Method for reinforcing treatment of aquaculture tail water and resource utilization

Abstract

The application discloses a method for strengthening treatment of aquaculture tail water and resource utilization. The method can treat aquaculture tail water with high nutrient elements, and can adapt to water quantity change and realize free combination treatment of nitrogen and antibiotic pollutants by using combined filler and microorganisms and algae.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of comprehensive treatment of eutrophic aquaculture wastewater, and particularly relates to a method for intensively treating aquaculture tail water and recycling. BACKGROUND

[0002] The Pearl River Delta region is a region with relatively large aquaculture pollution. Based on the current status of aquaculture and the requirements of precision agriculture, it is urgent to find a new aquaculture wastewater treatment technology that is low-cost, efficient and intelligent. Due to the regionalization and intensification of aquaculture, a large amount of wastewater is generated during the aquaculture process, which seriously pollutes the surrounding water body. In particular, tail water treatment faces three major problems. First, the treatment water volume is unstable, which is related to the aquaculture mode, and is easy to cause reactor blockage or loss of treatment capacity. Second, during long-term operation, the treatment efficiency of nitrogen and phosphorus is closely related to the cost; third, new pollutants such as disinfectants and antibiotics threaten the treatment effect.

[0003] Generally speaking, microorganisms are a relatively economical means of removing nitrogen, especially in the fields of aquaculture and waterfowl farming. The denitrification process includes ammonia oxidation, nitrification, denitrification, and anaerobic ammonia oxidation processes. How to stably combine several microorganisms is also a difficulty in removing nitrogen. Phosphorus removal is also achieved by the intracellular superaccumulation of phosphorus by microorganisms, and the removal of organisms. The removal of traditional biological and physicochemical technologies consumes energy on the one hand, and further maintains the activity of microorganisms and deep treatment to achieve efficient removal of nitrogen and phosphorus elements. The ordered superposition or cooperation of multiple microorganisms is the key to tail water treatment. In addition, antibiotics in aquaculture tail water are a threat to the safety of the water environment. Therefore, further treatment is also required. Due to the characteristics of large water volume, rich pollutants and large concentration fluctuations of aquaculture tail water, intensive treatment is required. SUMMARY

[0004] The present application solves the problems existing in the prior art, and provides a method for intensively treating aquaculture tail water and recycling. The present application adopts the preparation of hydrated glue and porous material to meet the treatment under the condition of large hydraulic load of tail water treatment, and has the effects of efficient pollutant interception and microbial adhesion, so as to achieve good treatment effect.

[0005] The present application provides a method for intensively treating aquaculture tail water and recycling, which comprises the following steps:

[0006] (1) The pulverized chestnut shell is passed through 10-20 mesh, and hydrochloric acid is added to the chestnut shell for treatment. After washing and drying, the chestnut shell carbon conversion substrate T0 is obtained. The washed chestnut shell can release carbon source for a long time and can be used as a substrate for microorganisms in tail water treatment. The breeding tail water is coarsely filtered and centrifuged after 5-15 mesh, and the concentrated liquid is obtained by suction filtration, and the precipitate is collected. The precipitate is transferred to the A0 liquid medium, and cultured at room temperature for 5-6 days to obtain the preliminary culture A. After dilution and centrifugation of the preliminary culture A, the collected preliminary culture A precipitate is inoculated into the mixture of A0 liquid medium and chestnut shell carbon conversion substrate T0. The mixture is added at a ratio of 40-60 g per liter of preliminary culture A precipitate, and continuously cultured for 5-7 days under stirring. The removal rate of COD is monitored until the COD removal rate reaches more than 90%, and the biomass on the chestnut shell is measured to reach 0.8-2 g of microorganisms per 100 g of chestnut shell, which is the end of the culture. The chestnut shell loaded with microorganisms is obtained.

[0007] (2) After the pulverized chestnut shell is passed through 200-300 mesh, anhydrous ether is added at a mass-volume ratio of 1:2-4 to extract for 6-8 h. Then anhydrous ethanol is added, and the chestnut shell is soaked and extracted with anhydrous ethanol at a mass-volume ratio of 1:0.5-1.5 for 3-5 h to remove proteins, and then decolorized with activated carbon to obtain a chestnut shell solution. The chestnut shell solution is extracted by microwave at 200-600 W, ultrasonic at 100-200 W, temperature at 60℃-90℃, and time at 80-160 min. Then the solution is cooled to room temperature, and the cycle of microwave and ultrasonic extraction is repeated 2-3 times. The supernatant and the precipitate are separated to obtain the attached filler T1 of deaminase and ammonia-oxidizing microorganisms. The supernatant contains a large amount of polysaccharides, which can be further utilized. After the remaining chestnut shell removes most of the organic matter, the pores are expanded, and the remaining carbon source of the chestnut shell can be further removed. The chestnut shell after removing proteins and organic matter can increase the adsorption of nitrogen and trace carbon sources such as antibiotics, and provide a basis for culturing microorganisms that remove trace carbon sources such as antibiotics.

