A FeNCN / MgO-supported material from livestock and poultry manure biochar, its preparation method and application

Abstract

This invention relates to the field of water pollution control and resource utilization technology, specifically disclosing a FeNCN / MgO-supported material from livestock and poultry manure biochar, its preparation method, and its applications. The method includes the following steps: grinding and mixing 10-50g of dried livestock and poultry manure with 1.0-10.0g of an organic acid iron salt, 2.0-10.0g of thiourea, and 1.0-5.0g of magnesium hydroxide; then calcining the mixture at 350-600℃ for 2-4 hours in the absence of air; and finally cooling to room temperature to obtain the FeNCN / MgO-supported material from livestock and poultry manure biochar. The preparation method provided by this invention is simple, low-cost, and convenient to use, and the prepared livestock and poultry manure biochar carrier itself exhibits good adsorption performance for antibiotics, ARGs, and heavy metals in livestock wastewater.

Description

Technical Field

[0001] This invention relates to the field of water pollution control and resource utilization technology, specifically to a material of livestock and poultry manure biochar loaded with FeNCN / MgO, its preparation method and application. Background Technology

[0002] Currently, livestock and poultry wastewater treatment processes mainly consist of different combinations of anaerobic, aerobic, and facultative anaerobic biological treatment technologies, as well as advanced treatment technologies such as oxidation ponds, constructed wetlands, and disinfection. In fact, these biological and ecological treatment technologies primarily focus on removing conventional pollutants such as COD, BOD, TN, and TP. Their ability to remove heavy metals, antibiotics, and ARGs from livestock and poultry wastewater is extremely limited, and they may even exacerbate the transfer of these pollutants between bacteria.

[0003] Similarly, current traditional disinfection technologies (such as chlorine and ozone) are not targeted at ARBs and ARGs. Ineffective disinfection doses or technologies will not completely inactivate ARGs; on the contrary, they may accelerate their transfer and spread in the aquatic environment.

[0004] In recent years, advanced oxidation processes (AOPs) have gained high recognition for removing recalcitrant organic pollutants. Studies have found that AOPs can also destroy bacterial cell membranes and DNA structures through reactions with active free radicals (OH·, SO·4-, O2·-, etc.). Therefore, this type of technology has attracted attention for removing ARGs from water. However, existing AOPs technologies still have shortcomings such as high catalyst preparation costs, difficulty in large-scale application, and secondary pollution caused by leakage of heavy metals.

[0005] In conclusion, existing livestock and poultry wastewater treatment technologies are indeed insufficient to effectively remove pollutants such as heavy metals, antibiotics, and ARGs. Seeking economical, practical, and efficient deep removal technologies for these pollutants has become an urgent priority for achieving the sustainable development of the livestock and poultry farming industry. Summary of the Invention

[0006] The purpose of this invention is to overcome the aforementioned problems in the prior art.

[0007] To achieve the above objectives, a first aspect of the present invention provides a method for preparing FeNCN / MgO-supported biochar from livestock and poultry manure, the method comprising the following steps:

[0008] 10–50 g of dried livestock and poultry manure was ground and mixed with 1.0–10.0 g of organic acid iron salt, 2.0–10.0 g of thiourea and 1.0–5.0 g of magnesium hydroxide. Then, the mixture was calcined at 350–600 °C for 2–4 h in the absence of air. After cooling to room temperature, a material of livestock and poultry manure biochar supported on FeNCN / MgO was obtained.

[0009] The second aspect of the present invention provides a material of livestock and poultry manure biochar loaded with FeNCN / MgO prepared by the method described in the first aspect above.

[0010] The third aspect of this invention provides the application of the FeNCN / MgO-loaded animal manure biochar material described in the second aspect above in the removal of antibiotics from animal husbandry wastewater.

