Innovative process for extracting effective components from tylosin waste liquid for liquid fertilizer

Abstract

The invention discloses an innovative process for extracting effective components from tylosin waste liquid for liquid fertilizer, and relates to the technical field of fertilizer preparation, and the innovative process comprises the steps of tylosin pretreatment, extraction separation, concentration purification and nutrition proportioning. On one hand, the ultrasonic cavitation effect can effectively break agglomerated particles possibly existing in the tylosin waste liquid, so that filtering is more sufficient and efficient, on the other hand, the polydopamine coating modified ceramic membrane can better intercept tiny impurity particles, meanwhile, the adsorption and blocking phenomena of impurities on the surface of the membrane are relieved, and the filtering efficiency is improved. Compared with a traditional pure physical filtering mode, the tylosin waste liquid treatment device has the advantages that suspended particles, colloids, part of macromolecular impurities and the like in the waste liquid can be more effectively removed, and the tylosin waste liquid is magnetized, so that the treatment efficiency is improved, and the treatment cost is reduced. The interaction between effective components of the tylosin and other subsequently available components and substances such as an extracting agent can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizer preparation, in particular to an innovative process for extracting effective components from tylosin waste liquid for use in liquid fertilizer. Background Art

[0002] Tylosin belongs to the macrolide antibiotics and is a veterinary antibiotic widely used in animal husbandry. It is mainly used to prevent and treat various bacterial diseases of livestock and poultry. It has a good preventive and therapeutic effect on mycoplasma infection and plays an important role in improving livestock and poultry breeding efficiency and ensuring animal health. In the production process of tylosin, a large amount of waste liquid will inevitably be generated. The composition of these waste liquids is complex. In addition to some incompletely reacted tylosin raw materials and intermediates in its synthesis process, it also contains a variety of organic substances, inorganic salts and other components. The waste liquid may contain a certain amount of sugars, protein degradation products and some metal ions introduced in the production process. At present, most tylosin production enterprises mainly adopt traditional treatment methods for the waste liquid they produce, including chemical oxidation method, biological treatment method, etc. The chemical oxidation method usually uses strong oxidants (such as ozone, hydrogen peroxide, etc.) to oxidize and decompose the organic pollutants in the waste liquid, converting them into relatively harmless small molecules, thereby achieving the purpose of reducing the concentration of pollutants in the waste liquid. However, although this method can reduce the pollution indicators such as the chemical oxygen demand (COD) of the waste liquid to a certain extent, the treatment cost is high and it will consume a lot of chemical agents. At the same time, some secondary pollutants that are difficult to further treat may be generated during the oxidation process. Biological treatment methods are mostly The organic components in the waste liquid are degraded by the metabolism of microorganisms, an activated sludge system is constructed, or a specific microbial flora is used for anaerobic or aerobic treatment. Although this method is relatively environmentally friendly, its treatment efficiency is often limited by multiple factors such as the growth environment and adaptability of the microorganisms. The treatment cycle is long, and some biologically toxic components in the waste liquid (such as a small amount of residual tylosin itself and its analogues) may inhibit the activity of microorganisms, resulting in unsatisfactory treatment effects. It is difficult to completely harmlessly treat the waste liquid and achieve effective recycling of resources. To this end, we propose an innovative process for extracting active ingredients from tylosin waste liquid for use in liquid fertilizer. Summary of the invention

[0003] The purpose of the invention is to provide an innovative process for extracting effective components from tylosin waste liquid for use in liquid fertilizer.

[0004] In order to solve the problems raised in the above background technology, the present invention provides the following technical solutions: an innovative process for extracting effective components from tylosin waste liquid for liquid fertilizer, including pretreatment, extraction and separation, concentration and purification of tylosin, and nutrient ratio. The specific operation steps of extracting effective components from tylosin waste liquid for liquid fertilizer are as follows: Step 1, collecting the tylosin waste liquid and performing ultrasonic filtration treatment, adjusting the pH value of the filtered waste liquid, transferring the adjusted waste liquid into a magnetizing device for magnetization treatment, and preparing the pre-treated waste liquid after completion; Step 2: Add a specific extractant to the pre-treated waste liquid, mix it and transfer it into a constant temperature oscillating extraction box. After the extraction is completed, let it stand for separation, collect the organic phase for later use, and treat the remaining aqueous phase for environmental protection; Step 3, transferring the collected organic phase into a rotary evaporator for concentration treatment, volatilizing the organic solvent to obtain a concentrated solution, adding modified activated carbon to the concentrated solution for treatment, stirring and mixing, and filtering to obtain a mixed liquid extract containing the active ingredient of tylosin; Step 4: Mix the mixed liquid extract, organic monoammonium phosphate, polyaspartic acid urea, natural plant-derived amino acid chelated trace element complex, potassium humate and deionized water, and mix and stir to obtain a liquid fertilizer product; Step 5: Conduct quality inspection on the finished liquid fertilizer, including tylosin active ingredient inspection, nutrient element content inspection, physical property inspection and fertilizer efficiency inspection, and put it into use after passing the inspection.

[0005] As a further scheme of the present invention: in the step 1, the waste liquid generated in the production process of tylosin is collected and transferred to a filtering device with an ultrasonic device, the working frequency of the ultrasonic device is set between 20kHz-40kHz, the power is 500W-1000W, and after ultrasonic treatment for 15min-30min, it is filtered through the filtering device, the filtering device is a surface-modified ceramic membrane, and its average particle size is 0.1um-0.2um. Before the filtering operation, the ceramic membrane is immersed in a Tris-HCl buffer solution containing dopamine hydrochloride, and the reaction is continuously stirred at room temperature for 12h-24h to obtain the waste liquid after preliminary filtration.

