A method for the resource utilization of livestock and poultry manure

Abstract

The present invention relates to a method for the resource utilization of livestock and poultry manure. The dried and ground mixed livestock and poultry manure powder is added with KOH and deionized water, stirred and reacted, and then filtered. The filter residue is anaerobically digested to collect biogas; the filtrate is dried to obtain an organic potassium salt. The organic potassium salt is ground and sieved, and under an N2 atmosphere, it is carbonized to obtain a carbonized potassium salt. The carbonized potassium salt is mixed and ground with polychlorinated naphthalene, and under an N2 atmosphere, it is activated to obtain an activated potassium salt; the activated potassium salt is washed with deionized water, soaked in nitric acid and then rinsed with deionized water, and dried to obtain the anode material for lithium-ion batteries. The livestock and poultry manure of the present invention can achieve resource-based, harmless and reduction treatment. At the same time, the residues generated during the reaction process can also be utilized for energy. The livestock and poultry manure is converted into two high-value materials, including the anode material for lithium-ion batteries and biogas, providing new ideas for achieving the goals of carbon emission reduction and carbon neutrality of livestock and poultry manure.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy utilization of agricultural and forestry waste, and particularly relates to a method for preparing lithium batteries from livestock and poultry manure and converting the residue into biogas energy for resource utilization. Background Art

[0002] The livestock and poultry breeding industry is the most traditional and oldest industry in the world. With the progress of the times, the livestock and poultry breeding industry has also developed rapidly and is moving towards intensification and large-scale development. Livestock and poultry are mainly divided into pigs, livestock, poultry, sheep, etc. The Food and Agriculture Organization of the United Nations (FAO) counted the number of different livestock species from 2000 to 2020 and found that the number of all livestock species is huge and increasing year by year. By the end of 2020, the number of sheep (including sheep and goats) reached 2.39×10 9 heads, the number of cattle reached 1.53×10 9 heads, the number of pigs reached 9.53×10 8 heads, and the number of chickens reached 3.31×10 10 heads. While these livestock and poultry provide meat, eggs and dairy products needed for human life, they also produce a large amount of livestock and poultry manure through digestion and metabolism.

[0003] Livestock and poultry manure usually contains a large amount of heavy metal elements (such as iron, copper, arsenic, etc.), various antibiotics (such as tetracycline, enrofloxacin, amoxicillin, etc.), and pathogens adapted to multiple hosts (such as Escherichia coli, Salmonella, etc.) that are harmful to humans and the environment. If randomly stacked, it may cause the leakage of heavy metals and antibiotics into the soil or surface water, and then harm the health of animals, plants and humans through the food chain. At the same time, livestock and poultry manure also contains rich nutrient salts, which will cause eutrophication of water bodies when dissolved in water. Moreover, randomly stacking livestock and poultry manure will produce a large amount of greenhouse gases, which will be emitted into the atmosphere and exacerbate global warming and cause the greenhouse effect. Currently, it has become the main source of agricultural non-point source pollution in the world and one of the environmental problems that countries around the world are jointly concerned about. Therefore, the resource utilization of livestock and poultry manure is extremely urgent. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention prepares the anode material of a lithium-ion battery from livestock and poultry manure, and at the same time collects biogas generated by anaerobic digestion technology using the residue generated during the reaction process.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A method for the resource utilization of livestock and poultry manure, the steps are as follows:

[0007] (1) Dry the mixed livestock and poultry manure and then grind and sieve it;

[0008] (2) Take 20 g of the dried and ground mixed livestock and poultry manure powder, add 3 - 5 g of KOH and 50 - 100 mL of deionized water. Place the mixture in a 250 mL three-necked flask and magnetically stir the reaction for a certain period of time within a temperature range at a certain rotation speed. Filter with qualitative filter paper to separate the filter residue and the filtrate;

[0009] (3) Anaerobically digest the filter residue obtained in step (2) through an anaerobic digestion device to collect biogas;

[0010] (4) Dry the filtrate obtained in step (2) in an oven. The product obtained after drying is the organic potassium salt;

[0011] (5) Grind and sieve the obtained organic potassium salt. Under the condition of N2 atmosphere in a tubular furnace, calcine at a certain temperature for a certain period of time for carbonization treatment to obtain a potassium salt product after carbonization;

[0012] (6) Mix the potassium salt product after carbonization with polychlorinated naphthalene and grind for 10 - 30 min. Then, under the condition of N2 atmosphere in a tubular furnace, calcine at a certain temperature for a certain period of time for activation treatment to obtain an activated potassium salt product;

[0013] (7) Wash the obtained activated potassium salt product with deionized water, then soak it with nitric acid and rinse with deionized water. After drying, a negative electrode material for lithium-ion batteries is obtained.

