Purification device for aquaculture tail water containing antibiotics and control method thereof

Abstract

The present disclosure provides a purification device for aquaculture tail water containing antibiotic drugs and a control method thereof. The purification device includes: an adsorption tank and an electromagnetic mechanism: the adsorption tank includes: a tank body, the tank body is made of non-magnetic material; the tank body is provided with a feed port for adding magnetic material into the tank body, wherein the magnetic material is a hydrophilic magnetic polymer obtained by cross-linking with a magnetic mixed hydroxide as a carrier and 3-amino-1,2,4-triazole as a functional monomer; the tank body is provided with a water inlet for adding aquaculture tail water into the tank body, wherein the aquaculture tail water contains antibiotic drugs, and the antibiotic drugs include at least one of quinolones and tetracyclines; a stirring mechanism, the stirring mechanism is installed in the tank body, and is used to disperse the magnetic material in the aquaculture tail water; the electromagnetic mechanism is arranged on the outside of the tank body, and is used to apply a magnetic field to the tank body to magnetically separate the magnetic material from the aquaculture tail water.

Description

Technical Field

[0001] The present invention belongs to the technical field of aquaculture tail water treatment, and relates to a purification device for aquaculture tail water containing antibiotics and a control method thereof. Background Art

[0002] The extensive use and even abuse of antibiotics in the aquaculture industry, as well as their inefficient treatment, not only deteriorates the environment of aquaculture waters, leading to drug resistance in fish, shrimps, crabs, etc., but also makes aquaculture effluent one of the main sources of antibiotics in surface water.

[0003] In recent years, relevant research institutions at home and abroad have proposed using physical elimination, photodegradation, chemical oxidation, microbial degradation, and phytoremediation to carry out antibiotic remediation. Based on the sewage treatment methods used, corresponding purification devices and control methods have been proposed.

[0004] Adsorption is a commonly used method for removing antibiotics in wastewater treatment. Magnetic polymer materials, with their large surface area and magnetic properties, enable high-volume adsorption and rapid separation. However, most common magnetic polymer materials are synthesized in non-polar organic solvents and exhibit optimal performance only in non-aqueous environments. They are unsuitable for adsorbing antibiotics in aqueous media, thus limiting research on methods and devices for purifying antibiotic-containing aquaculture tailwater using these materials. Summary of the Invention

[0005] The present disclosure provides a purification device for aquaculture tail water containing antibiotics and a control method thereof, which can effectively solve the above problems.

[0006] The present disclosure is achieved as follows:

[0007] In a first aspect, the present disclosure provides a device for purifying aquaculture tail water containing antibiotic drugs, the device comprising an adsorption tank and an electromagnetic mechanism:

[0008] The adsorption tank comprises:

[0009] a tank body made of non-magnetic material;

[0010] The tank body is provided with a feed port for adding magnetic material into the tank body, wherein the magnetic material is a hydrophilic magnetic polymer obtained by cross-linking with a magnetic mixed hydroxide as a carrier and 3-amino-1,2,4-triazole as a functional monomer;

[0011] The tank body is provided with a water inlet for adding aquaculture tail water into the tank body, wherein the aquaculture tail water contains antibiotic drugs, and the antibiotic drugs include at least one of quinolone drugs and tetracycline drugs;

[0012] a stirring mechanism installed in the tank body and used to disperse the magnetic material in the aquaculture tail water;

[0013] The electromagnetic mechanism is arranged on the outside of the tank body and is used to apply a magnetic field to the tank body to magnetically separate the magnetic material from the aquaculture tail water.

[0014] In a second aspect, the present disclosure provides a method for controlling the above-mentioned device, the method comprising:

[0015] Adding the aquaculture tail water into the tank through the water inlet;

[0016] Using the stirring mechanism to stir the aquaculture tail water;

[0017] Adding the magnetic material into the tank through the feed port;

[0018] Continuing to stir until the magnetic material completes the adsorption of the antibiotic drug in the aquaculture tail water;

[0019] Using an electromagnetic mechanism to magnetically adsorb the magnetic material to magnetically separate the magnetic material from the aquaculture tail water;

[0020] Discharge the aquaculture tail water from the tank;

[0021] Release the magnetic attraction of the electromagnetic mechanism.

[0022] The beneficial effects of the present disclosure are:

[0023] This disclosure provides a device for purifying aquaculture tailwater containing antibiotics. The adsorbent used is HMP, which has strong hydrophilicity, is easily prepared, and does not require rigorous experimental conditions, resulting in low synthesis costs. The HMP has a rapid adsorption rate, reaching equilibrium in 120 to 150 seconds. In static adsorption experiments, the equilibrium adsorption capacity of the antibiotic reached 10.901 mg / g.

[0024] Furthermore, in the HMP, the polymer layer formed on the surface of MMH is an ideal gel-type mesh pore structure with a looser spatial structure and a larger specific surface area, which makes the HMP adsorb target molecules more fully and the internal mass transfer process more rapid.

[0025] Furthermore, the magnetization intensity of the HMP reaches 7.6 emu / g. Under the action of an external magnetic field, the HMP dispersed in water can be quickly separated within 10 seconds. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present disclosure and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without creative work.

[0027] Figure 1 It is a structural schematic diagram of a purification device for aquaculture tail water containing antibiotic drugs provided by an embodiment of the present disclosure.

[0028] Figure 2 The HMP adsorption isotherm diagram provided for the embodiments of the present disclosure.