[0008] The aquaculture tail water is treated by 5-15 mesh coarse filtration and centrifugation, and then concentrated liquid is obtained by suction filtration, and the precipitate is collected and transferred to A0 liquid medium for culture at room temperature for 5-6 days to obtain preliminary culture B. After dilution and centrifugation of the preliminary culture B, the precipitate of the preliminary culture B is inoculated into a mixture of A1 liquid medium and attached filler T1 of deaminated nitrogen and ammonia-oxidizing microorganisms, and the mixture is added at a proportion of 100-200 g per liter of the precipitate of the preliminary culture B, so that the dissolved oxygen is not less than 2-3 mg / L, and the culture is continuously cultured at 250-300 rpm for 5-7 days, and the ammonia nitrogen concentration of the supernatant is determined every 3-5 days. If the ammonia nitrogen degradation efficiency reaches more than 90% and the nitrate generation rate reaches more than 50%, an aerobic ammonia oxidation culture loaded microbial filler B1 of chestnut shell is obtained. Half of the microbial filler B1 is taken out, and the above-mentioned A1 liquid medium is replaced with an equal volume of A2 liquid medium, and the culture is stirred under non-aeration conditions to make the dissolved oxygen less than 0.5-1.0 mg / L, and the attached filler T1 of deaminated nitrogen and ammonia-oxidizing microorganisms is added, and the culture is cultured for 1-2 weeks under the above-mentioned culture conditions, and the ammonia nitrogen concentration and nitrate of the supernatant are determined every 5 days. If the nitrate degradation efficiency reaches more than 90% and the cumulative increase rate of ammonia nitrogen is less than 30%, a denitrification culture loaded microbial filler B2 of chestnut shell is obtained.

[0009] (3) Chlorella is cultured with A3 liquid medium, and the supernatant is irradiated for 12 hours every day, and the ammonia nitrogen concentration of the supernatant is determined every 5 days. If the ammonia nitrogen degradation efficiency reaches more than 90%, the A3 liquid medium is replaced by centrifugation, and the algal microbial filler B3 is continuously cultured for 3 cycles to obtain the algal microbial filler B3.

[0010] (4) The microbial filler A loaded chestnut shell obtained in step (1) is used as a first module; the aerobic ammonia oxidation culture loaded microbial filler B1 of chestnut shell obtained in step (2) is resuspended in liquid medium A1, and polyvinyl alcohol is added to the A1 liquid medium at a mass concentration of 3%-6% per liter; 100-500 mg of sodium bicarbonate is added, and then a solution of boric acid with a mass fraction of 1%-2% and calcium chloride with a mass fraction of 2%-5% is added to form small balls as a second module; the denitrification culture loaded microbial filler B2 of chestnut shell obtained in step (2) is resuspended in A2 liquid medium, and polyvinyl alcohol is added to the A2 liquid medium at a mass concentration of 5%-7% per liter; 100-500 mg of glucose is added, and the mixture is thoroughly mixed; finally, a solution of boric acid with a mass fraction of 1%-2% and calcium chloride with a mass fraction of 2%-5% is added dropwise to form small balls as a third module; the microbial filler B3 is resuspended in A3 liquid medium, and polyvinyl alcohol is added to the A3 liquid medium at a mass concentration of 5%-7% per liter; 100-500 mg of glucose is added as a fourth module.

[0011] The A0 liquid culture medium: NaNO3 1500mg / L, K2HPO4 0.04mg / L, MgSO4 7H2O 75mg / L, CaCl2 2H2O 36mg / L, sodium acetate 6mg / L, EDTA 1mg / L, Na2CO3 20mg / L;

[0012] The A1 liquid culture medium: in 1L water, add NH4Cl 0.1g, NaHCO3 0.2g, adjust pH to about 7.0-7.5 with NaHCO3, and add 1%-5% zeolite powder with a mesh of 200, soak with 10% hydrochloric acid by volume, then wash and use;

[0013] The A2 liquid culture medium: in 1L water, add NH4Cl 0.1g, NaHCO3 0.2g, adjust pH to about 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamide and tetracycline with a mass ratio of 1:1:1, the mass concentration of the mixture is 1-10mg / L, and add 1%-5% zeolite powder and 1-5% sponge iron powder;

[0014] The A3 liquid culture medium: in 1L water, add NH4Cl 0.1g, NaHCO3 1g, adjust pH to about 7.5-8.0 with NaHCO3.

[0015] (5) The first module (first layer), the second module (second layer), the third module (third layer) and the fourth module (fourth layer) described in step (4) are sequentially added to the reactor, and the mass ratio of the first module, the second module, the third module and the fourth module in the reactor is 4-6:1-3:1-3:1, and the breeding tail water is introduced to sequentially pass through the first module, the second module, the third module and the fourth module for continuous operation for treatment, so that the tail water is discharged up to standard.

[0016] The first part of the application uses chestnut shell as the substrate, adds slow-release carbon source and microbial wrapping to form the filler. The active filler is composed of different types of microorganisms to realize the simultaneous treatment of carbon and nitrogen in the tail water. The second part uses the remaining chestnut shell substrate after the extraction of functional products as the filler for subsequent low-nitrogen carbon simultaneous conversion.

[0017] Preferably, the solid-liquid ratio of chestnut shell to hydrochloric acid in step (1) is 1:8-10, and the volume fraction of hydrochloric acid is 8%-12%.

[0018] Preferably, the mass ratio of A0 liquid culture medium to chestnut shell carbon conversion substrate T0 in step (1) is 20:1-30:1.

[0019] Preferably, the chestnut shell solution is extracted by adding anhydrous ether in a mass-volume ratio of 1:3 for 7 hours, then adding anhydrous ethanol in a mass-volume ratio of 1:1 for 4 hours, and decolorizing with activated carbon.

[0020] Preferably, the mass ratio of A1 liquid medium to the attached filler T1 of deaminated nitrogen and ammonia-oxidizing microorganisms in step (2) is 1:100-1:200.

[0021] Preferably, the chestnut shell solution is extracted by microwave 400W, ultrasonic 150W, temperature 75℃, for 120 minutes, then cooled to room temperature, and then extracted by microwave and ultrasonic for 2-3 times, and the supernatant and precipitate are separated to obtain the attached filler T1 of deaminated nitrogen and ammonia-oxidizing microorganisms.

[0022] Preferably, the A1 liquid medium in step (4) is prepared by adding 0.1g of NH4Cl and 0.2g of NaHCO3 in 1L of water, adjusting the pH to about 7.0-7.5 with NaHCO3, and adding 3% zeolite powder with a mesh size of 200, then soaking with 10% hydrochloric acid, and then washing and waiting for use.

