CN111704262A - Magnetic separation treatment and purification method of antibiotic wastewater - Google Patents
Magnetic separation treatment and purification method of antibiotic wastewater Download PDFInfo
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- CN111704262A CN111704262A CN202010419807.4A CN202010419807A CN111704262A CN 111704262 A CN111704262 A CN 111704262A CN 202010419807 A CN202010419807 A CN 202010419807A CN 111704262 A CN111704262 A CN 111704262A
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The invention relates to a magnetic separation treatment and purification method of antibiotic wastewater, wherein magnetic composite carbon spheres serving as an adsorbent are filled in a cylinder body, two ends of the cylinder body are sealed with microfiltration membranes, electromagnetic coils are wound on the periphery of the cylinder body, and the magnetic composite carbon spheres are uniformly distributed in the cylinder body in a suspended state after the electromagnetic coils are powered on to form an expanded bed type adsorption system; the antibiotic wastewater enters from the lower end of the cylinder body, is adsorbed by the magnetic composite carbon balls, leaves from the upper end of the cylinder body after adsorption, and enters the next purification treatment process; after adsorption, the eluent enters an adsorption system to desorb the adsorbent, and then the eluent enters a crystallization reactor; and after the desorption of the adsorbent is finished, washing the adsorbent with water. The purification treatment process of the antibiotic wastewater by utilizing magnetic separation is a continuous adsorption process, adsorption, desorption and regeneration of the adsorbent can be completed without dismounting a device, and the magnetic field intensity is increased by adjusting current, so that the adsorbent is fully separated from the feed liquid.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a magnetic separation treatment and purification method for antibiotic wastewater.
Background
The research and use of antibiotics has progressed rapidly since the discovery of penicillin in the 19 th century. The antibiotics are used in a large amount in clinic, breeding industry and agriculture, so that the environmental pollution of the antibiotics is serious, a plurality of residual antibiotics are found in water and soil in many regions of China, and the long-term existing antibiotics can cause the drug resistance of microorganisms and the like, thereby further threatening the ecological system and human health. At present, chemical oxidation, membrane treatment, adsorption and the like are commonly used as methods for treating antibiotics in water. Among them, adsorption is a commonly used method in research for removing antibiotics. In the wastewater treatment, solid materials such as activated carbon, molecular sieves, adsorption resins and the like are often used as adsorbents, but a large amount of powdery adsorbents have difficulty in solid-liquid separation, and the molecular sieves and the adsorption resins have problems of low adsorption capacity, large amount of waste liquid generated during regeneration, low adsorption recovery rate and high use cost.
Patent CN108311115A proposes a magnetic chitosan loaded TiO2Preparation and application of composite material prepared by mixing chitosan, titanium dioxide and Fe3O4The magnetic nano particle composite material is used for adsorbing tetracycline wastewater, the mass concentration of tetracycline in the wastewater is 0.01-0.1 g/L, and the removal rate of the composite material to antibiotics reaches 92% under an acidic condition (pH is 2). Patent CN107570116A proposes a magnetic MOFs adsorbing material for adsorbing antibiotics in water, and prepared SiO2@Fe3O4Addition of magnetic carriers to MOFs precursorsIn the solution, magnetic particles are attached to the surface of the MOFs to form the magnetic MOFs adsorption material. The material has an adsorption rate of 60% on antibiotic levofloxacin in water, and has great advantages in separation, recovery and recycling of the adsorbent. The patent CN104888706A provides a magnetic separation composite adsorbent, a preparation method and an application thereof, the magnetic separation composite adsorbent is prepared by taking a carbon nano tube as a main material and loading ferroferric oxide and manganese dioxide on the surface of the carbon nano tube, the removal rate of tetracycline with the concentration of not more than 300mg/L in antibiotic wastewater reaches 96%, the adsorption in 12 hours reaches balance, and the adsorption amount is 500-800 mg/g. Patent CN106475071A proposes a magnetic microsphere and a preparation method thereof and application thereof in treating antibiotic wastewater, wherein ethylenediamine and chloroacetic acid are adopted to modify chloromethyl polystyrene microspheres, the modified polystyrene microspheres and an ammonium ferric oxalate solution are subjected to solvothermal reaction to prepare the magnetic microsphere, and magnetic nanoparticles are on the surface or in the microsphere. The magnetic microspheres are used for treating 100mg/L tetracycline wastewater in the presence of a proper amount of hydrogen peroxide, and 90% tetracycline can be adsorbed and degraded within 2 hours.
The above patents all apply magnetic composite materials to separate antibiotics in wastewater through adsorption reaction, and the chitosan coated magnetic carrier and polystyrene microsphere high polymer materials described in the above patents have poor relative mechanical properties, cannot resist high temperature and acid-base corrosion, and the like; the magnetic MOFs adsorption material and the magnetic carbon nano tube load magnetic nano particles on the surface of the material, and the magnetic nano particles are easily oxidized and corroded by acid, so that the saturation magnetization intensity and the service life of the magnetic composite material are influenced. And the preparation conditions of the magnetic carbon nanotube, the magnetic graphene oxide and the like are harsh, the batch production is difficult, and the regeneration of the adsorbent is difficult.
In addition, the above patents mostly focus on the preparation of the magnetic composite adsorbent, and the process for treating antibiotic wastewater by using the magnetic composite adsorbent is not deeply studied.
