Method for removing residual lincomycin in emissions by using hydrated hydrogen ions

Abstract

The invention belongs to the technical field of animal husbandry pollution prevention and control, and particularly relates to a method for removing residual lincomycin in emissions by using hydrous hydrogen ions. The method comprises the following steps: (1) material pretreatment: dehydrating, drying and crushing solid emissions, and directly feeding liquid emissions; and (2) adding hydrated hydrogen ions. (3) catalytic hydrolysis: putting the mixed material into a closed reaction kettle, and reacting the solid material for 3-5 hours under the conditions that the temperature is 80-120 DEG C and the rotating speed is 100-200 rpm; or a liquid with the pH value of 2.0 is prepared from a mixed solution of hydrated hydrogen ions with the pH value of 0 and liquid discharge, the prepared liquid is placed in a constant-temperature oscillation reactor, and the liquid material reacts for 2-4 hours under the conditions that the temperature is 70-90 DEG C and the oscillation rate is 100-300 rpm. (4) separation: filtering a solid material, and recycling a filter cake; and the liquid material is discharged after reaching the standard after being neutralized. The method has the characteristics of high degradation efficiency, low cost, environment friendliness and high universality.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of pollution prevention and control in animal husbandry, and particularly relates to a method for removing residual lincomycin in emissions by using hydronium ions. BACKGROUND

[0002] Lincomycin is a broad-spectrum antibiotic and is widely used in human medical treatment and livestock and poultry breeding fields. However, its production process (such as microbial fermentation) will produce a large amount of industrial waste containing residual lincomycin and residual lincomycin in the field of livestock and poultry breeding, including: solid emissions: fermentation dregs (containing mycelium, unconsumed culture medium and residual antibiotics), residual lincomycin in livestock and poultry manure. Liquid emissions: waste filtrate (mother liquor after extraction process), equipment cleaning water, etc.

[0003] Residual lincomycin has biological toxicity, and if directly discharged, it will cause the following environmental problems: Microbial drug resistance: long-term residual causes environmental microorganisms to produce drug resistance genes, threatening public health safety.

[0004] Ecotoxicity: inhibits the activity of beneficial microorganisms (such as nitrifying bacteria) in water and soil, and destroys the ecological balance.

[0005] Secondary pollution: lincomycin has stable structure and is difficult to be completely degraded by conventional treatment (such as biochemical treatment and adsorption), and is easy to be enriched in the environment.

[0006] In the prior art, the methods for treating residual lincomycin mainly include: 1. Chemical oxidation method (such as Fenton oxidation and ozone oxidation): a large amount of oxidizing agent (H2O2, O3) needs to be added, the cost is high (the cost of ton of water treatment is more than 50 yuan), and secondary pollutants (such as iron mud and bromate) are easy to be produced.

[0007] 2. Biological degradation method: it depends on specific degradation bacteria (such as pseudomonas and bacillus), but lincomycin has inhibitory effect on microorganisms, the degradation efficiency is low (the degradation rate is less than 60% in 7 days), and it is greatly affected by temperature and pH fluctuation.

[0008] 3. Adsorption method (such as activated carbon and resin): only the transfer of pollutants is realized, complete degradation cannot be achieved, and after adsorption saturation, regeneration or incineration is needed, and the resource utilization rate is low.

[0009] Therefore, it is urgent to develop a low-cost, efficient and environmentally friendly lincomycin residue treatment technology. SUMMARY

[0010] The application aims at the above-mentioned deficiencies and provides a method for removing residual lincomycin in emissions by using hydronium ions.

[0011] The technical solution of the present application is a method for removing residual lincomycin in emissions by using hydronium ions, comprising the following steps: (1) Material pretreatment: dewatering, drying and crushing of solid emissions to increase the reaction surface area; or direct sampling of liquid emissions.

[0012] (2) Hydronium ion adjustment: adding hydronium ions with a concentration of 0.1-1.0 mol / L to configure a hydronium ion liquid with a pH value of 2.3; for solid emissions, the amount of liquid to solid ratio is (3-6):1; or for liquid emissions, the amount of liquid emissions to hydronium ions is (2-5):1. The pH value is diluted to 1.5-3.5. Preferably, the pH value is 2.0-3.0, and further preferably, the pH value is 2.3.

[0013] (3) Catalytic hydrolysis: placing the mixed material in a sealed reaction kettle, and under the conditions of a temperature of 80-120℃ and a rotation speed of 100-200 rpm, reacting for 3-5 hours; or placing the liquid emissions in a constant-temperature oscillation reactor, and under the conditions of a temperature of 70-90℃ and an oscillation speed of 100-300 rpm, reacting for 2-4 hours.