[0023] The A2 liquid medium is prepared by adding 0.1g of NH4Cl and 0.2g of NaHCO3 in 1L of water, adjusting the pH to about 7.0-7.5 with NaHCO3, and adding a mixture of ciprofloxacin, sulfonamide and tetracycline in a mass ratio of 1:1:1, the mass concentration of the mixture is 5mg / L, and 3% zeolite powder and 3% sponge iron powder are added.

[0024] Preferably, the mass ratio of the first module, the second module, the third module and the fourth module in step (5) is 5:2:2:1.

[0025] In order to construct a three-dimensional filler, the present application uses microorganisms and agricultural waste chestnut shell to prepare a biological filler, which is wrapped in a skeleton material, realizes the cooperation of different size biological fillers and different microorganisms, and can realize the maximum utilization of the filler. By utilizing the characteristics of microorganisms and different oxygen gradient utilization, the microorganisms and the filler are combined in layers to form a composite biological filler, and the controlled reaction of nitrogen transformation is realized. Especially in the filler, different types of microorganisms are filled in multiple layers to complete the assembly of microbial community and realize multiple treatment functions.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] 1、The method can process higher nutrient element aquaculture tail water, and can adapt to water volume change and realize free combination type treatment of nitrogen and antibiotic pollutants by using combined filler and microorganisms and algae.

[0028] 2、The method can adapt to different pollutant conditions of wastewater treatment capacity, realize organic combination of microorganisms and filler, strengthen aquaculture tail water treatment, use modified chestnut shells, and establish multiple layers of filler with different microorganisms, and can be recycled by algae. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 For the operation of COD and ammonia nitrogen in Example 1 and Comparative Example 1;

[0030] Figure 2 For the removal of total phosphorus and norfloxacin in Example 1 and Comparative Example 1;

[0031] Figure 3 For the comparison of the two processes for treating aquaculture tail water in Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0032] The following examples are further illustrations of the present application and are not intended to limit the present application.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present application. Unless otherwise specified, the experimental materials and reagents in this paper are commonly used in the art.

[0034] A method for strengthening aquaculture tail water treatment and resource utilization, comprising the following steps:

[0035] (1) Carbon and nitrogen conversion filler T0 preparation: crush the chestnut shells, select the crushed ones with a particle size of 10-20 mesh, wash the filler with tap water, then add 8000-10000 mL of hydrochloric acid (1:9 by volume, hydrochloric acid: pure water) per 1000 g of chestnut shells for internal treatment to obtain more cavities, then add clean water for washing, then centrifuge and wash the carbon conversion substrate T0 of the chestnut shells clean, and wait for use. The washed chestnut shells can release carbon source for a long time, and can be used as a substrate for microorganisms in tail water treatment.

[0036] (2) Preparation of ammonia-removing and ammonia-oxidizing microbial attached filler T1: To realize simultaneous ammonia oxidation and denitrification, different oxygen gradients need to be distributed according to certain rules.

[0037] First, the pulverized chestnut shell is selected to pass 200-300 mesh, and the filler is washed with tap water and then dried for use. Add anhydrous ether to the ratio of 1:2-4 (m / v) for Soxhlet extraction for 6-8 hours to remove fat, then use anhydrous ethanol as the solvent, soak for 3-5 hours at a mass concentration of 0.5-1.5 g / mL to remove protein, and decolorize with activated carbon. The part of the chestnut shell powder can be used as an attached filler for deaminase nitrogen and ammonia-oxidizing microorganisms.

[0038] Then, the chestnut shell solution after activated carbon decolorization treatment is placed in a container, and the extraction time is 80-160 min under microwave 200-600 W, ultrasonic 100-200 W, and temperature control at 60-90°C. Then, after cooling to room temperature, the cycle is repeated 2-3 times, and the supernatant and precipitate are separated. The precipitate is the attached filler T1 of deaminase nitrogen and ammonia-oxidizing microorganisms. The supernatant contains a large amount of polysaccharides, which can be further utilized. After the remaining chestnut shell removes most of the organic matter, the pore is expanded, and the remaining carbon source of the chestnut shell can be further removed. The chestnut shell after removing protein and organic matter can increase the adsorption of nitrogen and trace carbon sources such as antibiotics, providing a basis for cultivating microorganisms that remove trace carbon sources such as antibiotics.

[0039] (3) Cultivation of tail water treatment microorganisms (cultivation and acquisition of carbon removal microorganisms; cultivation and acquisition of ammonia-oxidizing microorganisms).

[0040] a. Cultivation and acquisition of carbon removal microorganisms: The carbon removal used for aquaculture tail water treatment can be screened from wastewater. First, 20-40 L of aquaculture tail water is obtained, and suspended solids and large plankton are removed by 5-15 mesh coarse filtration and 5000 rpm centrifugation. The concentrated solution is obtained by further 0.22 μm filtration, and the precipitate is collected on the filter membrane and transferred to A0 liquid medium. The preliminary culture A is obtained after 5-6 days of cultivation at 25°C. Due to the instability of COD and water volume of tail water, the carbon removal microorganisms cultured in this stage need to be cultured with fixed carbon source for pre-screening.

[0041] The preliminary culture A is diluted and centrifuged at 5000 r / min, and the precipitate is inoculated into the mixture of A0 liquid medium and chestnut shell carbon conversion substrate T0. The mixture is added at a ratio of 40-60 g per liter of preliminary culture A, and the mixture is continuously cultured for 5-7 days under stirring at 250-300 rpm. The removal rate of COD is monitored, which is stably increased from 60% at the beginning to more than 90%, and the biomass on the chestnut shell is measured (using microbial protein determination), obtaining 0.4-1 g / 50 g of microbial biomass as the end of cultivation, obtaining carbon removal microorganisms. The chestnut shell and the grown microorganisms are harvested for use, which is a chestnut shell loaded microbial filler A.