Patent CN205398325U discloses an antibiotic waste water processing apparatus, comprises catch basin, active carbon adsorption chamber, ozone/ultraviolet ray reaction chamber, pH equalizing basin and ozone generator etc. to get rid of pollutants such as high COD, high SS among the antibiotic waste water. The patent CN103011526A discloses a method for treating erythromycin thiocyanate wastewater, which comprises six treatment units of yeast treatment, catalytic micro-electrolysis, two-phase anaerobic treatment, CASS treatment, advanced oxidation and an aeration biological filter, and has high removal efficiency of ammonia nitrogen and COD in the wastewater. The patent CN102583880B discloses a treatment process of antibiotic pharmaceutical wastewater, which comprises the steps of pretreatment of antibiotic wastewater, immobilized bio-enzyme treatment, immobilized activated sludge treatment and the like, and the treatment effect is increased by 2-3 times compared with that of the treatment process by using an immobilized microorganism technology alone by combining two treatment methods of bio-enzyme and activated sludge.
The above patents and the existing numerous antibiotic wastewater treatment devices almost use the removal rate of COD in wastewater as an index, and have no specific adsorption removal process for antibiotics and corresponding compounds in antibiotic wastewater.
The prior art documents relating to the adsorption of antibiotics by magnetic composite carbon spheres are described below:
article Photo-fenton refreshable Fe3O4@ HCS adsorbent for the ionization of tetracycline hydrochloride discloses a magnetic carbon sphere Fe of yolk shell structure3O4The technical scheme of @ HCS for adsorbing tetracycline hydrochloride adopts a solvothermal method to prepare Fe3O4Then, a layer of SiO is coated outside the magnetic core by two times of coating, namely a Stober method2To obtain Fe3O4@SiO2Then coating resorcinol-formaldehyde resin on Fe3O4@SiO2Outside, Fe is obtained3O4@SiO2@ RF, carbonizing, etching and removing silicon to obtain magnetic carbon sphere Fe with yolk shell structure3O4@ HCS, the specific surface area of the carbon sphere being 213.2m2And the content of micropores is 43.7 percent, the adsorption is used for adsorbing tetracycline hydrochloride, ultrasonic oscillation is used for adsorbing 60mg/L tetracycline hydrochloride solution, the adsorption reaches balance within 6 hours, and the maximum adsorption capacity is 49 mg/g. The adsorbent can be regenerated within 10min by photo-fenton reaction.
The magnetic composite carbon ball prepared by the method adopts twice coating, and then is carbonized and etched to remove silicon, the process is complex, and the specific surface area obtained is 213.2m2/g。
The article "Preparation and characterization of chitosan/halloyite magnetic microspheres and the" upper application for removal of a tetracycline from aqueous solutions "discloses a method of using chitosan/kaolin nanotube microspheres as an adsorbent for antibiotics, which comprises preparing magnetic nanotubes first, and then preparing chitosan/kaolin nanotube microspheres (CTS/HNT-Fe) as a magnetically separable adsorbent by emulsion cross-linking3O4) Wherein the magnetic nano-tube is loaded on the surface and inside of the chitosan microsphere. The particle size of the microspheres is 4-8 μm, and the average particle size is 5.7 μm. The microspheres are used as an adsorbent for removing tetracycline in an aqueous solution. Adsorbing 100mg/L tetracycline at 25 deg.C, and reaching equilibrium at 80min, with maximum adsorption amount of 38 mg/g. An article, namely preparation of a core-shell type magnetic carbon nano adsorbent and adsorption research on aureomycin in a water environment, discloses a magnetic nano adsorbent coated by a graphitized carbon layer, wherein inorganic ferric salt and glucose are used as precursors, magnetic nano ferroferric oxide particles coated by a hydrophilic carbon layer are firstly synthesized, and then the magnetic nano adsorbent coated by the graphitized carbon layer is obtained by high-temperature (850 ℃) treatment under the protection of nitrogen. Adsorbing 0.02g/L aureomycin solution, and the maximum adsorption capacity is 909 mg/g. Article "preparation of high specific surface area magnetic carbon material and study of adsorption properties to sulfonamides antibiotics" discloses magnetic carbon composite microspheres: according to the method, ferroferric oxide is prepared by a hydrothermal method, glucose, soluble starch and cyclodextrin are compared to be used as carbon sources, finally, glucose is selected to be used as the carbon source to prepare the magnetic carbon composite microspheres, and an industrial activated carbon mode (ZnCl is used)2Impregnated and then calcined) to prepare magnetic carbon spheres with high specific surface area. 25mg/L of sulfanilamide and sulfadiazine are adsorbed, and the maximum adsorption quantity is 31 and 28 mg/g.
The magnetic carbon spheres prepared by the above documents are not typical core-shell type magnetic composite carbon spheres, and do not undergo a pore-forming preparation process of a surface mesoporous structure, and the antibiotics adsorbed by the above documents are mainly antibiotics with relatively small molecular weights such as tetracycline, aureomycin, sulfonamides, and the like.
