed; the problems that high-concentration erythromycin residual titer and thiocyanate ions exist in the erythromycin wastewater, so that the inhibition performance on the anaerobic biological process is high, and the erythromycin wastewater is difficult to enter an anaerobic biological treatment process for efficient organic matter removal are effectively solved, and the erythromycin wastewater has a very good industrial application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of industrial wastewater treatment, and in particular to a method for synchronously reducing antibiotics and thiocyanate bioinhibition in erythromycin wastewater. Background Art

[0002] Erythromycin wastewater is a type of high-concentration organic wastewater with high pollution load, high toxicity and strong antibacterial properties. It mainly comes from the waste fermentation liquid or synthetic waste liquid after the raw material extraction in the erythromycin production process. Because a large amount of sodium thiocyanate needs to be added during the production process to promote the concentration and crystallization of erythromycin to obtain erythromycin products, the wastewater generated in this process has a high concentration of erythromycin residual titer and thiocyanate, and a large amount of fermentation medium components or organic raw materials remain, with the characteristics of large water volume, high COD and high suspended solids. Long-term operation experience at home and abroad has proved that wastewater treatment technology with biological method as the main process has the characteristics of small chemical reagent addition, economical operation cost, and not easy to produce secondary pollution compared with physical and chemical technology. It is the first choice for treating antibiotic pharmaceutical wastewater.

[0003] However, high concentrations of residual erythromycin titers and thiocyanate in erythromycin wastewater have strong inhibitory effects and toxicity on microbial activity, which limits the effect of biological treatment and makes it difficult to meet the effluent quality requirements. In addition, the presence of high concentrations of residual erythromycin titers will also cause a large number of drug-resistant bacteria and drug-resistant genes to be produced during the biological treatment process. These drug-resistant bacteria, drug-resistant genes, and undegraded antibiotics enter the environment with the treated wastewater and residual sludge, which may bring major safety hazards. Therefore, the efficient and selective removal of erythromycin residual titers and thiocyanate in advance has become the key to efficient and low-cost biological treatment of this type of wastewater.

[0004] At present, hydrolysis is usually used to selectively destroy the pharmacological functional groups of antibiotics, but it is difficult to achieve the simultaneous removal of thiocyanate in the process of antibiotic removal. The treatment methods for single thiocyanate mainly include coagulation, ion exchange, adsorption, oxidation and other methods. These methods have poor selectivity for antibiotic removal, low treatment efficiency and high treatment cost. Therefore, it is necessary to develop a synchronous pretreatment technology to achieve the simultaneous and efficient removal of erythromycin titer and thiocyanate under relatively simple and mild conditions, and relieve its inhibitory effect on anaerobic biological processes. Summary of the invention

[0005] The object of the present invention is to provide a method for simultaneously reducing antibiotics and thiocyanate bioinhibition in erythromycin wastewater, so as to solve the problem that the erythromycin residual titer and the microbial toxicity of thiocyanate in existing erythromycin wastewater are difficult to be efficiently and simultaneously reduced.

[0006] In order to solve the above technical problems, the present invention specifically provides the following technical solutions: The invention discloses a method for treating erythromycin wastewater, comprising: First, the pH of erythromycin wastewater is adjusted, and then a selective reaction reagent is added to react to obtain treated wastewater; the selective reaction reagent includes an oxidant and a catalytic aid, and the dosage ratio of the oxidant to erythromycin wastewater is 2-15g:1L. The mechanism of action of the selective reaction reagent is closely related to the structure and functional groups of the pollutant molecules. According to the electron-absorbing characteristics, molecular size, structure and functional group properties of thiocyanate and erythromycin, a matching oxidant is selected, or a catalytic aid is coupled with the oxidant to achieve precise regulation of the active site, thereby improving the degradation efficiency and stability of thiocyanate and erythromycin in complex wastewater.

[0007] Preferably, the COD in the erythromycin wastewater is 10000-100000 mg / L, the erythromycin residual titer is 10-1000 mg / L, and the thiocyanate ion is 1000-9000 mg / L.

[0008] Preferably, the oxidant is at least one of hydrogen peroxide, calcium peroxide, perchlorate, ferrate, persulfate, percarbonate, peracetic acid and vanadium trichloride.