[0042] b. Carbon source and nitrogen synchronous degradation microorganism acquisition: Carbon removal used in aquaculture tail water treatment can be screened from wastewater. First, 20-40 L of aquaculture tail water is obtained, suspended solids and large plankton are removed by 10 mesh coarse filtration and 5000 rpm centrifugation, and a concentrated solution is obtained by further 0.22 μm filtration. The precipitate is collected on the filter membrane, transferred to A0 liquid medium, and cultured at 25°C for 5-6 days to obtain preliminary culture B, which is used to culture B1 and B2 below.

[0043] After dilution and 5000 rpm centrifugation, the preliminary culture B can be collected and inoculated into a mixture of A1 liquid medium and attached filler T1 of deaminating nitrogen and ammonia-oxidizing microorganisms. The mixture is added at a ratio of 100-200 g per liter of culture, and the dissolved oxygen is not less than 2-3 mg / L. Under 250-300 rpm stirring, it is continuously cultured for 5-7 days, and the supernatant ammonia nitrogen concentration is measured every 3-5 days. If the ammonia nitrogen degradation efficiency reaches more than 90%, and the nitrate generation rate reaches more than 50%, it is the microbial filler B1 of chestnut shell loaded with aerobic ammonia oxidation culture.

[0044] Then half of the microbial filler B1 is taken out, and the above-mentioned A1 liquid medium is replaced with an equal volume of A2 liquid medium. Under non-aeration conditions, the dissolved oxygen is less than 0.5-1.0 mg / L, and the attached filler T1 of deaminating nitrogen and ammonia-oxidizing microorganisms is added. Under the above-mentioned culture conditions, it is cultured for 1-2 weeks, and the supernatant ammonia nitrogen concentration and nitrate are measured every 5 days. If the nitrate degradation efficiency reaches more than 90%, and the ammonia nitrogen cumulative rate (increase rate) is less than 30%, it is the microbial filler B2 of chestnut shell loaded with denitrification culture.

[0045] c. Cultivation of algal microbial filler: Algae can be used to improve resource utilization efficiency. Chlorella can be purchased and cultured with A3 liquid medium. After rejuvenation, the purchased Chlorella is cultured with A3 liquid medium, with 12 hours of light per day, and the supernatant ammonia nitrogen concentration is measured every 5 days. If the ammonia nitrogen degradation efficiency reaches more than 90%, the A3 liquid medium is replaced by centrifugation, and the algal microbial filler B3 is obtained by continuous culture for 3 cycles.

[0046] (4) Preparation of bioactive filler:

[0047] S1, load the microbial filler A of chestnut shell into a mesh bag with a void of 1-2 mm, and place it in the first layer, i.e. the first module, of the tail water treatment;

[0048] S2, the aerobic ammonia oxidation culture loaded chestnut shell microbial filler B1 is configured in the following manner. The aerobic ammonia oxidation culture loaded chestnut shell microbial filler B1 is resuspended in A1 liquid medium, and polyvinyl alcohol is added to a mass concentration of 3%-6% per liter of the A1 liquid medium; 100-500 mg of sodium bicarbonate is added; then a solution of boric acid with a mass fraction of 1%-2% and calcium chloride with a mass fraction of 2%-5% is added to form a pellet as a second module.

[0049] S3, the denitrification culture loaded chestnut shell microbial filler B2 is configured in the following manner. The denitrification culture loaded chestnut shell microbial filler B2 is resuspended in A2 liquid medium, and polyvinyl alcohol is added to a mass concentration of 5%-7% per liter of the A2 liquid medium; 100-500 mg of glucose is added and mixed thoroughly; finally, a solution of boric acid with a mass fraction of 1%-2% and calcium chloride with a mass fraction of 2%-5% is dripped through a pipe with a diameter of 1 cm to form a pellet as a third module.

[0050] S4, the microbial filler B3 is configured in the following manner. The microbial filler B3 is resuspended in A3 liquid medium, and polyvinyl alcohol is added to a mass concentration of 5%-7% per liter of the A3 liquid medium; 100-500 mg of glucose is added as a fourth module.

[0051] Step (1) The solid-liquid ratio of chestnut shell to hydrochloric acid is 1:8-10, and the volume fraction of hydrochloric acid is 8%-12%; the mass ratio of A0 liquid medium to chestnut shell carbon conversion substrate T0 is 20:1-30:1.

[0052] In the following examples, it is preferred that in step (2), anhydrous ether is added in a mass-volume ratio of 1:3 of chestnut shell to anhydrous ether for extraction for 7 h, then anhydrous ethanol is added, and the chestnut shell solution is obtained by soaking in anhydrous ethanol for 4 h in a mass-volume ratio of 1:1 of chestnut shell to anhydrous ethanol and decolorizing with activated carbon.

[0053] In the following examples, it is preferred that in step (2), the mass ratio of A1 liquid medium to the attached filler T1 of deaminated nitrogen and ammonia oxidation microorganisms is 1:100-1:200. The chestnut shell solution is extracted by microwave at 400 W and ultrasonic at 150 W at a temperature of 75℃ for 120 min, then cooled to room temperature, and then extracted by microwave and ultrasonic for 2-3 times, and the supernatant and precipitate are separated to obtain the attached filler T1 of deaminated nitrogen and ammonia oxidation microorganisms.

[0054] Medium composition:

[0055] A0 liquid medium: NaNO3(1500mg / L), K2HPO4(0.04), MgSO4 7H2O(75mg / L), CaCl2 2H2O(36mg / L), NaAc(6mg / L), EDTA(1mg / L), Na2CO3(20mg / L).

