A method for simultaneously and rapidly treating multiple pollutants of heavy metals, harmful bacteria and resistance genes in chicken manure

Abstract

The present application relates to a kind of method for simultaneously and quickly treating heavy metal, harmful bacteria and resistance gene multiple pollutants in chicken manure, the method of the present application is carried out irradiation under specific catalyst and vacuum ultraviolet, so that advanced oxidation is extremely played, heavy metal, harmful bacteria and resistance gene in chicken manure are effectively managed, and simultaneously it is quickly converted into containing fulvic acid.The present application is treated with simple method, low cost, short time, and does not produce secondary pollution, simple operation, chicken manure does not need to be pretreated, so that heavy metal, harmful bacteria and resistance gene in chicken manure are effectively managed, and simultaneously macromolecule is quickly converted into small molecule fulvic acid, the content of heavy metal in chicken manure after treatment is greatly reduced, resistance gene is almost completely eliminated, harmful bacteria is well inactivated, realizes the management of multiple pollutants in chicken manure, and realizes chicken manure resource utilization at the same time.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for simultaneously and rapidly treating multiple pollutants such as heavy metals, harmful bacteria and resistance genes in chicken manure, and belongs to the field of manure treatment. BACKGROUND

[0002] The main components of chicken manure are plant nutrients such as nitrogen, phosphorus and potassium. Returning chicken manure to the field can improve the soil environment and increase soil fertility. However, the pollutants in chicken manure will cause soil compaction and various pollution problems when chicken manure enters the soil. At present, the mainstream treatment technology of livestock and poultry manure at home and abroad is aerobic composting and anaerobic fermentation. Livestock and poultry manure is converted into mature organic fertilizer through aerobic composting; anaerobic fermentation with the goal of energy production produces biogas, as well as a large amount of biogas slurry and biogas residue. However, the composting process of livestock and poultry manure is long, occupies a large area, is easy to produce odors and leachate, and the mature organic fertilizer is bulky; the biogas slurry / biogas residue produced by anaerobic fermentation has high water content, high transportation cost, and is easy to cause secondary pollution. In addition, neither anaerobic fermentation nor aerobic composting can effectively solve the problem of heavy metal residues in livestock and poultry manure fermentation products. With the application of compost products or biogas slurry / biogas residue as fertilizer, soil and crop heavy metal accumulation occurs, leading to food safety problems.

[0003] In summary, the multiple pollutants such as heavy metals, harmful bacteria and resistance genes in chicken manure are pollutants that need to be treated urgently. The existing treatment methods have high treatment cost, long cycle, are easy to cause secondary pollution, and cannot effectively solve the problem of heavy metal residues. How to use simple and low-cost methods to realize the simultaneous treatment of multiple pollutants in chicken manure and realize harmless treatment and resource utilization is a problem that needs to be solved urgently.

[0004] Red mud is a solid industrial waste produced in the process of producing alumina from bauxite. It looks like dark red soil, hence the name red mud. Generally, 1-2 tons of red mud are produced for every ton of alumina. Red mud contains alkaline earth elements and has strong metal fixation, which can be used in environmental treatment; it has a porous structure, a large specific surface area, and contains metal elements such as Fe, which can be used as a catalyst and a catalyst to reduce the cost of commercial catalysts. Improving the resource utilization of red mud is expected to solve the ecological environmental pollution and large land occupation caused by the large-scale storage of red mud.

[0005] Chinese patent document CN111892462A discloses a method for processing chicken manure into fertilizer, which comprises the following steps: adding ferrous sulfate heptahydrate and sodium borohydride into deionized water, passing nitrogen gas, and recovering the product with a magnet to obtain zero-valent nanometer iron; mixing the zero-valent nanometer iron, ethylenediaminetetraacetic acid and diatomite to obtain a nanometer carrier; electrolyzing sulfuric acid to obtain peroxodisulfuric acid, reacting the peroxodisulfuric acid with ammonium sulfate to obtain an ammonium persulfate solution, and adding manganese dioxide to obtain a manganese dioxide / ammonium persulfate solution; and adding the nanometer carrier and the manganese dioxide / ammonium persulfate solution into fresh chicken manure in sequence. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a method for simultaneously and rapidly treating heavy metals, harmful bacteria and resistance gene pollutants in chicken manure.