[0009] Preferably, the catalyst promoter is at least one of metal oxides, bicarbonates, metal salts, ion exchange resins, zeolite molecular sieves and mesoporous materials.

[0010] Preferably, the dosage ratio of the catalyst aid to erythromycin wastewater is 2-100 g:1 L.

[0011] Preferably, the ion exchange resin is at least one of a strongly acidic perfluorosulfonic acid cation exchange resin, a macroporous strongly basic styrene-based anion exchange resin and a strongly basic modified anion resin, and the strongly basic modified anion resin is prepared from chloromethyl polystyrene gel resin, 3,3-diaminoacrylonitrile and 1,4-dichloromethylnaphthalene. Strongly basic modified anion resins have many functional groups and good stability. Using strongly basic modified anion resins as catalyst aids can effectively promote the degradation of erythromycin and thiocyanate in erythromycin wastewater, thereby improving the erythromycin residual titer removal rate, thiocyanate removal rate and anaerobic methanogenesis activity.

[0012] Preferably, the pH is 3-11.

[0013] Preferably, the reagents used to adjust the pH are sodium hydroxide solution and hydrochloric acid solution, the sodium hydroxide solution consists of sodium hydroxide and water, the dosage ratio of sodium hydroxide to water is 0.4-40g:1L, and the hydrochloric acid solution consists of hydrochloric acid and water, the dosage ratio of hydrochloric acid to water is 3-37g:1L.

[0014] Preferably, the reaction temperature is 50-100° C., and the reaction time is 5-480 min.

[0015] Preferably, the reaction adopts at least one of mechanical stirring and magnetic stirring, and the rotation speed is 50-400 rpm.

[0016] The invention discloses a method for treating erythromycin wastewater, comprising: Firstly, the pH value of erythromycin wastewater is adjusted to 3-11, and then a selective reaction reagent is added to react at 50-100° C. and 50-400 rpm for 5-480 min to obtain treated wastewater.

[0017] Preferably, the COD in the erythromycin wastewater is 10000-100000 mg / L, the erythromycin residual titer is 10-1000 mg / L, and the thiocyanate ion is 1000-9000 mg / L.

[0018] Preferably, the erythromycin wastewater also contains complex salt ions of sulfate, chloride and nitrate.

[0019] Preferably, the erythromycin wastewater is at least one of erythromycin fermentation broth, erythromycin crystallization extraction mother liquor and erythromycin equipment cleaning wastewater.

[0020] Preferably, the selective reaction reagents include an oxidizing agent and a catalyst promoter.

[0021] More preferably, the oxidant is at least one of hydrogen peroxide, calcium peroxide, perchlorate, ferrate, persulfate, percarbonate, peracetic acid and vanadium trichloride, and the oxidant is capable of generating free radicals and free radical derivatives, including hydroxyl radicals, sulfate radicals, superoxide anion radicals, singlet oxygen and hydrogen peroxide.

[0022] More preferably, the dosage ratio of the oxidant to erythromycin wastewater is 2-15 g:1 L.

[0023] More preferably, the catalyst promoter is at least one of metal oxides, bicarbonates, metal salts, ion exchange resins, zeolite molecular sieves and mesoporous materials. The catalyst promoter can provide active sites or accelerate electron transfer and transmission.

[0024] Preferably, the dosage ratio of the catalyst aid to erythromycin wastewater is 2-100 g:1 L.

[0025] More preferably, the metal oxide is at least one of bismuth oxyiodide, iron oxychloride, aluminum oxide, zinc oxide, an aluminum oxide-iron oxide composite, and a calcium oxide-zirconium oxide composite.

[0026] More preferably, the metal salt is at least one of aluminum phosphate, iron sulfate, and potassium carbonate-γ-alumina.

[0027] More preferably, the ion exchange resin is at least one of a strongly acidic perfluorosulfonic acid cation exchange resin, a macroporous strongly basic styrene-based anion exchange resin and a strongly basic modified anion resin, and the strongly basic modified anion resin is prepared from chloromethyl polystyrene gel resin, 3,3-diaminoacrylonitrile and 1,4-dichloromethylnaphthalene.

