Purifying device for breeding tail water containing antibiotic drugs and control method of purifying device

Abstract

The invention provides a purification device for breeding tail water containing antibiotic drugs and a control method thereof.The purification device comprises an adsorption tank and an electromagnetic mechanism, the adsorption tank comprises a tank body, and the tank body is made of a non-magnetic material; a feeding hole is formed in the tank body and is used for adding a magnetic material into the tank body, and the magnetic material is a hydrophilic magnetic polymer obtained by cross-linking a magnetic mixed hydroxide serving as a carrier and 3-amino-1, 2, 4-triazole serving as a functional monomer; a water inlet is formed in the tank body and used for adding breeding tail water into the tank body, the breeding tail water contains antibiotic drugs, and the antibiotic drugs comprise at least one of quinolone drugs and tetracycline drugs; the stirring mechanism is mounted in the tank body and is used for dispersing the magnetic material in the culture tail water; the electromagnetic mechanism is arranged on the outer side of the tank body and is used for applying a magnetic field into the tank body so as to magnetically separate the magnetic material from the breeding 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 antibiotic drugs and a control method thereof. Background Art

[0002] The extensive use and even abuse of antibiotics in aquaculture, 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 waters.

[0003] In recent years, relevant research institutions at home and abroad have proposed to carry out antibiotic treatment by means of physical elimination, photodegradation, chemical oxidation, microbial degradation, phytoremediation, etc. Based on the sewage treatment method adopted, the corresponding purification device and control method are proposed.

[0004] Adsorption is a commonly used method for removing antibiotics in wastewater treatment. Magnetic polymer materials have the characteristics of large specific surface area and magnetism, which can achieve large-scale adsorption and rapid separation. However, most common magnetic polymer materials are synthesized in non-polar organic solvents and only show optimal performance in non-aqueous environments. They are not suitable for the adsorption of antibiotics in aqueous media, which limits the research on the purification method of aquaculture tail water containing antibiotics and the device using the corresponding method. Summary of the invention

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

[0006] The present disclosure is implemented as follows:

[0007] In a first aspect, the present disclosure provides a purification device for 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, wherein the tank body is 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, the stirring mechanism is installed in the tank body and is 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, so as to magnetically separate the magnetic material from the aquaculture tail water.

[0014] In a second aspect, the present disclosure provides a control method for 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] Continue stirring 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] Discharging 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] The present invention discloses a purification device for aquaculture tail water containing antibiotic drugs, wherein the adsorbent used is HMP, which has strong hydrophilicity, and the preparation method is simple and easy, and does not require strict experimental conditions, and the synthesis cost is low. The HMP adsorption rate is fast, and the adsorption equilibrium can be reached in 120s to 150s. In the static adsorption experiment, the equilibrium adsorption amount of the antibiotic drug reaches 10.901mg / 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, so that the HMP can adsorb the target molecules more fully and the internal mass transfer process is faster.

[0025] Furthermore, the magnetization intensity of the HMP reaches 7.6emu / 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 drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present disclosure and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

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

[0028] Figure 2 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 the TEM image of the iron-aluminum MMH provided in the embodiment of the present disclosure; (b) is the TEM image of the HMP (50 nm); and (c) is the TEM image of the HMP (200 nm).

[0035] Fig. 9 In the figure, (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] Fig.10 VSM diagram of iron and aluminum MMH and HMP provided in the embodiments of the present disclosure.

[0037] Fig.11 It is a flow chart of the control method of the device provided in 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 purification device for aquaculture tail water containing antibiotic drugs, 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 tank 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 tank body is made of a non-magnetic alloy material, such as an 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 from being gathered prematurely 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 part of the tank body 11, and after the device is added with 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 and then enters the aquaculture tail water.

[0050] Furthermore, the dispersion mechanism may be a dispersion hopper. The dispersion hopper may receive the magnetic material added to the tank 11, and then disperse 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, and one end of the rotating roller is connected to the rotating shaft of the stirring mechanism 14 to achieve circular motion on the dispersion hopper to 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 that of the experiment.