[0007] The present application uses a simple advanced oxidation method to treat chicken manure. The method of the present application uses a specific catalyst and irradiation under vacuum ultraviolet to maximize the advanced oxidation, so that the heavy metals, harmful bacteria and resistance genes in the chicken manure are effectively treated, and the macromolecules are rapidly converted into small molecule fulvic acid. After treatment, the content of heavy metals in the chicken manure is greatly reduced, the resistance genes are almost completely eliminated, and the harmful bacteria are well inactivated, achieving the simultaneous treatment of multiple pollutants in chicken manure and the resource utilization of chicken manure.

[0008] The present application is achieved by the following technical solutions:

[0009] A method for simultaneously and rapidly treating heavy metals, harmful bacteria and resistance gene pollutants in chicken manure, comprising the following steps:

[0010] 1) mixing red mud, diatomite and citric acid uniformly to obtain a composite catalyst;

[0011] 2) dissolving persulfate powder in water to prepare a persulfate solution;

[0012] 3) adding the composite catalyst obtained in step 1) and the persulfate solution obtained in step 2) into fresh chicken manure, and adding calcium oxide at the same time, mixing uniformly, and adding water to adjust the uniformity to obtain a mixture;

[0013] 4) placing the mixture obtained in step 3) under vacuum ultraviolet irradiation, and stirring during irradiation to simultaneously and rapidly treat heavy metals, harmful bacteria and resistance genes in chicken manure.

[0014] Preferably, according to the present invention, in step 1), the mass ratio of red mud, diatomaceous earth and citric acid is (0.5-1.5): (1-3): (0.2-0.8).

[0015] Preferably, according to the present invention, in step 1), the mixing is performed by mechanical stirring at a stirring speed of 300-500 rpm.

[0016] According to a preferred embodiment of the present invention, in step 2), the persulfate is selected from one or a mixture of two or more of potassium persulfate, ammonium persulfate, and sodium persulfate.

[0017] Preferably according to the present invention, in step 2), the persulfate is ammonium persulfate.

[0018] According to the preferred embodiment of the present invention, in step 2), the concentration of persulfate is 0.1-1.75 mol / L.

[0019] Most preferably, in step 2), the concentration of persulfate is 0.75-1.25 mol / L.

[0020] According to the preferred embodiment of the present invention, in step 3), the mass ratio of the composite catalyst to fresh chicken manure is (0.5-3): (5-10).

[0021] According to the preferred embodiment of the present invention, in step 3), the mass volume ratio of the composite catalyst to the persulfate solution is (0.5-3):(1-10), in units of g / ml.

[0022] Further preferably, in step 3), the mass volume ratio of the composite catalyst to the persulfate solution is (0.5-3):(1-5), in g / ml.

[0023] According to a preferred embodiment of the present invention, in step 3), the ratio of the amount of calcium oxide added to the total volume of water in the mixture is 0.01-30 g / L.

[0024] Further preferably, in step 3), the ratio of the amount of calcium oxide added to the total volume of water in the mixture is 0.04-15 g / L.

[0025] According to the preferred embodiment of the present invention, in step 4), the irradiation amount of vacuum ultraviolet is 10-20mJ / cm 2 , the stirring speed is 100-300rpm, and the irradiation time is 30-70min.

[0026] Preferably according to the present invention, in step 4), the vacuum degree of vacuum ultraviolet irradiation is less than or equal to 0.05 MPa.

[0027] The method of the present invention is irradiated under a specific catalyst and vacuum ultraviolet light, so that advanced oxidation can be brought into play to the extreme, so that the heavy metals, harmful bacteria and resistance genes in chicken manure are effectively controlled, and are quickly converted into fulvic acid. The present invention is processed in a simple method, with low cost, short time and no secondary pollution, simple operation, no need to pre-treat chicken manure, and the oxidation process can eliminate the odor of chicken manure; the red mud in the catalyst contains alkaline earth elements, which achieves the fixation of heavy metals in chicken manure, and the advanced oxidation method promotes the removal of heavy metals. At the same time, red mud and added calcium oxide can effectively activate persulfate, achieve the elimination of bacteria and resistance genes in chicken manure, and promote the production of fulvic acid in chicken manure. Most importantly, irradiation under vacuum ultraviolet light greatly improves the treatment effect of multiple pollutants such as heavy metals, harmful bacteria and resistance genes in chicken manure. While realizing the rapid treatment of multiple pollutants in chicken manure, the present invention realizes the dual resourceization of chicken manure and red mud, fundamentally solving the environmental pollution and resource recycling problems caused by the storage of feces and red mud produced by the aquaculture industry.