[0028] Preferably, the reagents used to adjust the pH are sodium hydroxide solution and hydrochloric acid solution, the sodium hydroxide solution consists of sodium hydroxide and water, the dosage ratio of sodium hydroxide to water is 0.4-40g:1L, and the hydrochloric acid solution consists of hydrochloric acid and water, the dosage ratio of hydrochloric acid to water is 3-37g:1L.

[0029] Preferably, the reaction adopts at least one of mechanical stirring and magnetic stirring, and the electron transfer is optimized by stirring and temperature control, so as to promote the destruction of the erythromycin pharmacodynamic functional group and the thiocyanate structure and improve the treatment efficiency.

[0030] The present invention discloses a method for preparing a strongly alkaline modified anionic resin, which is specifically: S1: Add N,N-dimethylformamide to chloromethyl polystyrene gel resin for swelling, then add 3,3-diaminoacrylonitrile, react at 50-70°C for 15-25h, and filter after the reaction to obtain the modified resin.

[0031] S2: Add N,N-dimethylformamide to the modified resin for swelling, then add 1,4-dichloromethylnaphthalene, react at 50-70°C for 5-15h, and filter and wash after the reaction to obtain a strongly alkaline modified anion resin.

[0032] Preferably, the amount ratio of chloromethyl polystyrene gel resin and N,N-dimethylformamide in S1 is 0.05-0.2 g: 1 ml.

[0033] Preferably, the mass ratio of the chloromethyl polystyrene gel resin to 3,3-diaminoacrylonitrile in S1 is 1:0.5-1.

[0034] Preferably, the solvent used for washing in S1 includes water, hydrochloric acid solution and sodium hydroxide solution, and the mixture is first washed with water until neutral, and then washed with hydrochloric acid solution, water and sodium hydroxide solution in sequence.

[0035] More preferably, the hydrochloric acid solution consists of hydrochloric acid and water, and the usage ratio of hydrochloric acid to water is 30-40g:1L.

[0036] More preferably, the sodium hydroxide solution consists of sodium hydroxide and water, and the dosage ratio of sodium hydroxide to water is 30-50g:1L.

[0037] Preferably, the ratio of the modified resin to the added N,N-dimethylformamide in S2 is 0.05-0.2 g: 1 ml.

[0038] Preferably, the mass ratio of the modified resin to 1,4-dichloromethylnaphthalene in S2 is 1:1.2-2.

[0039] Preferably, the solvent used for washing in S2 includes ethanol solution, ethanol and water, and washing is carried out with ethanol solution, ethanol and water in sequence.

[0040] More preferably, the ethanol solution consists of ethanol and triethylamine, and the mass ratio of ethanol to triethylamine is 1:0.05-0.15.

[0041] More preferably, in the process of treating erythromycin wastewater, the present invention uses modified chitosan on the basis of using strongly basic modified anionic resin. The use of modified chitosan can further promote the degradation of erythromycin wastewater by oxides, and can synergistically promote flocculation, reduce the amount of suspended matter, thereby improving the erythromycin residual titer removal rate, thiocyanate removal rate and anaerobic methanogenesis activity.

[0042] Preferably, the dosage ratio of modified chitosan to erythromycin wastewater is 0.04-0.25 g:1L.

[0043] The present invention discloses a method for preparing modified chitosan, which specifically comprises: Dissolve chitosan in hydrochloric acid solution and adjust the pH to 4-6 to obtain chitosan solution. Dissolve 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride in N,N-dimethylformamide to obtain a mixed solution. Then add the mixed solution to the chitosan solution and react at 20-30°C for 1-3h, then drop 3-sulfopropionic acid solution and 5-phenylpentane-2,4-dicarboxylic acid solution, and react at 20-30°C for 3-5h. After the reaction is completed, add acetone to filter and separate the precipitate, and wash and dry the precipitate to obtain modified chitosan.

[0044] Preferably, the hydrochloric acid solution is composed of hydrochloric acid and water, the usage ratio of hydrochloric acid to water is 8-12 g:1 L, and the usage ratio of chitosan to hydrochloric acid solution is 0.005-0.015 g:1 ml.

