A method for treating antibiotics in livestock and poultry manure

Abstract

The present invention discloses a method for treating antibiotics in livestock and poultry manure. This method utilizes the material properties of a high-efficiency emulsifying dispersant to reduce interfacial energy and a fermentation optimizer to stabilize the system temperature, providing sufficient conditions for efficient anaerobic fermentation of the manure. After degradation is complete, a flocculant is used to remove the fermentation optimizer, resulting in low-antibiotic manure.

Description

Technical Field

[0001] The present invention relates to the technical field of resource utilization of livestock and poultry breeding waste, and more particularly to a method for treating antibiotics in livestock and poultry manure. Background Art

[0002] The livestock and poultry industry accounts for approximately 70% of global antibiotic use, and in my country, annual antimicrobial usage has reached 6,000 tons in recent years. Antibiotics are poorly absorbed in the intestines, with only a small amount being absorbed by the body. These substances undergo hydroxylation, cleavage, and glucuronidation to produce harmless substances. Approximately 60% to 90% of these substances are excreted unchanged in feces and urine, resulting in significant amounts of antibiotic-laden manure.

[0003] There are two general ways to utilize manure: producing fertilizer or using it for biogas production. Antibiotics are often added to the soil along with fertilizer. When antibiotics accumulate in the soil to a certain level, they significantly impact bacteria, fungi, actinomycetes, and other organisms in the soil. This not only affects the structure of microbial communities but also induces drug resistance in microorganisms and inhibits or enhances their metabolic pathways. Antibiotics in livestock and poultry manure can inhibit the growth of a variety of microorganisms in the soil, including bacteria, fungi, and actinomycetes. The reduction of these microorganisms hinders nitrification and mineralization in the soil, thereby hindering the normal nutrient cycle in the soil.

[0004] Our company uses a fully automated manure collection, storage and transportation system to collect manure and maintain its TS concentration at 6% to 8%. This allows the manure to contain the richest bacterial species, which can effectively degrade the antibiotics contained therein during composting under normal circumstances. However, manure and sludge have complex compositions, including a variety of organic matter and inorganic mineral particles and a large amount of water. During composting, the uneven mixing system can easily cause losses to microorganisms, affecting the degradation efficiency of antibiotics. In order to efficiently degrade antibiotics in manure, there are usually two types of solutions. One is to optimize the composting system to create an environment where microorganisms can easily survive, and the other is to use carriers to protect the bacterial agents. The present invention uses a high-efficiency emulsifying dispersant to evenly disperse the organic matter in manure and sludge in the water, so that the solid particles are suspended in the water and can efficiently penetrate to improve the system environment and create an environment for microbial survival.

[0005] Ionic reagents can easily disrupt the balance of compost components, while reagents with poor degradation efficiency and high biotoxicity are not conducive to the reuse of manure resources. Therefore, environmentally friendly non-ionic reagents are used. Among these, fatty acid polyoxyethylene esters, nonylcyclohexanol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, secondary alcohol polyoxyethylene ether, alkyl glycosides, fatty acid polyoxyethylene methyl ether, Tween, and Span, nonylcyclohexanol polyoxyethylene ether, which has the best emulsification and dispersion effect, has no relevant application in the field of manure resource utilization. The present invention provides a method for efficiently degrading antibiotics during the composting process using high-efficiency emulsifying dispersants and fermentation optimizers. Summary of the Invention

[0006] The technical problem to be solved by the present invention is that antibiotics cannot be efficiently degraded during the composting process in the resource utilization of manure and sewage:

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

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

[0009] (2) Mix 80-100 parts of manure and 25-35 parts of biogas residue powder to obtain mixture A;

[0010] (3) Take 10 parts of the emulsifying dispersant, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0011] (4) Add 9-15 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C, keep introducing carbon dioxide gas at 0.4 L / min, and stir for 15 minutes;

[0012] (5) Add 20-30 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50 °C;

[0013] (6) Maintain the temperature and stir at 75 rpm for anaerobic fermentation for 2 days;

[0014] (7) Let it cool down to room temperature naturally, add 5-10 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low-antibiotic manure.

[0015] 2. Furthermore, the emulsifying dispersant component is nonylcyclohexanol polyoxyethylene ether.