[0054] The magnetic material is dispersedly added into the aquaculture tail water, so that more particles can be sheared by the stirring 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 (iron-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 (II) hexahydrate and aluminum chloride hexahydrate in a molar ratio of 2:1, add them to deionized water, and stir mechanically until they are completely dissolved. Then quickly add sodium hydroxide aqueous solution to keep the pH value at about 10. Stir mechanically at 500r / min for 10min. After the reaction is completed, stand and separate, discard the supernatant, collect the black product with a magnet, and wash with deionized water to obtain iron-aluminum 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 into deionized water and stir mechanically at 500 r / min until it is completely dispersed, and continue for 10 minutes to prepare an iron-aluminum MMH suspension.

[0063] Dissolve the hydrophilic 3-amino-1,2,4-triazole (ATA) in 250 mL of deionized water, add it to the above-mentioned iron-aluminum MMH suspension after it is completely dissolved, continue mechanical stirring for 30 minutes, then add the crosslinker dimethyl ethylene glycol acrylate (EGDMA), continue stirring for 30 minutes under the same conditions, and then quickly add the initiator ammonium persulfate (APS). The mixture is transferred to a vacuum glove box pre-filled with nitrogen, and the polymerization reaction is carried out in a 40°C water bath at 300r / min for 5 hours. After the reaction is completed, the supernatant is discarded, the product is collected, and washed with deionized water. Then dry it at 80°C for 5 hours to obtain HMP, which is stored at room temperature for later 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 with a standard test sieve of 150 mesh (aperture 0.1 mm), and a material with a diameter greater than 0.1 mm is used to increase its surface area for adsorption and reduce the magnetic field strength required for magnetic separation. Materials with too small a diameter will float on the water surface, which is not conducive to subsequent separation.

[0066] Static adsorption experiment of HMP

[0067] Standards

[0068] Sulfapyridine, Sulfadiazine, Sulfamethoxazole, Sulfathiazole, Sulfamerazine, Sulfisoxazole, Sulfamethizol, Sulfamethazine, Sulfameter, Sulfachloropyridazine, Sulfachinoxalin, Sulfadoxine, Sulfadimethoxine, 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, Marbofloxacin, with a purity greater than 92%; Sarafloxacin hydrochloride, with a purity greater than 87%; Oxytetracycline hydrochloride hydrochloride), tetracycline hydrochloride, doxycycline hydrochloride, with a purity greater than 90%; purchased from Manhage (Shanghai) Biotechnology Co., Ltd. The above standards were all prepared into 200 μg / mL standard stock solutions with methanol and stored at -20°C in the dark (the weight of the standard is the weight corrected for purity). Methanol was then used to prepare 20 μg / mL sulfonamide antibiotic standard mixed solutions, 20 μg / mL quinolone antibiotic standard mixed solutions, and 20 μg / mL tetracycline antibiotic standard mixed solutions, respectively, and stored at -20°C in the dark.

[0069] Taking the tetracycline antibiotic standard mixture as an example, the tetracycline antibiotic standard mixture includes all the antibiotic drugs under the tetracycline antibiotics in the above standard products, namely, oxytetracycline hydrochloride, tetracycline hydrochloride and doxycycline hydrochloride. And the concentration of each antibiotic drug contained in the antibiotic standard mixture is the same, which is 20μg / mL.

[0070] Instruments and Equipment

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

[0072] HPLC-MS / MS conditions

[0073] Chromatographic conditions: CAPCELL PAK-MGⅡC18 chromatographic column (2.1mm×150mm×5μm); column temperature 35°C; flow rate 0.25mL / min; injection volume 5μL; mobile phase: A is 0.005mol / L ammonium acetate-0.1% formic acid aqueous solution, B is 0.1% formic acid methanol; elution gradient: 0-5min (10%-90% B), 5-9min (90%-100% B), 9-10min (100%-10% B), 10-15min (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: 0.7u, Q3 half peak width: 0.7u, collision gas pressure: argon, 0.2Pa.

