Immature bitter orange pharmaceutical wastewater treatment system

Abstract

The invention relates to the technical field of pharmaceutical wastewater treatment, and discloses an immature bitter orange pharmaceutical wastewater treatment system which comprises a pretreatment unit, wastewater enters the pretreatment unit, colloidal protein in the wastewater is removed through agglomeration and flocculation, generated flocculation impurities form agglomeration agglomerates, and impurities in the wastewater are filtered through the agglomeration agglomerates; the molecular imprinting treatment unit is used for receiving the wastewater output by the pretreatment unit, performing targeted absorption on flavone substances in the wastewater by adopting a Fe3O4 (at) S < O2 > core-shell adsorption material taking hesperidin as a template as an adsorbent in cooperation with a magnetic field fluidization effect, and completing recovery of the flavone substances and regeneration of the adsorbent in cooperation with a magnet assistance and regeneration process; and a bioelectrochemical reaction unit. Through a multi-mechanism synergistic effect, complex organic matters are decomposed and mineralized step by step, especially, pollutants such as macromolecular drug residues, pigments and the like which are difficult to treat by a traditional process are excellently removed, and the effluent quality is ensured to be stable and reach the standard.

Description

Technical Field

[0001] The present invention relates to the technical field of pharmaceutical wastewater treatment, and particularly to a treatment system for Fructus Aurantii Immaturus pharmaceutical wastewater. Background Art

[0002] Wastewater treatment in the pharmaceutical process is of great importance. In the field of pharmaceutical industrial wastewater treatment, there are significant deficiencies in the existing technologies for high-concentration flavonoid substances (such as hesperidin and naringin) in Fructus Aurantii Immaturus wastewater. Conventional physico-chemical methods (such as coagulation sedimentation and activated carbon adsorption) have a removal efficiency of less than 30% for dissolved flavonoid substances, and the regeneration cost of the adsorbent is high (> $0.5 per kilogram). Although biological treatment technologies (such as the activated sludge method and the biofilm method) can degrade some organic substances, the antibacterial properties of flavonoid compounds cause a decrease in microbial activity of more than 50%, and the sludge age needs to be extended to more than 20 days to maintain the system stability, resulting in a sharp increase in operating costs. In addition, although multi-stage tandem processes (such as Fenton oxidation-biofilm coupling) can improve the treatment efficiency, problems such as chemical dosing (such as H 2 O 2 ) and membrane fouling lead to the cost per ton of water rising to $2.2 - $2.8, and high-moisture-content sludge of 0.37 kg / m³ is generated, further increasing the disposal burden.

[0003] Existing advanced treatment technologies (such as reverse osmosis membranes and advanced oxidation) face core challenges in the application of flavonoid wastewater: reverse osmosis membranes are easily blocked by colloidal substances in the wastewater, with a flux decay rate exceeding 60% per month, and high-value-added components cannot be selectively recovered; Fenton oxidation relies on excessive chemicals to cause iron sludge pollution (0.3 kg / m³), and the non-selective oxidation of hydroxyl radicals (·OH) results in high energy consumption of 0.7 kWh / kg COD. Although some studies have attempted to introduce molecular imprinting technology into wastewater treatment, traditional imprinting materials have problems such as low pore size matching and large mass transfer resistance, and the adsorption capacity for hesperidin is less than 30 mg / g. At the same time, existing technology combinations mostly remain in the simple superposition stage and fail to achieve an energy-matter closed loop (such as in-situ utilization of H 2 O 2 and algae resource utilization), resulting in poor system synergy and low resource recovery rate, making it difficult to meet the needs of green and low-carbon transformation. Summary of the Invention

[0004] In view of the deficiencies of the existing technology, the present invention provides a treatment system for Fructus Aurantii Immaturus pharmaceutical wastewater, which solves the problems existing in the traditional pharmaceutical wastewater treatment system.

[0005] To achieve the above objectives, the present invention is realized through the following technical solutions: A treatment system for Fructus Aurantii Immaturus pharmaceutical wastewater, comprising:

[0006] Pretreatment unit: Wastewater enters the pretreatment unit, where colloidal proteins in the wastewater are removed through flocculation aggregation, and the generated floc impurities form agglomerated aggregates. The agglomerated aggregates are used to filter the impurities in the wastewater;

[0007] Molecular imprinting treatment unit: It receives the wastewater output from the pretreatment unit. By using Fe 3 O 4 @SiO 2 core-shell adsorption material as an adsorbent, combined with magnetic field fluidization, to target-absorb flavonoid substances in the wastewater, and combined with magnet-assisted and regeneration processes to complete the recovery of flavonoid substances and the regeneration of the adsorbent;

[0008] Bioelectrochemical reaction unit: It uses graphene aerogel loaded with electroactive bacteria as the anode and carbon fiber cloth loaded with Fe / N co-doped carbon quantum dots as the cathode. The surface of the graphene aerogel is modified with carboxylated carbon quantum dots, and the specific surface area is ≥1500m 2 / g, and the pore size distribution includes 0.8 - 2nm micropores and 5 - 10nm mesopores. Among them, the micropores are used to adsorb small molecule pollutants, and the mesopores are used to promote the colonization of bacteria. The wastewater output from the molecular imprinting treatment unit enters the bioelectrochemical reaction unit. After the organic pollutants in the wastewater are removed through the oxidation reaction at the anode, a reduction reaction occurs at the cathode and H 2 O 2 is generated;