Disclosure of Invention
The invention aims to provide a magnetic separation treatment and purification method of antibiotic wastewater, which applies magnetic composite carbon balls as an adsorbent to the technical process of continuously adsorbing and treating antibiotic wastewater.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a magnetic separation treatment and purification method of antibiotic wastewater, which comprises the following steps:
magnetic composite carbon spheres serving as an adsorbent are filled in the cylinder, microfiltration membranes are sealed at two ends of the cylinder, electromagnetic coils are wound on the periphery of the cylinder, and the magnetic composite carbon spheres are uniformly distributed in the cylinder in an expanded bed suspension state after the electromagnetic coils are powered on to form an adsorption system;
the antibiotic wastewater enters the interior of the cylinder from the microfiltration membrane at the lower end of the cylinder, is adsorbed by the magnetic composite carbon balls, and then leaves the interior of the cylinder from the microfiltration membrane at the upper end of the cylinder to enter the next purification treatment process;
after adsorption, enabling the eluent to enter an adsorption system to desorb the adsorbent, enabling the eluent to enter a reaction crystallizer, reacting and crystallizing the antibiotic in the eluent, and recovering the antibiotic in a solid-liquid separation mode;
after the desorption of the adsorbent is finished, the adsorbent is washed, and the adsorbent after washing can be used for next round of wastewater adsorption and purification, so that the continuity of the adsorption process is ensured.
In one embodiment of the present invention, the magnetic composite carbon spheres are yolk-eggshell type magnetic composite carbon spheres having a mesoporous structure, in which Fe is used3O4The magnetic nano particles are used as magnetic cores; the shell layer is formed by taking resorcinol-formaldehyde resin as a carbon source, tetraethoxysilane as a silicon source and hydrolysate silicon dioxide of the tetraethoxysilane as a hard template through hydrothermal reaction, and is characterized in that a mesoporous structure is generated in the carbon layer.
In some embodiments of the present invention, the magnetic composite carbon sphere has an average particle size of 2 to 4 μm, a magnetic core particle size of 0.9 to 1.1 μm, a carbon layer thickness of 0.5 to 0.7 μm, and a specific surface area of 500-600m2(ii)/g, the average pore diameter is 7-10 nm.
In one aspect of the inventionIn a preferred embodiment, the magnetic composite carbon sphere has an average particle diameter of 3 μm, a magnetic core particle diameter of 0.9 to 1.1 μm, a carbon layer thickness of 0.6 μm, and a specific surface area of 553m2In terms of/g, the mean pore diameter is 8.7 nm.
In one embodiment of the present invention, the preparation method of the magnetic composite carbon sphere comprises: method for preparing magnetic nano particle Fe by adopting solvothermal method3O4Improvement of Fe by addition of dispersant PSSMA3O4The dispersibility and the uniformity solve the problem of easy agglomeration; and then preparing the magnetic composite carbon spheres by adopting an improved hard template method, wherein resorcinol formaldehyde is used as a carbon source, tetraethoxysilane is used as a silicon precursor, a surfactant cetyl trimethyl ammonium bromide is used as an auxiliary reagent, in-situ polymerization reaction is carried out, silicon is etched and removed by using a sodium hydroxide solution after carbonization, the yolk eggshell type magnetic composite carbon spheres are prepared, and most of the carbon layers are of mesoporous structures.
In one embodiment of the present invention, the specific preparation method of the magnetic composite carbon sphere (5) is:
1.Fe3O4the preparation of (1): dissolving ferric trichloride hexahydrate in ethylene glycol, adding anhydrous sodium acetate, violently stirring, adding a dispersing agent PSSMA, and violently stirring to uniformly mix the solution. Transferring the uniformly mixed brown yellow solution into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction. After the reaction, the black precipitate was separated from the reaction solution with a neodymium magnet to produce Fe3O4The nanoparticles are washed three times by deionized water and ethanol in sequence and dried.
2.Fe3O4Preparation of @ C: the prepared Fe3O4Dispersing magnetic nanoparticles into an ethanol-water mixed solvent, adding ammonia water as an alkaline catalyst, sequentially adding resorcinol, a surfactant, a formaldehyde solution and a silicon source TEOS, uniformly mixing, stirring for reaction under a water bath condition, transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into an oven for hydrothermal reaction, washing with deionized water and absolute ethyl alcohol to remove impurities after the reaction is finished, drying the product, carbonizing in a nitrogen atmosphere, and performing surface carbonizationThe activator CTAB is removed during carbonization, and RF is carbonized; then, etching the hard template silicon dioxide in the material by using a sodium hydroxide solution in a water bath environment to obtain Fe3O4@ C, namely, the magnetic composite carbon sphere.
In the preparation method of the magnetic composite carbon ball provided by the invention, Fe3O4The preparation process of the magnetic nanoparticle adopts PSSMA as a dispersing agent, effectively improves the hydrophilicity and the dispersibility of the magnetic nanoparticles, and the dispersion liquid formed in water has long stabilization time and is not easy to coagulate and aggregate.
In the preparation method of the magnetic composite carbon sphere, the mesoporous magnetic composite carbon sphere is prepared by coating the magnetic core by using an improved hard template method.
In one embodiment of the invention, the pore diameter of the microfiltration membrane is 0.2-0.3 μm, and the pore diameter adopted in one embodiment of the invention is 0.22 μm, so that solid pollutants are prevented from entering the adsorption bed and the leakage of the magnetic composite carbon sphere adsorbent is prevented.
In one embodiment of the invention, the cartridge is a cylindrical cartridge.
In one embodiment of the invention, the concentration of the antibiotics in the antibiotic wastewater is 200-600mg/L, the flow rate of the antibiotic wastewater entering the adsorption system is 5-8 mL/min, and the addition amount of the magnetic composite carbon ball adsorbent required for treating each liter of antibiotic wastewater is 1.3-2.0 g.
The temperature of the adsorption process was 293-313K.
