Method for microbial degradation of antibiotics in livestock manure

Abstract

The application discloses a method for degrading antibiotics in livestock and poultry manure by microorganisms. The method uses a load bacteria agent supplemented with an adsorbent to provide a strain, creates a fermentation high-quality reaction environment to strengthen the degradation of fluoroquinolone antibiotics, uses a modified conditioner to enrich nutrients in the compost and improve the defects caused by the load bacteria agent and the adsorbent, and fully degrades the antibiotics in the manure.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of livestock and poultry breeding waste resource technology, more particularly to a method for degrading antibiotics in livestock and poultry manure by microorganisms. BACKGROUND

[0002] The use of antibiotics in livestock and poultry breeding accounts for about 70% of the total production in the world, and the use of antibiotics in China has reached 6000 tons per year in recent years. The absorption of antibiotics in the intestinal tract is very small, only a small amount of antibiotics is absorbed by the body, and the body generates non-toxic and harmless substances through processes such as hydroxylation, cleavage and glucuronidation, about 60% to 90% of which is excreted in the form of original shape with urine and feces, so a large amount of feces containing antibiotics is produced.

[0003] There are generally two ways of feces resourceization, producing fertilizer or being used for biogas production, and antibiotics will be applied to the soil together with the fertilizer, and when the amount of antibiotics in the soil accumulates to a certain amount, it will significantly affect the bacteria, fungi and actinomycetes and other organisms in the soil, not only affecting the microbial species community structure, but also inducing the production of drug resistance by microorganisms, inhibiting or enhancing the metabolic pathways of microorganisms. The antibiotics in livestock and poultry manure can inhibit the growth of various microorganisms in the soil, including bacteria, fungi, actinomycetes, etc., and the reduction of these microorganisms will hinder the nitrification and mineralization in the soil, thereby hindering the normal nutrient cycle of the soil.

[0004] In the composting process, the feces collected by the full-quantity feces collection, storage and transportation system of the present application is used, and the TS concentration is maintained at 6% to 8%. In this state, the most abundant microbial strains can better degrade most antibiotics, but when the use of fluoroquinolone antibiotics increases during special breeding periods, the degradation effect of the microorganisms in the feces on the antibiotics is greatly weakened, and the increase of the antibiotics also causes the loss of microorganisms during anaerobic fermentation, greatly weakening the overall degradation efficiency. Therefore, additional strains need to be added to enhance the effect of fluoroquinolone antibiotics, and to prevent the loss of the externally added strains in the feces composting environment, a carrier is used to support and protect the strains for efficient degradation of composting.

[0005] Mesoporous Cs3PMo 12 O 40 is a new type of catalyst for aldose epimerization reaction in aqueous phase, which has excellent stability but no corresponding report in the field of livestock and poultry breeding waste resource technology, and it has special worm-like mesopores of 2.5 nm and 6 nm, which may have excellent effect on the adsorption and binding protection of strains and the creation of fermentation environment. The present application confirms the effect of the function through application.

[0006] The present application provides a method for efficiently degrading antibiotics in feces by microorganisms to make the antibiotics effectively resourceized. SUMMARY

[0007] The technical problem solved by the present application is that antibiotics cannot be efficiently degraded in the composting process in the resource utilization of fecal pollution:

[0008] To solve the above technical problems, the technical solution provided by the present application comprises the following steps:

[0009] (1) The semi-solid biogas residue is dehydrated to obtain a solid biogas residue, which is then crushed and sieved to obtain a biogas residue powder with a mesh size of 30;

[0010] (2) Take 80-100 parts of fecal pollution and 25-35 parts of biogas residue powder to obtain a mixture A;

[0011] (3) Take 8-14 parts of a loaded bacteria agent, mixture A and 15-25 parts of an adsorbent;

[0012] (4) The adsorbent is added to the loaded bacteria agent to make the adsorbent adhere to the surface of the loaded bacteria agent;

[0013] (5) The loaded bacteria agent with the adsorbent is placed in the mixture A to proliferate the bacterial colonies for 8 days;

[0014] (6) After the proliferation is completed, 20-30 parts of a modified conditioner are added and stirred for 5 minutes to obtain a mixture B;

[0015] (7) Nitrogen gas is introduced into an ideal mixing reactor at a rate of 1 L / min, and the mixture B is transferred into the reactor after the air is completely discharged;

[0016] (8) The system is heated to 50°C and stirred at 75R / min, and anaerobic fermentation is carried out for 2 days to obtain low-antibiotic fecal pollution.

[0017] 2. Further, the loaded bacteria agent has a Brucella WXX-3 strain, and the preparation method is as follows:

[0018] (1) Take 50 parts of mesoporous Cs3PMo 12 O 40 carrier and 3 parts of Brucella WXX-3 strain culture solution;

[0019] (2) The mesoporous Cs3PMo 12 O 40 is crushed to form granular material, which is sieved to a mesh size of 30;

[0020] (3) The granular mesoporous Cs3PMo 12 O 40 is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0021] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried to remove water, a stable loaded bacteria agent is obtained.

[0022] 3. Further, the adsorbent is modified YZr-MOF, and the preparation method is as follows:

[0023] (1) take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0024] (2) mix the prepared raw materials, and ultrasonic oscillation is completely dissolved to obtain a mixed solution;

[0025] (3) the mixed solution is transferred to a polytetrafluoroethylene acid lined reaction kettle, and a vacuum environment is created by pumping;

[0026] (4) the reaction kettle is heated to 120 DEG C, and reaction is carried out for 12H, and then 20 parts of hydroxymethylated chitosan is taken out and mixed;

[0027] (5) the mixture is placed on filter cloth and extended, and then a part of the mixture is taken out after being semi-solidified for 2H, and a semi-solidified mixture is obtained;

[0028] (6) the semi-solidified mixture is transferred into the reaction kettle, heated to 120 DEG C, and vacuum reaction is carried out for 12H;

[0029] (7) after the reaction is completed, 0.1% sodium hydroxide solution is used for soaking for 1min, and then distilled water and DMF are used for cleaning;

[0030] (8) drying is carried out in an oven at 45 DEG C for 12H, and then crushing and grinding are carried out, and the modified YZr-MOF is obtained.