[0029] Figure 3 This is a graph showing the adsorption kinetics of HMP according to an embodiment of the present disclosure.

[0030] Figure 4 This is a pseudo-first-order adsorption kinetics fitting diagram of HMP provided in an embodiment of the present disclosure.

[0031] Figure 5 This is a pseudo-second-order adsorption kinetics fitting diagram of HMP provided in an embodiment of the present disclosure.

[0032] Figure 6 XRD patterns of the iron-aluminum MMH and HMP provided in the embodiments of the present disclosure.

[0033] Figure 7 This is the FTIR graph of iron-aluminum MMH and HMP.

[0034] Figure 8 In the figure, (a) is a TEM image of the iron-aluminum MMH provided in an embodiment of the present disclosure; (b) is a TEM image of the HMP (50 nm); and (c) is a TEM image of the HMP (200 nm).

[0035] Figure 9 , (a) is a SEM image of the iron-aluminum MMH provided in an embodiment of the present disclosure; (b) is a SEM image of the HMP.

[0036] Figure 10 VSM diagrams of iron and aluminum MMH and HMP provided in the embodiments of the present disclosure.

[0037] Figure 11 It is a flowchart of the control method of the device provided by the embodiment of the present disclosure. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solutions and advantages of the embodiments of the present disclosure clearer, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings in the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present disclosure. Therefore, the following detailed description of the embodiments of the present disclosure provided in the drawings is not intended to limit the scope of the present disclosure for protection, but merely represents the selected embodiments of the present disclosure. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present disclosure.

[0039] The present disclosure provides a device for purifying aquaculture tail water containing antibiotics, such as Figure 1 As shown, the device includes an adsorption tank 1 and an electromagnetic mechanism 2.

[0040] The adsorption tank 1 comprises:

[0041] The tank body 11 is made of non-magnetic material.

[0042] In some embodiments, the can is made of plastic.

[0043] For example, the tank body material is polyethylene plastic, polyvinyl chloride plastic, polypropylene plastic, glass fiber reinforced plastic, etc.

[0044] In some embodiments, the can body is made of a non-magnetic alloy material, such as aluminum alloy.

[0045] The tank body 11 is provided with a feed port for adding magnetic material into the tank body 11 .

[0046] like Figure 1 As shown, a feeding mechanism is provided on the top of the tank body 11. Figure 1 As shown, it is a feed pipe 12, and the feed pipe 12 is connected with the tank body 11 through the feed port.

[0047] Furthermore, the feed port is arranged in the middle position of the tank body 11, which can prevent the magnetic material from being added from the side away from the middle and prematurely gathering to the outer part of the tank body 11 (radially) under the centrifugal effect of the stirring water flow, thereby reducing the contact with more aquaculture tail water.

[0048] In some embodiments, a dispersion mechanism is provided on the upper portion of the tank 11. After the device is added to the aquaculture tail water, the dispersion mechanism is located above the aquaculture tail water. The dispersion mechanism is used to improve the dispersion effect of the magnetic material in the aquaculture tail water.

[0049] For example, the magnetic material added to the tank 11 is dispersed before entering the aquaculture tail water.

[0050] Furthermore, the dispersion mechanism may be a dispersion hopper that receives the magnetic material added to the tank 11 and disperses the magnetic material into the aquaculture tail water through dispersed holes provided on the dispersion hopper.

[0051] The dispersion hopper may be provided with a vibration component for dispersing the magnetic material on the hopper and moving it into the various holes.

[0052] Alternatively, a rotating roller is provided on the dispersion hopper, one end of which is connected to the rotating shaft of the stirring mechanism 14 to achieve circular motion on the dispersion hopper, disperse the magnetic material on the hopper, and move it into each hole.

[0053] The dispersion mechanism can overcome the technical problem that the magnetic material is added to the aquaculture tail water in a concentrated manner, and it is difficult to achieve complete dispersion even if stirring is performed, resulting in the adsorption capacity effect being worse than the experimental result.

[0054] The magnetic materials are dispersedly added into the aquaculture tail water, so that more particles can be sheared by the stirred water flow, thereby further dispersing.

[0055] The magnetic material is a hydrophilic magnetic polymer obtained by cross-linking a magnetic mixed hydroxide as a carrier and 3-amino-1,2,4-triazole as a functional monomer.

[0056] In some embodiments, the magnetic mixed hydroxide (MMH) is magnetic iron-aluminum mixed hydroxide (Fe-Aluminum MMH).

[0057] In some embodiments, the preparation of iron-aluminum MMH comprises:

[0058] Iron-aluminum MMH was prepared by low supersaturation co-precipitation method at room temperature.

[0059] Weigh ammonium ferrous sulfate hexahydrate and aluminum chloride hexahydrate in a 2:1 molar ratio, add them to deionized water, and mechanically stir until completely dissolved. Then, quickly add aqueous sodium hydroxide solution to maintain a pH of approximately 10. Mechanically stir at 500 rpm for 10 minutes. After the reaction is complete, allow the mixture to stand and separate, discard the supernatant, collect the black product with a magnet, and wash with deionized water to obtain FeAl-MMH.

[0060] Add an appropriate amount of deionized water with a pH value of 7 to the upper layer of the prepared iron-aluminum MMH and store it at room temperature for later use.

[0061] In some embodiments, the preparation of HMP comprises:

[0062] Add the iron-aluminum MMH to deionized water and mechanically stir at 500 r / min until it is completely dispersed, and continue for 10 minutes to prepare an iron-aluminum MMH suspension.