[0028] The technical features and advantages of the present invention are as follows:

[0029] 1. The inventive method is irradiated under a specific catalyst and vacuum ultraviolet light, so that advanced oxidation is brought into play to the extreme, and the heavy metals, harmful bacteria and resistance genes in chicken manure are effectively managed, and are quickly converted into fulvic acid. The present invention is processed in a simple method, with low cost, short time and no secondary pollution, simple operation, no need to pre-treat chicken manure, and the heavy metals, harmful bacteria and resistance genes in chicken manure are effectively managed, and are quickly converted into fulvic acid. After the treatment, the heavy metal content in the chicken manure is greatly reduced, and the resistance genes are almost completely eliminated. The harmful bacteria are well inactivated, and the resource utilization of chicken manure is realized while the multiple pollutants in chicken manure are managed.

[0030] 2. The raw material red mud used in the present invention is solid waste, which is easily available and inexpensive, thus realizing the resource utilization of solid waste.

[0031] 3. The present invention can deodorize chicken manure within 5 minutes, significantly reducing the environmental pressure of chicken manure.

[0032] 4. The present invention can effectively passivate heavy metals in chicken manure and reduce heavy metal pollution in the environment.

[0033] 5. The present invention can achieve inactivation of more than 75% of bacteria in chicken manure within 40 minutes, eliminate resistance genes in chicken manure, and greatly reduce the harm to the environment when chicken manure is applied.

[0034] 6. The present invention can convert macromolecular organic matter in chicken manure into fulvic acid within 20-40 minutes. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Changes in Cu in chicken manure after treatment of Example 1 2+

[0036] Figure 2 Changes in Zn in chicken manure after treatment of Example 1 2+

[0037] Figure 3 Changes in the number of bacteria in chicken manure after treatment of Example 1

[0038] Figure 4 Changes in resistant genes in chicken manure after treatment of Example 1

[0039] Figure 5 Fulvic acid content in chicken manure after treatment of Examples 1, 2, 3, 4, 5

[0040] Figure 6 Changes in Cu in chicken manure after treatment of Comparative Example 2 2+

[0041] Figure 7 Changes in Zn in chicken manure after treatment of Comparative Example 2 2+

[0042] Figure 8 Changes in the number of bacteria in chicken manure after treatment of Comparative Example 2

[0043] Figure 9 Changes in resistant genes in chicken manure after treatment of Comparative Example 2. DETAILED DESCRIPTION

[0044] It should be noted that the following detailed description is illustrative only, and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0045] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, devices, components and / or combinations thereof, but do not preclude the presence or addition of one or more other features, steps, operations, devices, components and / or combinations thereof.

[0046] In order to enable persons skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in combination with specific examples and experimental examples.

[0047] ​​​​The chicken manure used in the embodiment is taken from Yuncheng County, Heze City, Shandong Province, and other raw materials used are conventional commercially available products.

[0048] The atomic absorption spectrometer is a commercially available product.

[0049] Embodiment 1

[0050] A method for simultaneously and rapidly treating multiple pollutants such as heavy metals, harmful bacteria and resistance genes in chicken manure, comprising the following steps:

[0051] (1) 0.6 g of red mud, 1.1 g of diatomite (analytical pure) and 0.3 g of citric acid (analytical pure) are uniformly mixed under mechanical stirring at 350 rpm to obtain a composite catalyst;

[0052] (2) Ammonium persulfate powder is dissolved in water to prepare a 1.25 mol / L ammonium persulfate solution;

[0053] (3) 2 g of the composite catalyst obtained in step (1), 2 mL of the ammonium persulfate solution obtained in step (2) and 0.04 g of calcium oxide are sequentially added to 7.5 g of fresh chicken manure, and water is added and mixed uniformly to form a paste, thereby obtaining a mixture; the addition amount of calcium oxide is 0.04 g / L based on the total volume of water in the mixture;

[0054] (4) The mixture obtained in step (3) is irradiated under vacuum ultraviolet with an irradiation amount of 15 mJ / cm 2 and a vacuum degree of 0.01 MPa for 40 minutes to realize treatment of multiple pollutants in the chicken manure, thereby obtaining treated chicken manure.

