Method for treating harmful substances in aquaculture waste

Abstract

The application discloses a method for treating harmful substances in breeding waste. The method comprises the following steps: degrading vitamins by using a compost anaerobic fermentation method, separating heavy metals by using a composite chelating agent and an EKR-PRB device, killing pests in the manure pile by using a composite microbial agent, and finally adjusting the system environment by using a stabilizer, so that the treated manure pile is easy to be recycled.

Description

Technical Field

[0001] This invention relates to the field of livestock and poultry breeding waste resource utilization technology, and more specifically to a method for treating harmful substances in breeding waste. Background Technology

[0002] Popularizing knowledge about livestock and poultry manure, and taking reasonable and feasible measures for the harmless and resource-based utilization of livestock and poultry manure, are of great significance to ecological environmental protection, promoting the development of modern animal husbandry, and building an environmentally friendly society.

[0003] In the process of livestock and poultry farming, antibiotics and feed containing metal elements such as Zn, Cu, and As are used in large quantities to promote growth and inhibit harmful bacteria. However, their digestion, absorption and utilization rate in the livestock and poultry body is extremely low. Only a small amount of antibiotics and heavy metals are absorbed by the body, and about 60% to 90% are excreted in their original form with feces and urine. In addition, they carry a large number of parasites. Using them directly as fertilizer will cause irreparable damage to the soil.

[0004] There are two main uses for manure resource recovery: fertilizer production and biogas production. However, antibiotics, heavy metals, and parasites are often introduced into the soil along with the fertilizer. When antibiotics accumulate to a certain level in the soil, they significantly affect soil bacteria, fungi, and actinomycetes, impacting not only the microbial community structure but also inducing antibiotic resistance and inhibiting or enhancing microbial metabolic pathways. Heavy metals entering the soil hinder plant growth and can be ingested by humans through the food chain, causing health problems. Parasites, on the other hand, spread diseases and affect soil biodiversity.

[0005] Therefore, it is necessary to remove antibiotics and heavy metals from manure before it can be utilized as a resource. Our company collects manure through a comprehensive manure collection, storage, and transportation system, controlling its total sulfur (TS) concentration to 6%~8%. This system possesses the richest variety of microorganisms, which exhibit good degradation effects on most antibiotics during anaerobic fermentation. This invention, however, uses anaerobic fermentation to degrade antibiotics, a highly efficient and comprehensive chelating agent to remove heavy metal ions, and a compound microbial agent to remove parasite eggs, resulting in harmless livestock manure piles that are readily available for resource utilization. Summary of the Invention

[0006] The technical problem this invention aims to solve is the obstacle to resource utilization caused by antibiotics, heavy metals, and parasite eggs contained in fecal waste.

[0007] 1. To solve the above-mentioned technical problems, the technical solution provided by the present invention includes the following steps:

[0008] (1) The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh screen to obtain biogas residue powder;

[0009] (2) Take 80-100 parts of manure, 25-35 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0010] (3) Introduce nitrogen into the ideal mixing reactor at a rate of 1 L / min, and transfer the mixture A into the reactor after the air has been completely purged.

[0011] (4) The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low antibiotic manure pile;

[0012] (5) Take 3-7 parts of the compound chelating agent and mix it into the low antibiotic manure pile to obtain mixture B;

[0013] (6) Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0014] (7) The filtered solids are mixed with the treatment liquid to obtain a low antibiotic and low heavy metal manure pile;

[0015] (8) Transfer the low antibiotic and low heavy metal manure pile to an ideal mixing reactor and add 20-30 parts of compound microbial agent;

[0016] (9) After the insects are killed, stir at 75 R / min and add 10-15 parts of stabilizer to obtain a harmless septic tank.

[0017] 2. Further, the composite chelating agent is composed of 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine.

[0018] 3. Furthermore, the strains of the compound microbial agent are *Pseudomonas conifera* and *Rhizoctonia solani*, of which 63% is *Pseudomonas conifera* and 37% is *Rhizoctonia solani*.