[0063] Dissolve hydrophilic 3-amino-1,2,4-triazole (ATA) in 250 mL of deionized water. Once completely dissolved, add it to the iron-aluminum MMH suspension and continue mechanically stirring for 30 minutes. Then, add the crosslinker, dimethyl ethylene glycol acrylate (EGDMA). Stir under the same conditions for another 30 minutes, followed by the rapid addition of the initiator, ammonium persulfate (APS). Transfer the mixture to a nitrogen-filled vacuum glove box and polymerize in a 40°C water bath at 300 rpm for 5 hours. After completion of the reaction, discard the supernatant, collect the product, and wash with deionized water. Dry it at 80°C for 5 hours to obtain HMP, which is stored at room temperature until ready for use.

[0064] The molar ratio of the cross-linking agent EGDMA to ATA is 5:1.

[0065] In some embodiments, the dried product is sieved through a 150-mesh (0.1 mm pore size) standard test sieve. Using materials with a diameter greater than 0.1 mm increases the surface area for adsorption and reduces the magnetic field strength required for magnetic separation. Materials with a diameter that is too small may float on the water surface, hindering subsequent separation.

[0066] Static adsorption experiment of HMP

[0067] Standards

[0068] Sulfapyridine, Sulfadiazine, Sulfamethoxazole, Sulfathiazole, Sulfamerazine, Sulfisoxazole, Sulfamethizol, Sulfamethazine, Sulfameter, Sulfachloropyridazine, Sulfachinoxalin, Sulfadoxine, Sulfadimethoxine, with a purity greater than 95%; Pipemidic Acid, Nalidixic Acid, Oxolinic Acid acid), flumequine, norfloxacin, ciprofloxacin, enrofloxacin, fleroxacin, enoxacin, pefloxacin, lomefloxacin hydrochloride, danofloxacin mesylate, ofloxacin, sparfloxacin, difloxacin hydrochloride, cinoxacin, orbifloxacin, and marbofloxacin, with a purity greater than 92%; sarafloxacin hydrochloride, with a purity greater than 87%; oxytetracycline hydrochloride Hydrochloride, tetracycline hydrochloride, and doxycycline hydrochloride (purity greater than 90%) were purchased from Manhage (Shanghai) Biotechnology Co., Ltd. All of the above standards were prepared in methanol to a 200 μg / mL standard stock solution and stored at -20°C in the dark (the weight of the standard is the weight corrected for purity). Furthermore, methanol was used to prepare a 20 μg / mL sulfonamide antibiotic standard mixture, a 20 μg / mL quinolone antibiotic standard mixture, and a 20 μg / mL tetracycline antibiotic standard mixture, respectively, and stored at -20°C in the dark.

[0069] For example, a tetracycline antibiotic standard mixture includes all the antibiotics listed in the standard sample, namely oxytetracycline hydrochloride, tetracycline hydrochloride, and doxycycline hydrochloride. Each antibiotic in the standard mixture is at the same concentration of 20 μg / mL.

[0070] Instruments and Equipment

[0071] A TSQ Quantum Ultra high-performance liquid chromatography-tandem mass spectrometer equipped with an electrospray ionization source was used by ThermoFisher Scientific (FEI), USA; an IRAffinity-1 Fourier transform infrared spectrometer was used by Shimadzu Corporation, Japan; a Nova Nano SEM scanning electron microscope was used by Thermo Fisher Scientific (FEI), USA; a Talos F200s transmission electron microscope was used by Thermo Fisher Scientific (FEI), USA; a 7410 vibrating sample magnetometer was used by LakeShore, USA; an LC-ES-60SH mechanical stirrer was used by Shanghai Lichen Bangsi Instrument Technology Co., Ltd.; an MS3 vortex mixer was used by IKA, Germany; an LC-WB-2 constant temperature water bath was used by Shanghai Lichen Bangsi Instrument Technology Co., Ltd.; an MT008-C vacuum glove box was used by Miqi Instrument Equipment Co., Ltd. in Changsha; a DHG-9245A electric blast drying oven was used by Yiheng Scientific Instrument Co., Ltd. in Shanghai; a Milli-Q water purification system was used; and a 150-mesh standard test sieve was used by Yinhe Testing Instrument Factory in Shangyu City.

[0072] Liquid chromatography-mass spectrometry (HPLC-MS / MS) conditions

[0073] Chromatographic conditions: CAPCELL PAK-MGⅡC18 column (2.1 mm×150 mm×5 μm); column temperature 35°C; flow rate 0.25 mL / min; injection volume 5 μL; mobile phase: A: 0.005 mol / L ammonium acetate-0.1% formic acid aqueous solution, B: 0.1% formic acid methanol; elution gradient: 0-5 min (10%-90% B), 5-9 min (90%-100% B), 9-10 min (100%-10% B), 10-15 min (10% B).

[0074] Mass spectrometry conditions: electrospray ion source, positive ion detection mode, spray voltage: 3500 V, sheath gas pressure: 241 kPa, auxiliary gas pressure: 2 L / min, ion transfer capillary temperature: 320 °C, selected reaction monitoring (SRM), parent ion, product ion and collision energy are listed in Table 1, Q1 half-peak width: 0.7 u, Q3 half-peak width: 0.7 u, collision gas pressure: argon, 0.2 Pa.

[0075] Table 1 Selected reaction monitoring parent ions, product ions and collision energies

[0076]

[0077]

[0078] Note: “*” indicates quantification ion.