[0056] A1 liquid medium: NH4Cl 0.1g, NaHCO3 0.2g, adjust pH to about 7.0-7.5 with NaHCO3, and add 1%-5% zeolite powder, zeolite powder, use purchased powder, pass 200 mesh, use 1:9 hydrochloric acid soaking treatment, then wash and use.

[0057] A2 liquid medium: NH4Cl 0.1g, NaHCO3 0.2g, adjust pH to about 7.0-7.5 with NaHCO3, and add 1%-5% zeolite powder, 1-5% sponge iron powder.

[0058] A3 liquid medium: NH4Cl 0.1g, NaHCO3 1g, adjust pH to about 7.5-8.0 with NaHCO3.

[0059] (5) the first module, the second module, the third module and the fourth module of step (4) are sequentially added into the reactor, the mass ratio of the first module, the second module, the third module and the fourth module in the reactor is 4-6:1-3:1-3:1, and the breeding tail water is introduced to sequentially pass through the first module, the second module, the third module and the fourth module for continuous operation to process the tail water to meet the discharge standard.

[0060] In the following examples, the mass ratio of the first module, the second module, the third module and the fourth module is preferably 5:2:2:1.

[0061] Example 1

[0062] A method for strengthening and treating breeding tail water and recycling, comprising the following steps:

[0063] (1) Microbial filler A loaded with chestnut shell preparation: The chestnut shell is crushed, and the crushed one is selected to pass through 10 mesh. The filler is washed with tap water, then 9000 mL of hydrochloric acid (10% by volume, hydrochloric acid: pure water = 1:9) is added for internal treatment per 1000 g of chestnut shell to obtain more cavities, then clean water is added for washing, and then the chestnut shell carbon conversion substrate T0 is washed clean by centrifugation. The aquaculture tail water is coarsely filtered through 10 mesh and treated by centrifugation, and then the concentrated liquid is obtained by suction filtration. The precipitate is collected and transferred to the A0 liquid medium. The preliminary culture A is obtained by culturing at room temperature for 5 days. The preliminary culture A is diluted and treated by centrifugation. The collected preliminary culture A precipitate is inoculated into a mixture of A0 liquid medium and chestnut shell carbon conversion substrate T0. The mass ratio of A0 liquid medium to chestnut shell carbon conversion substrate T0 is 25:1. The mixture is added at a ratio of 50 g per liter of preliminary culture A precipitate. The mixture is continuously cultured for 5-7 days under stirring. The COD removal rate is monitored until the COD removal rate reaches more than 90%, and the biomass on the chestnut shell reaches 1.4 g of microorganism per 100 g of chestnut shell. The culture is ended, and the microbial filler A loaded with chestnut shell is obtained.

[0064] (2) Preparation of deaminase nitrogen and ammonia oxidizing microbial attached filler T1: First, the chestnut shell is crushed, and the crushed one is selected to pass through 200 mesh. The filler is washed with tap water and then dried for use. Anhydrous diethyl ether is added at a ratio of 1:3 (m / v) for Soxhlet extraction for 7 h to remove fat. Then, anhydrous ethanol is used as a solvent to soak and extract for 4 h at a mass concentration of 1 g / mL to remove protein, and activated carbon is used for decolorization. Then, the chestnut shell solution after activated carbon decolorization treatment is placed in a container. The extraction temperature is controlled at 75°C under microwave 400W and ultrasonic 150W. The extraction time is 120 min. Then, after cooling to room temperature, the step is recycled twice. The supernatant and precipitate are separated, and the precipitate is the deaminase nitrogen and ammonia oxidizing microbial attached filler T1.

[0065] (3) Preparation of microbial fillers B1-B3

[0066] a. Carbon source and nitrogen synchronous degradation microorganism acquisition: 30 L of aquaculture tail water is coarsely filtered through 10 mesh and centrifuged at 5000 rpm to remove suspended solids and large plankton. The concentrated liquid is obtained by further suction filtration through a 0.22 μm filter membrane. The precipitate is collected and transferred to the A0 liquid medium. The preliminary culture B is obtained by culturing at 25°C for 5 days. It is used to culture B1 and B2 below.

[0067] The preliminary culture B is diluted, a certain amount is sucked, and the precipitate is collected after centrifugation at 5000 r / min, and then inoculated into a mixture of A1 liquid medium and attached filler T1 of deaminating nitrogen and ammonia-oxidizing microorganisms, the mass ratio of A1 liquid medium to attached filler T1 of deaminating nitrogen and ammonia-oxidizing microorganisms is 1:150, and the mixture is added in a proportion of 150 g per liter of culture, so that the dissolved oxygen is not less than 2-3 mg / L, and the culture is continuously cultured under stirring at 250 rpm for 6 days, and the ammonia nitrogen concentration of the supernatant is determined every 3-5 days. If the ammonia nitrogen degradation efficiency reaches more than 90% and the nitrate generation rate reaches more than 50%, it is the microbial filler B1 of chestnut shell loaded with aerobic ammonia oxidation culture.

[0068] Then half of the microbial filler B1 is taken out, replaced with an equal volume of A2 liquid medium, and cultured under stirring with dissolved oxygen less than 0.5-1 mg / L without aeration, and deaminating nitrogen and ammonia-oxidizing microbial attached filler T1 is added, and cultured for 1-2 weeks under the above culture conditions, and the ammonia nitrogen concentration and nitrate in the supernatant are determined every 5 days. If the nitrate degradation efficiency reaches more than 90% and the cumulative rate (increase rate) of ammonia nitrogen is less than 30%, the denitrification culture loaded chestnut shell microbial filler B2 is obtained.

