Process for preparing multifunctional liquid fertilizer from tylosin waste liquid

Abstract

The invention discloses a process for preparing a multifunctional liquid fertilizer from tylosin waste liquid, and belongs to the technical field of fertilizer preparation. The method comprises the following steps: pretreating the tylosin waste liquid to obtain pretreated waste liquid; adjusting the pH value of the pretreated waste liquid to obtain the pH-adjusted waste liquid; sterilizing and filtering the waste liquid subjected to pH regulation to obtain pure treatment liquid; the pure treatment liquid is subjected to nutrient substance blending, and the multifunctional liquid fertilizer prepared from the tylosin waste liquid is obtained. According to the method, a tylosin degradation catalyst is synthesized in the waste liquid in the pretreatment and pH adjustment processes, tylosin in the waste liquid is degraded in the sterilization process, and soil pollution caused by residual tylosin in the waste liquid is prevented while the steps are shortened; in the blending of the nutrient substances, the acidic substances are added to chelate metal ions, so that the release of the nutrient substances in the fertilizer is delayed, the resource utilization rate is increased, and the fertilizer is worthy of wide-range popularization.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizer preparation, and in particular to a process for preparing multifunctional liquid fertilizer from tylosin waste liquid. Background Art

[0002] With the rapid development of industries such as animal husbandry and aquaculture, more and more antibiotics are used as feed additives, veterinary injections and agricultural antibiotics due to their powerful antibacterial effects. The production of antibiotics usually involves multiple process steps such as microbial fermentation, extraction, and purification. During these production processes, a large amount of waste liquid is generated.

[0003] Tylosin is a macrolide antibiotic widely used in the veterinary field. Tylosin waste liquid is the wastewater generated during the production process of tylosin, which contains tylosin residues that have not been completely separated, unused organic nutrients, and residual substances such as salts and organic acids. With the discharge of waste liquid, these residual substances will damage the water ecosystem and soil structure. Even the antibiotic residues in the waste liquid will promote bacteria to develop antibiotic resistance, increase the difficulty of antibiotic treatment, and pose a threat to human health.

[0004] Therefore, the treatment and recycling of tylosin waste liquid is of great significance for the recycling of resources, environmental protection and the sustainable development of antibiotic production. Summary of the invention

[0005] In order to solve the technical problems existing in the prior art, the present invention provides a process for preparing multifunctional liquid fertilizer from tylosin waste liquid, and the specific contents are as follows.

[0006] The present invention provides a process for preparing multifunctional liquid fertilizer from tylosin waste liquid, comprising pretreatment, pH adjustment, sterilization and filtration of the tylosin waste liquid and preparation of nutrients. The process for preparing multifunctional liquid fertilizer from the tylosin waste liquid comprises the following steps: Step 1, pretreatment of tylosin waste liquid, placing the tylosin waste liquid in a high-speed centrifuge for high-speed centrifugation, adding activated carbon powder to adsorb insoluble impurities and microorganisms in the waste liquid, adding hydrogen peroxide solution to oxidize and sterilize the microorganisms in the waste liquid, adding FeSO4·7H2O to complex and aggregate protein precipitates in the solution, and using ultrasound to disperse the activated carbon and hydrogen peroxide more evenly in the waste liquid, so as to more completely adsorb impurities and inactivate microorganisms, thereby obtaining pretreated waste liquid; Step 2: adjusting the pH value of the pretreated waste liquid, transferring the pretreated waste liquid into a reactor, adding algae limestone powder, alkaline salt and Na2S2O3·5H2O, stirring to mix them evenly, neutralizing the acidic substances in the waste liquid, and obtaining a waste liquid after pH adjustment; Step 3: sterilize and filter the waste liquid after pH adjustment, control the temperature in the reactor and the stirring rate in the reactor, and filter the liquid in the reactor after stirring for a certain period of time to obtain a pure treated liquid; Step 4: prepare nutrients with the purified treated liquid. The purified treated liquid is transported into a preparation tank, and acidic substances are added to supplement the nutrients in the waste liquid while fixing the trace elements and metal elements. After stirring and mixing evenly, a multifunctional liquid fertilizer for preparing tylosin waste liquid is obtained.