[0079] Measure 10 mL of deionized water into a 50 mL test tube and add the standard mixture of sulfonamide antibiotics, the standard mixture of quinolone antibiotics, and the standard mixture of tetracycline antibiotics to prepare a mixed antibiotic solution. The concentrations of the various antibiotics in the mixed antibiotic solution are listed in Table 2.

[0080] Table 2 Concentrations of various antibiotics in mixed antibiotic solutions

[0081]

[0082]

[0083] The solution was adjusted to pH 6-8, and then 5 mg of HMP prepared in Example 6 was added, vortexed at 2000 rpm for 120 s, and the supernatant was obtained by magnetic separation and the pH value of the supernatant was adjusted to 4 with 3% by mass formic acid solution.

[0084] Take 1 mL of supernatant, add 0.25 mL of methanol, vortex mix at 2000 r / min for 30 s, pass through 0.22 μm filter membrane, and detect by HPLC-MS / MS, and measure three times in parallel.

[0085] Calculate the adsorption amount Q. The adsorption amount calculation formula (1) is as follows:

[0086]

[0087] Where V (mL) is the volume of the solution, m (mg) is the mass of the adsorbent HMP, C0 and C e (μg / mL) are the initial concentration and equilibrium concentration of the solution, respectively.

[0088] To realistically simulate the conditions of actual aquaculture tailwater, the pH of the simulated solution was adjusted to match that of tailwater (pH 6-8). Furthermore, the simulated solution contained sulfonamides, quinolones, and tetracyclines, drugs commonly found in aquaculture tailwater. Under these conditions, static adsorption experiments were conducted to simultaneously adsorb multiple drugs and examine the selectivity of the adsorption material.

[0089] Under the conditions of constant temperature and pH value of 6-8, the adsorption amount of HMP in solutions of sulfonamides, quinolones and tetracyclines with different mass concentrations was determined respectively.

[0090] The experimental results showed that HMP could not effectively adsorb sulfonamides, but with the increase of the initial drug concentration, the adsorption capacity of HMP for quinolones and tetracyclines gradually increased.

[0091] like Figure 2 As shown in the figure, when the drug concentration increases to 0.8 μg / mL, the adsorption capacity of HMP for quinolones and tetracyclines approaches saturation, reaching maximum adsorption capacity, with an equilibrium adsorption capacity Q of 10.901 mg / g. This may be because a higher initial concentration provides a stronger driving force for quinolones and tetracyclines, overcoming the mass transfer resistance between the solid and liquid phases. This increases the contact time and collision frequency of quinolones and tetracyclines with the adsorbent, increasing the chance of binding to the active sites of HMP.

[0092] like Figure 2 As shown in the figure, there are significant differences in the equilibrium adsorption capacity of HMP for each drug. Specifically: Q 多西环素 (1.460mg / g)>Q 土霉素 (1.211mg / g)>Q 四环素 (0.856mg / g)>Q 达氟沙星 (0.749mg / g)>Q 萘啶酸 (0.694mg / g)>Q 环丙沙星 (0.633mg / g)>Q 二氟沙星 (0.616mg / g)>Q 司帕沙星 (0.581mg / g)>Q 吡哌酸 (0.576mg / g)>Q 氧氟沙星 (0.530mg / g)>Q 氟甲喹 (0.521mg / g)>Q 依诺沙星 (0.509mg / g)>Q 沙拉沙星 (0.417mg / g)>Q 诺氟沙星 (0.365mg / g)>Q 培氟沙星 (0.291mg / g)>Q 恩诺沙星 (0.264mg / g)>Q 氟罗沙星(0.243mg / g)>Q 洛美沙星 (0.227mg / g)>Q 奥比沙星 (0.192mg / g)>Q 马波沙星 (0.181mg / g).

[0093] This shows that when the pH value of aquaculture tail water is 6-8, HMP has the characteristics of preferentially adsorbing tetracyclines and quinolones. Compared with sulfonamides, the magnetic material basically does not adsorb sulfonamides, and its adsorption capacity for tetracyclines is significantly better than that for quinolones.

[0094] Dynamic adsorption experiment of HMP

[0095] Measure 10 mL of deionized water into a 50 mL test tube and add a mixed standard solution of quinolone and tetracycline antibiotics to prepare a mixed antibiotic solution with a concentration of 0.50 μg / mL of both quinolone and tetracycline antibiotics. Adjust the solution pH to neutral, add 5 mg of HMP prepared in Example 6, and vortex at 2000 rpm for 10, 30, 60, 90, 120, 150, and 180 seconds, respectively. Magnetic separation is performed to obtain the supernatant, and the pH of the supernatant is adjusted to 4 with 3% formic acid solution.

[0096] Take 1 mL of supernatant, add 0.25 mL of methanol, vortex mix at 2000 r / min for 30 s, pass through 0.22 μm filter membrane, and detect by HPLC-MS / MS. The determination is repeated three times to calculate the adsorption amount Q.

[0097] To further evaluate the adsorption mechanism, the adsorption kinetics of quinolones and tetracyclines on HMP were studied. The experimental data were fitted with two of the most common kinetic models: pseudo-first-order and pseudo-second-order. The mathematical expressions of these two models are shown in Equations (2) and (3).