[0016] 3. Furthermore, the fermentation optimizer component is modified lightweight calcium plastic, and the preparation method is as follows:

[0017] 1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0018] 2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0019] 3) Mix the microporous silicate base into the semi-solid calcium plastic and stir evenly;

[0020] 4) Cool to room temperature to solidify the calcium plastic into a solid state;

[0021] 5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0022] 4. Furthermore, the flocculant is polysilicon sulfate titanium aluminum, and the preparation method is as follows:

[0023] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0024] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0025] The beneficial effects of the present invention are:

[0026] 1) The present invention relies on anaerobic fermentation of microorganisms to degrade antibiotics in manure, uses emulsifiers and dispersants to assist in homogenizing the compost components, and then uses fermentation adjuvants to stabilize the temperature changes of the system, thereby efficiently optimizing the living environment of microorganisms, enhancing the degradation effect and shortening the degradation time. Finally, flocculants are used to adsorb and separate the fermentation adjuvants to obtain low-antibiotic manure.

[0027] 2) Pre-rinse with distilled water to allow the emulsifying dispersant to form micelles in advance, maintain the temperature at 70°C to give the emulsifying dispersant sufficient energy to assist in promoting the rapid formation of micelles at the interface in the manure, and make a large number of cyclohexyl groups in the micelles form a high-energy boat-type conformation to increase molecular activity, enhance the compatibility of the emulsifying dispersant with the aqueous phase, and strengthen the emulsifying dispersion effect. The introduction of carbon dioxide gas increases the gas-liquid interface in the system, and the emulsifying dispersant is attracted to the interface to form micelles in advance. After the sludge and fermentation optimizer are mixed in the subsequent process, the micelles can immediately wrap the surface of the solid particles to reduce the surface energy and evenly disperse them in the system, so that the raw materials are fully contacted and the fermentation optimizer is fully dispersed in the system to play its most efficient role, thereby improving the fermentation efficiency.

[0028] 3) Nonylcyclohexanol polyoxyethylene ether has significantly better emulsification and dispersion efficiency than other surfactants. It also has low biological toxicity and is 100% degradable. After the antibiotic treatment is completed, it will be degraded by fermentation during the back-end composting, without affecting subsequent use.

[0029] 4) Calcium plastic can be partially softened when heated and fully mixed with the compost contents. Its own surface energy is higher than that of the liquid system, so it does not wet and is easy to separate. The incorporation of microporous silicate alkali forms a microporous structure that can better absorb heat energy, keep the temperature of the entire system from dissipating to the external environment, and effectively keep warm and maintain degradation efficiency.

[0030] 5) The addition of modified calcium plastic during the composting process can maintain the temperature difference between the overall internal and external surface temperatures of the composting system and keep the overall temperature within a reasonable range, thereby stabilizing the degradation efficiency of antibiotics by microorganisms and preventing fluctuations in environmental conditions from affecting the degradation efficiency.

[0031] 6) The titanium and oxygen-silicon bonds in polysilicate titanium aluminum sulfate form a framework titanium structure, forming multiple gaps in the crystal, giving it excellent adsorption capacity. When mixed in the composting system, it can fully absorb the solid fermentation optimizer free in the system into large particles, thereby increasing the separation efficiency.

[0032] 7) The titanium framework of polysilicate titanium aluminum sulfate gives it sufficient adsorption capacity. At the same time, the aluminum silicon polymer has a strong electrical neutralization ability, which can carry out targeted electrical adsorption of inorganic fillers in the fermentation optimizer, thereby increasing the efficiency of separating free solid-state fermentation optimizer. DETAILED DESCRIPTION

[0033] The present invention will be further described in detail below with reference to the embodiments.

[0034] In the embodiment of the present invention, manure with a TS concentration of 6% to 8% was collected by our company's full-scale manure collection, storage and transportation system. Other raw materials or chemical reagents, unless otherwise specified, were obtained through conventional commercial channels.

[0035] Example 1

[0036] 1. Prepare the fermentation optimizer modification, the steps are as follows:

[0037] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0038] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0039] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0040] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0041] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0042] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0043] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0044] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

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

[0046] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0047] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0048] 6. Add 12 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0049] 7. Add 25 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0050] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0051] 9. Let the temperature drop to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, and sieve to separate the fermentation optimizer to obtain low antibiotic manure.

[0052] Example 2

[0053] 1. Prepare the fermentation optimizer, the steps are as follows:

[0054] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0055] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0056] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0057] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0058] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0059] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0060] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0061] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0062] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0063] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0064] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0065] 6. Add 9 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0066] 7. Add 20 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0067] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0068] 9. Let it cool down to room temperature naturally, add 10 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low antibiotic manure.