[0006] As a further solution of the present invention: In the step 1, the pH value of the waste liquid after preliminary filtration is adjusted, and a citric acid-sodium citrate buffer solution with a mass concentration of 10%-15% is slowly dripped into the waste liquid after preliminary filtration, and its pH value is monitored in real time, and the pH value of the waste liquid is adjusted to between 6.0 and 7.0. The acid-base equilibrium reaction equation of its buffering effect is as follows:

[0007] In wastewater As it increases, the reaction moves to the left. Combined consumption After the pH value adjustment is completed, the pretreated waste liquid is obtained.

[0008] As a further scheme of the present invention: in the step 2, a specific mixed extractant is prepared, which is composed of ethyl acetate, n-butanol and an ionic liquid, and the mixed extractant is added to the pretreated waste liquid, and the volume ratio of the mixed extractant to the pretreated waste liquid is controlled to be 1:2-3. After the mixed extractant and the pretreated waste liquid are mixed, they are transferred to a constant temperature oscillating extraction box, and the temperature of the constant temperature oscillating extraction box is set to 35°C-40°C, the oscillation frequency is 180r / min-240r / min, and the oscillation extraction operation duration is 40min-60min. During the oscillation extraction process, the functional groups in the molecular structure of tylosin interact with the anions and cations of the ionic liquid to dissolve it in the organic phase containing the ionic liquid.

[0009] As a further solution of the present invention: in the step 2, after the extraction is completed, the mixed system is transferred to a separating funnel for standing and stratifying operation, and the standing time is 25min-35min, so that the tylosin effective ingredient and the aqueous phase are fully separated. After the separation is completed, the organic phase floats on the upper layer, and after the layers are washed, the upper organic phase and the lower aqueous phase are collected for standby use, and the organic phase is collected for standby use, and the remaining aqueous phase is treated for environmental protection.

[0010] As a further solution of the present invention: In the step 3, the collected organic phase is transferred to a rotary evaporator for concentration treatment, and a new type of anti-violent boiling agent is added to the rotary evaporator, and the addition amount is 0.5%-1% of the mass of the organic phase. In the preparation process of nanoparticles, tetraethyl orthosilicate (TEOS) is used as a silicon source, and a hydrolysis and polycondensation reaction is carried out in an ethanol solution under the catalysis of ammonia water to prepare silicon dioxide nanoparticles. The specific reaction equation is as follows:

[0011] In the above reaction, ethyl orthosilicate is in the alkaline environment provided by amino acids, and ethoxy Hydrolysis reaction with water to generate hydroxyl groups After completion, the hydroxyl groups between adjacent molecules further undergo condensation reaction to gradually form a three-dimensional network structure of silica, and finally generate silica nanoparticles. The silica nanoparticles are dispersed in a toluene solution containing polyethylene glycol. Under the temperature condition of 80℃-100℃, the polyethylene glycol is grafted to the surface of the silica nanoparticles through the action of a silane coupling agent. After modification, the temperature of the rotary evaporator is set to 50℃-55℃, the vacuum degree is maintained at 0.08MPa-0.09MPa, and the rotary evaporation operation is performed at a rotation speed of 80r / min-100r / min to gradually volatilize the organic solvent in the organic phase until the volume of the remaining substance is 20%-25% of the original volume, thereby obtaining a concentrated solution.

[0012] As a further scheme of the present invention: in the step three, the activated carbon is immersed in a chitosan acetic acid solution with a mass concentration of 2%-5% for 2h-4h, and the chitosan is fully adsorbed on the surface of the activated carbon. After the immersion is completed, a solution containing metal ions is added, and the reaction is continued by stirring for 1h-2h. The modified activated carbon is taken out and added to the concentrated solution at a ratio of 6%-8% of the mass of the concentrated solution. The mixture is stirred at a temperature of 25°C and a stirring speed of 100r / min-120r / min for 30min-40min. After the stirring is completed, the mixture is filtered using a filtering device, and a polytetrafluoroethylene filter membrane of 0.22um-0.45um is selected as the filtering medium. The activated carbon and the adsorbed impurities are removed by vacuum filtration to obtain a mixed liquid extract containing the effective ingredient of tylosin.

[0013] As a further scheme of the present invention: in the step 4, 12-18 parts, 6-10 parts of organic monoammonium phosphate, 9-13 parts of polyaspartic acid urea, 4-6 parts of natural plant-derived amino acid chelated trace element complex and 6-10 parts of potassium humate are accurately weighed according to their mass fractions, added into a stirring device and stirred at a stirring rate of 50r / min-60r / min for 10min-15min, then the prepared deionized water is slowly added, the stirring rate is increased to 80r / min-100r / min, and stirring is continued for 30min-40min to fully disperse the components in the solution, and the addition of deionized water is stopped when the total volume of the liquid fertilizer reaches 100 parts to obtain a liquid fertilizer product.

[0014] As a further scheme of the present invention: in the step 5, the finished liquid fertilizer is weighed, placed in a centrifuge tube, centrifuged at a speed of 4000r / min-5000r / min for 10min-15min, the supernatant is transferred to a clean container, acetonitrile solution is added and vortexed for 1min-2min, and the nutrient element content, appearance, density and pH value thereof are detected. The nutrient element content includes nitrogen, phosphorus, potassium and trace elements. After the detection is completed, a fertilizer efficiency test is performed, and a suitable test plot is selected. According to scientific test layout methods such as random block design, the quality, safety and fertilizer efficiency of the finished liquid fertilizer are evaluated. After all the test indicators are qualified, the liquid fertilizer is put into use.