Preferably, during the adsorption process, the pH of the biological-resistant wastewater is adjusted to facilitate the adsorption of antibiotics. For example, for adsorption of macrolide antibiotics represented by erythromycin, the pH range of the antibiotic wastewater is preferably 9 to 11, and adsorption of macrolide antibiotics represented by erythromycin is favored under the pH range.
In one embodiment of the present invention, the antibiotic includes macrolide antibiotics and derivatives thereof, selected from erythromycin antibiotics, midecamycin antibiotics, spiramycin antibiotics, ketolides, macrolide lactam antibiotics, polyene macrolide antibiotics, and 18-membered novel macrolide antibiotics, further, the antibiotic is selected from one or more of erythromycin (base), clarithromycin, azithromycin, midecamycin, acetylmidecamycin, spiramycin, acylated spiramycin, telithromycin, amphotericin B, pentamycin, fidaxomycin, and the like, preferably erythromycin.
In one embodiment of the present invention, the adsorbed antibiotic wastewater is separated from the interior of the cylinder through the microfiltration membrane at the upper end of the cylinder, and then enters the antibiotic concentration detection unit, and the antibiotic concentration detection unit detects the antibiotic concentration in the adsorbed antibiotic wastewater, and then the antibiotic wastewater enters the next purification treatment process.
In one embodiment of the present invention, the antibiotic concentration detection unit is an ultraviolet spectrophotometer.
In the invention, the removal rate of the antibiotics is required to be more than 80 percent, even can reach 95 percent in some embodiments, so the removal rate of the antibiotics can be 80-96 percent by adopting the method.
The removal rate of the antibiotics is calculated according to the concentration of the antibiotics in the original antibiotic wastewater to be treated and the concentration of the antibiotics in the antibiotic wastewater detected in the antibiotic concentration detection unit.
The concentration of the antibiotics in the original antibiotic wastewater to be treated can be calculated by adopting an antibiotic concentration detection unit (such as an ultraviolet spectrophotometer), and during actual operation, the removal rate of the antibiotics in the wastewater in the purification process can be calculated according to the concentration of the adsorbed antibiotics wastewater detected in real time in the antibiotic concentration detection unit.
The antibiotic concentration detection unit (7) detects the antibiotic concentration in real time, and when the antibiotic adsorption amount calculated based on the antibiotic concentration detected at a certain moment and the antibiotic concentration in the initial antibiotic wastewater to be treated is greater than 80% of the saturated adsorption amount of the input magnetic composite carbon balls, the adsorbent is indicated to reach saturated adsorption.
In one embodiment of the invention, the antibiotic wastewater is pretreated to remove solid particles, stored in an antibiotic wastewater feeding tank, and pumped into an adsorption system for adsorption treatment by a feeding pump from the antibiotic wastewater feeding tank, and fed at a constant speed;
when the adsorbent is confirmed to reach saturated adsorption by calculating the concentration detected in real time in the antibiotic concentration detection unit, the feed pump is closed, the current of the electromagnetic coil is increased to increase the magnetic field intensity, so that the adsorbent is attached to the inner side of the cylinder body and is completely separated from the antibiotic wastewater, and the antibiotic wastewater to be treated is emptied;
storing an eluent in an eluent feeding tank, opening an eluent feeding valve, recovering the magnetic field intensity to enable the adsorbent to be uniformly suspended in the barrel, enabling the eluent to flow through the adsorbent from the lower part of the barrel at the flow rate of 2-5 mL/min, eluting the antibiotics adsorbed by the adsorbent, closing the eluent feeding valve after the elution lasts for 30-60 min, storing the eluent in an eluent storage tank, increasing the magnetic field intensity to fully separate the adsorbent from the eluent, and emptying the eluent;
the water washing liquid is stored in the water washing feeding tank, a valve of the water washing feeding tank is opened, the magnetic field intensity is recovered to enable the adsorbent to be uniformly suspended in the cylinder, and the adsorbent can be adsorbed again after being washed, so that continuous adsorption is realized.
In one embodiment of the invention, the eluent is selected from n-butyl acetate or acetone.
In one embodiment of the invention, the eluent in the eluent liquid storage tank contains antibiotics, the eluent in the eluent liquid storage tank enters the crystallization reactor, thiocyanic acid is added to react to generate thiocyanic acid antibiotic salt, and the crystal mush is subjected to solid-liquid separation to obtain thiocyanic acid antibiotic salt crystals.
In one embodiment of the invention, the adsorption capacity of the adsorbent is reduced by only 10% -15% of the initial adsorption capacity after the adsorbent is recycled for 5 times, which shows that the magnetic composite carbon spheres have good reusability and reduce the cost of one-time use of the adsorbent.
The process of the invention is suitable for purifying treatment of bulk antibiotic wastewater. The magnetic composite carbon sphere of the adsorbent consists of shell carbon and Fe3O4Magnetic core composition, shellThe carbon has good chemical stability and thermal stability, the magnetic core gives magnetism to the adsorbent, the magnetic core is suspended in a wastewater medium under the action of an external magnetic field to form an expanded bed, and the adsorption process has the advantages of large operation flux, low pressure and difficult blockage. And the whole adsorption process is simple and convenient to operate, the adsorbent can be repeatedly used, and the process cost is low.
Although the technical scheme of the invention has related reports on the preparation raw materials of the magnetic composite carbon spheres and the structures of the magnetic carbon spheres, one improvement of the invention is as follows: the yolk-eggshell type magnetic carbon spheres are prepared by a one-step method; the obtained magnetic carbon spheres have larger specific surface area (500-600 m)2And/g) mainly adopts a mesoporous structure, and has better adsorption performance on antibiotics.