[0069] b. Cultivation of algal microbial filler: Algae can improve resource utilization efficiency. Algae can be purchased as chlorella, and cultured in A3 liquid medium. After rejuvenation, the purchased chlorella is cultured in A3 liquid medium, with 12 hours of light per day, and the ammonia nitrogen concentration of the supernatant is determined every 5 days. If the ammonia nitrogen degradation efficiency reaches more than 90%, the medium is replaced by centrifugation. Continuous culture for 3 cycles obtains algal microbial filler B3.

[0070] A0 liquid medium: NaNO3 1500 mg / L, K2HPO4 0.04 mg / L, MgSO4 7H2O 75 mg / L, CaCl2 2H2O 36 mg / L, NaOAc 6 mg / L, EDTA 1 mg / L, Na2CO3 20 mg / L;

[0071] A1 liquid medium: add NH4Cl 0.1 g and NaHCO3 0.2 g to 1 L water, adjust the pH to about 7.0-7.5 with NaHCO3, and add 3% zeolite powder with a mesh size of 200, soak with 10% hydrochloric acid by volume, then wash and wait for use;

[0072] A2 liquid medium: add NH4Cl 0.1 g and NaHCO3 0.2 g to 1 L water, adjust the pH to about 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamide and tetracycline with a mass ratio of 1:1:1, the mass concentration of the mixture is 5 mg / L, and add 3% zeolite powder and 3% sponge iron powder;

[0073] A3 liquid medium: add NH4Cl 0.1g, NaHCO3 1g in 1L water, adjust pH to about 7.5-8.0 with NaHCO3

[0074] (4) Preparation of bioactive filler:

[0075] S1, preparation of carbon removal microbial filler layer, load microbial filler A with chestnut shell on the board into a mesh bag with a void of 1-2mm, and place it in the first layer of tail water treatment as the first module;

[0076] S2, aerobic ammonia oxidation culture loaded microbial filler B1 is resuspended in A1 liquid medium, and polyvinyl alcohol is added to a mass concentration of 4.5% per liter of A1 liquid medium; 300mg of sodium bicarbonate; then add a solution of 1.5% boric acid and 3.5% calcium chloride to form a small ball as the second module;

[0077] S3, denitrifying culture loaded microbial filler B2 is resuspended in A2 liquid medium, and polyvinyl alcohol is added to a mass concentration of 6% per liter of A2 liquid medium; 300mg of glucose, mix thoroughly; finally, a solution of 1.5% boric acid and 3.5% calcium chloride is dripped through a 1cm diameter pipe to form a small ball as the third module;

[0078] S4, microbial filler B3 is resuspended in A3 liquid medium, and polyvinyl alcohol is added to a mass concentration of 6% per liter of A3 liquid medium; 300mg of glucose, as the fourth module;

[0079] S5, the first module, the second module, the third module and the fourth module are sequentially configured in a mass ratio of 5:2:2:1.

[0080] This example uses a reactor to treat the tail water of freshwater shrimp culture, and the four modules are sequentially added to a 20L reactor. The cultured tail water is introduced for continuous operation and treatment. When the concentration of potassium permanganate in the treated aquaculture tail water is 20-30mg / L, the concentrations of ammonia nitrogen and total phosphorus are 5-6mg / L and 1-2mg / L respectively, norfloxacin is 10-20mg / L; ss is 30-50mg / L.

[0081] After 60 days of continuous treatment of aquaculture tail water, the removal rates of potassium permanganate, nitrate, total nitrogen and total phosphorus are as follows Figure 1 and Figure 2 , Figure 1 and 2 It can be seen from the above that the removal rates of COD, ammonia nitrogen, phosphorus and norfloxacin in the effluent are basically above 90%, and the effect is good.

[0082] Comparative Example 1

[0083] The reactor is not filled with the filler.

[0084] By comparison, it is found that the reactor treatment capacity is improved after adding the cultivated module filler (comparing without adding the filler, comparing without implementing the above-mentioned cultivated filler). The original treatment process is not ideal for removing ammonia nitrogen and total nitrogen, and the removal capacity is less than 20%. After adding the filler, the treatment capacity of the reactor is improved, close to 70%-80% or more, and the removal of COD and total phosphorus is also higher than the treatment of the reactor.

[0085] Example 2

[0086] The same as Example 1, except that (2) the carbon and nitrogen co-conversion filler T1 is prepared: add anhydrous ether in a ratio of 1:2 (m / v) for Soxhlet extraction for 8h to remove fat, soak for 5h according to a mass concentration of 0.5g / mL, and put the chestnut shell solution after decolorization treatment of activated carbon into a container, under microwave 200W, ultrasonic 100W, temperature 60℃, and extraction time 160min.

[0087] (4) Preparation of biologically active filler:

[0088] S2, the microbial filler B1 of the aerobic ammonia oxidation culture loaded chestnut shell is resuspended in A1 liquid medium, and polyvinyl alcohol with a mass concentration of 3% is added per liter of A1 liquid medium; 100mg of sodium bicarbonate; then add a solution of 1% boric acid and 2% calcium chloride with a mass of 1%;

[0089] S3, the denitrifying microbial filler B2 is resuspended in A2 liquid medium, and polyvinyl alcohol with a mass concentration of 5% is added per liter of A2 liquid medium; 100mg of glucose, fully mixed; finally, a solution of 1% boric acid and 2% calcium chloride with a mass of 1% is dropped through a pipe with a diameter of 1cm;

[0090] S4, the microbial filler B3 is resuspended in A3 liquid medium, and polyvinyl alcohol with a mass concentration of 5% is added per liter of A3 liquid medium; 100mg of glucose;

[0091] S5, the mass ratio of the first layer, the second layer, the third layer, and the fourth layer is 4:3:2:1, and they are configured in sequence.