[0031] 4. Further, the modified conditioner is modified sea-buckthorn sawdust, and the preparation method is as follows:

[0032] (1) take 40~60 parts of sea-buckthorn sawdust, and finely crush and sieve to 80 meshes;

[0033] (2) take 8~12 parts of phenolic imine resin and heat to semi-solid state, and then put the sea-buckthorn sawdust into the resin and mix;

[0034] (3) after the sawdust and the resin are uniformly mixed, the sawdust fully covers the surface of the resin to form granular particles, and then the resin is cooled and solidified, and the modified sea-buckthorn sawdust is obtained.

[0035] The beneficial effects of the present application are:

[0036] 1) The present application uses the load bacteria agent to carry out targeted degradation of fluoroquinolone antibiotics to make up for the problem of insufficient degradation efficiency, and then uses the adsorbent and the modified conditioner to make up for the problem of insufficient nutrient attraction ability of the load bacteria agent.

[0037] 2) mesoporous Cs3PMo 12 O 40The carrier-loaded strain can prevent the strain from excessive contact with the compost environment and loss of the strain in the compost process due to various antibiotics in the manure, so as to maintain the content of the strain and maintain the high degradation efficiency.

[0038] 3) Additional addition of Brucella WXX-3 strain in the composting process optimizes the degradation effect of fluoroquinolone antibiotics, and avoids the fact that the bacteria carried by the manure cannot produce good degradation effect on fluoroquinolone antibiotics.

[0039] 4) The Brucella WXX-3 strain is loaded on mesoporous Cs3PMo 12 O 40 The carrier has molybdenum and cesium, which can combine with the metabolic cycle of the bacterial agent to form more efficient degradation proteases, improve hydrogen production in the anaerobic fermentation process, decompose the substrate into nutrients to improve the fermentation rate and efficiently degrade antibiotics, and at the same time, the strain is active in the mesoporous Cs3PMo 12 O 40 The special pore channels of 2.5 nm and 6 nm formed by molybdenum, cesium, and phosphorus oxygen in the mesoporous Cs3PMo

[0040] 5) The adsorbent is combined on the surface of the carrier, so that the surface of the carrier can adsorb nutrients in the compost to the surface to promote the exchange of internal and external nutrient components, thereby promoting the anaerobic fermentation process of the bacterial colony and improving the degradation efficiency of antibiotics.

[0041] 6) Y and Zr have excellent adsorption capacity for phosphorus-containing organic matter, which can adsorb most of the phosphorus-containing organic matter in the compost to the surface layer of the bacterial agent for anaerobic fermentation nutrients. Hydroxymethylated chitosan can enhance its adsorption of nitrogen-containing organic matter and other inorganic mineral ions, so that the adsorbent has sufficient adsorption of various nutrients, thereby enhancing the microbial metabolism and degradation efficiency of antibiotics.

[0042] 7) Mixing and modification of YZr-MOF and hydroxymethylated chitosan can lead to filling of the metal framework pores by hydroxymethylated chitosan, mutual influence of the two adsorbents leading to a decrease in their respective performance, although the difference in adsorption capacity of different nutrients is compensated for, but the overall function is weakened. The process uses a modifier, hydroxymethylated chitosan, to be added during the preparation of YZr-MOF, so as to form a stable interface layer between the adsorbents instead of mutual adsorption and penetration, thereby forming different pore cycles of the two adsorbents. Not only can the performance be avoided, but also the adsorption of each nutrient can be enhanced.

[0043] 8) Sea buckthorn wood has more abundant protein, fat, and carbohydrates than other woods, which can supplement sufficient nutrients for the anaerobic fermentation of microorganisms in the compost, promote the efficiency of anaerobic fermentation, and accelerate the degradation of antibiotics.

[0044] 9) Phenolic imine resin has good adhesion and can polymerize loose wood chips into larger particle groups. Its unique molecular chain rigidity can provide spatial support to the particle groups after the wood chips are solidified. It is more tough than other resin-cured brittle materials and is suitable for continuous stirring anaerobic fermentation process.

[0045] 10) The sea buckthorn wood modified by phenolic imine resin is endowed with spatial support effect, which helps the wood chips to adsorb water and control the water content to optimize the efficiency of anaerobic fermentation, while avoiding water loss in the system. The pores caused by the spatial support effect can effectively slow down the heat transfer efficiency in the compost system, maintain the system temperature, ensure the microorganisms at an appropriate temperature, and accelerate the degradation efficiency of antibiotics.

[0046] 11) The combined use of the bacterial agent and the adsorbent protects the bacterial agent and fully utilizes the nutrients while causing large changes in the local pH value. The addition of the modified conditioner can play a PH buffering role, adhere to the surface to prevent large changes in the PH value caused by nutrient concentration, and the adsorption of harmful substances by the modified conditioner can assist the bacterial metabolism to exclude the nutrients and metabolic waste from the carrier, avoiding the problem of carrier pore blockage. DETAILED DESCRIPTION

[0047] The application will be further described in detail below with reference to the examples.

[0048] The TS concentration of the fecal pollution used in the examples of the application is 6% to 8%, which is collected by the full-fecal pollution collection, storage and transportation system of the company. Other raw materials or chemical reagents, unless otherwise specified, are obtained through conventional commercial channels.