[0007] Preferably, the mass concentration of the hydrogen peroxide solution is 20% to 40%.

[0008] Preferably, the algae limestone powder is obtained by crushing the algae limestone with a crusher and passing through a 200-400 mesh sieve.

[0009] Preferably, the alkaline salt is at least one of urea, zinc oxide, boric acid and manganese dioxide.

[0010] Preferably, the reaction conditions for sterilization and filtration are: heating the waste liquid after pH adjustment at 160-180° C. for 12-16 hours, irradiating it with ultraviolet light using a xenon lamp for 1.5-2 hours, and using a filter with a pore size of 20 nm to 40 nm.

[0011] Preferably, the acidic substance is at least one of L-cysteine, citric acid and fulvic acid.

[0012] Preferably, in the step 1, the tylosin waste liquid is pumped into a high-speed centrifuge, the centrifugal speed of the centrifuge is set to 10000r / min~13000r / min, the centrifugal time is 20~40min, the macromolecular substances in the waste liquid are transferred to the edge of the centrifuge by centrifugation, and after the centrifugation is completed, the supernatant in the centrifuge is transferred to a storage tank, and activated carbon powder is added thereto for adsorption, wherein the mesh number of the activated carbon powder is 200 meshes, and the mass ratio of the activated carbon powder to the supernatant is 3~5:100, and the hydrogen peroxide solution is added to the microorganisms in the waste liquid. The material is oxidized and sterilized, wherein the ratio of hydrogen peroxide solution to supernatant is 1:40-50, and FeSO4·7H2O is added to complex and aggregate the insoluble proteins in the solution, wherein the ratio of FeSO4·7H2O to supernatant is 3-4:800-1000. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring is continuously performed, the stirring rate is 60r / min-80r / min, the stirring time is 30-60min, and then ultrasonication is performed for 20-40min to obtain the pretreated waste liquid.

[0013] Preferably, in the step 2, the pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, alkaline salt and Na2S2O3·5H2O are added, wherein the mass ratio of the pretreated waste liquid, algae limestone powder, alkaline salt and Na2S2O3·5H2O is 800~1000:30~50:20~40:40~50, and the mixture is stirred at a stirring rate of 100r / min-120r / min for 30min~45min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid so that the pH of the waste liquid is suitable for the environment required for plant growth.

[0014] Preferably, in the step three, the temperature in the reactor is controlled to be 160-180°C and maintained for 12-16 hours, and then the liquid in the reactor is irradiated with ultraviolet light for 1.5-2 hours using a xenon lamp light source, and the stirring rate in the reactor is controlled to be 100r / min-120r / min, and stirring is continued during the irradiation of the xenon lamp light source, and then the liquid in the reactor is filtered through a filter with a pore size of 20nm-40nm to obtain a pure treated liquid.

[0015] Preferably, in the step 4, the pure treated liquid is transported into a mixing tank, and an acidic substance is added thereto to supplement the nutrient elements of the waste liquid, wherein the mass ratio of the pure treated liquid to the acidic substance is 800-1000:70-90, the stirring rate is controlled to be 800r / min-1200r / min, and the stirring time is 30-40min, to obtain a multifunctional liquid fertilizer prepared from tylosin waste liquid.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention comprises the following steps: pretreating tylosin waste liquid to obtain pretreated waste liquid; adjusting the pH value of the pretreated waste liquid to obtain pH-adjusted waste liquid; sterilizing and filtering the pH-adjusted waste liquid to obtain a pure treated liquid; and mixing nutrients in the pure treated liquid to obtain a multifunctional liquid fertilizer prepared from tylosin waste liquid.