[0015] By adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are: The invention uses ultrasonic vibration to assist filtration. On the one hand, ultrasonic cavitation can effectively break the agglomerated particles that may exist in the tylosin waste liquid, so that the filtration is more sufficient and efficient. On the other hand, the ceramic membrane modified by the polydopamine coating can better intercept tiny impurity particles, and at the same time reduce the adsorption and clogging of impurities on the membrane surface, thereby improving the filtration flux and the service life of the membrane. Compared with the traditional simple physical filtration method, the invention can more effectively remove suspended particles, colloids and some macromolecular impurities in the waste liquid. By magnetizing the tylosin waste liquid, the interaction between the tylosin effective component and other subsequently available components and the extractant and other substances can be improved, and at the same time, the efficiency and effect of subsequent extraction and separation steps can be improved to a certain extent. By adding polyethylene glycol-modified silicon dioxide nanoparticles and chitosan-metal ion composite modified activated carbon in the concentration and purification step, the organic phase can be concentrated and purified more efficiently, more stably and more specifically, and the quality and quality of the final liquid fertilizer product can be further improved. The invention adopts a mixed extractant composed of ethyl acetate, n-butanol and a specific ionic liquid in the extraction and separation step, so as to enhance the extraction selectivity and efficiency of the effective components in the tylosin waste liquid, so that the target effective components are more inclined to be transferred from the aqueous phase to the organic phase. Compared with the traditional extraction method using only conventional organic solvents, the invention can extract the effective components of tylosin more accurately and efficiently, lay a solid foundation for the subsequent preparation of high-quality liquid fertilizer products, and also help to reduce the usage of organic solvents and the burden of subsequent treatment, thereby reducing the potential impact on the environment while improving the resource utilization efficiency. Through the waste liquid after magnetization treatment, the interaction between the effective components of tylosin and other subsequently available components and the extractant and other substances added subsequently can be significantly enhanced, so that these components are more easily transferred from the waste liquid system to the extraction phase in the subsequent extraction and separation step, thereby improving the efficiency and effect of subsequent steps such as extraction and separation to a certain extent, reducing the waste of resources caused by incomplete extraction, and also helping to optimize the time cost and resource input-output ratio of the entire process. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the process of preparing liquid fertilizer from tylosin waste liquid in an embodiment of the present invention. DETAILED DESCRIPTION

[0017] The specific embodiments of the present invention are further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0018] The present invention discloses an innovative process for extracting effective components from tylosin waste liquid for use in liquid fertilizer, comprising pretreatment of tylosin, extraction and separation, concentration and purification, and nutrient matching. The specific operation steps for extracting effective components from tylosin waste liquid for use in liquid fertilizer are as follows: Step 1, collecting the tylosin waste liquid and performing ultrasonic filtration treatment, adjusting the pH value of the filtered waste liquid, transferring the adjusted waste liquid into a magnetizing device for magnetization treatment, and preparing the pre-treated waste liquid after completion; Step 2: Add a specific extractant to the pre-treated waste liquid, mix it and transfer it into a constant temperature oscillating extraction box. After the extraction is completed, let it stand for separation, collect the organic phase for later use, and treat the remaining aqueous phase for environmental protection; Step 3, transferring the collected organic phase into a rotary evaporator for concentration treatment, volatilizing the organic solvent to obtain a concentrated solution, adding modified activated carbon to the concentrated solution for treatment, stirring and mixing, and filtering to obtain a mixed liquid extract containing the active ingredient of tylosin; Step 4: Mix the mixed liquid extract, organic monoammonium phosphate, polyaspartic acid urea, natural plant-derived amino acid chelated trace element complex, potassium humate and deionized water, and mix and stir to obtain a liquid fertilizer product; Step 5: Conduct quality inspection on the finished liquid fertilizer, including tylosin active ingredient inspection, nutrient element content inspection, physical property inspection and fertilizer efficiency inspection, and put it into use after passing the inspection.

[0019] In one embodiment of the present invention: in step 1, the waste liquid generated in the production process of tylosin is collected and transferred to a filtering device with an ultrasonic device, the working frequency of the ultrasonic device is set between 20kHz-40kHz, the power is 500W-1000W, and after ultrasonic treatment for 15min-30min, it is filtered through the filtering device, the filtering device is a surface-modified ceramic membrane, and its average particle size is 0.1um-0.2um. Before the filtering operation, the ceramic membrane is immersed in a Tris-HCl buffer solution containing dopamine hydrochloride, and the reaction is continuously stirred at room temperature for 12h-24h to obtain a waste liquid after preliminary filtration.

[0020] In one embodiment of the present invention: in step 1, the pH value of the waste liquid after preliminary filtration is adjusted, and a citric acid-sodium citrate buffer solution with a mass concentration of 10%-15% is slowly dripped into the waste liquid after preliminary filtration, and its pH value is monitored in real time, and the pH value of the waste liquid is adjusted to between 6.0-7.0. The acid-base equilibrium reaction equation of its buffering effect is as follows:

[0021] In wastewater As it increases, the reaction moves to the left. Combined consumption After the pH value adjustment is completed, the pretreated waste liquid is obtained.