[0014] (4) Separation: filtering the solid material, and resource utilization of the filter cake, which can be used to make organic fertilizer; neutralizing the liquid material to meet the standard and converting it into foliar fertilizer.

[0015] In the above method, the following steps are further included: The solid emissions are dewatered, dried to a moisture content of 30%-50%, and crushed to a particle size of 0.1-2 mm. The liquid emissions are directly sampled.

[0016] The solid emissions or liquid emissions refer to lincomycin production residues, other fermentation residues containing lincomycin, waste filtrate (pharmaceutical wastewater, medical wastewater), and livestock and poultry manure.

[0017] The hydronium ion belongs to the prior art. For example, a preparation method for preparing hydronium ions from diatomite was disclosed in the Chinese invention patent specification, application number 202210089650.2, and granted on September 5, 2023. The technical indicators of hydronium ions are sulfuric acid root content <0.1%, and pH value <0.7. For example, a preparation method for preparing hydronium ions from diatomite, the steps are as follows: (1) mixing and stirring inorganic acid with diatomite in proportion, and the pH value of the mixed solution of diatomite and inorganic acid is <2. (2) The mixed solution is allowed to stand and precipitate, and the supernatant is taken. (3) Detecting the supernatant, and adding diatomite and stirring until the supernatant meets the hydronium ion indicators.

[0018] The application proposes an innovative method for catalytic hydrolysis of lincomycin residues based on hydronium ions (H3O⁺). By precisely controlling the reaction conditions and utilizing the unique catalytic properties of hydronium ions, efficient degradation of lincomycin residues in solid waste (such as lincomycin solid emissions and animal manure) and liquid waste (such as lincomycin liquid emissions, pharmaceutical wastewater, and medical wastewater) is achieved.

[0019] Core principle: "Dual-track catalysis" mechanism of hydronium ions.

[0020] The molecular structure of lincomycin is composed of glycosidic bonds (connecting sugar chains and lincomycin amide groups) and thioether bonds (connecting thio groups). The key to its degradation lies in breaking the stability of these two core functional groups. The application activates the "weak bond cleavage-radical chain reaction" pathway within the molecule through the catalytic action of hydronium ions: Protonation pretreatment: As a strong electrophile, hydronium ions first bind to the heteroatoms (S, O) in the thioether bonds (-S-) and glycosidic bonds (-O-) of lincomycin molecules. By protonation, the bond energy is reduced (such as the polarity of the C-S bond in the thioether bond is enhanced, and the acetal structure of the glycosidic bond is loosened), providing "weak points" for subsequent hydrolysis.

[0021] Directed hydrolysis and cleavage: Under the continuous action of hydronium ions, the thioether bond of lincomycin preferentially undergoes a nucleophilic substitution reaction (Nu⁻ attack), generating an unstable intermediate. Subsequently, the glycosidic bond undergoes acetal hydrolysis under acidic conditions, ultimately decomposing lincomycin into inactive small molecule products, completely losing antibacterial activity.

[0022] Technical advantages: "Three-in-one" solution with high efficiency, mildness, and universality.

[0023] The beneficial effects of the application are: 1. Efficient degradation. Under the catalysis of hydronium ions, the glycosidic bond (connecting sugar chains and lincomycin amide groups) and the thioether bond (connecting thio groups) of lincomycin rapidly break down. In 4 hours, the lincomycin residue in solid materials decreases from 100-500 mg / L to <8 ug / L (degradation rate >98%), and the residue in liquid materials decreases from 10-100 mg / L to <5 ug / L (degradation rate >99%).

[0024] 2. Low cost. Using sulfuric acid or hydrochloric acid as a source of hydronium ions, the raw material cost is reduced by more than 50% compared to other materials. The reaction conditions are mild (temperature <120℃), and the energy consumption is only 1 / 3-1 / 2 of that of chemical oxidation.

[0025] 3. Environmentally friendly. The degradation products are short-chain fatty acids such as acetic acid, propionic acid, butyric acid, and pentose, which can be further utilized by microorganisms without secondary toxicity. The solid filter cake can be resourcefully utilized after being made into organic fertilizer, and the liquid filtrate can be converted into foliar fertilizer.

