CN108726829B

CN108726829B - Method for reducing livestock and poultry manure antibiotic by in-situ catalysis of persulfate

Info

Publication number: CN108726829B
Application number: CN201810630111.9A
Authority: CN
Inventors: 孙英; 刘航; 陈俊豪; 黄鑫
Original assignee: China Agricultural University
Current assignee: China Agricultural University
Priority date: 2018-06-19
Filing date: 2018-06-19
Publication date: 2020-09-01
Anticipated expiration: 2038-06-19
Also published as: CN108726829A

Abstract

The invention discloses a method for reducing antibiotics in livestock and poultry manure by in-situ catalysis of persulfate, aiming at the propagation risk of antibiotics and heavy metals existing in livestock and poultry solid waste returning application, the method comprises the steps of adding an auxiliary agent for promoting the release of the antibiotics and copper ions in the livestock and poultry manure, and utilizing the released copper ions to catalyze and activate the persulfate to generate sulfate radical free radicals to reduce the antibiotics released by the solid phase of the livestock and poultry manure, wherein the main components of the auxiliary agent comprise a chelating agent and inorganic acid, and the molar ratio of the chelating agent to the inorganic acid is 5:1-7.5: 1; the chelating agent comprises disodium ethylene diamine tetraacetate or sodium citrate, and the inorganic acid comprises hydrochloric acid, sulfuric acid or phosphoric acid. The auxiliary agent and the persulfate are mixed and then added into the livestock and poultry manure in a proportion of 0.02-0.5 wt% for treatment, and the removal rate can be improved by 30-60%. Can realize the method for treating the antibiotics in the livestock and poultry solid waste by efficiently catalyzing persulfate oxidation in situ so as to lead the product to reach the standard of the agricultural fertilizer.

Description

Method for reducing livestock and poultry manure antibiotic by in-situ catalysis of persulfate

Technical Field

The invention belongs to the technical field of environmental catalysis and waste resource utilization, and provides a method for reducing livestock and poultry manure antibiotics by in-situ catalysis of persulfate.

Background

With the development of livestock and poultry breeding industry, a large number of antibiotics are used in livestock and poultry breeding industry. However, antibiotics can not be completely absorbed in livestock and poultry bodies, and 30-70% of antibiotics can be discharged out of the bodies along with excrement. The livestock and poultry manure as an organic fertilizer is an important source of antibiotic pollution in farmlands.

The existing methods for treating the livestock and poultry manure mainly comprise aerobic composting and anaerobic digestion, and the methods have a certain removal effect on antibiotics, but the antibiotics in the treated livestock and poultry manure still have higher pollution risk and prevent further safe utilization of the antibiotics. Aiming at the problem that antibiotics in the livestock and poultry manure are difficult to remove at present, the invention provides the method for promoting the release of the antibiotics and copper ions in the livestock and poultry manure by using an auxiliary agent, and reducing the antibiotics released from a solid phase of the livestock and poultry manure by using sulfate radicals generated by catalytically activating persulfate by using the released copper ions so as to enable the product to reach the standard of agricultural fertilizers.

Disclosure of Invention

According to the invention, the auxiliary agent for promoting the release of antibiotics and copper ions in the livestock and poultry feces is added, the released copper ions are utilized to catalytically activate persulfate, sulfate radicals are generated to reduce the antibiotics released from the livestock and poultry feces, the antibiotics in the livestock and poultry feces are efficiently treated by in-situ catalytic persulfate oxidation, and the product reaches the agricultural fertilizer standard.

The specific content of the invention comprises:

a method for reducing livestock and poultry manure antibiotics by in-situ catalysis of persulfate comprises the steps of mixing an auxiliary agent and persulfate, adding the mixture into livestock and poultry manure in a proportion of 0.02-0.5 wt% for treatment, wherein the main components of the auxiliary agent comprise a chelating agent and inorganic acid, and the molar ratio of the chelating agent to the inorganic acid is 5:1-7.5: 1; the chelating agent comprises disodium ethylene diamine tetraacetate or sodium citrate, and the inorganic acid comprises hydrochloric acid, sulfuric acid or phosphoric acid. The antibiotics include tetracycline, sulfanilamide and quinolone antibiotics commonly used in livestock and poultry breeding, but are not limited to the antibiotics.

Furthermore, the livestock and poultry manure is fresh pig manure, chicken manure, cow manure with the solid content of less than 30 percent and biogas residues produced after fermentation. The livestock and poultry manure is fresh manure with solid content of less than 30% in semi-solid state, semi-liquid state and liquid state, and is particularly suitable for being used before solid-liquid separation of livestock and poultry manure in a farm.

Further, the concentration range of the antibiotic in the livestock and poultry feces is 100-.

Further, the auxiliary agent and the persulfate are mixed in proportion, and the molar ratio is 20: 1-80: 1.

Further, the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate.

Further, the treatment process is carried out at room temperature, the pH value is 4-6, and the treatment time is 4 hours.