[0055] Experimental Example 1

[0056] 1. The content of Cu 2+ in the chicken manure treated in Embodiment 1 is determined, and the results are shown in Table 1. Figure 1

[0057] The results show that the content of Cu 2+ in the chicken manure is determined by the atomic absorption spectrometer. The content of Cu 2+ in the pure chicken manure without treatment is 46.63 mg / kg, and the content of Cu 2+ in the chicken manure after treatment according to Embodiment 1 is reduced to 7.25 mg / kg. The content of Cu 2+ in the chicken manure is greatly reduced, indicating that the method has a good fixing effect on Cu 2+ .

[0058] 2. The content of Zn 2+ in the chicken manure treated in Embodiment 1 is determined, and the results are shown in Table 2. Figure 2

[0059] ​​The results show that: the content of Zn in the chicken manure is determined by using atomic absorption spectrometer, the content of Zn in the pure chicken manure without treatment is 210.72 mg / kg, after the treatment of example 1, the content of Zn in the chicken manure is reduced to 123.47 mg / kg, the content of Zn in the chicken manure is reduced, which indicates that the method has a good fixation effect on Zn. 2+ 2+ 2+ 2+ 2+

[0060] 3, the number of bacteria in the chicken manure treated by example 1 is determined, and the results are shown in the table. Figure 3

[0061] The results show that: the bacteria in the chicken manure are counted by using dilution coating plate method, and it is found that the number of bacteria in the chicken manure is greatly reduced after the treatment of example 1, which indicates that the method has a good inactivation effect on bacteria.

[0062] 4, the concentration of resistance genes in the chicken manure treated by example 1 is determined, and the results are shown in the table. Figure 4

[0063] The results show that: the concentration of resistance genes in the chicken manure is determined by using fluorescence quantitative PCR, and it is found that the tetA, tetB and tetC resistance genes in the chicken manure are almost completely eliminated after the treatment of example 1, which indicates that the method has an excellent removal effect on resistance genes.

[0064] Example 2

[0065] The method is the same as that in example 1, except that:

[0066] In step (3), the concentration of ammonium persulfate solution is 0.25 mol / L, and the rest of the operation, amount is the same as that in example 1.

[0067] Example 3

[0068] The method is the same as that in example 1, except that:

[0069] In step (3), the concentration of ammonium persulfate solution is 0.75 mol / L, and the rest of the operation, amount is the same as that in example 1.

[0070] Example 4

[0071] The method is the same as that in example 1, except that:

[0072] In step (3), the concentration of ammonium persulfate solution is 1.75 mol / L, and the rest of the operation, amount is the same as that in example 1.

[0073] ​​​​​​​Comparative Example 1

[0074] As described in Example 1, except that:

[0075] In step (3), the concentration of the ammonium persulfate solution is 0, and the remaining operations and dosages are exactly the same as those in Example 1.

[0076] Experimental Example 2

[0077] The fulvic acid content in the chicken manure after treatment in Examples 1, 2, 3, 4 and Comparative Example 1 was measured, and the results were as follows: Figure 5 shown.

[0078] The results showed that the content of fulvic acid in the treated chicken manure was determined using the national standard method (NY / T 3162-2017). It was found that the content of fulvic acid in the chicken manure first increased and then decreased with the increase of persulfate concentration. When the added persulfate concentration was 1.25 mol / L, the fulvic acid content in the treated chicken manure was 2.9 times that of the untreated chicken manure.

[0079] Comparative Example 2

[0080] As described in Example 1, except that:

[0081] Step (4) of vacuum ultraviolet irradiation is not performed, and steps (1) to (3) are performed as in Example 1.

[0082] Experimental Example 3

[0083] 1. Cu in chicken manure after treatment in Comparative Example 2 2+ The content of Figure 6 shown.