[0017] (2) In the present invention, the activated carbon added in the pretreatment process has a porous structure and has a good adsorption effect on the insoluble impurities and microorganisms in the tylosin waste liquid. The added hydrogen peroxide has an oxidative bactericidal effect on the microorganisms in the waste liquid. The adsorption effect of the activated carbon and the bactericidal effect of hydrogen peroxide are enhanced during ultrasound. At the same time, because the activity of hydrogen peroxide is enhanced by ultrasound, the activated carbon will be oxidized by hydrogen peroxide, and carboxyl and hydroxyl functional groups will be introduced on the surface, thereby increasing the adsorption performance of heavy metal ions. The FeSO4·7H2O added in the pretreatment process will complex with the remaining protein molecules in the waste liquid to generate Insoluble precipitate, which helps to remove impurities; FeSO4·7H2O will also combine with Na2S2O3·5H2O added during the pH adjustment process to generate FeS2, which will combine with the carboxyl groups on the surface of the oxidized activated carbon through a complex reaction and be fixed on the surface of the oxidized activated carbon. FeS2 has an excellent degradation effect on tylosin under light conditions. In the subsequent xenon light irradiation process, it can sterilize and degrade tylosin at the same time to prevent soil pollution; and the FeS2 fixed by the activated carbon can be recovered and recycled many times after filtration, which improves the utilization efficiency of resources.

[0018] (3) The algae limestone powder and alkaline salt added in the pH adjustment of the present invention generate corresponding ion salts in the acidic waste liquid through a neutralization reaction, thereby releasing a large amount of calcium ions and other metal ions. These metal ions have a promoting effect on plant growth; the small molecule acidic substances added in the nutrient preparation step are suitable for direct absorption and utilization by plants. At the same time, these acidic substances will be fixed with metal ions through complexation reaction and electrostatic bonding, converting metal ions into a form suitable for plant absorption while preventing the loss of nutrient elements. For example, L-cysteine ​​therein will generate a water-soluble complex with calcium ions, which can directly act on the metabolic reaction of plants, greatly improving the absorption and utilization efficiency of plants.

[0019] (4) The acidic substance added to the multifunctional liquid fertilizer prepared by the present invention from the tylosin waste liquid can desorb the metal ions in the soil, thereby generating salt ion forms suitable for plant absorption. At the same time, the generated complex metal ion salt structure is stable, and the release cycle and action time are long. Therefore, the multifunctional liquid fertilizer prepared by the present invention is a long-acting slow-release liquid fertilizer. It uses the tylosin waste liquid as a raw material, recycles waste resources, reduces resource waste and environmental pollution, and has the advantages of being green, environmentally friendly, having a long release cycle, providing trace elements, and having a high plant absorption and utilization rate, and is worthy of large-scale promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention is a schematic diagram of a process for preparing a multifunctional liquid fertilizer from tylosin waste liquid in an embodiment. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Example 1 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption. The mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:100. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid. The ratio of the hydrogen peroxide solution to the supernatant was 1:40. FeSO4·7H2O was added to complex and aggregate the insoluble proteins in the solution. The ratio of FeSO4·7H2O to the supernatant was 4:1000. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 40 min to obtain the pretreated waste liquid.

[0023] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O is 1000:20:10:10:5:50. The mixture is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0024] (3) The temperature in the reactor was controlled at 180°C and maintained for 16 hours. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 hours. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 40 nm to obtain a pure treated liquid.

[0025] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and humic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and humic acid is 1000:50:20:20. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0026] Example 2 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption. The mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:80. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid. The ratio of the hydrogen peroxide solution to the supernatant was 1:40. FeSO4·7H2O was added to complex and aggregate the insoluble proteins in the solution. The ratio of FeSO4·7H2O to the supernatant was 4:800. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 30 min to obtain the pretreated waste liquid.

[0027] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O is 800:20:10:10:5:50. The waste liquid is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0028] (3) The temperature in the reactor was controlled at 180°C and maintained for 16 hours. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 hours. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 40 nm to obtain a pure treated liquid.