[0049] Example 1

[0050] 1. Preparation of the bacterial agent, the steps are as follows:

[0051] (1) Take mesoporous Cs3PMo 12 O 40 Carrier 50 parts, Brucella WXX-3 strain culture solution 3 parts;

[0052] (2) Crush the mesoporous Cs3PMo 12 O 40 Carrier to form granules, sieve 30 mesh;

[0053] (3) Granular mesoporous Cs3PMo 12 O 40The carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0054] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed, dried and dehydrated, a stable loaded bacterial agent is obtained.

[0055] 2. Preparation of adsorbent modified YZr-MOF, the steps are as follows:

[0056] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0057] (2) Mix the prepared raw materials, ultrasonic oscillation to completely dissolve to obtain a mixed solution;

[0058] (3) Transfer the mixed solution to a polytetrafluoroethylene acid lined reaction kettle, and pump out the gas to create a vacuum environment;

[0059] (4) The reaction kettle is heated to 120°C, and the reaction is carried out for 12H, and then mixed with 20 parts of hydroxymethylated chitosan;

[0060] (5) Spread on the filter cloth and take out after 2H part of the semi-solidification, get semi-solidification mixture;

[0061] (6) Transfer the semi-solidification mixture into the reaction kettle, heat to 120°C, and vacuum react for 12H;

[0062] (7) After the reaction is completed, soak in 0.1% sodium hydroxide solution for 1min, take out and clean with distilled water and DMF;

[0063] (8) Dry in an oven at 45°C for 12H, and then crush and grind to obtain modified YZr-MOF.

[0064] 3. Preparation of modified conditioner, the steps are as follows:

[0065] (1) Take 40~60 parts of sea buckthorn sawdust, finely crush and sieve to 80 mesh;

[0066] (2) Take 8~12 parts of phenolic imine resin and heat to semi-solid state, and mix the sea buckthorn sawdust into it;

[0067] (3) After the sawdust and resin are completely mixed and uniform, cool and solidify to obtain modified sea buckthorn sawdust.

[0068] 4. After the semi-solid sludge is dehydrated, solid sludge is obtained, and then it is crushed and sieved to 30 mesh to obtain sludge powder;

[0069] 5. Take 90 parts of fecal pollution and 30 parts of sludge powder to mix to obtain mixture A;

[0070] 6. Take 11 parts of loaded bacterial agent, mixture A, and 20 parts of adsorbent;

[0071] 7. Add the adsorbent to the carrier bacteria agent, so that the adsorbent is attached to the surface of the carrier bacteria agent;

[0072] 8. Place the carrier bacteria agent with the adsorbent into the mixture A, and proliferate the bacterial colonies for 8 days;

[0073] 9. After the proliferation is completed, add 25 parts of the modified conditioner and stir for 5 minutes to obtain the mixture B;

[0074] 10. Introduce nitrogen into the ideal mixing reactor at 1 L / min, and after the air is completely discharged, transfer the mixture B into the reactor;

[0075] 11. The system is heated to 50°C, and stirring is maintained at 75R / min, and anaerobic fermentation is performed for 2 days to obtain the low-antibiotic fecal sludge.

[0076] Example 2

[0077] 1. Prepare the carrier bacteria agent, and the steps are as follows:

[0078] (1) Take 50 parts of the mesoporous Cs3PMo12O40 carrier and 3 parts of the Brucella WXX-3 strain culture solution; 12 O 40 (2) Crush the mesoporous Cs3PMo12O40 carrier into granular material, and sieve it to 30 mesh;

[0079] (3) Place the granular mesoporous Cs3PMo12O40 carrier into the Brucella WXX-3 strain culture solution for adsorption; 12 O 40 (4) After the Brucella WXX-3 strain culture solution is completely adsorbed, dry and remove the water to obtain the stable carrier bacteria agent.

[0080] (5) The stable carrier bacteria agent is obtained. 12 O 40 (6) The stable carrier bacteria agent is obtained.

[0081] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed, dry and remove the water to obtain the stable carrier bacteria agent.

[0082] 2. Prepare the adsorbent modified YZr-MOF, and the steps are as follows:

[0083] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0084] (2) Mix the prepared raw materials, and ultrasonically oscillate to completely dissolve to obtain a mixed solution;

[0085] (3) Transfer the mixed solution to a reaction kettle lined with polytetrafluoroethylene acid, and pump out the air to create a vacuum environment;

[0086] (4) Heat the reaction kettle to 120°C, and react for 12 hours, and then take out and mix with 20 parts of hydroxymethylated chitosan;

[0087] (5) The semi-solid mixture is taken out after 2H of the semi-solidification, and a semi-solid mixture is obtained;

[0088] (6) The semi-solid mixture is transferred into a reaction kettle, heated to 120°C, and vacuum reacted for 12H;

[0089] (7) After the reaction, the semi-solid mixture is soaked in 0.1% sodium hydroxide solution for 1 min, and then washed with distilled water and DMF;

[0090] (8) The semi-solid mixture is dried in an oven at 45°C for 12H, and then ground to obtain the modified YZr-MOF.

[0091] 3. Preparation of a modified conditioner, the steps are as follows:

[0092] (1) Take 40-60 parts of sea buckthorn sawdust, finely crush and sieve to 80 mesh;

[0093] (2) Take 8-12 parts of phenolic imine resin and heat to semi-solid state, and mix the sea buckthorn sawdust into it;

[0094] (3) After the sawdust and resin are completely mixed and uniform, the temperature is lowered to solidify, and the modified sea buckthorn sawdust is obtained.