[0019] 4. Further, the stabilizer is ethyl 2-pyrrolecarboxylate.

[0020] The beneficial effects of this invention are as follows:

[0021] (1) When potassium dihydroxybutylaminobenzoate is added to the manure pile, it can remove potassium ions and replenish the potassium fertilizer content of the manure pile. At the same time, the dihydroxybutylaminobenzoate group can adsorb heavy metal ions such as zinc, chromium, copper, lead and other heavy metal ions in the system to form stable chelates. In the weak acid manure pile system, the chelate will not be dechelated and can effectively chelate with heavy metal ions. At the same time, the hydroxybutyl group can provide a weak acid environment in the aqueous solution system to facilitate the survival of microorganisms and provide electron donors to attract heavy metal ions, thereby improving the chelation efficiency of the dihydroxybutylaminobenzoate group for heavy metal ions. The dihydroxybutylaminobenzoate group can effectively regulate the activity of protease required by bacteria, improve their metabolic efficiency, and promote the resource utilization of substances in the manure pile by microorganisms.

[0022] (2) N,N-(1,2-dithio-1,2-ethylenediyl) diglycine is a glycine derivative with a symmetrical structure. In the system, it provides N,N-(1,2-dithio-1,2-ethylenediyl) diglycine ions, which have a good chelating effect on high-valence heavy metal ions. This can make up for the problem of insufficient chelation of high-valence heavy metal ions by potassium dihydroxyethylamine. At the same time, its high degradability can supplement the system with nitrogen and sulfur elements as nutrients for microbial metabolism, maintain the weakly acidic environment of the system, improve chelation efficiency and stabilize microbial metabolism, and optimize subsequent resource utilization.

[0023] (3) Pseudomonas conifera is a parasitic bacterium that can be mixed into the manure pile. It can parasitize the insect eggs in the manure pile, plunder nutrients and secrete metabolic toxins that are highly toxic to the insect eggs, causing the insect eggs to die before they develop, thus achieving an excellent insecticidal effect.

[0024] (4) Light-colored red shell fungus agent can decompose nutrients such as proteins in the fecal environment. After metabolism, it produces a variety of antibacterial and harmful alkalis, quinones and peptides. It can kill the larvae after they hatch from undamaged insect eggs placed in the fecal environment to prevent them from continuing to grow into adults.

[0025] (5) The combined use of Pseudomonas pineinae and Pseudomonas pallens can form a highly efficient insect control system in the manure pile, killing insect growth from eggs to larvae and optimizing the utilization of manure pile in subsequent resource recovery processes.

[0026] (6) Ethyl 2-pyrrolecarboxylate has both hydrophilic and lipophilic properties, which can regulate the compatibility between organic and inorganic substances in the system and avoid the impact of adding chelating agents and compound bacterial agents on the stability of the organic phase in the aqueous solution system when removing heavy metal ions and insect eggs, thus preventing the loss of various bacteria in the manure pile.

[0027] (7) Ethyl 2-pyrrolecarboxylate can also provide acid-base buffering capacity, restore the acid-base balance in the system caused by the extra consumption of metal ions and nutrients. At the same time, the ester group and pyrrole ring structure of ethyl 2-pyrrolecarboxylate also have good biodegradability, providing a nitrogen source and stabilizing the compatibility of various components in the septic tank. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to the embodiments.

[0029] In the embodiments of this invention, the raw materials used for the compound chelating agent and stabilizer were purchased from Shanghai Zhongyin Industrial Co., Ltd. and Sigma-Aldrich (Shanghai) Trading Co., Ltd., the raw materials used for the compound microbial agent were purchased from Shanghai Xuanke Biotechnology Co., Ltd. and Shanghai Fusheng Industrial Co., Ltd., and the manure was collected by our company through a full-scale manure collection, storage and transportation system with a TS concentration of 6%~8%. Other raw materials or chemical reagents, unless otherwise specified, were obtained through conventional commercial channels.