[0029] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and humic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and humic acid is 800:50:20:20. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0030] Example 3 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption. The mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:80. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid. The ratio of the hydrogen peroxide solution to the supernatant was 1:40. FeSO4·7H2O was added to complex and aggregate the insoluble proteins in the solution. The ratio of FeSO4·7H2O to the supernatant was 3:800. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 30 min to obtain the pretreated waste liquid.

[0031] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O is 800:30:10:5:5:40. The mixture is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0032] (3) The temperature in the reactor was controlled at 160°C and maintained for 12 h. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 h. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 20 nm to obtain a pure treated liquid.

[0033] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and fulvic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and fulvic acid is 800:40:15:15. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0034] Example 4 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption. The mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:80. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid. The ratio of the hydrogen peroxide solution to the supernatant was 1:40. FeSO4·7H2O was added to complex and aggregate the insoluble proteins in the solution. The ratio of FeSO4·7H2O to the supernatant was 3:800. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 30 min to obtain the pretreated waste liquid.

[0035] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O is 800:30:10:5:5:40. The mixture is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0036] (3) The temperature in the reactor was controlled at 160°C and maintained for 12 h. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 h. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 20 nm to obtain a pure treated liquid.

[0037] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and fulvic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and fulvic acid is 800:40:15:15. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0038] Example 5 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption, wherein the mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:100. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid, wherein the ratio of the hydrogen peroxide solution to the supernatant was 1:40. During the addition of the activated carbon powder and the hydrogen peroxide solution, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 40 min to obtain the pretreated waste liquid.

[0039] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid, manganese dioxide and Na2S2O3·5H2O is 1000:20:10:10:5:50. The mixture is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0040] (3) The temperature in the reactor was controlled at 180°C and maintained for 16 hours. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 hours. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 40 nm to obtain a pure treated liquid.

[0041] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and humic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and humic acid is 1000:50:20:20. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0042] Example 6 This embodiment provides a method for preparing multifunctional liquid fertilizer from tylosin waste liquid (1) The tylosin waste liquid was pumped into a high-speed centrifuge, and the centrifugal speed of the centrifuge was set to 13000 r / min and the centrifugal time was set to 40 min. The macromolecular substances in the waste liquid were transferred to the edge of the centrifuge by centrifugation. After the centrifugation was completed, the supernatant in the centrifuge was transferred to a storage tank, and activated carbon powder was added thereto for adsorption. The mesh size of the activated carbon powder was 200 mesh, and the mass ratio of the activated carbon powder to the supernatant was 5:100. Hydrogen peroxide solution was added to oxidize and sterilize the microorganisms in the waste liquid. The ratio of the hydrogen peroxide solution to the supernatant was 1:40. FeSO4·7H2O was added to complex and aggregate the insoluble proteins in the solution. The ratio of FeSO4·7H2O to the supernatant was 4:1000. During the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, stirring was continued at a rate of 80 r / min and a stirring time of 60 min. Then, ultrasonic treatment was performed for 40 min to obtain the pretreated waste liquid.

[0043] (2) The pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, urea, zinc oxide, boric acid and manganese dioxide are added. The mass ratio of the pretreated waste liquid, algae limestone powder, urea, zinc oxide, boric acid and manganese dioxide is 1000:20:10:10:5. The waste liquid is stirred at a stirring rate of 120 r / min for 30 min to fully dissolve the algae limestone powder and alkaline salt to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

[0044] (3) The temperature in the reactor was controlled at 180°C and maintained for 16 hours. The liquid in the reactor was then irradiated with ultraviolet light using a xenon lamp light source for 2 hours. The stirring rate in the reactor was controlled at 120 r / min. The stirring was continued during the irradiation with the xenon lamp light source. The liquid in the reactor was then filtered through a filter with a pore size of 40 nm to obtain a pure treated liquid.