[0098] ln(Q e -Q t )=lnQ e -k1t (2)

[0099]

[0100] Among them, Q e and Q t are the amount of drug adsorbed on HMP at equilibrium and time t (s), respectively (mg / g), k1 is the first-order rate constant (g / mg / s), and k2 is the second-order rate constant (g / mg / s).

[0101] In order to investigate the saturation adsorption time of HMP for quinolones and tetracyclines, dynamic adsorption experiments were conducted. The results are as follows: Figure 3 As shown, the kinetic adsorption curve shows a trend of initial gradual increase followed by stabilization. This indicates that in the initial adsorption phase, the adsorbent has abundant active sites, allowing it to quickly bind to the drug in the aquaculture tailwater. As adsorption progresses, the solution concentration decreases, the number of sites on the adsorbent that have not yet been bound to the drug decreases, and the adsorption rate slows. Notably, the adsorbent reaches adsorption equilibrium within 120-150 seconds, indicating that it has very fast adsorption rates for quinolones and tetracyclines.

[0102] Figure 4 and Figure 5 They are the fitting diagrams obtained using the kinetic model, and the kinetic parameters obtained after processing are shown in Table 3.

[0103] Table 3 Adsorption kinetics fitting parameters

[0104]

[0105]

[0106] As shown in Table 3, the correlation coefficients of the pseudo-second-order adsorption kinetics model are significantly higher than those of the pseudo-first-order adsorption kinetics model. This indicates that the pseudo-second-order model can more accurately describe the adsorption behavior of the adsorbent on drugs in aquaculture tail water. The equilibrium adsorption capacity Q of the pseudo-second-order adsorption kinetics was then calculated based on the model. e , the data are shown in Table 3. These calculated values are consistent with the actual adsorption amount Q observed in the experiment e The results are very close, further verifying the accuracy of the pseudo-second-order adsorption kinetic model. This indicates that the adsorption of quinolones and tetracyclines by this adsorbent is primarily based on a chemical adsorption mechanism, rather than simple physical adsorption. This chemical adsorption involves chemical bonding between the adsorbent and the target molecule, resulting in a stronger binding force. Electrostatic interactions are also involved, and chemical adsorption is the main reason limiting the adsorption rate. This also means that the adsorption process does not involve mass transfer in the solution, further improving adsorption efficiency and stability.

[0107] Iron and aluminum MMH and MHP characterization

[0108] X-ray diffraction (XRD)

[0109] There are four crystal structures of iron oxide, among which γ-Fe2O3 and Fe3O4 have roughly the same crystal structure and both belong to the inverse spinel structure. Figure 6 shown.

[0110] pass Figure 6It can be seen that both materials have diffraction peaks at 30.4°, 35.8°, 43.2°, 53.7°, 57.5° and 63.1°, corresponding to the (220), (311), (400), (422), (511) and (440) crystal planes of γ-Fe2O3, respectively. The diffraction peaks at 21.3° and 36.8° correspond to the (110) and (311) crystal planes of γ-Al(OH)3, respectively. The XRD results of HMP are very consistent with those of γ-Fe2O3 (39-1346) and γ-Al(OH)3 (7-0324), indicating that the products are fully crystalline γ-Fe2O3 and γ-Al(OH)3. The results show that the polymer layer is successfully coated on the surface of Fe-Al MMH. Since the surface of the Fe-Al-MMH particles in HMP is covered with a polymer layer, the intensity of all diffraction peaks of HMP is weaker than that of Fe-Al-MMH, but the physical structure of Fe-Al-MMH does not change during the polymerization process.

[0111] Fourier transform infrared spectroscopy (FTIR)

[0112] The FTIR spectra of iron-aluminum MMH and HMP are as follows: Figure 7 As shown. 800cm -1 The following absorption peaks are caused by the stretching and bending vibrations of iron oxide and aluminum oxide in FeAl MMH. -1 The broad peak between 1630 cm -1 The characteristic absorption peak at 3200-3500cm is the OH bond vibration peak of water. From the FTIR spectrum of HMP, we can see that -1 Nearby (NH stretch), 1610-1660cm -1 Near (C=N) and 1318cm -1 、1260cm -1 The peaks of (aromatic secondary amine) are all characteristic absorption peaks of ATA, and the peaks at 950 cm -1 、860cm -1 The characteristic absorption peak at is caused by the out-of-plane bending vibration of the CH substituted by triazole, which indicates that ATA is involved in the polymerization reaction.

[0113] 1728cm -1 (C=O stretching) and 1100-1200 cm -1 The characteristic absorption peak of EGDMA near (COC stretching) confirms the presence of the crosslinker in the polymer.

[0114] FTIR spectrum results proved that HMP was successfully prepared.

[0115] Transmission electron microscopy (TEM) and scanning electron microscopy (SEM)

[0116] In order to further reveal the microscopic characteristics of the two materials, iron-aluminum MMH and HMP, transmission electron microscopy and scanning electron microscopy were used to obtain high-resolution images of the two.

[0117] Figure 8 The following are TEM images of Fe-Al MMH and HMP. The morphological characteristics of the two were studied by transmission electron microscopy. Figure 8 As shown in (a), particles of varying sizes and irregular shapes were observed in the TEM image of MMH. Figure 8 (a), Figure 8 (b) There is an additional light grey outer layer, which indicates that the polymer layer has been successfully prepared on the surface of FeAl MMH. Figure 8 (c) It can be seen that after polymerization, the synthesized HMP has an obvious network pore structure.