[0011] Compared with the prior art, the present invention has at least the following advantages:

[0012] 1. The present invention uses livestock and poultry manure as raw material, and the livestock and poultry manure biochar carrier prepared by the invention has good adsorption performance for antibiotics, ARGs and heavy metals in livestock and poultry wastewater, providing good conditions for the simultaneous removal of the above pollutants.

[0013] 2. The FeNCN / MgO-supported biochar material from livestock and poultry manure prepared by this invention can achieve the activation of persulfate to generate OH· and SO·4 through optimized control of its FeNCN and MgO components. - The coupling with 1O2 enhances its efficient and deep oxidative removal of antibiotics and ARGs;

[0014] 3. The technical solution of this invention is guided by "waste treatment", based on safety and efficiency, and based on economic applicability. The technology provided is characterized by safety, efficiency, economy, simplicity and ease of application. It can effectively achieve deep purification and removal of antibiotics, ARGs and heavy metals in livestock and poultry breeding wastewater, and effectively ensure the sustainable development of the livestock and poultry breeding industry. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] It should be noted that, in all aspects of the present invention, the same components or terms in each aspect are described only once in one aspect and not repeatedly, and those skilled in the art should not understand this as a limitation of the present invention.

[0017] As mentioned above, the first aspect of the present invention provides a method for preparing FeNCN / MgO-supported biochar from livestock and poultry manure, the method comprising the following steps:

[0018] 10–50 g of dried livestock and poultry manure was ground and mixed with 1.0–10.0 g of organic acid iron salt, 2.0–10.0 g of thiourea and 1.0–5.0 g of magnesium hydroxide. Then, the mixture was calcined at 350–600 °C for 2–4 h in the absence of air. After cooling to room temperature, a material of livestock and poultry manure biochar supported on FeNCN / MgO was obtained.

[0019] Preferably, the livestock and poultry manure is the manure of livestock and poultry such as pigs, cattle, sheep, and chickens.

[0020] More preferably, the organic acid iron salt is one or more of ferric ammonium oxalate trihydrate and ferric ammonium citrate.

[0021] In a preferred embodiment, the persulfate is one of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0022] As previously stated, the second aspect of the present invention provides a material of livestock and poultry manure biochar loaded with FeNCN / MgO prepared by the method described in the first aspect above.

[0023] As mentioned above, the third aspect of the present invention provides the application of the FeNCN / MgO-loaded animal manure biochar material described in the second aspect above in the removal of antibiotics from animal husbandry wastewater.

[0024] Preferably, the effluent from the existing wastewater treatment process of the livestock and poultry farm is used as the target for advanced treatment. 0.5 to 5.0 g / L of the livestock and poultry manure biochar-loaded FeNCN / MgO material is added to the wastewater to be treated, followed by the addition of 1 mmol / L to 10 mmol / L of persulfate. The mixture is continuously stirred at room temperature for 1 to 5 hours to achieve simultaneous removal of antibiotics, ARGs, and heavy metals from the water.

[0025] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, the raw materials used are all commercially available products.

[0026] Unless otherwise specified, "room temperature" in this invention means 25±2℃.

[0027] Example 1

[0028] This embodiment illustrates the method for preparing FeNCN / MgO-supported livestock manure biochar according to the present invention, which is carried out according to the following steps:

[0029] 10g of dried pig manure was ground and mixed with 1.5g of ferric ammonium oxalate trihydrate, 2.0g of thiourea and 1.0g of magnesium hydroxide. Then, the mixture was calcined at 500℃ for 2 hours under air-isolated conditions. After cooling to room temperature, a material of FeNCN / MgO supported on livestock and poultry manure biochar was obtained and named P1.

[0030] Example 2

[0031] This embodiment illustrates the method for preparing FeNCN / MgO-supported livestock manure biochar according to the present invention, which is carried out according to the following steps:

[0032] 10g of dried cow manure was ground and mixed with 2.0g of ferric ammonium oxalate trihydrate, 2.0g of thiourea and 1.2g of magnesium hydroxide. Then, the mixture was calcined at 450℃ for 2 hours under air-isolated conditions. After cooling to room temperature, a material of FeNCN / MgO supported on livestock and poultry manure biochar was obtained and named P2.