[0014] In step (1), the mixed livestock and poultry manure is obtained by uniformly mixing pig manure, cow manure, chicken manure, and sheep manure in a mass ratio of 3 - 10:5 - 10:1 - 5:1 - 3.

[0015] In step (1), the drying is to dry the uniformly mixed livestock and poultry manure in an oven at 60 - 105 °C until constant weight, then pass through a 100 - 200 mesh sieve, and take the material on the sieve.

[0016] In step (2), the stirring reaction temperature is 25 - 50 °C, the stirring rotation speed is 500 - 1500 rpm, and the stirring time is 3 - 5 h.

[0017] In step (3), the waste residue generated during the filtration is anaerobically digested through an anaerobic digestion device. The anaerobic digestion conditions are controlled as follows: the temperature is about 35 - 60 °C; add hydrochloric acid with a concentration of 0.1 - 0.5 mol / L to adjust the pH value to about 6.8 - 7.25, and collect biogas.

[0018] In step (4), dry the obtained filtrate in an oven at 60 - 105 °C. The product obtained after drying is the organic potassium salt product.

[0019] In step (5), grind the obtained organic potassium salt through a 100 - 200 mesh sieve and take the material on the sieve.

[0020] In step (5), the oversize after sieving the organic potassium salt is placed under the condition of N2 atmosphere in a tubular furnace and calcined at 500-600 °C for 1-2 h at a heating rate of 1-3 °C / min for carbonization treatment to obtain a carbonized potassium salt product.

[0021] In step (6), polynaphthalene chloride accounting for 10%-50% of the mass of the carbonized potassium salt sample is incorporated.

[0022] In step (6), it is placed under the condition of N2 atmosphere in a tubular furnace and calcined at 500-700 °C for 1-2 h at a heating rate of 1-3 °C / min for activation treatment to obtain an activated potassium salt product.

[0023] In step (7), the obtained activated potassium salt product is washed 3-5 times with deionized water, then soaked in 1-3 mol / L nitric acid for 10-30 min and rinsed 3-5 times with deionized water.

[0024] Advantages of the present invention:

[0025] (1) The present invention can reduce the pollution to the environment caused by the random stacking or improper treatment of livestock and poultry manure, such as polluting the soil, surface water, and groundwater, or burning to produce a large amount of VOCs, which is harmful to the atmospheric environment, or stacking to produce a series of greenhouse gases, thus generating the greenhouse effect.

[0026] (2) The livestock and poultry manure treated by the present invention can achieve the goals of resource utilization, harmlessness, and reduction.

[0027] (3) The residue generated during the reaction process of the present invention can also be utilized for energy, and biogas is generated through anaerobic digestion technology, providing a new idea for achieving carbon emission reduction and carbon neutrality of livestock and poultry manure.

[0028] (4) Among various rechargeable energy storage devices, lithium-ion batteries play an important role due to their extraordinary energy storage capacity and high working potential. The high-value-added lithium-ion battery anode material prepared by the present invention can be applied to lithium-ion batteries.

[0029] (5) The present invention not only provides a new idea for the treatment of livestock and poultry manure but also enables it to achieve the goals of carbon reduction and pollution reduction. Description of the drawings

[0030] Figure 1 It is a flow chart of the method of the present invention;

[0031] Figure 2 Test charts of the electrochemical performance of Examples 1-3;

[0032] Figure 3 Biogas production rates of Examples 1-3. Detailed implementation mode

[0033] The above content of the present invention will be further described in detail through the following embodiments. However, it should not be understood that the scope of the above subject matter of the present invention is limited to the following embodiments. All technologies implemented based on the above content of the present invention belong to the scope of the present invention.

[0034] The livestock and poultry manure in the present invention is sourced from Guangken Animal Husbandry and is collected for standby.