[0030] Example 1

[0031] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0032] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0033] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0034] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0035] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0036] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0037] 7. Take 5 parts of the compound chelating agent and mix it into the low-antibiotic manure pile to obtain mixture B;

[0038] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0039] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0040] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 25 parts of compound microbial agent;

[0041] 11. After the insects have been killed, add 12.5 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0042] Example 2

[0043] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0044] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0045] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0046] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0047] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0048] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0049] 7. Take 7 parts of the compound chelating agent and mix it into the low antibiotic manure pile to obtain mixture B;

[0050] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0051] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0052] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 20 parts of compound microbial agent;

[0053] 11. After the insects have been killed, add 15 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0054] Example 3

[0055] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0056] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0057] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0058] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0059] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0060] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0061] 7. Take 3 parts of the compound chelating agent and mix it into the low-antibiotic manure pile to obtain mixture B;

[0062] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0063] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0064] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 30 parts of compound microbial agent;

[0065] 11. After the insects have been killed, add 10 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0066] Comparative Example 1

[0067] The difference between this comparative example and Example 1 is that the potassium dihydroxybutylaminobenzoate in step 1 is potassium aminobenzoate, while the rest of the implementation method is the same as in Example 1.

[0068] Comparative Example 2

[0069] The difference between this comparative example and Example 1 is that the N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine in step 1 is EDTA, and the rest of the implementation methods are the same as in Example 1.

[0070] Comparative Example 3

[0071] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0072] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0073] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0074] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0075] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0076] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0077] 7. Take 1 part of the compound chelating agent and mix it into the low antibiotic manure pile to obtain mixture B;

[0078] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0079] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0080] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 25 parts of compound microbial agent;

[0081] 11. After the insects have been killed, add 12.5 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0082] Comparative Example 4

[0083] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0084] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0085] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0086] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0087] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0088] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0089] 7. Take 10 parts of the compound chelating agent and mix it into the low-antibiotic manure pile to obtain mixture B;

[0090] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0091] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0092] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 15 parts of compound microbial agent;

[0093] 11. After the insects have been killed, add 12.5 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0094] Comparative Example 5

[0095] The difference between this comparative example and Example 1 is that the *Pseudomonas conifera* agent in step 2 is *Pseudomonas thunbergii*, while the rest of the implementation methods are the same as in Example 1.

[0096] Comparative Example 6

[0097] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0098] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0099] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0100] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0101] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0102] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0103] 7. Take 5 parts of the compound chelating agent and mix it into the low-antibiotic manure pile to obtain mixture B;

[0104] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0105] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0106] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 10 parts of compound microbial agent;

[0107] 11. After the insects have been killed, add 12.5 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0108] Comparative Example 7

[0109] 1. A composite chelating agent was prepared by using 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine;

[0110] 2. Prepare a compound fungal agent by using 63% of *Pseudomonas conifera* and 37% of *Rhizoctonia solani*.

[0111] 3. The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh sieve to obtain biogas residue powder;

[0112] 4. Take 100 parts of manure, 30 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A;

[0113] 5. Pour nitrogen gas into the ideal mixing reactor at a rate of 1 L / min, and transfer mixture A in after the air has been completely purged;

[0114] 6. The system was heated to 50℃ and stirred at 75 R / min for 4 days to obtain a low-antibiotic manure pile;

[0115] 7. Take 5 parts of the compound chelating agent and mix it into the low-antibiotic manure pile to obtain mixture B;

[0116] 8. Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid;

[0117] 9. The filtered solids are mixed with the treatment liquid to obtain a low-antibiotic, low-heavy-metal manure pile;

[0118] 10. Transfer the low-antibiotic, low-heavy-metal manure pile to an ideal mixing reactor and add 40 parts of compound microbial agent;

[0119] 11. After the insects have been killed, add 12.5 parts of ethyl 2-pyrrolecarboxylate while stirring at 75 R / min to obtain a harmless septic tank.

[0120] Comparative Example 8

[0121] The difference between this comparative example and Example 1 is that the 2-pyrrolecarboxylic acid ethyl ester in step 12 is ethoxylated nonylphenol, and the rest of the implementation method is the same as in Example 1.