[0033] Example 3

[0034] This embodiment illustrates the method for preparing FeNCN / MgO-supported livestock manure biochar according to the present invention, which is carried out according to the following steps:

[0035] 15g of dried pig manure was ground and mixed with 2.0g of ferric ammonium oxalate trihydrate, 2.5g of thiourea and 1.5g of magnesium hydroxide. Then, the mixture was calcined at 550℃ for 2 hours under air-isolated conditions. After cooling to room temperature, the FeNCN / MgO-supported material of livestock and poultry manure biochar was obtained and named P3.

[0036] Test Example 1

[0037] The FeNCN / MgO-loaded livestock and poultry manure biochar material P1 prepared in the above examples was subjected to a water treatment effect test. Specifically:

[0038] Using the treated effluent from the existing wastewater treatment process of a pig farm as the target for advanced treatment, the wastewater was found to contain tetracycline antibiotics (tetracycline, oxytetracycline) at 47.3 μg / L and sulfonamide antibiotics (sulfadiazine, sulfamethoxazole) at 11.54 μg / L. Heavy metals Zn were detected at 4.87 mg / L and AS at 0.13 mg / L. ARGs mainly included tetracyclines (tetA, tetE, and tetQ), macrolides (ermB), sulfonamides (sul 2), and a class 1 integrase gene (intl1). The abundance levels of tetA, tetE, tetQ, ermB, sul 2, and intl1 were 8.74, 7.21, 8.13, 8.49, 8.79, and 6.97 logs, respectively.

[0039] 0.5 g / L of P1 was added to the wastewater to be treated, followed by 1.2 mmol / L of potassium persulfate. The mixture was stirred continuously at room temperature for 1.5 h. After treatment, the effluent contained 1.07 μg / L of tetracycline antibiotics and 0.37 μg / L of sulfonamide antibiotics. The concentrations of Zn and AS were not detected. The abundance levels of tetA, tetE, tetQ, ermB, sul2, and intl1 were 2.67, 2.34, 2.46, 3.01, 2.11, and 2.54 logs, respectively. Gel electrophoresis analysis confirmed that the above-mentioned advanced oxidation treatment destroyed the DNA structure, thereby effectively blocking the spread and contamination of ARGs. No horizontal transfer of ARGs was found in the conjugation transfer assay. The treatment achieved the expected deep purification effect.

[0040] Test Example 2

[0041] The FeNCN / MgO-loaded livestock and poultry manure biochar material P2 prepared in the above examples was subjected to a water treatment effect test. Specifically:

[0042] Using the treated effluent from the existing wastewater treatment process of a cattle farm as the target for advanced treatment, the wastewater mainly contained tetracycline antibiotics (79.35 μg / L), quinolone antibiotics (31.15 μg / L), and sulfonamide antibiotics (19.71 μg / L); the concentrations of heavy metals Cu and Cd were 0.59 mg / L and 0.23 mg / L, respectively; the detected ARGs were mainly tetA, tetO-O1, tetQ, ermF, sul2, and intl1, with abundance levels of 6.95, 8.16, 8.77, 9.89, 13.56, and 11.37 logs, respectively.

[0043] 0.7 g / L of P2 was added to the wastewater to be treated, followed by 2 mmol / L of ammonium persulfate. The mixture was stirred continuously at room temperature for 2.0 h. After treatment, tetracycline antibiotics were 3.12 μg / L, quinolone antibiotics were 2.36 μg / L, and sulfonamide antibiotics were not detected in the effluent. Heavy metals Cu and Cd were not detected. The abundance levels of tetA, tetO-O1, tetQ, ermF, sul2, and intl1 were 2.88, 2.15, 2.59, 2.73, 2.09, and 2.97 logs, respectively. Gel electrophoresis analysis confirmed that the above advanced oxidation treatment destroyed the DNA structure, thereby effectively blocking the spread and contamination of ARGs. No horizontal transfer of ARGs was found in the conjugation transfer assay, and the treatment achieved the expected deep purification effect.