The adsorbent prepared by the invention is a yolk-eggshell type magnetic composite carbon sphere, and magnetic nano particles are coated in shell carbon to prevent Fe3O4Oxidized or affected by an acidic environment; the shell carbon is obtained by high-temperature carbonization of resorcinol-formaldehyde resin, has high mechanical strength, chemical stability and thermal stability, and is resistant to acid and alkali corrosion; the magnetic composite carbon sphere prepared by the technology has good sphericity and high specific surface area, and the pores of the carbon layer are mainly of a mesoporous structure, so that the adsorption of antibiotics is facilitated.
The invention provides a complete magnetic separation and adsorption process of antibiotic wastewater, magnetic composite carbon spheres are suspended in a wastewater medium to form an expanded bed under the action of an external magnetic field to adsorb antibiotics in the wastewater, the adsorption process has the advantages of small resistance, difficulty in blockage and the like, the magnetic field intensity can be adjusted by adjusting the current, the rapid separation of an adsorbent and the wastewater is realized, the adsorbent has good regeneration cycle performance, and can be recycled after desorption and regeneration, and the continuous adsorption process can be realized.
The invention provides the adsorption and separation of wastewater antibiotics by taking external magnetic field separation as a core, and equipment used by the invention is specifically designed according to the characteristics of an adsorbent composite carbon magnetic ball.
Compared with the prior art, the invention utilizes the external magnetic field to make the magnetic adsorbent in an expanded bed suspension state to complete the continuous adsorption process, effectively removes antibiotics (especially erythromycin) in the antibiotic wastewater, and the antibiotics in the desorption solvent can be recovered in a reaction crystallization mode. The adsorption treatment of the large amount of industrial antibiotic wastewater can be realized, the regeneration performance of the adsorbent is good, the adsorption performance is reduced by 10-15% after five times of recycling, and the adsorbent can be repeatedly used.
The purification treatment process of the antibiotic wastewater by utilizing magnetic separation is a continuous adsorption process, adsorption, desorption and regeneration of the adsorbent can be completed without dismounting a device, and the magnetic field intensity is increased by adjusting current, so that the adsorbent is fully separated from the feed liquid.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for continuously treating antibiotic wastewater by using a magnetic separation technology, which is provided in embodiment 1.
Fig. 2a nitrogen adsorption and desorption curve (a) and a pore size distribution diagram (b) of the magnetic composite carbon sphere prepared in example 1;
fig. 3 a transmission electron micrograph of the magnetic composite carbon sphere prepared in example 1.
The reference numbers in fig. 1 are: 1-an antibiotic wastewater feeding tank, 2-a feeding pump, 3-a microfiltration membrane, 4-a barrel, 5-a magnetic composite carbon ball, 6-an electromagnetic coil, 7-an antibiotic concentration detection unit, 8-a purification treatment process, 9-an eluent feeding tank, 10-a water washing feeding tank, 11-an eluent liquid storage tank and 12-a crystallization reactor.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of the magnetic composite carbon spheres is provided:
1.Fe3O4the preparation of (1): dissolving 2.04g of ferric chloride hexahydrate in 60mL of ethylene glycol, adding 3.6g of anhydrous sodium acetate, stirring vigorously for 30min, adding 0.9g of dispersing agent PSSMA, and stirring vigorously for 30min to uniformly mix the solution. Transferring the uniformly mixed brown yellow solution into a stainless steel water heating kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction in an oven at 200 ℃ for 10 hours. After the reaction was complete, the black precipitate was reacted with neodymium magnetThe reaction solution is separated to produce Fe3O4The nanoparticles are washed three times by deionized water and ethanol in sequence and dried.
2.Fe3O4Preparation of @ C: the prepared Fe3O4Dispersing magnetic nanoparticles into 84mL of ethanol-water mixed solvent (volume ratio is 3: 4), adding 0.6mL of ammonia water as an alkaline catalyst, sequentially adding 0.6g of resorcinol, 0.6g of surfactant CTAB, 0.84mL of formaldehyde solution and 4mL of silicon source TEOS, uniformly mixing, stirring and reacting for 24h under the condition of 40 ℃ water bath, transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into a 100 ℃ drying oven for hydrothermal reaction for 24h, washing with deionized water and absolute ethyl alcohol to remove impurities after the reaction is finished, drying the product, carbonizing at 600 ℃ for 4h under the atmosphere of nitrogen, removing the surfactant CTAB in the carbonization process, and carbonizing RF; then etching to remove hard template silicon dioxide in the material by using 1mol/L sodium hydroxide solution in a water bath environment at 50 ℃ to obtain Fe3O4@ C, namely, the magnetic composite carbon sphere.
The average particle size of the magnetic composite carbon sphere obtained in this example was about 3 μm, the particle size of the magnetic core was 0.9 to 1.1. mu.m, the thickness of the carbon layer was about 0.6. mu.m, and the specific surface area was 553m2In terms of/g, the mean pore diameter is 8.7 nm.
The magnetic composite carbon sphere obtained in the embodiment has the performances of high mechanical strength, chemical stability, thermal stability, acid and alkali corrosion resistance and the like.