[0009] Microalgae photocatalysis coupling unit: The wastewater discharged from the bioelectrochemical reaction unit enters the microalgae photocatalysis coupling unit. The microalgae photocatalysis coupling unit includes a photobiological membrane carrier. The substrate of the photobiological membrane carrier is carbon fiber woven cloth, and TiO 2 nanowire arrays are densely arranged below it, and a dual-algae symbiotic membrane is arranged above it to absorb small molecule organic substances in the wastewater, and the H 2 O 2 generated by the cathode is input into the TiO 2 nanowire arrays through a diversion tube, and the reaction generates ·OH to degrade the refractory organic substances in the wastewater.

[0010] Preferably, the pretreatment unit includes a wastewater collection tank into which the wastewater in the pharmaceutical process is discharged and centrally stored. On one side of the wastewater collection tank, there is an impurity treatment module, which includes a base. A plurality of filter columns are embedded and fixedly connected to the upper part of the base. The bottom water inlets of the plurality of filter columns are connected in parallel and are connected to the inside of the wastewater collection tank through a pumping device. An independent valve is provided at the water inlet of each filter column. A stirring device is arranged in the center of the filter column, and a flocculant feeding port is arranged at the top. The flocculant is a cationic flocculant. The stirring device stirs and mixes the wastewater and the flocculant in the filter column. A first filter screen is covered and fixed in the upper part of the filter column, and a water outlet is opened above the first filter screen. The water outlets of the plurality of filter columns are connected in parallel, and the filtered wastewater flows into the molecular imprinting treatment unit through the parallel connection of the water outlets. A sewage outlet is opened in the middle and lower part of the filter column, and an independent valve is provided at the sewage outlet. One side of the base is fixedly connected with a coagulation treatment chamber, which is divided into an inner coagulation accumulation chamber and an outer water filtration chamber. Among them, the inside of the coagulation accumulation chamber is communicated with the sewage outlet of the filter column, and a piston is arranged in the coagulation accumulation chamber. One end of the coagulation accumulation chamber is provided with a driving device for driving the piston to move in the coagulation accumulation chamber, and the other end is of an open structure, and a plurality of limiting rods are fixedly connected to the outer wall of the opening. The ends of the plurality of limiting rods are fixedly connected with a limiting plate. A sealing cover is sleeved and slidably connected to the outer wall of the limiting rod. The sealing cover is connected to the limiting plate through a spring. The sealing cover is embedded and sealed at the opening of the coagulation accumulation chamber by the elastic force of the spring. The water filtration chamber is opened outside the opening of the coagulation accumulation chamber. The water filtration chamber is communicated with the coagulation accumulation chamber, and a second filter screen is arranged at the communication part between the two. The drainage port of the water filtration chamber extends into the wastewater collection tank through a pipeline. When the driving device pushes the piston towards the opening of the coagulation accumulation chamber, the wastewater in the coagulation accumulation chamber is filtered through the second filter screen under the action of air pressure and flows back into the wastewater collection tank through the pipeline. At the same time, the coagulation impurities in the coagulation accumulation chamber are compressed to discharge water and are located between the sealing cover and the piston. When the thrust of the driving device exceeds the spring elastic force threshold, the sealing cover is separated from the opening of the coagulation accumulation chamber, and the coagulation impurities are extruded to the outside.

[0011] Preferably, the molecular imprinting treatment unit includes an adsorption tank. The top of the adsorption tank is open, and a porous plate type water distributor is embedded and fixed below the opening. An adsorbent feeding port is provided on the tank body between the top opening and the porous plate type water distributor. An alternating magnetic field fluidization device is arranged in the middle and lower part of the adsorption tank for maintaining the adsorbent in a rotating and fluidized state. A support layer is arranged in the adsorption tank, which is within the magnetic field coverage range of the alternating magnetic field fluidization device. The support layer is composed of a conical porous sintered plate for intercepting the adsorbent. A drainage end and a backwashing end are sequentially arranged at the bottom of the adsorption tank. The drainage end is communicated with the water inlet of the bioelectrochemical reaction unit through a pipeline, and an ultraviolet sensor is arranged at the drainage end for detecting the concentration of hesperidin in the discharged wastewater. The backwashing end is connected to the output end of the backwashing device. An adsorbent discharge part is provided on the tank body above the support layer, and the discharge part extends into the permanent magnet separation device. The saturated adsorbent discharged from the adsorbent discharge part is collected by the permanent magnet separation device and input into the desorption device. After being regenerated by the desorption device, the saturated adsorbent is reused. A differential pressure transmitter is also arranged at the support layer for real-time monitoring of the differential pressure change of the support layer.