[0084] The results showed that the use of atomic absorption spectrometer to analyze the Cu 2+ The content of Cu in untreated pure chicken manure was determined. 2+ The content is 46.63 mg / kg, without step (4) of vacuum ultraviolet irradiation, the Cu 2+ The content dropped to 18.27 mg / kg, and the Cu content in chicken manure 2+ The reduction in content is much smaller than that in Example 1 of the present invention, indicating that irradiation under vacuum ultraviolet light has an important influence on the treatment.

[0085] 2. Zn in chicken manure after treatment in Comparative Example 2 2+ The content of Figure 7 shown.

[0086] The results showed that the use of atomic absorption spectrometer to analyze the Zn content in chicken manure 2+ The content of Zn in untreated pure chicken manure was determined.2+ The content of Zn in the chicken manure is 210.72 mg / kg, and the chicken manure is not irradiated under vacuum ultraviolet in step (4). 2+ The content of Zn in the chicken manure is reduced to 166.34 mg / kg. 2+ The content of Zn in the chicken manure is reduced to 166.34 mg / kg.

[0087] 3. The number of bacteria in the chicken manure treated in the comparative example 1 is determined, and it is found that the number of bacteria in the chicken manure is still high (see Table 2) without irradiation under vacuum ultraviolet in step (4). Figure 8

[0088] 4. The concentration of resistant genes in the chicken manure treated in the comparative example 1 is determined, and it is found that the concentration of resistant genes in the chicken manure is still high (see Table 3) without irradiation under vacuum ultraviolet in step (4). Figure 9

[0089] Comparative example 3

[0090] The method is the same as that described in the example 1, except that:

[0091] In step (1), 1.7 g of diatomite (analytical pure) and 0.3 g of citric acid (analytical pure) are uniformly mixed under mechanical stirring at 350 rpm to obtain a composite catalyst; and steps (2)-(4) are performed according to the example 1.

[0092] The content of Cu 2+ and Zn 2+ in the chicken manure treated in the comparative example 1 is determined, and it is found that the content of heavy metals in the chicken manure does not change much without adding red mud.

[0093] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.​​

Claims

1. A method for simultaneously and rapidly treating multiple pollutants of heavy metals, harmful bacteria and resistance genes in chicken manure, comprising the following steps: 1) mixing red mud, diatomite and citric acid uniformly to obtain a composite catalyst; 2) dissolving persulfate powder in water, 3) adding the composite catalyst obtained in step 1) and the persulfate solution obtained in step 2) into fresh chicken manure, adding calcium oxide and mixing uniformly, adding water to adjust the mixture to be uniform, to obtain a mixture; 4) placing the mixture obtained in step 3) under vacuum ultraviolet irradiation, and stirring during irradiation to simultaneously and rapidly treat heavy metals, harmful bacteria and resistance genes in chicken manure.

2. The method of claim 1, wherein, In step 1), the mass ratio of red mud, diatomite and citric acid is (0.5-1.5):(1-3):(0.2-0.8), and mechanical stirring is used for mixing, with a stirring speed of 300-500 rpm.

3. The method of claim 1, wherein, In step 2), the persulfate is ammonium persulfate.

4. The method of claim 1, wherein, In step 2), the concentration of persulfate is 0.75-1.25 mol / L.

5. The method of claim 1, wherein, In step 3), the mass ratio of the composite catalyst to fresh chicken manure is (0.5-3):(5-10).

6. The method of claim 1, wherein, In step 3), the mass-volume ratio of the composite catalyst to the persulfate solution is (0.5-3):(1-10) g / ml.

7. The method of claim 1, wherein, In step 3), the ratio of the amount of calcium oxide added to the total volume of water in the mixture is 0.01-30 g / L.

8. The method of claim 1, wherein, In step 3), the ratio of the amount of calcium oxide added to the total volume of water in the mixture is 0.04-15 g / L.

9. The method of claim 1, wherein, In Step 4), the irradiation amount of vacuum ultraviolet is 10-20 mJ / cm 2 , the stirring speed is 100-300 rpm, and the irradiation time is 30-70 min.

10. The method of claim 1, wherein, In step 4), the vacuum degree of vacuum ultraviolet irradiation is less than or equal to 0.05 MPa.

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