The nitrogen adsorption/desorption curve and the pore size distribution of the magnetic composite carbon spheres obtained in this example are shown in fig. 2. As can be seen from FIG. 2a, the nitrogen adsorption/desorption curve of the magnetic composite carbon sphere belongs to the type IV adsorption isotherm and is at the relative pressure P/P0>Within the 0.4 range there is a clear hysteresis loop type H2, which is indicative of the presence of mesopores. The pore size distribution plot shown in fig. 2b visually illustrates that the average pore size of the magnetic composite carbon spheres is 8.7 nm. The specific surface area of the magnetic composite carbon sphere obtained by the test of a specific surface area and pore size distribution tester is 553m2Per g, total pore volume of 0.604cm3The proportion of mesoporous volume is 83 percent. Therefore, the pore structure of the magnetic composite carbon sphere is mainly mesoporous. Drawing (A)The transmission electron microscope picture of the magnetic composite carbon sphere shown in 3 shows that the magnetic composite carbon sphere has a yolk-eggshell type core-shell structure, and the shell carbon has a rich disordered pore structure.
Example 2
The embodiment provides a magnetic separation treatment and purification method of erythromycin wastewater, and refers to fig. 1.
In the embodiment, the concentration of the erythromycin in the erythromycin wastewater to be treated is 300mg/L, the flow rate of the erythromycin wastewater entering the adsorption system is 5mL/min, and the adding amount of the magnetic composite carbon sphere 5 adsorbent required for treating each liter of the erythromycin wastewater is 1.5 g.
The method comprises the following steps:
1. the magnetic composite carbon spheres 5 prepared in the embodiment 1 are used as an adsorbent and filled in a cylinder 4, two ends of the cylinder 4 are sealed with microfiltration membranes 3, an electromagnetic coil 6 is wound on the periphery of the cylinder 4, and after the electromagnetic coil 6 is powered on, the magnetic composite carbon spheres 5 are uniformly distributed in the cylinder 4 in an expanded bed suspension state to form an adsorption system;
2. firstly, pretreating erythromycin wastewater to remove solid particles, storing the erythromycin wastewater in an erythromycin wastewater feeding tank 1, pumping the erythromycin wastewater from the erythromycin wastewater feeding tank 1 into a barrel 4 through a feeding pump 2 for adsorption treatment, keeping constant-speed feeding, wherein the temperature in the adsorption process is 298K, the pH of the erythromycin wastewater is 10, adsorbing the erythromycin wastewater by a magnetic composite carbon ball 5, allowing the adsorbed erythromycin wastewater to leave the barrel 4 from a microfiltration membrane 3 at the upper end of the barrel 4, allowing the erythromycin wastewater to enter an erythromycin concentration detection unit 7, and detecting the concentration of erythromycin in the adsorbed erythromycin wastewater by an erythromycin concentration detection unit 7 to enter a next purification treatment process 8 for treatment;
3. when the concentration detected in real time in the erythromycin concentration detection unit 7 exceeds a specified detection value (higher than 60mg/L), indicating that the adsorbent reaches saturated adsorption, closing the feed pump 2, increasing the current of the electromagnetic coil 6 to increase the magnetic field intensity, attaching the adsorbent to the inner side of the cylinder 4, completely separating the adsorbent from the erythromycin wastewater, and emptying the erythromycin wastewater to be treated;
4. storing an eluent in an eluent feeding tank 9, opening an eluent feeding valve, recovering the magnetic field intensity to enable the adsorbent to be uniformly suspended in the cylinder, enabling the eluent to flow through the adsorbent from the lower part of the cylinder 4 at the flow rate of 6mL/min, eluting erythromycin adsorbed by the adsorbent, closing an eluent feeding valve after the elution lasts for 60min, storing the eluent in an eluent storage tank 11, increasing the magnetic field intensity to fully separate the adsorbent from the eluent, and emptying the eluent;
5. the eluent in the eluent liquid storage tank 11 contains erythromycin, the eluent in the eluent liquid storage tank 11 enters the crystallization reactor 12, thiocyanic acid is added to react to generate a erythromycin thiocyanate salt, and crystal mush is subjected to solid-liquid separation to obtain erythromycin thiocyanate salt crystals;
6. the water washing liquid is stored in the water washing feeding tank 10, a valve of the water washing feeding tank is opened, the magnetic field intensity is recovered to enable the adsorbent to be uniformly suspended in the cylinder, and the adsorbent can be adsorbed again after being washed, so that continuous adsorption is realized.
In this embodiment, the aperture of the microfiltration membrane 3 is 0.22 μm, which is to prevent the leakage of the magnetic composite carbon sphere adsorbent while blocking the entry of solid contaminants.
In this embodiment, the cylinder 4 is a cylindrical cylinder.
In this embodiment, the erythromycin concentration detection unit 7 is an ultraviolet spectrophotometer.
In this example, n-butyl acetate was used as eluent.
In this embodiment, the removal rate of erythromycin is calculated based on the concentration of erythromycin in the erythromycin wastewater detected by the erythromycin concentration detection unit 7.
In this example, the removal rate of erythromycin reached 93.3%.
In this example, the adsorption capacity of the adsorbent is reduced by only 13.5% of the initial adsorption capacity after 5 times of cyclic regeneration, which shows that the magnetic composite carbon spheres have good reusability and reduce the cost of one-time use of the adsorbent.