After the assistant is adopted for concerted catalysis, the degradation effect on antibiotics is obviously improved under the condition of the same persulfate adding amount. The specific degree of enhancement is related to the relative proportion of the added auxiliaries and the reaction conditions. In comparison, under the same other factors, when the ratio of the auxiliary agent to the persulfate is more than 20:1, the improvement effect is obvious in the range of pH 4-6.

Compared with the existing processing method, the processing method provided by the invention has the remarkable characteristics that:

an auxiliary agent for promoting the release of antibiotics and copper ions from the livestock and poultry manure is added, the auxiliary agent can form a sulfate radical free radical in catalytic sites of activated persulfate in the livestock and poultry manure polluted by the copper ions and the antibiotics in a composite manner, the antibiotics are removed in situ while the catalytic performance of the persulfate is enhanced, and the removal rate can be improved by 30-60%. Can realize the method for treating the antibiotics in the livestock and poultry solid waste by efficiently catalyzing persulfate oxidation in situ so as to lead the product to reach the standard of the agricultural fertilizer.

Drawings

FIG. 1 is a comparison graph of the effect of antibiotic adjuvant in cooperation with persulfate to remove antibiotics from animal wastes.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and examples.

A method for reducing livestock and poultry manure antibiotics by in-situ catalysis of persulfate comprises the steps of mixing an auxiliary agent and persulfate, adding the mixture into livestock and poultry manure in a proportion of 0.02-0.5 wt% for treatment, wherein the main components of the auxiliary agent comprise a chelating agent and inorganic acid, and the molar ratio of the chelating agent to the inorganic acid is 5:1-7.5: 1; the chelating agent comprises disodium ethylene diamine tetraacetate or sodium citrate, the inorganic acid comprises hydrochloric acid, sulfuric acid or phosphoric acid, and the antibiotic comprises tetracycline, sulfanilamide and quinolone antibiotics commonly used for livestock and poultry breeding.

Example 1

The auxiliary agent and sodium persulfate are respectively mixed according to the mol ratio of 20:1,40:1 and 80:1, and are added into fresh cow dung containing 1000 mu g/kg of oxytetracycline according to the proportion of 0.1 percent, wherein the solid content of the cow dung is 30 percent. The removal rate of oxytetracycline after 4h was 34.7-67.3% with shaking at room temperature at pH 4. As shown in Table 1

Example 2

Mixing the auxiliary agent and sodium persulfate according to a molar ratio of 80:1, adding the mixture into 200 mu g/kg of biogas residue containing norfloxacin according to a proportion of 0.2 percent, wherein the solid content of the biogas residue is 10 percent, and oscillating the biogas residue at room temperature within the pH range of 4-6. The norfloxacin removal rate after 4 hours is 51.4-60.1%. As shown in table 1.

Example 3

Mixing the auxiliary agent and sodium persulfate according to a molar ratio of 80:1, adding 0.08% of the auxiliary agent into fresh pig manure containing 1000 mu g/kg of sulfadiazine, wherein the solid content of the pig manure is 20%, and the pH value is 4, and shaking at room temperature. The removal rate of sulfadiazine after 4 hours is 50.6 percent. As shown in table 1.

Example 4

The method for treating the livestock and poultry solid waste antibiotics by using the antibiotic auxiliary agent to synergistically catalyze the persulfate has the cost accounting that the price of the auxiliary agent is 7 yuan/kg, and the price of 7 x 19/1000 is 0.13 yuan calculated by 19g of the auxiliary agent for each 1 ton of livestock and poultry solid waste. The dosage of the persulfate is 1.2g, 1.2 divided by 1000 multiplied by 5.3 is 0.006 yuan, and 0.13 plus 0.006 is 0.136 yuan per ton.

TABLE 1 antibiotic adjuvant in cooperation with persulfate for antibiotic removal from livestock and poultry manure

The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.

Claims

1. The method for reducing the livestock and poultry manure antibiotics by in-situ catalysis of persulfate is characterized by comprising the steps of mixing an auxiliary agent and persulfate, adding the mixture into the livestock and poultry manure containing copper ions in a proportion of 0.02-0.5 wt% for treatment, wherein the main components of the auxiliary agent comprise a chelating agent and inorganic acid, and the molar ratio of the chelating agent to the inorganic acid is 5:1-7.5: 1; the chelating agent comprises disodium ethylene diamine tetraacetate or sodium citrate, the inorganic acid comprises hydrochloric acid, sulfuric acid or phosphoric acid, and the antibiotic comprises tetracycline, sulfanilamide and quinolone antibiotics commonly used for livestock and poultry breeding.

2. The method of claim 1, wherein the livestock and poultry manure is fresh pig manure, chicken manure, cow manure containing copper ions with a solid content of less than 30%, and biogas residues produced after fermentation.

3. The method as claimed in claim 1, wherein the concentration of the antibiotic in the livestock and poultry manure is in the range of 100-10000 μ g/kg.

4. The method according to claim 1, wherein the auxiliary agent and the persulfate are mixed in a molar ratio of 20:1 to 80: 1.

5. The method according to claim 1, wherein the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate.

6. The method according to claim 1, wherein the treatment process is carried out at room temperature, the pH is between 4 and 6, and the treatment time is 4 hours.