[0069] Example 3

[0070] 1. Prepare the fermentation optimizer, the steps are as follows:

[0071] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0072] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0073] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0074] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0075] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0076] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0077] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0078] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0079] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0080] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0081] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0082] 6. Add 15 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0083] 7. Add 30 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0084] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0085] 9. Let it cool down to room temperature naturally, add 5 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low antibiotic manure.

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 1 is that the nonylcyclohexanol polyoxyethylene ether in step 6 is fatty acid polyoxyethylene methyl ether, and the rest of the implementation manner is the same as Example 1.

[0088] Comparative Example 2

[0089] 1. Prepare the fermentation optimizer modification, the steps are as follows:

[0090] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0091] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0092] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0093] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0094] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0095] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0096] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0097] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0098] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0099] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0100] 5. Add mixed material A, 12 parts of micellar solution and 10 parts of nonylcyclohexanol polyoxyethylene ether into an ideal mixing reactor and stir for 15 minutes;

[0101] 6. Add 25 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0102] 7. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0103] 8. Let it cool down to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low antibiotic manure.

[0104] Comparative Example 3

[0105] 1. Prepare the fermentation optimizer, the steps are as follows:

[0106] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0107] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0108] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0109] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0110] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0111] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0112] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0113] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0114] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0115] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0116] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0117] 6. Add 5 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0118] 7. Add 25 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0119] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0120] 9. Let the temperature drop to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, and sieve to separate the fermentation optimizer to obtain low antibiotic manure.

[0121] Comparative Example 4

[0122] 1. Prepare the fermentation optimizer, the steps are as follows:

[0123] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0124] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0125] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0126] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0127] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0128] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0129] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0130] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0131] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0132] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0133] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0134] 6. Add 20 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0135] 7. Add 25 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0136] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0137] 9. Let the temperature drop to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, and sieve to separate the fermentation optimizer to obtain low antibiotic manure.

[0138] Comparative Example 5

[0139] 1. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0140] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0141] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0142] 2. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0143] 3. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0144] 4. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0145] 5. Add 20 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0146] 6. Add 25 parts of light calcium plastic particles to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0147] 7. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0148] 8. Let it cool down to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low antibiotic manure.

[0149] Comparative Example 6

[0150] 1. Prepare the fermentation optimizer, the steps are as follows:

[0151] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0152] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0153] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0154] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0155] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0156] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0157] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0158] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0159] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0160] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0161] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0162] 6. Add 12 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0163] 7. Add 10 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0164] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0165] 9. Let the temperature drop to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, and sieve to separate the fermentation optimizer to obtain low antibiotic manure.

[0166] Comparative Example 7

[0167] 1. Prepare the fermentation optimizer, the steps are as follows:

[0168] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0169] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0170] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0171] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0172] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0173] 2. Preparation of flocculant polysilicon sulfate titanium aluminum, the preparation method is as follows:

[0174] (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution;

[0175] (2) After mixing the raw materials, heat the mixture to 45% and stir the mixture for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.

[0176] 3. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0177] 4. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0178] 5. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0179] 6. Add 12 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0180] 7. Add 40 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0181] 8. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0182] 9. Let the temperature drop to room temperature naturally, add 7 parts of flocculant and stir for 2 minutes, and sieve to separate the fermentation optimizer to obtain low antibiotic manure.

[0183] Comparative Example 8

[0184] 1. Prepare the fermentation optimizer modification, the steps are as follows:

[0185] (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate;

[0186] (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solidified state;

[0187] (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly;

[0188] (4) Cooling to room temperature to solidify the calcium plastic into a solid state;

[0189] (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

[0190] 2. The semi-solid biogas residue is dehydrated on a plate and frame to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder;

[0191] 3. Mix 90 parts of manure and 30 parts of biogas residue powder to obtain mixture A;

[0192] 4. Take 10 parts of nonylcyclohexanol polyoxyethylene ether, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution;

[0193] 5. Add 12 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C and keep introducing carbon dioxide gas at 0.4 L / min, stirring for 15 minutes;

[0194] 6. Add 25 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50°C;

[0195] 7. Maintain the temperature and stir at 75R / min for anaerobic fermentation for 2 days;

[0196] 8. Cool down to room temperature naturally, add 7 parts of polyaluminum sulfate and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low antibiotic manure.