[0022] In one embodiment of the present invention: in step 2, a specific mixed extractant is prepared, which is composed of ethyl acetate, n-butanol and an ionic liquid, and the mixed extractant is added to the pretreated waste liquid, and the volume ratio of the mixed extractant to the pretreated waste liquid is controlled to be 1:2-3. After the mixed extractant and the pretreated waste liquid are mixed, they are transferred to a constant temperature oscillating extraction box, and the temperature of the constant temperature oscillating extraction box is set to 35°C-40°C, the oscillation frequency is 180r / min-240r / min, and the oscillation extraction operation duration is 40min-60min. During the oscillation extraction process, the functional groups in the molecular structure of tylosin interact with the anions and cations of the ionic liquid to dissolve it in the organic phase containing the ionic liquid.

[0023] In one embodiment of the present invention: in step 2, after the extraction is completed, the mixed system is transferred to a separatory funnel for standing and stratifying operation, the standing time is 25min-35min, and the tylosin effective ingredient and the aqueous phase are fully separated. After the separation is completed, the organic phase floats on the upper layer, and after the layers are washed, the upper organic phase and the lower aqueous phase are collected for standby use, and the organic phase is collected for standby use, and the remaining aqueous phase is treated for environmental protection.

[0024] In one embodiment of the present invention: in step 3, the collected organic phase is transferred to a rotary evaporator for concentration treatment, and a new type of anti-violent boiling agent is added to the rotary evaporator, and the addition amount is 0.5%-1% of the mass of the organic phase. In the preparation process of nanoparticles, tetraethyl orthosilicate (TEOS) is used as a silicon source, and a hydrolysis and polycondensation reaction is carried out in an ethanol solution under the catalysis of ammonia water to prepare silicon dioxide nanoparticles. The specific reaction equation is as follows:

[0025] In the above reaction, ethyl orthosilicate is in the alkaline environment provided by amino acids, and ethoxy Hydrolysis reaction with water to generate hydroxyl groups After completion, the hydroxyl groups between adjacent molecules further undergo condensation reaction to gradually form a three-dimensional network structure of silica, and finally generate silica nanoparticles. The silica nanoparticles are dispersed in a toluene solution containing polyethylene glycol. Under the temperature condition of 80℃-100℃, the polyethylene glycol is grafted to the surface of the silica nanoparticles through the action of a silane coupling agent. After modification, the temperature of the rotary evaporator is set to 50℃-55℃, the vacuum degree is maintained at 0.08MPa-0.09MPa, and the rotary evaporation operation is performed at a rotation speed of 80r / min-100r / min to gradually volatilize the organic solvent in the organic phase until the volume of the remaining substance is 20%-25% of the original volume, thereby obtaining a concentrated solution.

[0026] In one embodiment of the present invention: in step three, the activated carbon is immersed in a chitosan acetic acid solution with a mass concentration of 2%-5% for 2h-4h, and the chitosan is fully adsorbed on the surface of the activated carbon. After the immersion is completed, a solution containing metal ions is added, and the reaction is continued by stirring for 1h-2h. The modified activated carbon is taken out and added to the concentrated solution at a ratio of 6%-8% of the mass of the concentrated solution. The mixture is stirred at a temperature of 25°C and a stirring speed of 100r / min-120r / min for 30min-40min. After the stirring is completed, the mixture is filtered using a filtration device, and a polytetrafluoroethylene filter membrane of 0.22um-0.45um is selected as the filter medium. The activated carbon and the adsorbed impurities are removed by vacuum filtration to obtain a mixed liquid extract containing the effective ingredient of tylosin.

[0027] In one embodiment of the present invention: in step 4, 12-18 parts, 6-10 parts of organic monoammonium phosphate, 9-13 parts of polyaspartic acid urea, 4-6 parts of natural plant-derived amino acid chelated trace element complex and 6-10 parts of potassium humate are accurately weighed according to the mass fractions, added into a stirring device and stirred at a stirring rate of 50r / min-60r / min for 10min-15min, then the prepared deionized water is slowly added, the stirring rate is increased to 80r / min-100r / min, and stirring is continued for 30min-40min to fully disperse the components in the solution, and the addition of deionized water is stopped when the total volume of the liquid fertilizer reaches 100 parts to obtain a finished liquid fertilizer.

[0028] In one embodiment of the present invention: in step five, the finished liquid fertilizer is weighed, placed in a centrifuge tube, centrifuged at a speed of 4000r / min-5000r / min for 10min-15min, the supernatant is transferred to a clean container, acetonitrile solution is added and vortexed for 1min-2min, and its nutrient content, appearance, density and pH value are detected. The nutrient content includes nitrogen, phosphorus, potassium and trace elements. After the detection is completed, a fertilizer efficiency test is performed, and a suitable test plot is selected. According to scientific test layout methods such as random block design, the quality, safety and fertilizer efficiency of the finished liquid fertilizer are evaluated. After all the test indicators are qualified, the liquid fertilizer is put into use.

[0029] In one embodiment of the present invention, in step 1, the ceramic membrane is immersed in a Tris-HCl buffer solution (pH 8.5, concentration 10 mmol / L) containing 2 g / L-5 g / L dopamine hydrochloride. During the continuous reaction, dopamine undergoes self-polymerization reaction on the surface of the ceramic membrane to form a polydopamine coating, wherein the chemical structure of dopamine is Under alkaline conditions, its amino group gradually loses protons, undergoes oxidative self-polymerization, and forms a polydopamine coating on the surface of the ceramic membrane through intermolecular cross-linking. This coating has good hydrophilicity, anti-pollution properties, and rich active functional groups.

[0030] In one embodiment of the present invention: in step 1, in the acid-base equilibrium reaction equation, when the waste liquid When it increases, and Combined with water, the reaction shifts to the right and releases , maintaining the pH value of the system stable.