[0045] Preferably, the usage ratio of 4-dimethylaminopyridine to N,N-dimethylformamide is 0.006-0.009 g:1 ml.

[0046] Preferably, the usage ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to N,N-dimethylformamide is 0.03-0.1 g:1 ml.

[0047] Preferably, the volume ratio of the chitosan solution to the mixed solution is 1:0.1-0.5. Preferably, the 3-sulfopropionic acid solution is composed of 3-sulfopropionic acid and water, and the usage ratio of 3-sulfopropionic acid to water is 0.002-0.01 g:1 ml.

[0048] Preferably, the volume ratio of the chitosan solution to the 3-sulfopropionic acid solution is 1:0.35-0.7.

[0049] Preferably, the 5-phenylpentane-2,4-dicarboxylic acid solution consists of 5-phenylpentane-2,4-dicarboxylic acid and N,N-dimethylformamide, and the dosage ratio of 5-phenylpentane-2,4-dicarboxylic acid to N,N-dimethylformamide is 0.002-0.01 g: 1 ml. Preferably, the volume ratio of the chitosan solution to the 5-phenylpentane-2,4-dioic acid solution is 1:0.35-0.7.

[0050] Compared with the prior art, the present invention has the following beneficial effects: The present invention proposes a method for synchronously reducing the biological inhibition of antibiotics and thiocyanate in erythromycin wastewater. By regulating the water quality characteristics of the wastewater, adding a selective reaction reagent, and regulating the reaction temperature, time and stirring rate, the synchronous microbial toxicity reduction of antibiotics and thiocyanate in erythromycin wastewater is achieved. The present invention has high reaction efficiency, simple reaction conditions, strong selectivity, and shortens the treatment process; and can achieve a removal rate of more than 95% of the erythromycin residual titer and thiocyanate in erythromycin wastewater. According to anaerobic methanogenic activity monitoring, the anaerobic methanogenic activity of the erythromycin wastewater after treatment is increased by 50%-600% compared with the wastewater before treatment, and the relative abundance of drug-resistant genes in the treated water is less than 50 copies / cell; the wastewater treated by the present method and technology can be further treated by a subsequent biochemical treatment process, and finally reaches the discharge standard of the wastewater. The subsequent biochemical treatment process can be treated by hydrolysis acidification, anaerobic process, aerobic process or a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0052] Figure 1 The process flow chart of the method for simultaneously reducing antibiotic and thiocyanate bioinhibition in erythromycin wastewater; Figure 2 This is the cumulative anaerobic methane production diagram; Figure 3This is a graph showing the results of measuring the changes in wastewater during the reaction process. DETAILED DESCRIPTION

[0053] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0054] The following first describes the concepts involved in the present application in conjunction with the accompanying drawings. It should be noted that the following description of each concept is only to make the content of the present application easier to understand, and does not limit the scope of protection of the present application; at the same time, the embodiments and features in the embodiments of the present application can be combined with each other in the absence of conflict. The present application will be described in detail with reference to the accompanying drawings and in conjunction with the embodiments.

[0055] Embodiment 1: Treatment of erythromycin wastewater: add hydrochloric acid solution to erythromycin wastewater to adjust pH to 5, then add hydrogen peroxide, react at 95℃, 300rpm speed for 360min to obtain treated wastewater. Erythromycin wastewater is erythromycin thiocyanate fermentation waste mother liquor produced by a pharmaceutical production process, the erythromycin residual titer in erythromycin wastewater is 60mg / L, the amount of thiocyanate in erythromycin wastewater is 2000mg / L, the COD of erythromycin wastewater is 70000mg / L, the amount of sulfate ion in erythromycin wastewater is 4000mg / L, the amount of suspended matter in erythromycin wastewater is 1500mg / L, the hydrochloric acid solution is composed of hydrochloric acid and water, the dosage ratio of hydrochloric acid to water is 30g:1L, and the dosage ratio of hydrogen peroxide to erythromycin wastewater is 5.18g:1L.