[0118] Scanning electron microscopy was used to further analyze the morphology and size of Fe-Al MMH and HMP. Figure 9 As shown in (a), the Fe-Al MMH exhibits a spherical morphology and is tightly aggregated together. Figure 9 As shown in (b), after polymerization, the HMP particles have irregular shapes and uneven sizes, and the particle size has also increased.

[0119] Magnetic property analysis

[0120] The magnetic properties of iron and aluminum MMH and HMP were tested using a vibrating sample magnetometer.

[0121] Figure 10 The hysteresis curve (VSM) of iron and aluminum MMH and HMP is shown in Figure 2. Figure 10 As can be observed, both test materials exhibit centrosymmetry, a common characteristic of ferromagnetic materials. Further analysis reveals the presence of saturation magnetization and hysteresis loops in the curves. These two key features indicate that the prepared Fe-Al MMH and HMP possess superparamagnetic properties. Superparamagnetism is a special magnetic state that allows these materials to be rapidly attracted by a magnet under the influence of an external magnetic field and to rapidly lose their magnetism upon removal of the field. Specifically, the magnetization intensities of the Fe-Al MMH and HMP are 11.4 and 7.6 emu / g, respectively. This indicates that the magnetic strength of the materials decreases with the addition of the polymer shell. This decrease can be attributed to the shielding effect of the polymer shell on the Fe-Al MMH surface, which weakens the material's response to external magnetic fields. Under the influence of an external magnetic field, the HMP can be rapidly separated within 10 seconds. This result fully demonstrates the excellent magnetic properties of the polymer, which meets the requirements for rapid separation in practical applications.

[0122] The tank body is provided with a water inlet for adding aquaculture tail water into the tank body 11 .

[0123] like Figure 1 As shown, the top of the tank body 11 is provided with a water inlet mechanism, as shown in FIG. Figure 1 As shown, it is a water inlet pipe 13, and the water inlet pipe 13 is connected with the tank body 11 through the water inlet.

[0124] In some embodiments, the device includes a first filtering mechanism 13, and the aquaculture tail water enters the water inlet after being filtered by the first filtering mechanism 13.

[0125] For example, the first filtering mechanism 13 includes a filter membrane, and further, the pore size of the filter membrane is 0.22 μm.

[0126] The filter membrane is installed in the water inlet pipe 13. Alternatively, the aquaculture tail water is filtered by the first filtering mechanism 13 and then flows into the water inlet pipe 12.

[0127] The aquaculture tail water contains antibiotic drugs, and the antibiotic drugs include at least one of quinolone drugs and tetracycline drugs.

[0128] In some embodiments, the antibiotic drug is a tetracycline drug.

[0129] The experimental results show that when the pH value of aquaculture tail water is 6-8, the adsorption capacity of HMP for tetracyclines is significantly better than that for quinolones. Therefore, its efficiency can reach 100% when used to purify aquaculture tail water containing tetracyclines.

[0130] A stirring mechanism 14 is installed in the tank body 11 and is used to disperse the magnetic material in the aquaculture tail water.

[0131] In some embodiments, the stirring mechanism 14 includes a rotating shaft, a stirring roller disposed on the rotating shaft, and a stirring paddle disposed at an end of the rotating shaft.

[0132] Under the action of gravity, the magnetic material tends to settle downward. The stirring roller arranged along the direction of the rotating axis can increase the turbulence of the water flow in the tank body 11. In the process of the magnetic material moving downward, it is sheared multiple times along this direction to increase its suspension degree, make it more dispersed, and increase its contact time with the aquaculture tail water, thereby improving the adsorption effect.

[0133] The stirring paddles function to form a circulating reflux of the water flow in the tank body 11 along the direction of the rotation axis, thereby preventing the magnetic material from settling to the bottom of the tank body 11 .

[0134] In some embodiments, the stirring blade is a turbine stirring blade, such as a disc turbine or a double-cone vortex stirring blade, so as to increase the degree of turbulence formed by the water flow driven by the stirring blade.

[0135] The electromagnetic mechanism 2 is arranged on the outside of the tank body, and is used to apply a magnetic field to the inside of the tank body 11 to magnetically separate the magnetic material from the aquaculture tail water.

[0136] In some embodiments, as Figure 1 As shown, the electromagnetic mechanism 2 is arranged on the outer side of the lower part of the tank body and is arranged around a portion of the outer wall of the tank body 11.

[0137] The electromagnetic mechanism 2 can be arranged above the discharge port and away from the water outlet, so as to facilitate the discharge of the magnetic material from the tank body 11 and prevent the aquaculture tail water from being affected by excessive water flow and flowing out when it is discharged from the tank body.

[0138] In some embodiments, the magnetic material can be discharged from the tank 11 along with the aquaculture tail water and then subjected to magnetic separation by the electromagnetic mechanism 2. For example, a water reservoir is provided to hold the purified aquaculture tail water, and the electromagnetic mechanism 2 is provided in the water reservoir to adsorb the magnetic material in the aquaculture tail water, and then the aquaculture tail water after magnetic separation is discharged, and the magnetic material is recovered from the water reservoir.

[0139] In some embodiments, the magnetic field strength applied by the electromagnetic mechanism is 3000-5000 Oe.

[0140] Depend on Figure 10 The magnetization intensity of HMP is 7.6 emu / g. HMP can be evenly dispersed in water and can be quickly separated within 10-15 seconds under the action of an external magnetic field.