[0031] In one embodiment of the present invention: in step 2, the ionic liquid constituting the mixed extractant is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonyl imide salt. When synthesizing the ionic liquid, in a dry reaction container, equimolar amounts of 1-chloroethyl-3-methylimidazolium hydrochloride and lithium bistrifluoromethanesulfonyl imide are dissolved in acetonitrile solvent, and nitrogen is continuously introduced, and the reaction is carried out at a temperature of 60° C. to 80° C. for 12 h to 24 h. After the reaction is completed, the acetonitrile solvent and the generated lithium chloride precipitate are removed by reduced pressure distillation to obtain a pure ionic liquid product.

[0032] Example Waste liquid generated in the tylosin production workshop was collected, 100 L was measured, and the waste liquid was transferred to a filtering device with an ultrasonic device. The working frequency of the ultrasonic device was set to 30 kHz, the power was set to 800 W, and the ultrasonic treatment was performed for 20 minutes. After that, the waste liquid was filtered through the filtering device. The filtering device used a surface-modified ceramic membrane with an average particle size of 0.15 um. Before the filtering operation, the ceramic membrane was immersed in a Tris-HCl buffer solution containing a concentration of 3 g / L dopamine hydrochloride, and the reaction was continuously stirred at room temperature for 18 hours to allow dopamine to undergo self-polymerization reaction on the surface of the ceramic membrane to form a polydopamine coating. After ultrasonic filtration, the waste liquid was filtered. After treatment, a preliminary filtered waste liquid is obtained, the above-mentioned preliminary filtered waste liquid is taken, a citric acid-sodium citrate buffer solution with a mass concentration of 12% is slowly dripped into the waste liquid, and its pH value is monitored in real time using a precision pH meter, and the pH value of the waste liquid is adjusted to 6.5 by dropwise adding the buffer solution. After the pH value adjustment is completed, a pretreated waste liquid is obtained, and the pretreated waste liquid with adjusted pH value is transferred to a magnetizing device, the magnetic field strength generated by the magnetizing device is 0.4T, and the waste liquid is controlled to pass through the pipe inside the magnetizing device at a flow rate of 15mL / min, so that it stays in the magnetic field for 8min, and the magnetization treatment is completed to obtain a pretreated waste liquid that can be used for the next step; A specific mixed extractant is prepared, which is composed of ethyl acetate, n-butanol and 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonyl imide salt (ionic liquid) in a volume ratio of 3:2:1, and the mixed extractant is added to the pretreated waste liquid, and the volume ratio of the mixed extractant to the pretreated waste liquid is controlled to be 1:2.5. After the two are mixed, they are transferred to a constant temperature oscillating extraction box, and the temperature of the constant temperature oscillating extraction box is set to 38°C, the oscillation frequency is 200r / min, and an oscillation extraction operation is performed. The duration is set to 50min. During the oscillation extraction process, the functional groups in the molecular structure of tylosin are The anions and cations of the ionic liquid interact through hydrogen bonds, π-π stacking, etc., so that the effective ingredient of tylosin is dissolved in the organic phase containing the ionic liquid. After the extraction is completed, the mixed system is transferred to a separatory funnel for static stratification operation. The static stratification time is 30 minutes, so that the organic phase and the aqueous phase containing the effective ingredient of tylosin are fully separated. At this time, the organic phase floats on the upper layer. After the layers are clear, the upper organic phase and the lower aqueous phase are collected separately for standby use, and the collected aqueous phase is transferred to a special environmental protection treatment equipment for subsequent environmental protection treatment. The collected organic phase is used for the next step of concentration and purification operation; The collected 30L organic phase was transferred to a rotary evaporator, and a new type of anti-violent boiling agent, polyethylene glycol-modified silica nanoparticles, was added to the rotary evaporator in an amount of 0.8% of the mass of the organic phase. The temperature of the rotary evaporator was set to 52°C, the vacuum degree was maintained at 0.085MPa, and the rotary evaporation operation was performed at a rotation speed of 90r / min to gradually evaporate the organic solvent in the organic phase until the volume of the remaining substance was 22% of the original organic phase volume, and a concentrated solution was obtained. At this time, the volume of the concentrated solution was about 6.6L. The activated carbon was immersed in a chitosan acetic acid solution with a mass concentration of 3% for 3 hours to allow the chitosan to be fully adsorbed on the surface of the activated carbon. After the immersion was completed, a solution containing (the concentration of the salt solution is 0.3 mol / L), continue to stir and react for 1.5 hours, take out the modified activated carbon, add the modified activated carbon to 6.6L of the concentrate at a ratio of 7% of the mass of the concentrate (about 0.462 kg, the density of the concentrate is 1 g / mL), stir at a temperature of 25°C and a stirring speed of 110 r / min for 35 minutes, so that the activated carbon and the concentrate are fully in contact, and the residual organic solvent, pigment and possible trace impurities in the concentrate are adsorbed and removed. After the stirring is completed, filter through a filter device, select a 0.3um polytetrafluoroethylene filter membrane, and use a vacuum filtration method (the vacuum degree is maintained at about 0.05 MPa) to remove the activated carbon and the adsorbed impurities, and obtain a relatively pure mixed liquid extract containing the active ingredient of tylosin, and the volume is about 6L, which is stored for later use; Accurately weigh each raw material according to the mass fraction, take 15 parts of the above mixed liquid extract (i.e., take 6L, density is 1g / mL, converted to a mass of 6kg, equivalent to 0.4kg per part), 8 parts of organic monoammonium phosphate (take 3.2kg), 11 parts of polyaspartic acid urea (take 4.4kg), 5 parts of natural plant-derived amino acid chelated trace element complex (take 2kg) and 8 parts of potassium humate (take 3.2kg), add these raw materials in turn into a stainless steel stirring tank with a stirring device, first turn on the stirring device, stir at a stirring rate of 55r / min for 12min, so that the raw materials are initially mixed evenly under relatively mild stirring conditions, then slowly add the prepared deionized water, continue stirring during the water addition process, and gradually increase the stirring speed to 90r / min, continue stirring for 35min, so that the components are fully dispersed, dissolved and interact with each other in the solution, until the total volume of the liquid fertilizer reaches 100 parts (total volume reaches 100L), and the liquid fertilizer product is obtained, which is sealed in barrels for standby use; Weigh 500 mL of liquid fertilizer product, place it in a centrifuge tube, centrifuge it at 4500 r / min for 12 min, take the supernatant and transfer it to a clean glass container, add an equal volume (i.e. 500 mL) of acetonitrile solution and vortex mix for 1.5 min to obtain the sample solution to be tested; Nutrient content testing, Nitrogen content detection: Dumas nitrogen determination method was used to accurately weigh 1g of the sample solution to be tested, wrapped in a tin foil boat, and placed in the automatic sampler of the Dumas nitrogen determination instrument for detection. The nitrogen content in the liquid fertilizer was measured to be 12.5%; Phosphorus content detection: Using inductively coupled plasma optical emission spectrometry (ICP-OES), take 10 mL of the sample solution to be tested, digest it with a mixed acid of nitric acid and perchloric acid (volume ratio of 4:1), and then adjust the volume to 100 mL. The diluted sample solution is introduced into the ICP-OES instrument for detection, and the phosphorus content is measured to be 6.8%; Potassium content