[0095] 4. The semi-solid biogas residue is dehydrated to obtain a solid biogas residue, which is then crushed and sieved to 30 mesh to obtain a biogas residue powder;

[0096] 5. Take 90 parts of fecal pollution and 30 parts of biogas residue powder to obtain a mixture A;

[0097] 6. Take 8 parts of a loaded bacteria agent, mixture A, and 25 parts of an adsorbent;

[0098] 7. The adsorbent is added to the loaded bacteria agent, so that the adsorbent is attached to the surface of the loaded bacteria agent;

[0099] 8. The loaded bacteria agent with the adsorbent is placed in the mixture A, and the bacteria colony is expanded for 8 days;

[0100] 9. After the expansion is completed, 30 parts of a modified conditioner is added and stirred for 5 min to obtain a mixture B;

[0101] 10. Nitrogen gas is introduced into a desired mixing reactor at a rate of 1L / min, and the mixture B is transferred into the reactor after the air is completely discharged;

[0102] 11. The system is heated to 50°C and kept stirring at 75R / min, and anaerobic fermentation is carried out for 2 days to obtain low-antibiotic fecal pollution.

[0103] Example 3

[0104] 1. Preparation of a loaded bacteria agent, the steps are as follows:

[0105] (1) Take mesoporous Cs3PMo 12O 40 Carrier 50 parts, Brucella WXX-3 strain culture solution 3 parts;

[0106] (2) Mesoporous Cs3PMo 12 O 40 Carrier is crushed to form granules, and is sieved to 30 mesh;

[0107] (3) Granular mesoporous Cs3PMo 12 O 40 The carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0108] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried to remove water, a stable loaded microbial agent is obtained.

[0109] 2. Preparation of adsorbent modified YZr-MOF, the steps are as follows:

[0110] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0111] (2) Mix the prepared raw materials, and ultrasonically oscillate to completely dissolve to obtain a mixed solution;

[0112] (3) The mixed solution is transferred to a polytetrafluoroethylene acid-lined reaction kettle, and a vacuum environment is created by pumping;

[0113] (4) The reaction kettle is heated to 120°C, and the reaction is carried out for 12H, and then 20 parts of hydroxymethylated chitosan is taken out and mixed;

[0114] (5) Spread on filter cloth and wait for 2H to partially solidify into a semi-solid state, then take out to obtain a semi-solid mixture;

[0115] (6) The semi-solid mixture is transferred into the reaction kettle, heated to 120°C, and vacuum reacted for 12H;

[0116] (7) After the reaction is completed, soak in 0.1% sodium hydroxide solution for 1 min, and then take out and wash with distilled water and DMF;

[0117] (8) Dry in an oven at 45°C for 12H, and then crush and mill to obtain the modified YZr-MOF.

[0118] 3. Preparation of modified conditioner, the steps are as follows:

[0119] (1) Take 40-60 parts of sea buckthorn sawdust, finely crush and sieve to 80 mesh;

[0120] (2) Take 8-12 parts of phenolic imine resin and heat to semi-solid state, and then put the sea buckthorn sawdust into it and mix;

[0121] (3) After the sawdust and the resin are completely mixed and uniform, the temperature is lowered to solidify to obtain the modified sea-buckthorn sawdust.

[0122] 4. The semi-solid biogas residue is dehydrated to obtain a solid biogas residue, which is then crushed and sieved to obtain a biogas residue powder with a mesh size of 30;

[0123] 5. A mixture A is obtained by mixing 90 parts of fecal pollution and 30 parts of the biogas residue powder;

[0124] 6. A mixture A, an adsorbent 15 parts, and a load bacteria agent 14 parts are taken;

[0125] 7. The adsorbent is added to the load bacteria agent to make the adsorbent adhere to the surface of the load bacteria agent;

[0126] 8. The load bacteria agent with the adsorbent is placed in the mixture A to proliferate the bacterial colonies for 8 days;

[0127] 9. After the proliferation is completed, 20 parts of a modified conditioner are added and stirred for 5 minutes to obtain a mixture B;

[0128] 10. Nitrogen gas is introduced into an ideal mixing reactor at a rate of 1 L / min, and the mixture B is transferred after the air is completely discharged;

[0129] 11. The system is heated to 50°C and stirred at 75R / min, and anaerobic fermentation is carried out for 2 days to obtain low-antibiotic fecal pollution.

[0130] Comparative Example 1

[0131] 1. A load bacteria agent is prepared, and the steps are as follows:

[0132] (1) 50 parts of LPCS porous carbon carrier and 3 parts of Brucella WXX-3 strain culture solution are taken;

[0133] (2) The LPCS porous carbon carrier is crushed to form granular material, which is sieved to a mesh size of 30;

[0134] (3) The granular LPCS porous carbon carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0135] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed, dried and dehydrated, a stable load bacteria agent is obtained.

[0136] 2. A modified YZr-MOF adsorbent is prepared, and the steps are as follows:

[0137] (1) 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide are taken;

[0138] (2) The prepared raw materials are mixed and ultrasonically oscillated to completely dissolve to obtain a mixed solution;

[0139] (3) The mixed solution is transferred to a reaction kettle lined with polytetrafluoroacetate, and vacuum is created by pumping;

[0140] (4) The temperature in the reaction kettle is raised to 120°C, and reaction is carried out for 12H, and then 20 parts of hydroxymethylated chitosan are taken out and mixed;

[0141] (5) The mixture is spread on a filter cloth and left to stand, and then a part of the mixture is taken out after 2H and solidified into a semi-solid state to obtain a semi-solid mixture;

[0142] (6) The semi-solid mixture is transferred into the reaction kettle, the temperature is raised to 120°C, and vacuum reaction is carried out for 12H;

[0143] (7) After the reaction is completed, the mixture is soaked in 0.1% sodium hydroxide solution for 1 min, and then distilled water and DMF are used for cleaning;

[0144] (8) The mixture is dried in an oven at 45°C for 12H, and then it is ground and milled to obtain the modified YZr-MOF.