In the embodiment, the adsorption amount of the unit magnetic composite carbon sphere to erythromycin is 255mg/g, and the adsorption performance is superior to that of other adsorbents reported in the literature, such as: in the article research on purification of erythromycin by macroporous resin, the dynamic adsorption capacity of macroporous adsorption resin HZ816 on erythromycin is 134 mg/g; the adsorption quantity of the carbon nano tube to the erythromycin in article study on the adsorption characteristics of the carbon nano tube to the low-concentration erythromycin in water is 144 mg/g.
Example 3
The embodiment provides a method for purifying azithromycin wastewater by magnetic separation treatment, and the method is shown in figure 1.
In the embodiment, the concentration of azithromycin in the azithromycin wastewater to be treated is 400mg/L, the flow rate of the azithromycin wastewater entering the adsorption system is 5mL/min, and the addition amount of the magnetic composite carbon sphere 5 adsorbent required for treating each liter of azithromycin wastewater is 2.0 g.
The method comprises the following steps:
1. the magnetic composite carbon spheres 5 prepared in the embodiment 1 are used as an adsorbent and filled in a cylinder 4, two ends of the cylinder 4 are sealed with microfiltration membranes 3, an electromagnetic coil 6 is wound on the periphery of the cylinder 4, and after the electromagnetic coil 6 is powered on, the magnetic composite carbon spheres 5 are uniformly distributed in the cylinder 4 in an expanded bed suspension state to form an adsorption system;
2. solid particles of azithromycin wastewater are removed through pretreatment, the azithromycin wastewater is stored in an azithromycin wastewater feeding tank 1, the azithromycin wastewater is pumped into a barrel 4 from the azithromycin wastewater feeding tank 1 through a feeding pump 2 for adsorption treatment, constant-speed feeding is kept, the temperature in the adsorption process is 298K, the adsorbed azithromycin wastewater leaves the interior of the barrel 4 through a microfiltration membrane 3 at the upper end of the barrel 4 after being adsorbed by a magnetic composite carbon ball 5, the azithromycin wastewater enters an azithromycin concentration detection unit 7, and the azithromycin concentration in the adsorbed azithromycin wastewater is detected by the azithromycin concentration detection unit 7 and then enters a next purification treatment process 8 for treatment;
3. when the concentration detected in real time in the azithromycin concentration detection unit 7 exceeds a specified detection value (higher than 80mg/L), indicating that the adsorbent reaches saturated adsorption, closing the feed pump 2, increasing the current of the electromagnetic coil 6 to increase the magnetic field intensity, attaching the adsorbent to the inner side of the cylinder 4, completely separating the adsorbent from the azithromycin wastewater, and emptying the to-be-treated azithromycin wastewater;
4. storing an eluant in an eluant feeding tank 9, opening an eluant feeding valve, recovering the magnetic field intensity to enable the adsorbent to be uniformly suspended in the cylinder, enabling the eluant to flow through the adsorbent from the lower part of the cylinder 4 at the flow rate of 5mL/min, eluting azithromycin adsorbed by the adsorbent, closing an eluant feeding valve after the elution lasts for 60min, storing the eluant in an eluant storage tank 11, increasing the magnetic field intensity, fully separating the adsorbent from the eluant, and emptying the eluant;
5. the eluent in the eluent liquid storage tank 11 contains azithromycin, the eluent in the eluent liquid storage tank 11 enters a crystallization reactor 12, a methanol solution containing sodium hydroxide is added, the pH value of the solution is adjusted to 11, and the azithromycin is crystallized and recovered from an azithromycin salt solution;
6. the water washing liquid is stored in the water washing feeding tank 10, a valve of the water washing feeding tank is opened, the magnetic field intensity is recovered to enable the adsorbent to be uniformly suspended in the cylinder, and the adsorbent can be adsorbed again after being washed, so that continuous adsorption is realized.
In this embodiment, the aperture of the microfiltration membrane 3 is 0.22 μm, which is to prevent the leakage of the magnetic composite carbon sphere adsorbent while blocking the entry of solid contaminants.
In this embodiment, the cylinder 4 is a cylindrical cylinder.
In this embodiment, the azithromycin concentration detection unit 7 is an ultraviolet spectrophotometer.
In this example, dichloromethane was used as eluent.
In this embodiment, the removal rate of azithromycin is calculated based on the concentration of azithromycin in the azithromycin wastewater detected by the azithromycin concentration detection unit 7.
In this embodiment, the concentration of azithromycin in the azithromycin wastewater detected by the azithromycin concentration detection unit 7 is 30mg/L, and the removal rate of azithromycin reaches 92.5%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A magnetic separation treatment and purification method of antibiotic wastewater is characterized by comprising the following steps:
magnetic composite carbon spheres (5) serving as an adsorbent are filled in the cylinder body (4), the two ends of the cylinder body (4) are sealed with the microfiltration membrane (3), the periphery of the cylinder body (4) is wound with an electromagnetic coil (6), and after the electromagnetic coil (6) is powered on, the magnetic composite carbon spheres (5) are uniformly distributed in the cylinder body (4) in an expanded bed suspension state to form an adsorption system;
the antibiotic wastewater enters from the lower end of the cylinder (4), is adsorbed by the magnetic composite carbon balls (5), leaves from the upper end of the cylinder (4), and enters into the next purification treatment process (8);
after adsorption, the eluent enters an adsorption system to desorb the adsorbent, then the eluent enters a reaction crystallizer (12), the antibiotics in the eluent are reacted and crystallized, and the antibiotics are recovered by a solid-liquid separation mode;
and after the desorption of the adsorbent is finished, washing the adsorbent, wherein the adsorbent after washing can be used for next round of wastewater adsorption and purification.