[0056] Embodiment 2: Treatment of erythromycin wastewater: Calcium peroxide is added to the erythromycin wastewater, and then the treated wastewater is obtained by ultrasonic reaction at 60℃ for 360min under 400W ultrasonic power. The erythromycin wastewater is the erythromycin thiocyanate fermentation waste mother liquor produced by a pharmaceutical industry production process. The pH of the erythromycin wastewater is 6, the erythromycin residual titer in the erythromycin wastewater is 100mg / L, the amount of thiocyanate in the erythromycin wastewater is 6000mg / L, the COD of the erythromycin wastewater is 50000mg / L, the amount of sulfate ions in the erythromycin wastewater is 150mg / L, the amount of suspended matter in the erythromycin wastewater is 1300mg / L, and the dosage ratio of calcium peroxide to erythromycin wastewater is 3.604g:1L.

[0057] Embodiment 3: Preparation of modified resin: Add N,N-dimethylformamide to chloromethyl polystyrene gel resin for swelling, then add 3,3-diaminoacrylonitrile, react at 60°C for 20 hours, filter after the reaction and wash with water until neutral, then wash with hydrochloric acid solution, water and sodium hydroxide solution in sequence to obtain modified resin. The amount ratio of chloromethyl polystyrene gel resin and N,N-dimethylformamide is 0.1g:1ml, the mass ratio of chloromethyl polystyrene gel resin and 3,3-diaminoacrylonitrile is 1:0.64, the hydrochloric acid solution is composed of hydrochloric acid and water, the amount ratio of hydrochloric acid and water is 36.5g:1L, the sodium hydroxide solution is composed of sodium hydroxide and water, the amount ratio of sodium hydroxide to water is 40g:1L.

[0058] Preparation of strongly basic modified anion resin: N,N-dimethylformamide is added to the modified resin for swelling, and then 1,4-dichloromethylnaphthalene is added, and the reaction is carried out at 60°C for 10 hours. After the reaction is completed, it is filtered, and then washed with ethanol solution, ethanol and water in sequence to obtain a strongly basic modified anion resin. The ratio of the modified resin to the added N,N-dimethylformamide is 0.1g:1ml, the mass ratio of the modified resin to the amount of 1,4-dichloromethylnaphthalene is 1:1.74, and the ethanol solution is composed of ethanol and triethylamine, and the mass ratio of ethanol to triethylamine is 1:0.1.

[0059] Treatment of erythromycin wastewater: add calcium peroxide and strongly alkaline modified anion resin to erythromycin wastewater, then ultrasonically react at 400W power and 60℃ for 360min to obtain treated wastewater. Erythromycin wastewater is erythromycin thiocyanate fermentation waste mother liquor produced by a pharmaceutical industry production process, the pH of erythromycin wastewater is 6, the erythromycin residual titer in erythromycin wastewater is 100mg / L, the amount of thiocyanate in erythromycin wastewater is 6000mg / L, the COD of erythromycin wastewater is 50000mg / L, the amount of sulfate ion in erythromycin wastewater is 150mg / L, the amount of suspended matter in erythromycin wastewater is 1300mg / L, the dosage ratio of calcium peroxide to erythromycin wastewater is 3.604g:1L, and the dosage ratio of strongly alkaline modified anion resin to erythromycin wastewater is 40g:1L.

[0060] Embodiment 4: The preparation of the strongly basic modified anionic resin is the same as in Example 3.

[0061] Treatment of erythromycin wastewater: The treatment of erythromycin wastewater in this embodiment is compared with that in Example 3, except that the usage ratio of the strongly alkaline modified anion resin to erythromycin wastewater is 60 g:1 L, and other conditions and parameters are the same as in Example 3.

[0062] Embodiment 5: The preparation of the strongly basic modified anionic resin is the same as in Example 3.