[0045] (4) The purified treated liquid is transported into a mixing tank, and L-cysteine, citric acid and humic acid are added thereto to supplement the nutrient elements of the waste liquid. The mass ratio of the purified treated liquid to L-cysteine, citric acid and humic acid is 1000:50:20:20. The stirring rate is controlled to be 1200 r / min and the stirring time is 30 min. Thus, a multifunctional liquid fertilizer is obtained by preparing tylosin waste liquid.

[0046] Example 7 In this embodiment, the multifunctional liquid fertilizer prepared in Examples 1 to 6 was subjected to tylosin residue detection. In step (3) of Examples 1 to 6, when the xenon lamp is started to irradiate with ultraviolet light, time intervals of 1 min, 5 min, 10 min, 20 min, 30 min, and 60 min are used. Samples are collected using a 0.45 μm needle filter and collected in a 1.5 mL brown sample bottle for HPLC testing. The original concentration is recorded as C0, the detected real-time concentration is recorded as C1, and the concentration ratio C1 / C0 is calculated.

[0047] Table 1 is a table showing the tylosin residue detection of the multifunctional liquid fertilizer prepared in Examples 1 to 4.

[0048] As can be seen from Table 1, in the data of Examples 1 to 5, when the waste liquid was sterilized by ultraviolet irradiation with a xenon lamp, tylosin was also rapidly degraded, while the content of tylosin in Examples 5 to 6 was substantially not reduced. In Example 6, step (1) did not add FeSO4·7H2O, and in Example 7, step (2) did not add Na2S2O3·5H2O. It is speculated that FeSO4·7H2O and Na2S2O3·5H2O were combined in the waste liquid to generate FeS2, which catalyzed the degradation of tylosin. Therefore, the multifunctional liquid fertilizer prepared by the present invention promoted the degradation of tylosin and prevented the residual tylosin from polluting the soil.

[0049] Although the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that all equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A process for preparing multifunctional liquid fertilizer from tylosin waste liquid, comprising pre-treating the tylosin waste liquid, adjusting pH, sterilizing and filtering, and preparing nutrients, characterized in that: The process for preparing multifunctional liquid fertilizer from tylosin waste liquid comprises the following steps: Step 1, pretreatment of tylosin waste liquid, placing the tylosin waste liquid in a high-speed centrifuge for high-speed centrifugation, adding activated carbon powder to adsorb insoluble impurities and microorganisms in the waste liquid, adding hydrogen peroxide solution to oxidize and sterilize the microorganisms in the waste liquid, adding FeSO4·7H2O to complex and aggregate protein precipitates in the solution, and using ultrasound to disperse the activated carbon and hydrogen peroxide more evenly in the waste liquid, so as to more completely adsorb impurities and inactivate microorganisms, thereby obtaining pretreated waste liquid; Step 2: adjusting the pH value of the pretreated waste liquid, transferring the pretreated waste liquid into a reactor, adding algae limestone powder, alkaline salt and Na2S2O3·5H2O, stirring to mix them evenly, neutralizing the acidic substances in the waste liquid, and obtaining a waste liquid after pH adjustment; Step 3: sterilize and filter the waste liquid after pH adjustment, control the temperature in the reactor and the stirring rate in the reactor, and filter the liquid in the reactor after stirring for a certain period of time to obtain a pure treated liquid; Step 4: prepare nutrients with the purified treated liquid. The purified treated liquid is transported into a preparation tank, and acidic substances are added to supplement the nutrients in the waste liquid while fixing the trace elements and metal elements. After stirring and mixing evenly, a multifunctional liquid fertilizer for preparing tylosin waste liquid is obtained.

2. A process for preparing multifunctional liquid fertilizer from a tylosin waste liquid according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide solution is 20% to 40%.

3. A process for preparing multifunctional liquid fertilizer from a tylosin waste liquid according to claim 1, characterized in that: The algae limestone powder is obtained by crushing the algae limestone with a crusher and passing through a 200-400 mesh sieve.