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

[0076]

[0077]

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

[0079] 10 mL of deionized water was measured and placed in a 50 mL test tube, and the standard mixed solution of sulfonamide antibiotics, the standard mixed solution of quinolone antibiotics, and the standard mixed solution of tetracycline antibiotics were added to prepare a mixed antibiotic solution. The concentrations of various antibiotic drugs 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 pH was adjusted to 6-8, and then 5 mg of HMP prepared in Example 6 was added, and vortexed at 2000 r / min for 120 s. 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 a 0.22 μm filter membrane, and detect by HPLC-MS / MS, with the determination repeated three times.

[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] In order to truly simulate the conditions of actual aquaculture tail water, the pH of the simulated solution was adjusted to be consistent with the pH of the tail water (pH 6-8), and the simulated solution contained sulfonamides, quinolones, and tetracyclines commonly found in aquaculture tail water. Under these conditions, a static adsorption experiment of multiple drugs was carried out to investigate 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 show that HMP cannot effectively adsorb sulfonamides, but with the increase of initial drug concentration, the adsorption of quinolones and tetracyclines by HMP gradually increases.

[0091] like Figure 2 As shown in the figure, when the drug concentration increases to 0.8 μg / mL, the adsorption of quinolones and tetracyclines by HMP tends to saturation, the adsorption capacity reaches the maximum, and the equilibrium adsorption amount Q is 10.901 mg / g. This may be because the higher initial concentration provides a stronger driving force for quinolones and tetracyclines, overcoming the mass transfer resistance between the solid and liquid phases, thereby increasing the contact time and collision number of quinolones and tetracyclines with the adsorbent, and increasing the chance of binding with 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] 10 mL of deionized water was measured in a 50 mL test tube, and mixed standard solutions of quinolone and tetracycline antibiotics were added respectively to prepare a mixed antibiotic solution with a concentration of 0.50 μg / mL for both quinolone and tetracycline antibiotics. The pH of the solution was adjusted to neutral, 5 mg of HMP prepared in Example 6 was added, and the mixture was vortexed at 2000 r / min for 10 s, 30 s, 60 s, 90 s, 120 s, 150 s and 180 s respectively. The supernatant was obtained by magnetic separation, and the pH value of the supernatant was adjusted to 4 with a formic acid solution having a mass fraction of 3%.

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

[0097] In order to further evaluate the adsorption mechanism, the adsorption kinetics of quinolones and tetracyclines on HMP were studied. The experimental data were fitted with the two most common kinetic models, namely the pseudo-first-order equation and the pseudo-second-order equation. 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, 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 in the figure, the kinetic adsorption curve shows a trend of gradually increasing first and then stabilizing. This shows that in the early stage of adsorption, the adsorbent has abundant active sites and can quickly bind to the drugs in the aquaculture tail water. As the adsorption proceeds, the solution concentration decreases, the number of sites on the adsorbent that have not yet bound to the drug decreases, and the adsorption rate decreases. It is worth noting that the adsorbent can reach the adsorption equilibrium state within 120-150s, which shows that its adsorption rate for quinolones and tetracyclines is very fast.

[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 kinetic model are significantly higher than those of the pseudo-first-order adsorption kinetic 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. Then, the equilibrium adsorption amount Q of the pseudo-second-order adsorption kinetics was 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 Very close, further verifying the accuracy of the quasi-secondary adsorption kinetic model. This shows that the adsorption of quinolones and tetracyclines by the adsorbent is mainly based on a chemical adsorption mechanism rather than simple physical adsorption. This chemical adsorption involves chemical bonding between the adsorbent and the target molecule, so it has a stronger binding force, which also involves electrostatic interactions, and chemical adsorption is the main reason for limiting the adsorption rate. At the same time, this also means that the adsorption process does not involve mass transfer in the solution, thereby further improving the adsorption efficiency and stability.