[0145] 3. Preparation of a modified conditioner, the steps being as follows:

[0146] (1) 40-60 parts of seabuckthorn sawdust are finely crushed and sieved to 80 mesh;

[0147] (2) 8-12 parts of phenolic imine resin are heated to a semi-solid state, and the seabuckthorn sawdust is placed in the resin and mixed;

[0148] (3) After the sawdust and the resin are completely mixed and uniform, the temperature is lowered to solidify to obtain modified seabuckthorn sawdust.

[0149] 4. The semi-solid biogas residue is dehydrated to obtain a solid-state biogas residue, which is then ground and sieved to 30 mesh to obtain a biogas residue powder;

[0150] 5. 90 parts of fecal pollution and 30 parts of biogas residue powder are mixed to obtain a mixture A;

[0151] 6. 11 parts of a loaded bacteria agent, 20 parts of the mixture A, and 20 parts of an adsorbent are taken;

[0152] 7. The adsorbent is added to the loaded bacteria agent, so that the adsorbent is attached to the surface of the loaded bacteria agent;

[0153] 8. The loaded bacteria agent with the adsorbent is placed in the mixture A, and the bacteria colonies are multiplied for 8d;

[0154] 9. After the multiplication is completed, 25 parts of the modified conditioner are added and stirred for 5 min to obtain a mixture B;

[0155] 10. Nitrogen gas is introduced into an ideal mixing reactor at 1L / min, and after the air is completely discharged, the mixture B is transferred into the reactor;

[0156] 11. The system is warmed to 50℃ and kept at 75R / min stirring, anaerobic fermentation for 2d, to obtain low antibiotic manure.

[0157] Comparative Example 2

[0158] 1. Preparation of the carrier bacteria, the steps are as follows:

[0159] (1) Take mesoporous Cs3PMo 12 O 40 The carrier 50 parts, containing Brucella WXX-3 strain culture solution 3 parts;

[0160] (2) The mesoporous Cs3PMo 12 O 40 The carrier is crushed to form granular material, and sieved to 30 mesh;

[0161] (3) The granular mesoporous Cs3PMo 12 O 40 The carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0162] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried, the stable carrier bacteria are obtained.

[0163] 2. Preparation of adsorbent modified YZr-MOF, the steps are as follows:

[0164] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0165] (2) Mix the prepared raw materials, and ultrasonic oscillation to completely dissolve to obtain a mixed solution;

[0166] (3) The mixed solution is transferred to a polytetrafluoroethylene-lined reaction kettle, and a vacuum environment is created by pumping;

[0167] (4) The reaction kettle is heated to 120℃, and the reaction is carried out for 12H, and then mixed with 20 parts of hydroxymethylated chitosan;

[0168] (5) Spread on filter cloth and take out after 2H part of the semi-solidification, get semi-solidification mixture;

[0169] (6) The semi-solidification mixture is transferred to the reaction kettle, heated to 120℃, and vacuum reacted for 12H;

[0170] (7) After the reaction is completed, soak in 0.1% sodium hydroxide solution for 1min, and then take out and wash with distilled water and DMF;

[0171] (8) Dry in an oven at 45℃ for 12H, and then crush and mill to obtain the modified YZr-MOF.

[0172] 3. Preparation of modified conditioner, steps as follows:

[0173] (1) Take sea buckthorn wood chips 40~60 parts, finely crush and sieve 80 mesh;

[0174] (2) Take phenolic imine resin 8~12 parts to heat to semi-solid state, and mix the sea buckthorn wood chips;

[0175] (3) After the wood chips and resin are completely mixed and uniform, cool and solidify to obtain modified sea buckthorn wood chips.

[0176] 4. After the semi-solid biogas residue is dewatered, solid-state biogas residue is obtained, which is then crushed and sieved 30 mesh to obtain biogas residue powder;

[0177] 5. Take fecal pollution 90 parts, biogas residue powder 30 parts to obtain mixture A;

[0178] 6. Take load bacteria agent 3 parts, mixture A, adsorbent 20 parts;

[0179] 7. Add the adsorbent to the load bacteria agent, so that the adsorbent adheres to the surface of the load bacteria agent;

[0180] 8. Place the load bacteria agent with adsorbent into mixture A, and proliferate the bacterial colonies for 8 days;

[0181] 9. After the proliferation is completed, add 25 parts of modified conditioner and stir for 5 minutes to obtain mixture B;

[0182] 10. Introduce nitrogen gas into the ideal mixing reactor at 1L / min, and after the air is completely discharged, transfer mixture B into the reactor;

[0183] 11. The system is heated to 50℃ and kept stirring at 75R / min, and anaerobic fermentation is carried out for 2 days to obtain low antibiotic fecal pollution.

[0184] Comparative Example 3

[0185] 1. Preparation of load bacteria agent, steps as follows:

[0186] (1) Take mesoporous Cs3PMo 12 O 40 carrier parts, and Brucella WXX-3 strain culture solution 3 parts;

[0187] (2) Crush the mesoporous Cs3PMo 12 O 40 carrier to form granular material, and sieve 30 mesh;

[0188] (3) Place the granular mesoporous Cs3PMo 12 O 40 carrier into the Brucella WXX-3 strain culture solution for adsorption;

[0189] (4) Brucella WXX-3 strain culture solution is completely absorbed, dried and dehydrated to obtain a stable load bacteria agent.