[0197] Product determination:

[0198] Livestock and poultry manure was treated according to Examples 1-3 and Comparative Examples 1-7 respectively;

[0199] 1) The treated manure was composted. 10 g of each sample was taken, crushed, and passed through a 0.5 mm test sieve. 1.5 g of the sieved sample was weighed with an accuracy of 0.1 mg. The component concentrations were then determined according to GB / T 32951-2016 to obtain the content of each antibiotic. The results are shown in Table 1.

[0200] 2) Take 5g of the treated sample, place it in a container and heat it to 140℃. After the water is removed, the thermoplastic plastic is melted into a liquid state. Filter it while it is hot to retain the solid. The solid is rinsed three times with distilled water and then burned to remove water. Take 200g of distilled water and adjust the pH to 12-13 with sodium hydroxide. Place the solid in the solution and stir for 5min. Filter and retain the liquid, then titrate it with potassium ferrocyanide solution. Finally, measure the calcium ion content and obtain the fermentation optimizer residue. The results are shown in Table 1.

[0201] Table 1 Antibiotic content and fermentation optimizer residue

[0202] Tetracycline content (mg / kg) Sulfadiazine content (mg / kg) Penicillin content (mg / kg) Norfloxacin content (mg / kg) Fermentation optimizer residue (g / kg) Example 1 0.009 0.005 0.008 0.004 2.11 Example 2 0.008 0.004 0.009 0.005 2.02 Example 3 0.009 0.006 0.006 0.003 2.35 Comparative Example 1 0.645 0.401 0.694 0.381 3.42 Comparative Example 2 0.432 0.311 0.448 0.294 3.11 Comparative Example 3 0.081 0.034 0.074 0.085 3.26 Comparative Example 4 0.019 0.011 0.018 0.010 3.05 Comparative Example 5 0.351 0.229 0.387 0.206 3.36 Comparative Example 6 0.296 0.192 0.214 0.189 2.99 Comparative Example 7 0.010 0.007 0.011 0.008 3.22 Comparative Example 8 0.016 0.008 0.015 0.009 19.35

Claims

1. A method for treating antibiotics in livestock and poultry manure, characterized by: Here are the steps: (1) The semi-solid biogas residue is dehydrated to obtain solid biogas residue, which is then crushed and sieved through 30 mesh to obtain biogas residue powder; (2) Mix 80-100 parts of livestock and poultry manure and 25-35 parts of biogas residue powder to obtain a mixture A; (3) Take 10 parts of emulsifying dispersant, rinse with 20 parts of distilled water, then heat to 40°C, let stand and separate to remove the aqueous phase, then heat to 70°C and add 15 parts of distilled water five times each time to obtain a micellar solution, wherein the emulsifying dispersant is nonylcyclohexanol polyoxyethylene ether; (4) Add 9-15 parts of mixed material A and micelle solution into an ideal mixing reactor, heat to 70°C, keep introducing carbon dioxide gas at 0.4 L / min, and stir for 15 minutes; (5) Add 20-30 parts of fermentation optimizer to the reactor and stir for 15 minutes, evacuate the air to 5 Pa, and cool to 50 °C; (6) Maintain the temperature at 50°C and stir at 75 rpm for anaerobic fermentation for 2 days; (7) Let it cool down to room temperature naturally, add 5-10 parts of flocculant and stir for 2 minutes, sieve and separate the fermentation optimizer to obtain low-antibiotic manure.

2. The antibiotic treatment method according to claim 1, wherein: The fermentation optimizer is a modified lightweight calcium plastic, and the preparation method is as follows: (1) Take 100 parts of lightweight calcium plastic and 30 parts of microporous silicate; (2) Raise the temperature of the calcium plastic to 90-110°C to form a semi-solid state; (3) Mix the microporous silicate alkali into the semi-solid calcium plastic and stir evenly; (4) Cooling to room temperature to solidify the calcium plastic into a solid state; (5) Cut and crush the solid calcium plastic into granules, and sieve through 30 mesh to obtain modified lightweight calcium plastic.

3. The antibiotic treatment method according to claim 1, wherein: The flocculant is polysilicic acid titanium aluminum sulfate, and the preparation method is as follows: (1) Take 10 parts of 2.0% aluminum sulfate solution, 30 parts of 2.0% titanium sulfate solution, and 80 parts of 5.0% polysilicic acid solution; (2) After mixing the raw materials, heat them to 45°C and stir them for 2.5 hours to obtain polysilicon sulfate titanium aluminum flocculant.