detection: The ICP-OES method was also used. The sample pretreatment was the same as the digestion operation for phosphorus content detection. The potassium content was 8.2%; Trace element content detection (iron, zinc, manganese, boron, etc.): Using ICP-OES technology, the sample solution after the above digestion treatment is respectively tested for the intensity at the characteristic emission spectrum wavelength corresponding to each trace element. According to the standard curve method, the iron content is 150ppm, the zinc content is 80ppm, the manganese content is 60ppm, and the boron content is 30ppm; Physical property testing, Appearance and odor inspection: The color of the liquid fertilizer sample is light yellow, clear and transparent, without precipitation or suspended matter, and the odor is slightly sour, without abnormal pungent, rancid or other unpleasant odors. It is preliminarily judged that the appearance and odor of the finished liquid fertilizer meet the requirements; Density detection: Use a density meter to measure. Slowly put the density meter into the fully shaken liquid fertilizer sample. After it stabilizes, read the value displayed on the density meter. Repeat the measurement 3 times and take the average value as 1.1g / mL. pH value detection: Use a precision pH meter for detection. First, calibrate the pH meter with a pH standard buffer solution (pH 4.00, 6.86, 9.18 buffer solution), then insert the electrode into the fully stirred liquid fertilizer sample. After the reading stabilizes, record the pH value as 6.8, which is within the appropriate pH range (5.5-8.0) and meets the quality requirements of liquid fertilizer. Test the efficiency of qualified liquid fertilizers. A flat experimental field with an area of ​​about 1000m² was selected. The soil type was loam with medium and uniform fertility. According to the randomized block design method, the experimental field was divided into four treatment areas, each with an area of ​​250m 2 , respectively set to: Treatment 1 (application of the liquid fertilizer prepared by the present invention), treatment 2 (application of conventional commercially available liquid fertilizer) and treatment 3 (blank control without fertilizer application), each treatment was set up with 3 repetitions, the area of ​​each repetition area was about 83.3m², and a 1m wide isolation zone was set between the areas to prevent mutual interference; Before sowing, the soil in each treatment area was plowed and raked, and fertilization was performed according to the corresponding fertilizer application amount and fertilization method. In treatment 1, 50 L of the liquid fertilizer of the present invention was evenly spread on the soil surface and then shallowly turned into the soil. In treatment 2, the same amount of fertilizer was applied according to the recommended amount of commercially available liquid fertilizer. In treatment 3, no fertilizer was applied. After that, corn seeds were uniformly sown, and the sowing density, sowing depth, and subsequent irrigation, pest control and other farming operations were kept consistent in each treatment area; During the corn growth cycle, various growth indicators were regularly observed and recorded. The results are as follows: Seedling stage, The plant height, stem thickness and number of leaves of corn seedlings in each treatment area were measured 15 days and 30 days after sowing. The results are as follows: 15 days after sowing, The average height of corn seedlings in treatment 1 was 18 cm, the average height in treatment 2 was 15 cm, and the average height in treatment 3 was 12 cm. That is, the average height of corn seedlings in treatment 1 was 3 cm higher than that in treatment 2 and 6 cm higher than that in treatment 3. The average stem diameter of corn seedlings in treatment 1 was 2.2 mm, the average stem diameter in treatment 2 was 1.8 mm, and the average stem diameter in treatment 3 was 1.5 mm. Therefore, the average stem diameter was 0.4 mm thicker than that in treatment 2 and 0.7 mm thicker than that in treatment 3. The average number of leaves of corn seedlings in treatment 1 was 3.5, the average number of leaves in treatment 2 was 3, and the average number of leaves in treatment 3 was 2. The average number of leaves was 0.5 more than that in treatment 2 and 1.5 more than that in treatment 3. 30 days after sowing, The average height of corn seedlings in treatment 1 area reached 35 cm, the average height in treatment 2 area was 30 cm, and the average height in treatment 3 area was 22 cm. At this time, the average height of corn seedlings in treatment 1 area was 5 cm higher than that in treatment 2 area and 13 cm higher than that in treatment 3 area. The average stem diameter of corn seedlings in treatment 1 was 4.5 mm, the average stem diameter in treatment 2 was 3.8 mm, and the average stem diameter in treatment 3 was 3 mm. The average stem diameter was 0.7 mm thicker than that in treatment 2 and 1.5 mm thicker than that in treatment 3. The average number of leaves of corn seedlings in treatment 1 area was 6, the average number of leaves in treatment 2 area was 5, and the average number of leaves in treatment 3 area was 4. The average number of leaves was 1 more than that in treatment 2 area and 2 more than that in treatment 3 area. From jointing stage to tasseling stage, We continued to record the changes in corn plant height, stem thickness, number of leaves, leaf color, etc. and found that the corn plants in treatment 1 grew more vigorously, with dark green leaves. The plant height, stem thickness and other indicators continued to be better than those in treatment 2 and treatment 3. The difference with treatment 2 and treatment 3 gradually increased with the growth process. At the jointing stage (about 45 days after sowing), the average plant height of corn plants in treatment 1 reached 80 cm, the stem thickness reached 8 mm, and the number of leaves was about 10. The average plant height in treatment 2 was 70 cm, the stem thickness was 7 mm, and the number of leaves was 10. The average height of corn plants in treatment 3 was 55 cm, the stem thickness was 6 mm, and the number of leaves was 6. At the tasseling stage (about 70 days after sowing), the average height of corn plants in treatment 1 reached 180 cm, the stem thickness reached 18 mm, and the number of leaves was about 16. The leaves were large and dark green. The average height of corn plants in treatment 2 was 160 cm, the stem thickness was 15 mm, and the number of leaves was 14. The average height of corn plants in treatment 3 was 130 cm, the stem thickness was 12 mm, and the number of leaves was 12. The leaves were relatively narrow and slightly lighter in color. Maturity The corn yield-related indicators of each treatment area were counted, including the number of ears per unit area, the number of grains per ear, and the thousand-grain weight. After actual yield measurement, the average corn yield per mu in treatment area 1 reached 750 kg, the average yield per mu in treatment area 2 was 600 kg, and the average yield per mu in treatment area 3 was 400 kg. Through comparative analysis, it can be seen that the corn yield in treatment area 1, which was treated with the liquid fertilizer prepared by the present invention, was increased by 25% compared with treatment 2 (conventional commercially available liquid fertilizer), and was increased by 87.5% compared with blank control treatment 3; At the same time, at the time of harvest, corn samples were collected from each treatment area and sent to the laboratory for testing and analysis of corn kernel quality indicators, and the crude protein content, crude fat content, starch content, etc. of the kernels were measured. The results are as follows: Treatment 1 area: The average crude protein content of corn kernels was 10.5%, the average crude fat content was 4.8%, and the average starch content was 70%; Treatment 2 area: The average crude protein content of corn kernels was 9%, the average crude fat content was 4%, and the average starch content was 68%; Treatment 3 area: The average crude protein content of corn kernels was 8%, the average crude fat content was 3.5%, and the average starch content was 65%; Based on the above content, the quality indicators of corn kernels in treatment 1 area are also better than those in treatment 2 and 3 areas in terms of crude protein content, crude fat content, etc., which reflects the feasibility of extracting effective ingredients from tylosin waste liquid to prepare liquid fertilizer.