[0107] Iron and aluminum MMH and MHP characterization

[0108] X-ray diffraction (XRD)

[0109] There are four types of crystal structures of iron oxides, 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 the two materials have diffraction peaks at 30.4°, 35.8°, 43.2°, 53.7°, 57.5° and 63.1°, which correspond to the six crystal planes (220), (311), (400), (422), (511) and (440) of γ-Fe2O3, respectively. The diffraction peaks at 21.3° and 36.8° correspond to the two crystal planes (110) and (311) of γ-Al(OH)3. 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 γ-Fe2O3 and γ-Al(OH)3 with complete crystallization. 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 coated 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 and aluminum oxides in FeAl MMH. -1 The broad peak between 1630cm -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 Nearby (C=N) and 1318cm -1 、1260cm -1 The peaks of (aromatic secondary amine) are all characteristic absorption peaks of ATA, while 950cm -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 1100-1200cm -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 materials.

[0117] Figure 8 The TEM images of FeAl MMH and HMP are shown in Figure 2. The morphological characteristics of the two were studied by transmission electron microscopy. Figure 8 As shown in (a), particles of different 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 the 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 the iron-aluminum MMH and HMP. Fig. 9 As shown in (a), the FeAl MMH presents a spherical shape and is tightly aggregated together. Fig. 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 properties analysis

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

[0121] Fig.10 It is the hysteresis curve (VSM) of iron and aluminum MMH and HMP. Fig.10 It can be observed that both test materials present a centrally symmetrical state, which is a common characteristic of ferromagnetic materials. Further analysis shows that saturation magnetization and hysteresis loops appear in the curves. These two important features indicate that the prepared iron-aluminum MMH and HMP have superparamagnetic properties. Superparamagnetism is a special magnetic state that allows these materials to be quickly adsorbed by a magnet under the action of an external magnetic field and quickly lose their magnetism after the external magnetic field is removed. Specifically, the magnetization intensities of iron-aluminum MMH and HMP are 11.4 and 7.6 emu / g, respectively. This shows that with the increase of the polymer shell structure, the magnetic strength of the material gradually decreases. The reason for this decrease can be attributed to the shielding effect of the polymer shell on the surface of the iron-aluminum MMH, that is, the presence of the polymer shell weakens the material's ability to respond to the external magnetic field. Under the action of the external magnetic field, HMP can achieve rapid separation within 10s. This result fully proves that the polymer has good magnetic properties and can meet the needs of 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, a water inlet mechanism is provided on the top of the tank body 11. 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 introduced 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 between 6 and 8, the adsorption capacity of HMP for tetracyclines is significantly better than that for quinolones. Therefore, its efficiency can reach 100% when used for the purification of 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 function of the stirring paddle includes causing the water flow in the tank body 11 to form a circulating reflux along the direction of the rotation axis to prevent the magnetic material from settling to the bottom of the tank body 11 .

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

[0135] The electromagnetic mechanism 2 is disposed 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, 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 part of the outer wall of the tank body 11 .

[0137] The electromagnetic mechanism 2 can be arranged above the material 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 also be discharged from the tank 11 along with the aquaculture tail water and then magnetically separated by the electromagnetic mechanism 2. For example, a water reservoir is provided to accommodate the purified aquaculture tail water, the electromagnetic mechanism 2 is provided in the water reservoir, the magnetic material in the aquaculture tail water is adsorbed, the aquaculture tail water after magnetic separation is then 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 Fig.10 It can be seen that the magnetization intensity of HMP is 7.6emu / g. HMP can be evenly dispersed in water, and under the action of the external magnetic field, HMP can be quickly separated within 10-15s.

[0141] In some embodiments, 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 tail water after being adsorbed and purified by the magnetic material and magnetically separated from the tank body 11. The discharge port is used to discharge the magnetic material after adsorption and purification from the tank body 11. For example, after discharging the aquaculture tail water, clean water can be introduced into the tank body 11 to wash the tank body 11 and remove the magnetic material from the tank body 11.