[0063] Preparation of modified chitosan: Dissolve chitosan in hydrochloric acid solution, and then adjust the pH to 5 to obtain chitosan solution. Dissolve 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride in N,N-dimethylformamide to obtain a mixed solution. Then add the mixed solution to the chitosan solution and react at 25°C for 2h, then drop 3-sulfopropionic acid solution and 5-phenylpentane-2,4-dicarboxylic acid solution, and react at 25°C for 4h. After the reaction, add acetone to filter and separate the precipitate, and wash and dry the precipitate to obtain modified chitosan. The hydrochloric acid solution is composed of hydrochloric acid and water, the dosage ratio of hydrochloric acid to water is 10g:1L, the dosage ratio of chitosan to hydrochloric acid solution is 0.01g:1ml, the dosage ratio of 4-dimethylaminopyridine to N,N-dimethylformamide is 0.0075g:1ml, the dosage ratio of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to N,N-dimethylformamide is 0.065g:1ml, the volume ratio of chitosan solution to mixed solution is 1:0.2, and the 3-sulfopropionic acid solution is composed of 3-sulfopropionic acid. The solution is composed of propionic acid and water, the dosage ratio of 3-sulfopropionic acid and water is 0.005g:1ml, the volume ratio of chitosan solution to 3-sulfopropionic acid solution is 1:0.5, the 5-phenylpentane-2,4-dicarboxylic acid solution is composed of 5-phenylpentane-2,4-dicarboxylic acid and N,N-dimethylformamide, the dosage ratio of 5-phenylpentane-2,4-dicarboxylic acid and N,N-dimethylformamide is 0.003g:1ml, and the volume ratio of chitosan solution to 5-phenylpentane-2,4-dicarboxylic acid solution is 1:0.5.

[0064] Treatment of erythromycin wastewater: Calcium peroxide and strongly alkaline modified anion resin were added to the erythromycin wastewater, and then ultrasonically reacted at 60°C for 360 minutes under an ultrasonic power of 400 W, and then modified chitosan was added and the reaction was continued for 30 minutes to obtain the treated wastewater. The erythromycin wastewater is the waste mother liquor of erythromycin thiocyanate fermentation produced by a production process in a pharmaceutical industry. The pH of the erythromycin wastewater is 6, the residual titer of erythromycin in the erythromycin wastewater is 100 mg / L, the amount of thiocyanate in the erythromycin wastewater is 6000 mg / L, the COD of the erythromycin wastewater is 50000 mg / L, the amount of sulfate ions in the erythromycin wastewater is 150 mg / L, the amount of suspended matter in the erythromycin wastewater is 1300 mg / L, the dosage ratio of calcium peroxide to erythromycin wastewater is 3.604 g:1L, the dosage ratio of strongly alkaline modified anion resin to erythromycin wastewater is 40 g:1L, and the dosage ratio of modified chitosan to erythromycin wastewater is 0.08 g:1L.

[0065] Embodiment 6: The preparation of the strongly basic modified anionic resin is the same as in Example 3.

[0066] The preparation of modified chitosan is the same as in Example 5.

[0067] Treatment of erythromycin wastewater: The treatment of erythromycin wastewater in this embodiment is compared with that in Example 5, except that the usage ratio of modified chitosan to erythromycin wastewater is 0.2 g:1 L, and other conditions and parameters are the same as in Example 5.

[0068] Comparative Example 1: The preparation of the strongly basic modified anionic resin is the same as in Example 3.

[0069] Treatment of erythromycin wastewater: The treatment of erythromycin wastewater in this embodiment is compared with that in Example 3, except that the usage ratio of the strongly alkaline modified anion resin to the erythromycin wastewater is 1 g:1 L, and other conditions and parameters are the same as in Example 3.

[0070] Experimental Example 1: The removal rate of erythromycin titer in wastewater was measured, and the change of erythromycin concentration in wastewater was detected by UPLC / MS / MS. According to the Pharmacopoeia of the People's Republic of China (2010 edition), the change of residual biological titer in erythromycin wastewater was detected by turbidity method. Erythromycin titer removal rate % = (erythromycin titer in initial erythromycin wastewater - erythromycin titer in treated wastewater) / erythromycin titer in initial erythromycin wastewater × 100%. The wastewater includes the initial erythromycin wastewater and the treated wastewater obtained by treatment in Examples 1-7 and Comparative Example 1.