[0190] 2. The preparation of the adsorbent modified YZr-MOF is as follows:

[0191] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0192] (2) Mix the prepared raw materials and ultrasonically oscillate to completely dissolve to obtain a mixed solution;

[0193] (3) Transfer the mixed solution to a polytetrafluoroethylene-lined reaction kettle and pump out air to create a vacuum environment;

[0194] (4) Heat the reaction kettle to 120°C and react for 12H, then take out and mix with 20 parts of hydroxymethylated chitosan;

[0195] (5) Spread on filter cloth and take out after 2H of partial solidification into semi-solid state to obtain semi-solid mixture;

[0196] (6) Transfer the semi-solid mixture into the reaction kettle, heat to 120°C, and vacuum react for 12H;

[0197] (7) After the reaction is completed, soak in 0.1% sodium hydroxide solution for 1 min, and then take out and clean with distilled water and DMF;

[0198] (8) Dry in an oven at 45°C for 12H, and then crush and mill to obtain the modified YZr-MOF.

[0199] 3. The preparation of the modified conditioner is as follows:

[0200] (1) Take 40-60 parts of sea buckthorn sawdust and finely crush and sieve to 80 mesh;

[0201] (2) Take 8-12 parts of phenolic imine resin and heat to semi-solid state, and then mix the sea buckthorn sawdust into it;

[0202] (3) After the sawdust and resin are completely mixed and uniform, cool and solidify to obtain the modified sea buckthorn sawdust.

[0203] 4. After the semi-solid biogas residue is dehydrated, it becomes a solid-state biogas residue, which is then crushed and sieved to 30 mesh to obtain a biogas residue powder;

[0204] 5. Take 90 parts of fecal pollution and 30 parts of biogas residue powder to obtain mixture A;

[0205] 6. Take 20 parts of the load bacteria agent, mixture A, and 20 parts of the adsorbent;

[0206] 7. Add the adsorbent to the load bacteria agent to make the adsorbent adhere to the surface of the load bacteria agent;

[0207] 8. Put the adsorbent-loaded carrier inoculant into mixture A, and proliferate the bacterial colonies for 8 days;

[0208] 9. After the proliferation, add 25 parts of the modified conditioner and stir for 5 minutes to obtain mixture B;

[0209] 10. Introduce nitrogen into the ideal mixing reactor at 1 L / min, and after the air is completely discharged, transfer mixture B into the reactor;

[0210] 11. The system is heated to 50°C, and stirring is maintained at 75R / min, and anaerobic fermentation is performed for 2 days to obtain low-antibiotic fecal sludge.

[0211] Comparative Example 4

[0212] The difference between this comparative example and Example 1 is that the hydroxymethylated chitosan in step 2 described is nano-hydroxyapatite, and the rest of the implementation method is the same as that of Example 1.

[0213] Comparative Example 5

[0214] 1. Prepare the carrier inoculant, and the steps are as follows:

[0215] (1) Take 50 parts of mesoporous Cs3PMo 12 O 40 carrier and 3 parts of Brucella WXX-3 strain culture solution;

[0216] (2) Crush the mesoporous Cs3PMo 12 O 40 carrier into granules, and sieve them to 30 mesh;

[0217] (3) Put the granular mesoporous Cs3PMo 12 O 40 carrier into the Brucella WXX-3 strain culture solution for adsorption;

[0218] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried to remove water, a stable carrier inoculant is obtained.

[0219] 2. Prepare the adsorbent-modified YZr-MOF, and the steps are as follows:

[0220] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0221] (2) Mix the prepared raw materials, and ultrasonically oscillate to completely dissolve to obtain a mixed solution;

[0222] (3) Transfer the mixed solution to a polytetrafluoroethylene-lined reaction kettle, and pump out the air to create a vacuum environment;

[0223] (4) The reactor is heated to 120°C for 24 hours, and then washed twice with distilled water and DMF to obtain YZr-MOF;

[0224] (5) The mixture is dried in an oven at 45°C for 12 hours, and then ground and mixed with 20 parts of hydroxymethylated chitosan to obtain modified YZr-MOF.

[0225] 3. Preparation of modified conditioner, steps as follows:

[0226] (1) Take 40-60 parts of sea buckthorn wood chips and finely crush them to 80 mesh;

[0227] (2) Take 8-12 parts of phenolic imine resin and heat it to semi-solid state, then mix the sea buckthorn wood chips into it;

[0228] (3) After the wood chips and resin are completely mixed and uniform, cool and solidify to obtain modified sea buckthorn wood chips.

[0229] 4. After the semi-solid biogas residue is dehydrated, it becomes solid, and then it is crushed and sieved to 30 mesh to obtain biogas residue powder;

[0230] 5. Take 90 parts of fecal matter and 30 parts of biogas residue powder to obtain mixture A;

[0231] 6. Take 11 parts of loaded bacteria agent, mixture A, and 15 parts of adsorbent;

[0232] 7. Add the adsorbent to the loaded bacteria agent so that the adsorbent adheres to the surface of the loaded bacteria agent;

[0233] 8. Place the loaded bacteria agent with adsorbent into mixture A and propagate the bacterial colonies for 8 days;

[0234] 9. After propagation, add 25 parts of modified conditioner and stir for 5 minutes to obtain mixture B;

[0235] 10. Introduce nitrogen gas into the ideal mixing reactor at 1L / min, and when the air is completely discharged, transfer mixture B into it;

[0236] 11. The system is heated to 50°C and kept stirring at 75R / min for 2 days to obtain low-antibiotic fecal matter.

[0237] Comparative Example 6

[0238] 1. Preparation of loaded bacteria agent, steps as follows:

[0239] (1) Take 50 parts of mesoporous Cs3PMo 12 O 40 carrier and 3 parts of culture solution containing Brucella WXX-3 strain;

[0240] (2) Mix mesoporous Cs3PMo 12 O40 The carrier is crushed to form granules, and sieved to 30 mesh;

[0241] (3) The granular mesoporous Cs3PMo 12 O 40 The carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0242] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried to remove water, a stable loaded bacterial agent is obtained.