[0035] Embodiment 1

[0036] A method for preparing a negative electrode material for a lithium-ion battery and energy utilization of waste residues from livestock and poultry manure is as Figure 1 shown, and the steps are as follows:

[0037] (1) Select livestock and poultry manure as the target for organic solid waste treatment, and uniformly mix pig manure, cow manure, chicken manure, and sheep manure in a mass ratio of 3:5:1:1 to obtain mixed livestock and poultry manure;

[0038] (2) Dry the mixed livestock and poultry manure in an oven at 60°C until constant weight, and after drying, pass it through a 100-mesh sieve, and take the material on the sieve;

[0039] (3) Take 20 g of the dried and ground livestock and poultry manure powder, add 3 g of KOH and 50 mL of deionized water, place it in a 250-mL three-necked flask, and magnetically stir at a speed of 500 rpm at 25°C for 3 h;

[0040] (4) After magnetic stirring, filter with qualitative filter paper to separate the filter residue and the filtrate;

[0041] (5) The filter residue is anaerobically digested through an anaerobic digestion device, and the anaerobic digestion conditions are controlled as follows: the temperature is about 35°C, and hydrochloric acid with a concentration of 0.5 mol / L is added to adjust the pH value to about 6.8, and biogas is collected;

[0042] (6) Dry the obtained filtrate in an oven at 60°C, and the product obtained after drying is the organic potassium salt product;

[0043] (7) Grind the obtained organic potassium salt through a 100-mesh sieve, take the material on the sieve, and then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it at a heating rate of 1°C / min to 500°C and calcine for 1 h for carbonization treatment to obtain a carbonized potassium salt product;

[0044] (8) Add 10% of polychlorinated naphthalene by mass of the carbonized potassium salt product and mix and grind for 10 min, and then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it at a heating rate of 1°C / min to 500°C and calcine for 1 h for activation treatment to obtain an activated potassium salt product;

[0045] (9) Wash the activated potassium salt product three times with deionized water, then soak it in nitric acid with a concentration of 1 mol / L for 10 min, rinse it three times with deionized water, and dry it to obtain the anode material for lithium-ion batteries.

[0046] Mix the prepared anode material for lithium-ion batteries, carbon black, 0.6% polytetrafluoroethylene solution, and ethanol in a ratio of 3:5:230 (mg:mg:mg:mL), and ultrasonically agitate for 30 min at room temperature, then dry it in an oven at 60 °C; after evacuating five times in a glove box, take 30 mg of the dried mixture and coat it on a copper foil, and then vacuum-dry it at 70 °C for 24 h. In the glove box, place the copper foil loaded with the mixture, lithium foil, and sodium foil into the shell of a button battery, and put the electrolyte (prepared by mixing dimethyl carbonate, ethylene carbonate, and ethyl methyl carbonate in a volume ratio of 2:4:4) into the battery shell. Use the copper foil loaded electrode as the negative electrode, lithium foil as the positive electrode, and sodium foil as the counter electrode to prepare a lithium-ion battery, and test the battery performance.

[0047] Example 2

[0048] A method for preparing the anode material for lithium-ion batteries from livestock and poultry manure and the energy utilization of the waste residue is as follows:

[0049] (1) Select livestock and poultry manure as the target for organic solid waste treatment, and uniformly mix pig manure, cow manure, chicken manure, and sheep manure in a mass ratio of 6:8:3:2 to obtain mixed livestock and poultry manure;

[0050] (2) Dry the mixed livestock and poultry manure in an oven at 80 °C until it reaches a constant weight, and after drying, pass it through a 150-mesh sieve and take the material on the sieve;

[0051] (3) Add 20 g of the dried and ground livestock and poultry manure powder, 4 g of KOH, and 75 mL of deionized water to a 250-mL three-necked flask, and magnetically stir at a speed of 1000 rpm at 35 °C for 4 h;

[0052] (4) After magnetic stirring, filter it with qualitative filter paper to separate the filter residue and the filtrate;

[0053] (5) Subject the filter residue to anaerobic digestion in an anaerobic digestion device, and control the anaerobic digestion conditions as follows: the temperature is about 45 °C; add hydrochloric acid with a concentration of 0.3 mol / L to adjust the pH value to about 7, and collect the biogas;

[0054] (6) Dry the obtained filtrate in an oven at 80 °C, and the product obtained after drying is the organic potassium salt product;