[0141] In some embodiments, as Figure 1 As shown, the bottom of the tank body 11 is provided with a drain port and a discharge port. The drain port is used to discharge the aquaculture tailwater, which has been purified by magnetic material adsorption and magnetic separation, from the tank body 11. The discharge port is used to discharge the magnetic material, which has been purified by adsorption, from the tank body 11. For example, after the aquaculture tailwater is discharged, clean water can be introduced into the tank body 11 to wash the tank body 11 and remove the magnetic material.

[0142] The drain port is connected to a drain pipe 15 .

[0143] In some embodiments, a second filtering mechanism is provided in the drain pipe 15 for intercepting the magnetic material entering the pipe to prevent the magnetic material from remaining in the tank body 11 without the action of the electromagnetic mechanism 2. If the magnetic material is discharged with the flow of the aquaculture tail water, it will cause material loss.

[0144] For example, the second filtering mechanism is a filter.

[0145] Furthermore, the second filtering mechanism can be provided at the end of the drain pipe 15 other than the drain outlet, and can be detachably provided so as to regularly recycle this part of the magnetic material.

[0146] The discharge port is connected to a discharge pipe 16 .

[0147] In some embodiments, the tank body 11 is connected to a cleaning pipe for introducing clean water.

[0148] The drain pipe 15 and the discharge pipe 16 are respectively provided with valves for controlling the opening and closing thereof.

[0149] The valve avoids using a solenoid valve to avoid generating a magnetic field that affects the operation of the electromagnetic mechanism 2 .

[0150] In some embodiments, the amount of the magnetic material used is 0.125-0.15 g / L of aquaculture tail water.

[0151] Static adsorption experiments show that the adsorption capacity of the magnetic material can reach 10.901 mg / g. Therefore, the use of the magnetic material to purify aquaculture tail water requires a small amount of material, does not require a large amount of cost, and through magnetic separation, there is basically no loss and it is easy to recycle.

[0152] In some embodiments, the concentration of the antibiotic drug in the aquaculture tail water is not less than 0.8 μg / mL.

[0153] From the static adsorption experiment, we know that Figure 2 As shown in the figure, when the drug concentration increased to 0.8 μg / mL, the adsorption capacity of HMP for quinolones and tetracyclines tended to be saturated, and the adsorption capacity reached the maximum.

[0154] In some embodiments, the pH of the aquaculture tail water is neutral, that is, the pH value is 6-8.

[0155] In some embodiments, the antibiotic drug is a tetracycline drug.

[0156] Example 2

[0157] The embodiments of the present disclosure provide a control method for a purification device for aquaculture tail water containing antibiotic drugs.

[0158] It should be noted in advance that the order of the step numbers, such as S102 to S116, does not limit the order in which the steps are executed. It should be considered that in specific scenarios, the steps can be executed in parallel or in a different order.

[0159] refer to Figure 11 A method for controlling the device of embodiment 1, the method comprising:

[0160] S102, adding the aquaculture tail water into the tank body 11 through the water inlet;

[0161] S104, stirring the aquaculture tail water using the stirring mechanism 14;

[0162] S106, adding the magnetic material into the tank body 11 through the feed port;

[0163] S108, continuing stirring until the magnetic material completes adsorption of the antibiotic drug in the aquaculture tail water;

[0164] S110, using the electromagnetic mechanism 2 to magnetically adsorb the magnetic material to magnetically separate the magnetic material from the aquaculture tail water;

[0165] S112, discharging the aquaculture tail water from the tank 11;

[0166] S114, releasing the magnetic attraction of the electromagnetic mechanism 2.

[0167] In some embodiments, the method comprises:

[0168] S116 , discharging the magnetic material from the tank body 11 .

[0169] The magnetic material can be retained in the tank body 11 and reused multiple times to adsorb and purify multiple batches of lower concentration aquaculture tail water. After reaching its maximum adsorption capacity, it is discharged from the tank body 11 for impurity removal, purification, recovery, etc.

[0170] In some embodiments, S104, stirring the aquaculture tail water using the stirring mechanism 14, includes:

[0171] After adding the magnetic material, the stirring time is 120-150s.

[0172] The adsorbent HMP used in the device can reach an adsorption equilibrium state for quinolones and tetracyclines in aquaculture tail water within 120-150 seconds, and the adsorption rate is fast. Therefore, the purification efficiency of the device can be improved and the processing capacity can be increased.

[0173] In some embodiments, S110, using the electromagnetic mechanism 2 to magnetically adsorb the magnetic material to magnetically separate the magnetic material from the aquaculture tail water; and S112, discharging the aquaculture tail water from the tank 11, including:

[0174] The electromagnetic mechanism 2 is used to magnetically adsorb the magnetic material, and after 10-15 seconds, the aquaculture tail water is discharged from the tank body 11.

[0175] The HMP uniformly dispersed in the aquaculture tail water can be quickly separated within 10-15 seconds under the action of the external magnetic field. Therefore, the purification efficiency of the device can be further improved and the processing capacity can be increased.

[0176] In some embodiments, S102, adding the aquaculture tail water into the tank body 11 through the water inlet, includes:

[0177] S1021, the aquaculture tail water is filtered by the first filtering mechanism and then enters the water inlet.

[0178] In some embodiments, S104, using the stirring mechanism 14 to stir the aquaculture tail water; and, S108, continuing stirring until the magnetic material completes the adsorption of the antibiotic drug in the aquaculture tail water, including: the rotation speed of the stirring mechanism is 2000-2500r / min.