[0243] 2. Preparation of adsorbent modified YZr-MOF, the steps are as follows:

[0244] (5) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0245] (1) Mix the prepared raw materials and ultrasonically oscillate to completely dissolve to obtain a mixed solution;

[0246] (2) Transfer the mixed solution to a polytetrafluoroethylene-lined reaction kettle and pump to create a vacuum environment;

[0247] (3) Heat the reaction kettle to 120°C and react for 12H, then take out and mix with 20 parts of hydroxymethylated chitosan;

[0248] (4) Spread on filter cloth and wait for 2H to partially solidify into a semi-solid state, then take out to obtain a semi-solid mixture;

[0249] (5) Transfer the semi-solid mixture into the reaction kettle, heat to 120°C, and vacuum react for 12H;

[0250] (6) After the reaction is completed, soak in 0.1% sodium hydroxide solution for 1 min, then take out and wash with distilled water and DMF;

[0251] (7) Dry in an oven at 45°C for 12H, then crush and mill to obtain the modified YZr-MOF.

[0252] 3. Preparation of modified conditioner, the steps are as follows:

[0253] (1) Take 40-60 parts of sand sage wood chips and finely crush and sieve to 80 mesh;

[0254] (2) Take 8-12 parts of phenolic imine resin and heat to semi-solid state, then mix the sand sage wood chips into it;

[0255] (3) After the wood chips and resin are completely mixed and uniform, cool and solidify to obtain the modified sand sage wood chips.

[0256] 4. After the semi-solid biogas residue is dehydrated, a solid-state biogas residue is obtained, which is then crushed and sieved to 30 mesh to obtain a biogas residue powder;

[0257] 5. Take 90 parts of fecal pollution, 30 parts of biogas residue powder to obtain mixture A;

[0258] 6. Take 11 parts of the loaded bacteria agent, mixture A, and 10 parts of the adsorbent;

[0259] 7. The adsorbent is added to the loaded bacteria agent, and the adsorbent is attached to the surface of the loaded bacteria agent;

[0260] 8. The loaded bacteria agent with the adsorbent is placed in the mixture A, and the bacteria colony is expanded for 8 days;

[0261] 9. After the expansion is completed, 25 parts of the modified conditioner are added and stirred for 5 minutes to obtain mixture B;

[0262] 10. Nitrogen is introduced into the ideal mixing reactor at 1 L / min, and after the air is completely discharged, mixture B is transferred;

[0263] 11. The system is heated to 50°C and kept at 75R / min stirring, anaerobic fermentation for 2 days, to obtain low antibiotic fecal pollution.

[0264] Comparative Example 7

[0265] 1. Preparation of the loaded bacteria agent, the steps are as follows:

[0266] (1) Take 50 parts of mesoporous Cs3PMo 12 O 40 carrier and 3 parts of culture solution containing Brucella WXX-3 strain;

[0267] (2) The mesoporous Cs3PMo 12 O 40 carrier is crushed to form granular material, and sieved to 30 mesh;

[0268] (3) The granular mesoporous Cs3PMo 12 O 40 carrier is placed in the Brucella WXX-3 strain culture solution for adsorption;

[0269] (4) After the Brucella WXX-3 strain culture solution is completely adsorbed and dried to remove water, a stable loaded bacteria agent is obtained.

[0270] 2. Preparation of the adsorbent modified YZr-MOF, the steps are as follows:

[0271] (1) Take 55 parts of Y(NO)3·6H2O, 25 parts of ZrCl4, 42 parts of terephthalic acid, and 6 parts of dimethylformamide;

[0272] (2) Mix the prepared raw materials, and ultrasonic oscillation to completely dissolve to obtain a mixed solution;

[0273] (3) The mixed solution is transferred to a reaction kettle lined with polytetrafluoroacetate, and vacuum is created by pumping;

[0274] (4) The temperature in the reaction kettle is raised to 120°C, and reaction is carried out for 12H, and then 20 parts of hydroxymethylated chitosan are taken out and mixed;

[0275] (5) The mixture is spread on filter cloth and left to stand, and then a part of the mixture is taken out when it is semi-solidified, to obtain a semi-solidified mixture;

[0276] (6) The semi-solidified mixture is transferred to a reaction kettle, the temperature is raised to 120°C, and vacuum reaction is carried out for 12H;

[0277] (7) After the reaction is completed, the mixture is soaked in 0.1% sodium hydroxide solution for 1 min, and then distilled water and DMF are used for cleaning;

[0278] (8) The mixture is dried in an oven at 45°C for 12H, and then it is ground and milled, to obtain the modified YZr-MOF.

[0279] 3. A modified conditioner is prepared, and the steps are as follows:

[0280] (1) 40-60 parts of seabuckthorn sawdust are finely crushed and sieved to 80 mesh;

[0281] (2) 8-12 parts of phenolic imine resin are heated to semi-solid state, and the seabuckthorn sawdust is placed in the resin and mixed;

[0282] (3) After the sawdust and the resin are completely mixed and uniform, the temperature is lowered to solidify, to obtain the modified seabuckthorn sawdust.