[0033] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the scope of protection of the present invention.

[0034] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0035] The above contents are merely examples and explanations of the present invention. Various modifications or additions to the specific embodiments described or replacements in similar ways by technicians in the technical field shall fall within the protection scope of the present invention as long as they do not deviate from the invention or exceed the scope defined by the claims.

[0036] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An innovative process for extracting effective ingredients from tylosin waste liquid for use in liquid fertilizer, comprising pretreatment, extraction and separation, concentration and purification of tylosin and nutrient matching, characterized in that: The specific operation steps of extracting active ingredients from tylosin waste liquid for use in liquid fertilizer are as follows: Step 1, collecting the tylosin waste liquid and performing ultrasonic filtration treatment, adjusting the pH value of the filtered waste liquid, transferring the adjusted waste liquid into a magnetizing device for magnetization treatment, and preparing the pre-treated waste liquid after completion; Step 2: Add a specific extractant to the pre-treated waste liquid, mix it and transfer it into a constant temperature oscillation extraction box, let it stand for separation after the extraction is completed, and collect the organic phase and the aqueous phase for later use; Step 3, transferring the collected organic phase into a rotary evaporator for concentration treatment, volatilizing the organic solvent to obtain a concentrated solution, adding modified activated carbon to the concentrated solution for treatment, and filtering after the treatment to obtain a mixed liquid extract containing the active ingredient of tylosin; Step 4: Mix the mixed liquid extract, organic monoammonium phosphate, polyaspartic acid urea, natural plant-derived amino acid chelated trace element complex, potassium humate and deionized water, and mix and stir to obtain a liquid fertilizer product; Step 5: Conduct quality inspection on the finished liquid fertilizer, including tylosin active ingredient inspection, nutrient element content inspection, physical property inspection and fertilizer efficiency inspection, and put it into use after passing the inspection.

2. An innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 1, the waste liquid generated in the production process of tylosin is collected and transferred to a filtering device with an ultrasonic device, the working frequency of the ultrasonic device is set between 20kHz and 40kHz, the power is 500W-1000W, and after ultrasonic treatment for 15min-30min, it is filtered through the filtering device, the filtering device is a surface-modified ceramic membrane, and its average particle size is 0.1um-0.2um. Before the filtering operation is performed, the ceramic membrane is immersed in a Tris-HCl buffer solution containing dopamine hydrochloride, and the reaction is continuously stirred at room temperature for 12h-24h to obtain the waste liquid after preliminary filtration.

3. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 1, the pH value of the waste liquid after preliminary filtration is adjusted, and a citric acid-sodium citrate buffer solution with a mass concentration of 10%-15% is slowly dripped into the waste liquid after preliminary filtration, and its pH value is monitored in real time, and the pH value of the waste liquid is adjusted to between 6.0 and 7.

0. The acid-base equilibrium reaction equation of its buffering effect is as follows: ； In wastewater As it increases, the reaction moves to the left. Combined consumption After the pH value adjustment is completed, the pretreated waste liquid is obtained.

4. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 2, a specific mixed extractant is prepared, which is composed of ethyl acetate, n-butanol and an ionic liquid. The mixed extractant is added to the pretreated waste liquid, and the volume ratio of the mixed extractant to the pretreated waste liquid is controlled to be 1:2-3. After the mixed extractant and the pretreated waste liquid are mixed, they are transferred into a constant temperature oscillating extraction box, and the temperature of the constant temperature oscillating extraction box is set to 35°C-40°C, the oscillation frequency is 180r / min-240r / min, and the oscillation extraction operation duration is 40min-60min. During the oscillation extraction process, the functional groups in the molecular structure of tylosin interact with the anions and cations of the ionic liquid to dissolve it in the organic phase containing the ionic liquid.

5. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 2, after the extraction is completed, the mixed system is transferred to a separating funnel for standing and stratifying operation, and the standing time is 25min-35min, so that the tylosin effective ingredient and the aqueous phase are fully separated. After the separation is completed, the organic phase floats on the upper layer, and after the layers are washed, the upper organic phase and the lower aqueous phase are collected for standby use, and the organic phase is collected for standby use, and the remaining aqueous phase is treated for environmental protection.

6. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 3, the collected organic phase is transferred to a rotary evaporator for concentration treatment, and a new type of anti-violent boiling agent is added to the rotary evaporator, and the addition amount is 0.5%-1% of the mass of the organic phase. In the preparation process of nanoparticles, tetraethyl orthosilicate (TEOS) is used as a silicon source, and a hydrolysis and polycondensation reaction is carried out in an ethanol solution under the catalysis of ammonia water to prepare silicon dioxide nanoparticles. The specific reaction equation is as follows: ； In the above reaction, ethyl orthosilicate is in the alkaline environment provided by amino acids, and ethoxy Hydrolysis reaction with water generates hydroxyl groups After completion, the hydroxyl groups between adjacent molecules further undergo condensation reaction to gradually form a three-dimensional network structure of silica, and finally generate silica nanoparticles. The silica nanoparticles are dispersed in a toluene solution containing polyethylene glycol. Under the temperature condition of 80℃-100℃, the polyethylene glycol is grafted to the surface of the silica nanoparticles through the action of a silane coupling agent. After modification, the temperature of the rotary evaporator is set to 50℃-55℃, the vacuum degree is maintained at 0.08MPa-0.09MPa, and the rotary evaporation operation is performed at a rotation speed of 80r / min-100r / min to gradually volatilize the organic solvent in the organic phase until the volume of the remaining substance is 20%-25% of the original volume, thereby obtaining a concentrated solution.

7. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step three, the activated carbon is immersed in a chitosan acetic acid solution with a mass concentration of 2%-5% for 2h-4h, and the chitosan is fully adsorbed on the surface of the activated carbon. After the immersion is completed, a solution containing metal ions is added, and the stirring reaction is continued for 1h-2h. The modified activated carbon is taken out and added to the concentrated solution at a ratio of 6%-8% of the mass of the concentrated solution. The mixture is stirred at a temperature of 25°C and a stirring speed of 100r / min-120r / min for 30min-40min. After the stirring is completed, the mixture is filtered using a filtering device, and a polytetrafluoroethylene filter membrane of 0.22um-0.45um is selected as the filtering medium. The activated carbon and the adsorbed impurities are removed by vacuum filtration to obtain a mixed liquid extract containing the effective ingredient of tylosin.

8. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 4, 12-18 parts, 6-10 parts of organic monoammonium phosphate, 9-13 parts of polyaspartic acid urea, 4-6 parts of natural plant-derived amino acid chelated trace element complex and 6-10 parts of potassium humate are accurately weighed according to the mass fractions, added into a stirring device and stirred at a stirring rate of 50r / min-60r / min for 10min-15min, then the prepared deionized water is slowly added, the stirring rate is increased to 80r / min-100r / min, and stirring is continued for 30min-40min to fully disperse the components in the solution, and the addition of deionized water is stopped when the total volume of the liquid fertilizer reaches 100 parts to obtain a finished liquid fertilizer.

9. The innovative process for extracting effective ingredients from tylosin waste liquid for use as liquid fertilizer according to claim 1, characterized in that: In the step 5, the finished liquid fertilizer is weighed, placed in a centrifuge tube, and centrifuged at a speed of 4000r / min-5000r / min for 10min-15min. The supernatant is transferred to a clean container, and acetonitrile solution is added and vortexed for 1min-2min. The nutrient element content, appearance, density and pH value are detected. The nutrient element content includes nitrogen, phosphorus, potassium and trace elements. After the detection is completed, a fertilizer efficiency test is performed, and a suitable test plot is selected. According to scientific test layout methods such as random block design, the quality, safety and fertilizer efficiency of the finished liquid fertilizer are evaluated. After all the test indicators are qualified, the liquid fertilizer is put into use.

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