4. A process for preparing multifunctional liquid fertilizer from a tylosin waste liquid according to claim 1, characterized in that: The alkaline salt is at least one of urea, zinc oxide, boric acid and manganese dioxide.

5. A process for preparing multifunctional liquid fertilizer from a tylosin waste liquid according to claim 1, characterized in that: The reaction conditions of sterilization and filtration are as follows: heating the waste liquid after pH adjustment at 160-180° C. for 12-16 hours, irradiating it with ultraviolet light using a xenon lamp for 1.5-2 hours, and filtering the filter with a pore size of 20nm-40nm.

6. A process for preparing multifunctional liquid fertilizer from tylosin waste liquid according to claim 1, characterized in that: The acidic substance is at least one of L-cysteine, citric acid and fulvic acid.

7. A process for preparing multifunctional liquid fertilizer from tylosin waste liquid according to claim 1, characterized in that: In step 1, the tylosin waste liquid is pumped into a high-speed centrifuge, the centrifugal speed of the centrifuge is set to 10000r / min~13000r / min, the centrifugal time is 20~40min, the macromolecular substances in the waste liquid are transferred to the edge of the centrifuge by centrifugation, and after the centrifugation is completed, the supernatant in the centrifuge is transferred to a storage tank, and activated carbon powder is added thereto for adsorption, wherein the mesh number of the activated carbon powder is 200 meshes, and the mass ratio of the activated carbon powder to the supernatant is 3~5:100, and hydrogen peroxide solution is added to the microorganisms in the waste liquid. Oxidative sterilization, wherein the ratio of hydrogen peroxide solution to supernatant is 1:40~50, FeSO4·7H2O is added to complex and aggregate insoluble proteins in the solution, wherein the ratio of FeSO4·7H2O to supernatant is 3~4:800~1000, and continuous stirring is performed during the addition of activated carbon powder, hydrogen peroxide solution and FeSO4·7H2O, the stirring rate is 60r / min~80r / min, the stirring time is 30~60min, and then ultrasonication is performed for 20~40min to obtain the pretreated waste liquid.

8. A process for preparing multifunctional liquid fertilizer from tylosin waste liquid according to claim 1, characterized in that: In step 2, the pretreated waste liquid is transported into the reactor through an acid-resistant pipe, and algae limestone powder, alkaline salt and Na2S2O3·5H2O are added, wherein the mass ratio of the pretreated waste liquid, algae limestone powder, alkaline salt and Na2S2O3·5H2O is 800~1000:30~50:20~40:40~50, and the mixture is stirred at a stirring rate of 100r / min-120r / min for 30min~45min to fully dissolve the algae limestone powder, alkaline salt and Na2S2O3·5H2O to obtain a waste liquid after pH adjustment, thereby neutralizing the acidity of the waste liquid and making the pH of the waste liquid suitable for the environment required for plant growth.

9. A process for preparing multifunctional liquid fertilizer from a tylosin waste liquid according to claim 1, characterized in that: In step three, the temperature in the reactor is controlled at 160-180°C and maintained for 12-16 hours. The liquid in the reactor is then irradiated with ultraviolet light for 1.5-2 hours using a xenon lamp light source. The stirring rate in the reactor is controlled at 100 r / min-120 r / min. Stirring is continued during the irradiation with the xenon lamp light source. The liquid in the reactor is then filtered through a filter with a pore size of 20 nm to 40 nm to obtain a pure treated liquid.

10. A process for preparing multifunctional liquid fertilizer from tylosin waste liquid according to claim 1, characterized in that: In step 4, the pure treated liquid is transported into a mixing tank, and an acidic substance is added thereto to supplement the nutrient elements of the waste liquid, wherein the mass ratio of the pure treated liquid to the acidic substance is 800-1000:70-90, the stirring rate is controlled to be 800r / min-1200r / min, and the stirring time is 30-40min, to obtain a multifunctional liquid fertilizer prepared from tylosin waste liquid.

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