[0055] (7) Grind the obtained organic potassium salt through a 150-mesh sieve, take the material on the sieve, and then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it to 550 °C at a heating rate of 2 °C / min and calcine for 1.5 h for carbonization treatment to obtain a carbonized potassium salt product;

[0056] (8) Add the carbonized potassium salt product and mix it with 30% of its mass of polychlorinated naphthalene by grinding for 20 min. Then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it to 600 °C at a heating rate of 2 °C / min and calcine for 2 h for activation treatment to obtain an activated potassium salt product;

[0057] (9) Wash the activated potassium salt product 4 times with deionized water, then soak it in nitric acid with a concentration of 2 mol / L for 20 min, and then rinse it 4 times with deionized water. After drying, a negative electrode material for lithium-ion batteries is obtained.

[0058] According to the method of Example 1, take the negative electrode material prepared in this example to prepare a lithium-ion battery and conduct performance testing.

[0059] Example 3

[0060] A method for preparing a negative electrode material for lithium-ion batteries from livestock and poultry manure and the energy utilization of waste residues is as follows:

[0061] (1) Select livestock and poultry manure as the target for organic solid waste treatment, and uniformly mix pig manure, cow manure, chicken manure, and sheep manure in a mass ratio of 10:10:5:3 to obtain mixed livestock and poultry manure;

[0062] (2) Dry the mixed livestock and poultry manure in an oven at 105 °C until constant weight, and after drying, pass it through a 200-mesh sieve to take the material on the sieve;

[0063] (3) Take 20 g of the obtained dried and ground livestock and poultry manure powder, add 5 g of KOH and 100 mL of deionized water, place it in a 250 mL three-necked flask, and magnetically stir at 50 °C at a speed of 1500 rpm for 5 h;

[0064] (4) After magnetic stirring, filter it with qualitative filter paper to separate the filter residue and the filtrate;

[0065] (5) The filter residue is anaerobically digested in an anaerobic digestion device. The anaerobic digestion conditions are controlled as follows: the temperature is about 60 °C; add hydrochloric acid with a concentration of 0.1 mol / L to adjust the pH value to about 7.25, and collect the obtained biogas;

[0066] (6) Dry the obtained filtrate in an oven at 105 °C, and the product obtained after drying is the organic potassium salt product;

[0067] (7) Grind the obtained organic potassium salt through a 200-mesh sieve, take the material on the sieve, and then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it to 600 °C at a heating rate of 3 °C / min and calcine for 2 h for carbonization treatment to obtain a carbonized potassium salt product;

[0068] (8) Add the carbonized potassium salt product and mix and grind it with 50% of its mass of polychlorinated naphthalene for 30 min, and then place it in a tubular furnace. Under the condition of N2 atmosphere, heat it to 700 °C at a heating rate of 3 °C / min and calcine for 1.5 h for activation treatment to obtain an activated potassium salt product;

[0069] (9) Wash the obtained activated potassium salt product 5 times with deionized water, then soak it in nitric acid with a concentration of 3 mol / L for 30 min, and then rinse it 5 times with deionized water. After drying, a negative electrode material for a lithium-ion battery is obtained.

[0070] According to the method of Example 1, take the negative electrode material prepared in this example to prepare a lithium-ion battery and conduct performance testing.

[0071] The lithium-ion batteries prepared in Examples 1-3 were subjected to electrochemical performance tests, as Figure 2 shown. Among them, (a) is the CV curve and (b) is the EIS curve. Examples 1-3 all showed good electrochemical performance, indicating that the negative electrode materials of the lithium-ion batteries prepared in the examples meet the usage requirements. Compared with Examples 1 and 2, the current density of Example 3 increased, better improving the conductivity of the electrode material, increasing the specific capacitance of the anode area, and having a smaller resistance, with a more excellent charge transfer process at the electrode / electrolyte interface. The performance of the lithium battery prepared in Example 3 is more excellent.

[0072] According to the method of preparing the battery in Example 1, prepare the product NHPC-700 prepared by Zhang Haibang et al. [Zhang H B, Yang Z, Qiao K, et al. Green preparation of N-doped hierarchical porous carbon composites from humic acid extraction residue of lignite as anodes for lithium / sodium-ion batteries[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648: 129400.] into a lithium-ion battery and compare it with the data of Examples 1, 2, and 3. As shown in Table 1, it can be seen from the table that the performance of the negative electrode materials obtained in Examples 1, 2, and 3 is better than the products disclosed in the literature.