[0071] Table 1 The determination results of erythromycin titer removal rate

[0072] The results are shown in Table 1. The treatment of Example 1 and Example 2 has a better effect on the removal of erythromycin titer in erythromycin wastewater; Example 2 is compared with Example 3, indicating that the use of the strongly basic modified anion resin can improve the erythromycin titer removal rate of erythromycin wastewater; Example 3 is compared with Example 4, indicating that the use of the strongly basic modified anion resin is increased within a certain range, and the erythromycin titer removal rate of erythromycin wastewater can be further improved; Example 3 is compared with Example 5, indicating that on the basis of using the strongly basic modified anion resin, the erythromycin wastewater is treated with modified chitosan, which can improve the erythromycin titer removal rate of erythromycin wastewater; Example 5 is compared with Example 6, indicating that the use of modified chitosan is increased within a certain range, which can improve the erythromycin titer removal rate of erythromycin wastewater; Example 3 is compared with Comparative Example 1, indicating that the use of the strongly basic modified anion resin needs to be in a suitable range, and too low anion resin has no obvious effect on the improvement of the erythromycin titer removal rate of erythromycin wastewater.

[0073] Experimental Example 2: The thiocyanate removal rate in the wastewater was measured, and the concentration change of thiocyanate in the wastewater was detected by spectrophotometry. Thiocyanate removal rate % = (thiocyanate concentration in the initial erythromycin wastewater - thiocyanate concentration in the treated wastewater) / thiocyanate concentration in the initial erythromycin wastewater × 100%. The wastewater includes the initial erythromycin wastewater and the treated wastewater obtained by Examples 1-7 and Comparative Example 1.

[0074] Table 2 Determination results of thiocyanate removal rate

[0075] The results are shown in Table 2. The treatment of erythromycin wastewater by Example 1 and Example 2 has a better effect on the removal of thiocyanate in erythromycin wastewater; compared with Example 3, Example 2 shows that the use of the strongly basic modified anion resin can further improve the thiocyanate removal rate of erythromycin wastewater to a higher value; compared with Comparative Example 1, Example 3 shows that the usage of the strongly basic modified anion resin needs to be in an appropriate range, and too low an amount has no obvious effect on improving the thiocyanate removal rate of erythromycin wastewater.

[0076] Experimental Example 3: The wastewater was further treated with anaerobic sludge, and the anaerobic methanogenic activity was measured to evaluate the changes in the biological inhibition of the wastewater. The anaerobic sludge was municipal anaerobic digestion sludge, which was used as inoculum sludge, and the inoculum sludge concentration was set to 6000 mgVSS / L. The wastewater was diluted to make the COD 3000 mg / L. The inoculum sludge was mixed with the wastewater, cultured under mesophilic anaerobic conditions for 15 days at a culture temperature of 35°C, and the cumulative methane production during the process was detected. The wastewater includes the initial erythromycin wastewater and the treated wastewater obtained by treating Examples 1-7 and Comparative Example 1.

[0077] Table 3 Measurement results of cumulative methane production

[0078] The cumulative methane production results of the initial erythromycin wastewater and the treated wastewater obtained in Example 1 are shown in Tables 3 and Figure 2As shown, the cumulative methane production of the treated wastewater obtained in Example 1 is increased by 634% compared with the initial erythromycin wastewater. The results of the cumulative methane production of the treated wastewater obtained in Examples 2-6 and Comparative Example 1 are shown in Table 3. Compared with Example 3, Example 2 shows that the use of the strongly basic modified anion resin can increase the cumulative methane production of the treated wastewater, that is, improve the anaerobic methanogenesis activity; Compared with Example 4, Example 3 shows that the use of the strongly basic modified anion resin increases within a certain range, and the cumulative methane production of the treated wastewater can also be further increased; Compared with Example 5, Example 3 shows that on the basis of using the strongly basic modified anion resin, the treated wastewater obtained by treating erythromycin wastewater with modified chitosan can promote the further increase of the cumulative methane production; Compared with Example 6, Example 5 shows that the increase in the use of modified chitosan within a certain range can increase the cumulative methane production of the treated wastewater; Compared with Comparative Example 1, Example 3 shows that the use of the strongly basic modified anion resin needs to be in an appropriate range, and too low an amount has no obvious promoting effect on the increase of the cumulative methane production of the treated wastewater.