[0179] Example 3

[0180] Using the method described in Example 1, 10 L of aquaculture tailwater filtered through a 0.45 μm membrane was transferred to tank 11. 1.25 g of HMP was added and stirred at 2000 rpm for adsorption purification. After 120 seconds, magnetic separation was performed. The supernatant of the discharged aquaculture tailwater was collected and its pH was adjusted to 4 with a 3% by mass formic acid solution. 50 mL of the supernatant was transferred, 1.5 mL of methanol was added, and the mixture was mixed until the sample was loaded.

[0181] An Oasis HLB solid-phase extraction cartridge was preactivated with 6 mL of methanol and then 6 mL of water. Sample was then loaded at a flow rate of 4 mL / min, rinsed with 5 mL of water, dried under vacuum for 5 minutes, and eluted with 8 mL of methanol. The eluate was collected in a glass tube and dried with nitrogen at 45°C. The column was then sonicated with 1 mL of a pH 4.0 water-acetonitrile solution (8:2, v / v). The sample was then filtered through a 0.22 μm filter and analyzed by high-performance liquid chromatography-tandem mass spectrometry.

[0182] The composition of antibiotic pollutants in actual aquaculture tailwater and their removal rates are shown in Table 4.

[0183] Table 4 Removal efficiency of antibiotic pollutants in actual aquaculture tail water

[0184]

[0185] It can be seen from Table 4 that:

[0186] (1) The device has obvious adsorption and purification effects on quinolone and tetracycline pollutants.

[0187] (2) The device has better adsorption performance for tetracycline pollutants than quinolone pollutants, and the actual measurement results are similar to those of the simulation experiment.

[0188] (3) After adsorption, the removal efficiency of antibiotic pollutants in aquaculture tail water can reach more than 55%. The device has a high removal rate for antibiotic pollutants.

[0189] (4) The HMP adsorption capacity in the device was lower than the maximum adsorption capacity of the static adsorption experiment, which may be related to the larger volume of the actual tail water.

[0190] The results of practical applications show that the device provided by the present invention uses HMP as an adsorbent, has low material synthesis cost and strong hydrophilicity, and is suitable for the adsorption and purification of antibiotic pollutants in aquaculture tail water. The adsorbent has a large adsorption capacity, and a high adsorption amount can be achieved with a small dosage. The adsorption rate is fast and the removal rate is high. The adsorbent and tail water can be quickly separated, and it has great application prospects in the removal of antibiotic pollutants in aquaculture tail water.

[0191] The foregoing description is merely a preferred embodiment of the present disclosure and is not intended to limit the present disclosure. Those skilled in the art will readily appreciate that the present disclosure is susceptible to various modifications and variations. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present disclosure shall be included within the scope of protection of the present disclosure.

Claims

1. A method for using a purification device for aquaculture tail water containing antibiotics, characterized in that: The device includes an adsorption tank and an electromagnetic mechanism: The adsorption tank comprises: a tank body made of non-magnetic material; The tank body is provided with a feed port for adding magnetic material into the tank body, wherein the magnetic material is a hydrophilic magnetic polymer obtained by cross-linking with a magnetic mixed hydroxide as a carrier and 3-amino-1,2,4-triazole as a functional monomer; The tank body is provided with a water inlet for adding aquaculture tail water into the tank body, wherein the aquaculture tail water contains antibiotic drugs, and the antibiotic drugs include at least one of quinolone drugs and tetracycline drugs; a stirring mechanism installed in the tank body and used to disperse the magnetic material in the aquaculture tail water; The electromagnetic mechanism is arranged on the outside of the tank body, and is used to apply a magnetic field to the tank body to magnetically separate the magnetic material from the aquaculture tail water; The method for using the device comprises: Adding the aquaculture tail water into the tank through the water inlet; Using the stirring mechanism to stir the aquaculture tail water; Adding the magnetic material into the tank through the feed port; Continuing to stir until the magnetic material completes the adsorption of the antibiotic drug in the aquaculture tail water; Using an electromagnetic mechanism to magnetically adsorb the magnetic material to magnetically separate the magnetic material from the aquaculture tail water; Discharge the aquaculture tail water from the tank; Release the magnetic attraction of the electromagnetic mechanism.

2. The method of use according to claim 1, wherein: The device comprises a filtering mechanism, and the aquaculture tail water enters the water inlet after being filtered by the filtering mechanism.

3. The method of use according to claim 1, wherein: The magnetic field strength applied by the electromagnetic mechanism is 3000-5000 Oe.

4. The method of use according to claim 1, wherein: The dosage of the magnetic material is 0.125-0.15 g / L of aquaculture tail water.

5. The method of use according to claim 1, wherein: The concentration of the antibiotic drug in the aquaculture tail water is not less than 0.8 μg / mL.

6. The method of use according to claim 1, wherein: The pH value of the aquaculture tail water is 6-8.

7. The method of use according to claim 1, wherein: The antibiotic drug is a tetracycline drug.

8. The method of use according to claim 1, wherein: The aquaculture tail water is stirred using the stirring mechanism, comprising: After adding the magnetic material, the stirring time is 120-150 s.

9. The method of use according to claim 1, wherein: Using an electromagnetic mechanism to magnetically adsorb the magnetic material to magnetically separate the magnetic material from the aquaculture tail water; And, discharging the aquaculture tail water from the tank, comprising: The magnetic material is magnetically adsorbed using an electromagnetic mechanism, and after 10-15 seconds, the aquaculture tail water is discharged from the tank.

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