[0092] A1 liquid medium: add NH4Cl 0.1g, NaHCO3 0.2g to 1L water, adjust the pH to about 7.0-7.5 with NaHCO3, and add 1% zeolite powder with a mesh size of 200, then soak with 10% hydrochloric acid by volume fraction, then wash and wait for use;

[0093] A2 liquid medium: add NH4Cl 0.1 g, NaHCO3 0.2 g in 1 L water, adjust pH to about 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamide and tetracycline with a mass ratio of 1:1:1, the mass concentration of the mixture is 1 mg / L, and add 1% zeolite powder and 1% sponge iron powder.

[0094] Example 3

[0095] The same as example 1, except that: (2) Carbon and nitrogen co-conversion filler T1 preparation: add anhydrous ether in a ratio of 1:4 (m / v) for Soxhlet extraction for 6 h to remove fat, soak for 3 h at a mass concentration of 1.5 g / mL, and then put the chestnut shell solution after decolorization treatment into the container, microwave 600 W, ultrasonic 200 W, temperature 90℃, extraction time 80 min.

[0096] (4) Preparation and combination of multi-layer bioactive filler:

[0097] S2, aerobic ammonia oxidation culture loaded chestnut shell microbial filler B1 is resuspended in A1 liquid medium, and 6% polyvinyl alcohol, 500 mg of sodium bicarbonate, and 2% boric acid and 5% calcium chloride solution are added per liter of A1 liquid medium;

[0098] S3, denitrifying microbial filler B2 is resuspended in A2 liquid medium, and 7% polyvinyl alcohol, 500 mg of glucose, and 2% boric acid and 5% calcium chloride solution are added per liter of A2 liquid medium;

[0099] S4, microbial filler B3 is resuspended in A3 liquid medium, and 7% polyvinyl alcohol and 500 mg of glucose are added per liter of A3 liquid medium;

[0100] SS5, the mass ratio of the first layer, the second layer, the third layer and the fourth layer is 6:1:2:1.

[0101] A1 liquid medium: add NH4Cl 0.1 g, NaHCO3 0.2 g in 1 L water, adjust pH to about 7.0-7.5 with NaHCO3, and add 5% zeolite powder with a mesh size of 200, then soak with 10% hydrochloric acid, and then wash and use;

[0102] A2 liquid medium: in 1L water, add NH4Cl 0.1g, NaHCO3 0.2g, adjust pH to about 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamides and tetracycline with a mass ratio of 1:1:1, the mass concentration of the mixture is 10mg / L, and add 5% zeolite powder and 5% sponge iron powder.

[0103] The above description of the embodiments is only used to help understand the technical solutions of the present application and its core idea. It should be pointed out that for those skilled in the art, without departing from the principles of the present application, the present application can be improved and modified in several ways, and these improvements and modifications also fall within the protection scope of the claims of the present application.