[0283] 4. After the semi-solid biogas residue is dehydrated, a solid biogas residue is obtained, and then the solid biogas residue is crushed and sieved to 30 mesh to obtain a biogas residue powder;

[0284] 5. 90 parts of fecal pollution and 30 parts of the biogas residue powder are mixed to obtain a mixture A;

[0285] 6. 11 parts of a loaded bacteria agent, the mixture A, and 30 parts of an adsorbent are taken;

[0286] 7. The adsorbent is added to the loaded bacteria agent, so that the adsorbent is attached to the surface of the loaded bacteria agent;

[0287] 8. The loaded bacteria agent with the adsorbent is placed in the mixture A, and the bacteria colonies are multiplied for 8d;

[0288] 9. After the multiplication is completed, 25 parts of the modified conditioner are added and stirred for 5 min, to obtain a mixture B;

[0289] 10. Nitrogen gas is introduced into an ideal mixing reactor at 1L / min, and after the air is completely discharged, the mixture B is transferred into the reactor;

[0290] 11. The system is warmed to 50℃ and kept stirring at 75R / min, anaerobic fermentation for 2d, to obtain low antibiotic fecal pollution.

[0291] Comparative Example 8

[0292] The difference between this comparative example and Example 1 is that the phenolic imine resin in Step 3 is a phenolic resin, and the rest of the implementation method is the same as Example 1.

[0293] Product determination:

[0294] According to Examples 1-3 and Comparative Examples 1-7, livestock and poultry manure was treated, respectively.

[0295] 1) The treated manure was composted, 10g of sample was taken from each case, the sample was crushed and passed through a 0.5mm test sieve, 1.5g of sieved sample was weighed with an accuracy of 0.1mg, then the component concentration was determined according to GB / T 32951-2016 to obtain the antibiotic content, the results are shown in Table 1.

[0296] Table 1 Antibiotic residue

[0297] Tetracycline content Sulfadiazine content Penicillin content Fluoroquinolone content (mg / kg) (mg / kg) (mg / kg) (mg / kg) Example 1 0.011 0.007 0.012 0.002 Example 2 0.010 0.006 0.011 0.004 Example 3 0.011 0.008 0.009 0.003 Comparative Example 1 0.352 0.212 0.389 0.177 Comparative Example 2 0.732 0.511 0.713 0.399 Comparative Example 3 0.023 0.012 0.021 0.019 Comparative Example 4 0.057 0.021 0.061 0.015 Comparative Example 5 0.511 0.354 0.501 0.206 Comparative Example 6 0.651 0.411 0.621 0.294 Comparative Example 7 0.031 0.015 0.029 0.012 Comparative Example 8 0.112 0.078 0.101 0.029

Claims

1. A method for microbial degradation of antibiotics in livestock manure, characterized by: The steps are as follows: (1) After the semi-solid biogas residue is dewatered, solid-state biogas residue is obtained, and then the solid-state biogas residue is crushed and sieved to obtain biogas residue powder with a mesh size of 30; (2) 80-100 parts of fecal pollution and 25-35 parts of biogas residue powder are mixed to obtain mixture A; (3) 8-14 parts of a carrier bacteria agent, mixture A, and 15-25 parts of an adsorbent are taken; (4) The adsorbent is added to the carrier bacteria agent, so that the adsorbent adheres to the surface of the carrier bacteria agent; (5) The carrier bacteria agent with the adsorbent is placed in the mixture A, and the bacterial colonies are expanded for 8 days; (6) After the expansion is completed, 20-30 parts of a modified conditioner are added and stirred for 5 minutes to obtain mixture B; (7) Nitrogen is introduced into an ideal mixing reactor at a rate of 1 L / min, and mixture B is transferred into the reactor after the air is completely discharged; (8) The system is heated to 50℃ and stirred at 75R / min, and anaerobic fermentation is carried out for 2 days to obtain low-antibiotic fecal pollution. The carrier bacteria agent is Brucella WXX-3 strain, and the preparation method is as follows: (1) Take mesoporous Cs3PMo 12 O 40 Carrier 45-55 parts, containing Brucella WXX-3 strain culture fluid 2.5-3.5 parts; (2) The mesoporous Cs3PMo 12 O 40 The carrier is crushed to form granules, and sieved to 30 mesh. (3) The particulate mesoporous Cs3PMo 12 O40 carriers were placed in the culture solution of Brucella WXX-3 strain for adsorption; (4) After the Brucella WXX-3 strain culture solution is completely adsorbed, dried and dehydrated, a stable carrier bacteria agent is obtained.

2. The method for degrading antibiotics according to claim 1, characterized in that: The adsorbent is modified YZr-MOF, and the preparation method is as follows: (1) 50-60 parts of Y(NO)3•6H2O, 23-27 parts of ZrCl4, 38-56 parts of terephthalic acid, and 5.5-6.5 parts of dimethylformamide are taken; (2) The prepared raw materials are mixed and ultrasonically oscillated to completely dissolve to obtain a mixed solution; (3) The mixed solution is transferred to a polytetrafluoroethylene acid-lined reaction kettle, and a vacuum environment is created by air extraction; (4) The reaction kettle is heated to 120℃, and the reaction is carried out for 12 hours, and then 20 parts of hydroxymethylated chitosan is taken out and mixed; (5) The mixture is placed on a filter cloth and extended, and then taken out after the surface is solidified into a film; (6) The extended mixture is transferred to a reaction kettle, heated to 120℃, and vacuum reacted for 12 hours; (7) After the reaction is completed, the mixture is soaked in 0.1% sodium hydroxide solution for 1 minute, taken out, and cleaned with distilled water and DMF; (8) The mixture is dried in an oven at 45℃ for 12 hours, and then crushed and ground to obtain modified YZr-MOF.

3. The method of degrading an antibiotic of claim 1, wherein: The modified conditioner is modified sea buckthorn sawdust, and the preparation method is as follows: (1) 40-60 parts of sea buckthorn sawdust are finely crushed and sieved to 80 mesh; (2) 8-12 parts of phenolic imine resin are heated to a semi-solid state, and the sea buckthorn sawdust is placed and mixed therein; (3) After the sawdust and the resin are completely mixed and uniformly distributed, the modified sea buckthorn sawdust is obtained by granulating and cooling the resin to solidify.