[0079] Experimental Example 4: The changes in wastewater during the reaction process were monitored and measured. In the treatment process of erythromycin wastewater in Example 1, when hydrogen peroxide was added and the reaction was carried out, samples were taken at different times to measure the erythromycin residual titer, thiocyanate concentration, erythromycin titer removal rate and thiocyanate removal rate. The measurement method was the same as that of Experimental Examples 1 and 2.

[0080] Table 4 Determination results of wastewater changes during the reaction process

[0081] The results are shown in Table 4 and Figure 3 As shown, Figure 3 C in the figure is the residual titer of erythromycin and the concentration of thiocyanate measured at different times, and C0 is the initial residual titer of erythromycin and the concentration of thiocyanate. As the reaction time increases, the residual titer of erythromycin and the concentration of thiocyanate both decrease, and the removal rate of erythromycin titer and thiocyanate is effectively improved.

[0082] The embodiments and / or implementation methods described above are only used to illustrate the preferred embodiments and / or implementation methods for realizing the technology of the present invention, and are not intended to limit the implementation methods of the technology of the present invention in any form. Any technical personnel in this field may make slight changes or modifications to other equivalent embodiments without departing from the scope of the technical means disclosed in the content of the present invention, but they should still be regarded as technologies or embodiments that are essentially the same as the present invention.

[0083] This article uses specific examples to illustrate the principles and implementation methods of this application. The description of the above embodiments is only used to help understand the method and its core ideas of this application. The above is only the preferred implementation method of this application. It should be pointed out that due to the limitations of textual expression and the objective existence of infinite specific structures, ordinary technicians in this technical field can make several improvements, modifications or changes without departing from the principles of this application, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the concept and technical solution of the invention to other occasions without improvement, should be regarded as the scope of protection of this application.

Claims

1. A method for treating erythromycin wastewater, comprising: Firstly, the pH of erythromycin wastewater is adjusted, and then a selective reaction reagent is added to react to obtain treated wastewater; The selective reaction reagent comprises an oxidant and a catalytic aid, and the dosage ratio of the oxidant to the erythromycin wastewater is 2-15 g:1 L.

2. A method for treating erythromycin wastewater according to claim 1, characterized in that: The COD in the erythromycin wastewater is 10000-100000 mg / L, the residual titer of erythromycin is 10-1000 mg / L, and the thiocyanate ion is 1000-9000 mg / L.

3. A method for treating erythromycin wastewater according to claim 1, characterized in that: The oxidant is at least one of hydrogen peroxide, calcium peroxide, perchlorate, ferrate, persulfate, percarbonate, peracetic acid and vanadium trichloride.

4. A method for treating erythromycin wastewater according to claim 1, characterized in that: The catalyst promoter is at least one of metal oxides, bicarbonates, metal salts, ion exchange resins, zeolite molecular sieves and mesoporous materials.

5. A method for treating erythromycin wastewater according to claim 1, characterized in that: The dosage ratio of the catalyst auxiliary agent to erythromycin wastewater is 2-100g:1L.

6. A method for treating erythromycin wastewater according to claim 4, characterized in that: The ion exchange resin is at least one of a strongly acidic perfluorosulfonic acid cation exchange resin, a macroporous strongly basic styrene anion exchange resin and a strongly basic modified anion resin, and the strongly basic modified anion resin is prepared from chloromethyl polystyrene gel resin, 3,3-diaminoacrylonitrile and 1,4-dichloromethylnaphthalene.

7. A method for treating erythromycin wastewater according to claim 1, characterized in that: The pH is 3-11.

8. A method for treating erythromycin wastewater according to claim 1, characterized in that: The reagents used for adjusting pH are sodium hydroxide solution and hydrochloric acid solution. The sodium hydroxide solution consists of sodium hydroxide and water, and the dosage ratio of sodium hydroxide to water is 0.4-40g:1L. The hydrochloric acid solution consists of hydrochloric acid and water, and the dosage ratio of hydrochloric acid to water is 3-37g:1L.

9. A method for treating erythromycin waste water according to claim 1, characterized in that: The reaction temperature is 50-100° C., and the reaction time is 5-480 min.

10. A method for treating erythromycin waste water according to claim 1, characterized in that: The reaction adopts at least one of mechanical stirring and magnetic stirring, and the rotation speed is 50-400 rpm.

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