2. The method for magnetic separation, treatment and purification of antibiotic wastewater as claimed in claim 1, wherein the magnetic composite carbon spheres (5) are yolk-eggshell type magnetic composite carbon spheres having mesoporous structure, in which Fe is used3O4The magnetic nano particles are used as magnetic cores; the shell layer is formed by taking resorcinol-formaldehyde resin as a carbon source, tetraethoxysilane as a silicon source and hydrolysate silicon dioxide of the tetraethoxysilane as a hard template through hydrothermal reaction.
3. The method for magnetic separation, treatment and purification of antibiotic wastewater as claimed in claim 1 or 2, wherein the average particle diameter of the magnetic composite carbon spheres (5) is 2-4 μm, and the magnetic nuclei areThe particle size of the carbon layer is 0.9-1.1 μm, the thickness of the carbon layer is 0.5-0.7 μm, the specific surface area is 500-600m2(ii)/g, the average pore diameter is 7-10 nm.
4. The method for magnetic separation treatment and purification of antibiotic wastewater as claimed in claim 1 or 2, wherein the preparation method of the magnetic composite carbon spheres (5) comprises the following steps: method for preparing magnetic nano particle Fe by adopting solvothermal method3O4Improvement of Fe by addition of dispersant PSSMA3O4And then preparing the magnetic composite carbon spheres by adopting an improved hard template method, wherein resorcinol formaldehyde is used as a carbon source, tetraethoxysilane is used as a silicon precursor, a surfactant cetyl trimethyl ammonium bromide is used as an auxiliary reagent, and the magnetic composite carbon spheres are prepared by in-situ polymerization reaction, carbonization and etching silicon removal by using a sodium hydroxide solution, wherein the yolk eggshell type magnetic composite carbon spheres are obtained, and most of carbon layers have a mesoporous structure.
5. The method for magnetic separation treatment and purification of antibiotic wastewater as claimed in claim 1, wherein the antibiotic concentration in the antibiotic wastewater is 200-600mg/L, the flow rate of the antibiotic wastewater entering the adsorption system is 5-8 mL/min, and the addition amount of the magnetic composite carbon ball (5) adsorbent required for treating each liter of antibiotic wastewater is 1.3-2.0 g; the temperature of the adsorption process was 293-313K.
6. The method of claim 1, wherein the antibiotics comprise macrolide antibiotics and derivatives thereof, and are selected from the group consisting of erythromycin antibiotics, midecamycin antibiotics, spiramycin antibiotics, ketolide products, macrolide lactam antibiotics, polyene macrolide antibiotics, and 18-membered novel macrolide antibiotics.
7. The method for magnetic separation treatment and purification of antibiotic wastewater as claimed in claim 1, wherein the adsorbed antibiotic wastewater enters the antibiotic concentration detection unit (7) after leaving the interior of the cylinder (4) through the microfiltration membrane (3) at the upper end of the cylinder (4), and enters the next purification treatment process (8) after the antibiotic concentration detection unit (7) detects the antibiotic concentration in the adsorbed antibiotic wastewater.
8. The method for magnetic separation treatment and purification of antibiotic wastewater according to claim 7, wherein the antibiotic wastewater is first pretreated to remove solid particles, stored in an antibiotic wastewater feeding tank (1), and the antibiotic wastewater is pumped from the antibiotic wastewater feeding tank (1) into an adsorption system through a feeding pump (2) for adsorption treatment, and the feeding is kept at a constant speed;
the antibiotic concentration detection unit (7) detects the antibiotic concentration in real time, when the antibiotic adsorption amount calculated based on the antibiotic concentration detected at a certain moment and the antibiotic concentration in the initial antibiotic wastewater to be treated is greater than 80% of the saturated adsorption amount of the added magnetic composite carbon balls, the adsorbent reaches saturated adsorption, the feeding pump (2) is closed, the current of the electromagnetic coil (6) is increased to increase the magnetic field intensity, so that the adsorbent is attached to the inner side of the cylinder (4) and is completely separated from the antibiotic wastewater, and the antibiotic wastewater to be treated is drained;
storing an eluent in an eluent feeding tank (9), opening an eluent feeding valve, recovering the magnetic field intensity to enable the adsorbent to be uniformly suspended in the cylinder, enabling the eluent to enter from the lower part of the cylinder (4), enabling the eluent to flow upwards through the adsorbent, eluting the antibiotics adsorbed by the adsorbent, closing an eluent feeding valve after the elution lasts for 30-60 min, storing the eluent in an eluent storage tank (11), increasing the magnetic field intensity to enable the adsorbent to be fully separated from the eluent, and emptying the eluent;
the water washing liquid is stored in a water washing feeding tank (10), a valve of the water washing feeding tank is opened, the magnetic field intensity is recovered to enable the adsorbent to be uniformly suspended in the cylinder, and the adsorbent can be adsorbed again after being washed, so that continuous adsorption is realized.
9. The method for magnetic separation treatment and purification of antibiotic wastewater as claimed in claim 7, wherein the eluent in the eluent storage tank (11) contains antibiotics, the eluent in the eluent storage tank (11) enters the reactive crystallizer (12), the antibiotics in the eluent are reacted and crystallized, and the antibiotics are recovered by solid-liquid separation.
10. The method for magnetic separation, treatment and purification of antibiotic wastewater as claimed in claim 7, wherein the antibiotic concentration detection unit (7) is an ultraviolet spectrophotometer.
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