[0073] Table 1

[0074]

[0075]

[0076] Example 4

[0077] Take 20 g of livestock and poultry manure, and use semi-pit composting under anaerobic conditions. Stack the livestock and poultry manure layer by layer, compact it, and seal it. After 1 month, turn it over and ferment for 1 - 2 months in summer and autumn, and ferment for 3 - 4 months in winter. Collect the biogas produced and compare it with the present invention.

[0078] Figure 3 For the biogas production rates of Examples 1 - 3, it can be found that the biogas production rate of Example 3 is the highest and the effect is the best.

[0079] Compare the biogas production of Example 3 with conventional composting fermentation, and the data shown in Table 2 can be obtained. It can be found that the gas production of Example 3 is better than that of conventional composting fermentation in Example 4.

[0080] Table 2

[0081]

[0082] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can be made without departing from the gist of the present invention, and all are within the protection scope of the present invention.

Claims

1. A method for the resource utilization of livestock and poultry manure, characterized in that, The steps are as follows: (1) Dry the mixed livestock and poultry manure, then grind and sieve it; (2) Take 20 g of the ground mixed livestock and poultry manure powder, add 3 - 5 g of KOH and 50 - 100 mL of deionized water. After stirring and reacting the mixture, filter it to separate the filter residue and the filtrate; (3) Conduct anaerobic digestion on the filter residue obtained in step (2) to collect biogas; (4) Dry the filtrate obtained in step (2) to obtain organic potassium salt; (5) Grind and sieve the organic potassium salt, and conduct carbonization treatment to obtain potassium carbide salt; The carbonization treatment is carried out in an N2 atmosphere, with a heating rate of 1 - 3 °C / min to raise the temperature to 500 - 600 °C and calcine for 1 - 2 h; (6) Mix the potassium carbide salt with polychlorinated naphthalene and grind for 10 - 30 min, then conduct activation treatment to obtain activated potassium salt; (7) Wash the activated potassium salt with deionized water, soak it in nitric acid, then rinse it with deionized water again, and dry it to obtain the anode material for lithium-ion batteries; The activation treatment is carried out in an N2 atmosphere, with a heating rate of 1 - 3 °C / min to raise the temperature to 500 - 700 °C and calcine for 1 - 2 h.

2. The method for resource utilization of livestock and poultry manure according to claim 1, wherein In step (1), the mixed livestock and poultry manure is obtained by uniformly mixing pig manure, cow manure, chicken manure, and sheep manure in a mass ratio of 3 - 10:5 - 10:1 - 5:1 - 3; The drying is carried out at 60 - 105 °C until constant weight, then grind and sieve through a 100 - 200 mesh sieve, and take the material on the sieve.

3. The method for resource utilization of livestock and poultry manure according to claim 1, characterized in that In step (2), the stirring reaction temperature is 25 - 50 °C, the stirring speed is 500 - 1500 rpm, and the stirring time is 3 - 5 h.

4. The method for resource utilization of livestock and poultry manure according to claim 1, characterized in that In step (3), before anaerobic digestion, add hydrochloric acid with a concentration of 0.1 - 0.5 mol / L to adjust the pH value to 6.8 - 7.25, and the anaerobic digestion temperature is 35 - 60 °C.

5. The method for resource utilization of livestock and poultry manure according to claim 1, wherein In step (4), the drying temperature is 60 - 105 °C.

6. The method for resource utilization of livestock and poultry manure according to claim 1, characterized in that In step (5), the sieving is through a 100 - 200 mesh sieve, and take the material on the sieve.

7. The method for resource utilization of livestock and poultry manure according to claim 1, characterized in that, In step (6), the incorporation amount of polychlorinated naphthalene is 10% - 50% of the mass of the potassium carbide salt.

8. The method for resource utilization of livestock and poultry manure according to claim 1, characterized in that In step (7), wash with deionized water 3 - 5 times; soak in nitric acid for 10 - 30 min and then rinse with deionized water 3 - 5 times, and the concentration of nitric acid is 1 - 3 mol / L.

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