Claims

1. A method for enhanced treatment and resource utilization of aquaculture wastewater, characterized in that, Includes the following steps: (1) After crushing the chestnut shells, hydrochloric acid is added to the chestnut shells for treatment. After washing and drying, chestnut shell carbon conversion matrix T0 is obtained. After the aquaculture tail water is coarsely filtered through 5-15 mesh and centrifuged, the concentrated liquid is obtained by suction filtration. The precipitate is collected and transferred to A0 liquid culture medium. It is cultured at room temperature for 5-6 days to obtain preliminary culture A. After dilution and centrifugation, the precipitate of the preliminary culture A is inoculated into a mixture of A0 liquid culture medium and chestnut shell carbon conversion matrix T0. The mixture is added to the mixture at a ratio of 40-60 g of the mixture per liter of preliminary culture A precipitate. The mixture is continuously cultured for 5-7 days under stirring. The COD removal rate is monitored until the COD removal rate reaches more than 90%. The culture ends when the biomass on the chestnut shells reaches 0.8-2.0 g of microorganisms per 100 g of chestnut shells. The microbial packing material A loaded with chestnut shells is obtained. (2) After crushing the chestnut shells, pass them through a 200-300 mesh. Add anhydrous diethyl ether at a mass-to-volume ratio of chestnut shells to anhydrous diethyl ether of 1:2-4 and extract for 6-8 h. Then add anhydrous ethanol at a mass-to-volume ratio of chestnut shells to anhydrous ethanol of 1:0.5-1.5 and soak for 3-5 h. Decolorize with activated carbon to obtain chestnut shell solution. Extract the chestnut shell solution in microwave at 200-600 W, sonicate at 100-200 W, and at a temperature of 60℃-90℃ for 80-160 min. After cooling to room temperature, repeat the microwave and sonic extraction 2-3 times. Separate the supernatant from the precipitate to obtain the attachment packing material T1 for ammonia-reducing and ammonia-oxidizing microorganisms. After coarse filtration (5-15 mesh) and centrifugation, the aquaculture wastewater is concentrated by filtration. The precipitate is collected and transferred to A0 liquid culture medium. It is cultured at room temperature for 5-6 days to obtain preliminary culture B. Preliminary culture B is diluted and centrifuged. The precipitate of preliminary culture B is collected and inoculated into a mixture of A1 liquid culture medium and T1 packing material containing ammonia-reducing and ammonia-oxidizing microorganisms. The mixture is added at a ratio of 100-200 g of the mixture per liter of preliminary culture B precipitate to maintain dissolved oxygen at a level not lower than 2-3 mg / L. The mixture is continuously cultured at 250-300 rpm for 5-7 days with stirring. The ammonia nitrogen concentration in the supernatant is measured every 3-5 days. If the ammonia nitrogen degradation efficiency reaches over 90% and the nitrate formation rate reaches over 50%, chestnut shell microbial packing material B1 loaded with aerobic ammonia-oxidizing culture is obtained. Half of the microbial packing material B1 is removed, and the A1 liquid culture medium is replaced with an equal volume of A2 liquid culture medium. The mixture is then cultured without aeration with stirring until the dissolved oxygen level is below 0.5-1.0 mg / L. Add mg / L of the attached packing material T1 containing denitrifying and ammonia-oxidizing microorganisms, and culture under the above conditions for 1-2 weeks. Measure the ammonia nitrogen concentration and nitrate concentration in the supernatant every 5 days. If the nitrate degradation efficiency reaches more than 90% and the cumulative increase rate of ammonia nitrogen is less than 30%, obtain chestnut shell microbial packing material B2 loaded with denitrification culture. (3) Chlorella was cultured in A3 liquid medium with 12 hours of light per day. The ammonia nitrogen concentration in the supernatant was measured every 5 days. The ammonia nitrogen degradation efficiency reached more than 90%. After centrifugation, the A3 liquid medium was replaced. After three consecutive cycles of culture, algal microbial packing material B3 was obtained. (4) The chestnut shell-loaded microbial packing material A obtained in step (1) is used as the first module. The chestnut shell-loaded microbial packing material B1 obtained in step (2) is resuspended in liquid culture medium A1, and polyvinyl alcohol is added to each liter of liquid culture medium A1 to make its mass concentration 3%-6%; sodium bicarbonate 100-500 mg, and then a solution of boric acid 1%-2% and calcium chloride 2%-5% by mass is added to form small balls, which are used as the second module. The chestnut shell-loaded microbial packing material B2 obtained in step (2) is resuspended in liquid culture medium A2, and polyvinyl alcohol is added to each liter of liquid culture medium A2 to make its mass concentration 5%-7%; glucose 100-500 mg, and so on. mg, mix thoroughly; finally, add a solution of 1%-2% boric acid and 2%-5% calcium chloride by mass fraction to form small balls, as the third module; resuspend microbial packing material B3 in liquid culture medium A3, and add polyvinyl alcohol to each liter of liquid culture medium A3 to make its mass concentration 5%-7%; glucose 100-500 mg, as the fourth module; The A0 liquid culture medium contains: NaNO3 1500 mg / L, K2HPO4 0.04 mg / L, MgSO47H2O 75 mg / L, CaCl22H2O 36 mg / L, sodium acetate 6 mg / L, EDTA 1 mg / L, and Na2CO3 20 mg / L. A1 liquid culture medium: Add 0.1 g of NH4Cl and 0.2 g of NaHCO3 to 1 L of water, adjust the pH to 7.0-7.5 with NaHCO3, add 1%-5% zeolite powder that has passed through 200 mesh, soak in 10% hydrochloric acid, and then wash and set aside for use. A2 liquid culture medium: Add 0.1 g of NH4Cl and 0.2 g of NaHCO3 to 1 L of water, adjust the pH to 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamide and tetracycline in a mass ratio of 1:1:1, with a mass concentration of 1-10 mg / L, and add 1%-5% zeolite powder and 1%-5% sponge iron powder; A3 liquid culture medium: Add 0.1 g of NH4Cl and 1 g of NaHCO3 to 1 L of water, and adjust the pH to 7.5-8.0 with NaHCO3; (5) The first module, the second module, the third module and the fourth module mentioned in step (4) are added to the reactor in sequence. The mass ratio of the first module, the second module, the third module and the fourth module in the reactor is 4-6:1-3:1-3:

1. The aquaculture wastewater is introduced and continuously processed through the first module, the second module, the third module and the fourth module to make the wastewater meet the standards for discharge.

2. The method according to claim 1, characterized in that, The solid-liquid ratio of chestnut shell to hydrochloric acid in step (1) is 1:8-10, and the volume fraction of hydrochloric acid is 8%-12%.

3. The method according to claim 1, characterized in that, The mass ratio of A0 liquid culture medium to chestnut shell carbon conversion matrix T0 in step (1) is 20:1-30:

1.

4. The method according to claim 1, characterized in that, In step (2), anhydrous ether was added at a mass-volume ratio of 1:3 to chestnut shells and extracted for 7 h. Then anhydrous ethanol was added at a mass-volume ratio of 1:1 to chestnut shells and extracted for 4 h. The chestnut shell solution was then decolorized with activated carbon.

5. The method according to claim 1 or 4, characterized in that, The mass ratio of the A1 liquid culture medium to the T1 attachment packing material for deammonia nitrogen and ammonia oxidation microorganisms in step (2) is 1:100-1:

200.

6. The method according to claim 1, characterized in that, In step (2), the chestnut shell solution is extracted for 120 min by microwave at 400W, ultrasound at 150W, and temperature at 75℃. After cooling to room temperature, the extraction is repeated 2-3 times by microwave and ultrasound. The supernatant is then separated from the precipitate to obtain the attachment packing material T1 for ammonia-reducing and ammonia-oxidizing microorganisms.

7. The method according to claim 1, characterized in that, The A1 liquid culture medium in step (4) is as follows: Add 0.1 g of NH4Cl and 0.2 g of NaHCO3 to 1 L of water, adjust the pH to 7.0-7.5 with NaHCO3, add 3% zeolite powder that has passed through 200 mesh, soak in 10% hydrochloric acid, and then wash it before use. A2 liquid culture medium: Add 0.1 g of NH4Cl and 0.2 g of NaHCO3 to 1 L of water, adjust the pH to 7.0-7.5 with NaHCO3, and add a mixture of ciprofloxacin, sulfonamide and tetracycline in a mass ratio of 1:1:1, with a mass concentration of 5 mg / L, and add 3% zeolite powder and 3% sponge iron powder.

8. The method according to claim 7, characterized in that, The mass ratio of the first module, second module, third module and fourth module in step (5) is 5:2:2:1.

Images