[0026] 4. Strong universality: suitable for various types of industrial discharges such as lincomycin fermentation residue, waste filtrate, equipment cleaning water, and livestock and poultry manure containing lincomycin residues, and has a significant degradation effect on lincomycin with different initial concentrations (10-1000 mg / kg or 50-500 mg / L). DETAILED DESCRIPTION EMBODIMENT

[0027] Solid discharge (lincomycin fermentation residue) treatment Raw material: lincomycin fermentation residue from a pharmaceutical factory, initial moisture content 55%, lincomycin residue 320 mg / L (dry basis), pH: 6.8.

[0028] Treatment steps: Pretreatment: the residue is dewatered by pressure filtration (moisture content is reduced to 30%), then crushed to a particle size of 1 mm, and 1 L is taken for standby.

[0029] Hydronium ion adjustment: add hydronium ions, liquid-solid ratio 3:1, dilute pH to 2.3.

[0030] Catalytic hydrolysis: put the material into a sealed reaction kettle, constant temperature 90℃, 120 rpm stirring reaction for 4 hours.

[0031] Post-treatment: after reaction, filter, and detect the filter cake by liquid chromatography-tandem mass spectrometry, the lincomycin residue is 8 ug / L, and the treatment cost per ton of material is 36 yuan.

[0032] Experimental example 1 Traditional biochemical treatment Take the residue of example 1, directly perform aerobic biochemical treatment (temperature 25℃, time 7 days), and detect by liquid chromatography-tandem mass spectrometry, the lincomycin residue is only reduced to 128 ug / L (degradation rate 40%), and the treatment cost per ton of material is 78 yuan. It can be seen that the residue removal advantage of the present application is obvious. EMBODIMENT

[0033] Liquid discharge (lincomycin waste filtrate) treatment Raw material: 1 L of lincomycin extraction waste filtrate from a pharmaceutical factory is taken for standby, initial lincomycin residue 85 mg / L, pH 8.0.

[0034] Treatment steps: Hydronium ion adjustment: add hydronium ions, dosage: add 10 ml of hydronium ions with pH=0, dilute pH to 2.0. The ratio of hydronium ions to waste filtrate: 2:1.

[0035] Catalytic hydrolysis: the waste filtrate was placed in a constant temperature oscillator, 80℃, 200rpm, and the reaction was oscillated for 2 hours.

[0036] Post-processing: after the reaction, the precipitate was settled, and the supernatant was detected by liquid chromatography-tandem mass spectrometry. The lincomycin residual amount was 5ug / L, the ton liquid treatment cost was 18 yuan, and the discharge could reach the standard.

[0037] Experimental example 2 Traditional chemical oxidation method (Fenton oxidation) Take 1L of the waste filtrate of example 2, add H2O2, the molar ratio is 1:1, adjust the pH to 3, and react for 2 hours. The lincomycin residual amount is 11.1ug / L (degradation rate 86%) detected by liquid chromatography-tandem mass spectrometry. The ton liquid treatment cost is 65 yuan. It can be seen that the residual removal advantage of the present application is obvious.

[0038] The above description is only a specific embodiment of the present application, and various examples do not limit the essential content of the present application.

Claims

1. A method for removing residual lincomycin from emissions using hydrated hydrogen ions, characterized in that, Includes the following steps: (1) Material pretreatment: solid emissions are dehydrated, dried and pulverized; or liquid emissions are directly injected. (2) Adjustment of hydrated hydrogen ions: Add hydrated hydrogen ions at a concentration of 0.1-1.0 mol / L, with a liquid-to-solid ratio of 3-6:1 for solid waste; or a liquid ratio of 2-5:1 for liquid waste; dilute the pH to 1.5-3.

5. (3) Catalytic hydrolysis: Solid materials are reacted at a temperature of 80-120℃ and a rotation speed of 100-200rpm for 3-5 hours; or liquid materials are reacted at a temperature of 70-90℃ and a oscillation speed of 100-300rpm for 2-4 hours; (4) Separation: Solid materials are filtered and the filter cake is recycled; liquid materials are neutralized and converted into foliar fertilizer after meeting the standards.

2. The method for removing residual lincomycin from emissions using hydrated hydrogen ions according to claim 1, characterized in that: The solid emissions are dehydrated and dried to a moisture content of 30%-50%, and then pulverized to a particle size of 0.1-2 mm. Liquid emissions are directly injected into the sample.

3. The method for removing residual lincomycin from emissions using hydrated hydrogen ions according to claim 1, characterized in that... The solid or liquid emissions refer to lincomycin production residue and other fermentation residues, waste filtrate, and livestock and poultry manure containing lincomycin residue.