[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 to intercept the magnetic material entering the pipe to prevent the magnetic material from staying in the tank body 11 without the action of the electromagnetic mechanism 2. If the magnetic material is discharged with the flow of 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 arranged at the end of the drain pipe 15 other than the drain outlet, and can be detachably arranged 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 an electromagnetic 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] It can be seen from the static adsorption experiment that the adsorption capacity of the magnetic material can reach 10.901 mg / g. Therefore, the use amount of the magnetic material to purify aquaculture tail water is small, does not require a lot 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 of quinolones and tetracyclines by HMP approached saturation, 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 disclosed embodiment provides a control method for a purification device for aquaculture tail water containing antibiotic drugs.

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

[0159] refer to Fig.11 , a control method for the device in 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, continuously stirring until the magnetic material completes the 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 aquaculture tail water with lower concentrations. 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, using the stirring mechanism 14 to stir the aquaculture tail water 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 magnetic material is magnetically adsorbed by an electromagnetic mechanism 2 , and the aquaculture tail water is discharged from the tank body 11 after 10-15 seconds.

[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, comprises:

[0177] S1021, the aquaculture tail water enters the water inlet after being filtered by the first filtering mechanism.

[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 in Example 1, 10L of aquaculture tail water after passing through a 0.45μm filter membrane was transferred into the tank 11, and 1.25g of HMP was added, and stirred at 2000r / min for adsorption purification. After 120s, magnetic separation was performed, and the supernatant of the aquaculture tail water was taken, and the pH value of the supernatant was adjusted to 4 with a formic acid solution with a mass fraction of 3%. 50mL of the supernatant was transferred, 1.5mL of methanol was added, and mixed, and then loaded.

[0181] The Oasis HLB solid phase extraction column was pre-activated with 6 mL of methanol and 6 mL of water, and then loaded with sample, the flow rate was controlled at 4 mL / min, 5 mL of water was eluted, vacuum dried for 5 min, 8 mL of methanol was eluted, and all the eluents were collected in a glass test tube and blown to dryness with nitrogen at 45°C. 1 mL of pH 4.0 water-acetonitrile solution (8:2, V / V) was added and ultrasonically dissolved, and the mixture was filtered through a 0.22 μm filter membrane and then subjected to high performance liquid chromatography-tandem mass spectrometry.

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

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

[0184]

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

[0186] (1) The device has an obvious adsorption and purification effect 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 is lower than the maximum adsorption capacity of the static adsorption experiment, which may be related to the larger volume of 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 can achieve a high adsorption amount 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 above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure. For those skilled in the art, the present disclosure may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure shall be included in the protection scope of the present disclosure.

Claims

1. A purification device for aquaculture tail water containing antibiotic drugs, characterized in that: The device comprises an adsorption tank and an electromagnetic mechanism: The adsorption tank comprises: A tank body, wherein 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 quinolone drugs and tetracycline drugs; 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, so as to magnetically separate the magnetic material from the aquaculture tail water.

2. The device according to claim 1, characterized in that The device comprises a filtering mechanism, and the aquaculture tail water enters the water inlet after being filtered by the filtering mechanism.

3. The device according to claim 1, characterized in that The magnetic field strength applied by the electromagnetic mechanism is 3000-5000 Oe.

4. The device according to claim 1, characterized in that The dosage of the magnetic material is 0.125-0.15 g / liter of aquaculture tail water.

5. The device according to claim 1, characterized in that The concentration of the antibiotic drug in the aquaculture tail water is not less than 0.8 μg / mL.

6. The device according to claim 1, characterized in that The pH value of the aquaculture tail water is 6-8.

7. The device according to claim 1, characterized in that The antibiotic drug is a tetracycline drug.

8. A control method for the device according to any one of claims 1 to 7, characterized in that: The method 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; Continue stirring 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; Discharging the aquaculture tail water from the tank; Release the magnetic attraction of the electromagnetic mechanism.

9. The method according to claim 8, characterized in that The aquaculture tail water is stirred using the stirring mechanism, comprising: After adding the magnetic material, the stirring time is 120-150s.

10. The method according to claim 8, characterized in that 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 by an electromagnetic mechanism, and after 10-15 seconds, the aquaculture tail water is discharged from the tank.

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