[0122] Product testing:

[0123] Livestock and poultry manure was treated according to Examples 1-3 and Comparative Examples 1-7, respectively.

[0124] 1) The heavy metal content of the fecal waste before and after treatment was determined in accordance with GB / T 23349-2020 and GB / T 34764-2017. The heavy metal residues were obtained and the results are shown in Table 1.

[0125] 2) Take samples of the treated fecal waste, 10g of each sample, and measure the parasite egg mortality rate according to GB / T 19524.2-2004, using the ascarid egg mortality rate as a reference standard. The results are shown in Table 1.

[0126] 3) The treated harmless septic tank was subjected to anaerobic fermentation to obtain fertilizer. 10g of each sample was taken and the total nitrogen, total phosphorus and total potassium of the sample were determined in accordance with NY / T2542-2014, NY / T2541-2014 and NY / T 2540-2014. The results are shown in Table 1.

[0127] Table 1 Test Result Data Table

[0128] Cd removal rate Cu removal rate Zn removal rate Egg mortality rate Total nitrogen Total phosphorus Total potassium % % % % % mg / kg g / kg Example 1 73.41 82.41 54.38 89.51 0.42 912.46 2.33 Example 2 72.94 81.54 52.14 87.85 0.41 911.11 2.41 Example 3 74.81 83.11 52.59 88.48 0.46 913.58 2.39 Comparative Example 1 63.41 62.45 36.84 86.59 0.38 901.56 2.21 Comparative Example 2 49.51 74.15 45.61 86.31 0.39 902.41 2.26 Comparative Example 3 35.15 40.59 27.58 85.98 0.37 901.96 2.27 Comparative Example 4 71.51 80.03 51.68 86.91 0.39 902.36 2.24 Comparative Example 5 71.97 80.86 50.09 57.96 0.36 904.64 2.29 Comparative Example 6 71.11 80.13 50.17 40.45 0.38 903.76 2.25 Comparative Example 7 71.57 80.28 50.26 86.63 0.38 901.67 2.19 Comparative Example 8 72.01 81.46 51.51 86.22 0.26 727.56 1.47

Claims

1. A method for treating hazardous substances in livestock waste, characterized in that: The steps are as follows: (1) The semi-solid biogas residue is dewatered by plate and frame dewatering to obtain solid biogas residue, which is then crushed and sieved through a 30-mesh screen to obtain biogas residue powder; (2) Take 80-100 parts of manure, 25-35 parts of biogas residue powder, and 5 parts of microbial agent and mix them to obtain mixture A; (3) Introduce nitrogen into the ideal mixing reactor at a rate of 1 L / min, and transfer the mixture A in after the air has been completely purged. (4) The system was heated to 50°C and stirred at 75 R / min for 4 days to obtain a low antibiotic manure pile; (5) Take 3-7 parts of the compound chelating agent and mix it into the low antibiotic manure pile to obtain mixture B; (6) Filter the mixture B to separate solids and liquids, and transfer the filtrate to EKR-PRB for coupling removal to obtain the treated liquid; (7) The filtered solids are mixed with the treatment liquid to obtain a low antibiotic and low heavy metal manure pile; (8) Transfer the low antibiotic and low heavy metal manure pile to an ideal mixing reactor and add 20-30 parts of compound microbial agent; (9) After the insects are killed, stir at 75 R / min and add 10-15 parts of stabilizer to obtain a harmless septic tank. The composite chelating agent is composed of 68% potassium dihydroxybutylaminobenzoate and 32% N,N-(1,2-dithio-1,2-ethylenedimethyl)diglycine.

2. The hazardous substance treatment method as described in claim 1, characterized in that: The compound microbial agent contains *Pseudomonas conifera* and *Rhizoctonia solani* strains, with 63% being *Pseudomonas conifera* and 37% being *Rhizoctonia solani*.

3. The method for treating hazardous substances as described in claim 1, characterized in that: The stabilizer is ethyl 2-pyrrolecarboxylate.