[0044] Test Example 3

[0045] The FeNCN / MgO-supported biochar material P3 prepared in the above examples was subjected to a water treatment effect test. Specifically:

[0046] The effluent from the existing wastewater treatment process of a certain integrated livestock and poultry farm was used as the target for advanced treatment. The wastewater mainly contained tetracycline antibiotics (103.05 μg / L), quinolone antibiotics (40.35 μg / L), and sulfonamide antibiotics (20.45 μg / L); the concentrations of heavy metals Zn and Cd were 3.75 mg / L and 0.31 mg / L, respectively; the detected ARGs were mainly tetA, tetE, tetQ, ermB, sul2, and intl1, with abundance levels of 9.13, 8.27, 7.77, 9.45, 8.99, and 7.78 logs, respectively.

[0047] 1 g / L of P3 was added to the wastewater to be treated, followed by 2 mmol / L of sodium persulfate. The mixture was stirred continuously at room temperature for 2.0 h. After treatment, the effluent contained 2.05 μg / L of tetracycline antibiotics, 1.75 μg / L of quinolone antibiotics, and 0.15 μg / L of sulfonamide antibiotics. The concentrations of heavy metals Zn and Cd were not detected. The abundance levels of tet A, tet E, tet Q, erm B, sul2, and intl 1 were 2.15, 2.77, 2.87, 2.55, 2.37, and 3.15 logs, respectively. Gel electrophoresis analysis confirmed that the above-mentioned advanced oxidation treatment destroyed the DNA structure, thereby effectively blocking the spread and contamination of ARGs. No horizontal transfer of ARGs was found in the conjugation transfer assay, and the treatment achieved the expected deep purification effect.

[0048] The results above show that the method for preparing FeNCN / MgO-supported livestock and poultry manure biochar provided by the present invention is simple, low-cost, and easy to use. Furthermore, the prepared livestock and poultry manure biochar carrier itself has good adsorption performance for antibiotics, ARGs, and heavy metals in livestock and poultry wastewater.

[0049] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method of preparing a material of FeNCN / MgO supported on livestock manure biochar, characterized in that, The steps of the method include: 10-50 g of dried livestock and poultry manure is mixed with 1.0-10.0 g of organic acid iron salt, 2.0-10.0 g of thiourea and 1.0-5.0 g of magnesium hydroxide, and then calcined at 350-600°C for 2-4 h under air isolation conditions. After cooling to room temperature, a livestock and poultry manure biochar loaded FeNCN / MgO material is obtained.

2. The method of claim 1, wherein, Wherein, The livestock and poultry manure is the manure of pigs, cattle, sheep and chickens.

3. The method according to claim 1 or 2, characterized in that, Wherein, The organic acid iron salt is one or more of ammonium ferric oxalate trihydrate and ferric ammonium citrate.

4. The livestock and poultry manure biochar loaded FeNCN / MgO material prepared by the method of any one of claims 1-3.

5. The use of the livestock and poultry manure biochar loaded FeNCN / MgO material of claim 4 in removing antibiotics in livestock and poultry breeding wastewater.

6. Use according to claim 5, characterized in that, Wherein, The effluent of the original wastewater treatment process of a livestock and poultry farm is used as the object of advanced treatment. 0.5-5.0 g / L of the livestock and poultry manure biochar loaded FeNCN / MgO material is added to the wastewater to be treated, followed by the addition of 1 mmol / L-10 mmol / L of persulfate. The mixture is continuously stirred at room temperature for 1-5 h to achieve the simultaneous removal of antibiotics, ARGs and heavy metals in the water.

7. Use according to claim 6, wherein, The persulfate is one of ammonium persulfate, sodium persulfate and potassium persulfate.