[0012] Preferably, the Fe 3 O 4 @SiO 2 In the core-shell adsorbent material, the Fe 3 O 4 magnetic core is ellipsoidal, the SiO2 shell layer thickness is 6.5 - 7.5 nm, the mesopore diameter is 0.8 - 1.2 nm, and the imprinting site density ≥ 3.2×10 15 sites / cm 2 .

[0013] Preferably, the alternating magnetic field fluidization device includes an electromagnetic coil array. The electromagnetic coil array is composed of 12 groups of circular coils. The 12 groups of circular coils are circularly embedded and annularly arrayed on the outer tank wall of the adsorption tank with the central axis of the adsorption tank as the center. By controlling the current injected into the electromagnetic coil array, a non-uniform alternating magnetic field is formed. A water cooling system is also arranged in the electromagnetic coil array for cooling the electromagnetic coils.

[0014] Preferably, the permanent magnet separation device includes a drum. The inner wall of the drum is a permanent magnet part, and the outer wall is rotatably connected to a support seat. An external gear is inlaid and fixedly connected to the outer wall of the drum. A driving motor is fixedly connected to the outer wall of the support seat, and a driving gear is fixedly connected to the output end of the driving motor. The tooth end of the driving gear meshes with the tooth end of the external gear. The drum is driven by the driving motor to rotate along its central axis. A separation and conveying trough is arranged above the drum. The separation and conveying trough is obliquely placed. One end of the upper wall of the separation and conveying trough is attached to the upper inner wall of the drum, and the outer wall of the other end is fixedly connected to the feeding port of the desorption device. When the drum rotates, the adsorbent magnetically adsorbed on the inner wall of the drum is shoveled out by the upper wall of the separation and conveying trough and falls into the separation and conveying trough. Under the action of gravity, the adsorbent flows into the desorption device along the separation and conveying trough.

[0015] Preferably, the bioelectrochemical reaction unit includes a reaction tank. An ion exchange membrane is arranged in the reaction tank. The ion exchange membrane is made of sulfonated polyether ether ketone and divides the inner cavity of the reaction tank into an anode chamber and a cathode chamber. The anode is arranged in the anode chamber, and a baffle plate assembly is also arranged in the anode chamber to form an S-shaped flow channel. The cathode is arranged in the cathode chamber. The wastewater discharged from the molecular imprinting treatment unit enters the anode chamber. After the organic pollutants in the wastewater are removed by oxidation reaction, it is injected into the microalgae photocatalytic coupling unit by a suction device. At the same time, the H+ generated by the oxidation reaction migrates to the cathode chamber through the ion exchange membrane for oxygen reduction reaction.

[0016] Preferably, the microalgae photocatalytic coupling unit includes a photobioreactor. The photobioreactor is made of light-transmitting polymethyl methacrylate material. A photobiological membrane carrier is arranged inside the photobioreactor. A full-spectrum LED array is arranged around the outer wall of the photobioreactor at the dual-algae symbiotic membrane, and a UV LED array is arranged around the outer wall of the photobioreactor at the TiO2 nanowire array.

[0017] The present invention provides a system for treating Fructus Aurantii Immaturus pharmaceutical wastewater. It has the following beneficial effects:

[0018] 1. Through the synergistic action of multiple mechanisms (adsorption - photocatalysis - biodegradation), the step-by-step decomposition and mineralization of complex organic substances are realized. In particular, excellent removal effects are shown on pollutants such as macromolecular drug residues and pigments that are difficult to treat by traditional processes, ensuring that the effluent quality meets the standards stably.

[0019] 2. Through the recovery of high-value components and the co-production of microalgae to form a resource cycle, a sustainable operation mode of "using waste to support waste" is constructed, significantly reducing the full-life cycle treatment cost. For example, through the setting of the molecular imprinting treatment unit in the present invention, Fe 3 O 4 @SiO 2The core-shell material targets and adsorbs hesperidin, achieving a significant increase in the recovery rate of hesperidin. The output of algal powder in the microalgae photocatalytic coupling unit and the H 2 O 22 produced in the bioelectrochemical reaction unit are used for synergistic degradation in the microalgae photocatalytic coupling unit. The efficient purification and reuse of active ingredients in pharmaceutical wastewater are realized, and high-value-added algal-based products are simultaneously produced, forming a closed-loop system of "pollutant removal - resource regeneration - energy recovery" and promoting the transformation of wastewater treatment from energy-consuming to energy-producing. Brief Description of the Drawings

[0020] Figure 1 is the front perspective schematic diagram of the present invention;

[0021] Figure 2 is Figure 1 the enlarged view at A in

[0022] Figure 3 is the rear perspective schematic diagram of the present invention;

[0023] Figure 4 is Figure 3 the enlarged view at B in

[0024] Figure 5 is the structural schematic diagram of the impurity treatment module in the present invention;

[0025] Figure 6 is the structural schematic diagram of the flocculation treatment chamber in the present invention;

[0026] Figure 7 is the structural schematic diagram of the molecular imprinting treatment unit in the present invention;

[0027] Figure 8 is the structural schematic diagram of the microalgae photocatalytic coupling unit in the present invention.

[0028] Among them, 1. Molecular imprinting treatment unit; 101. Adsorption tank; 102. Porous plate water distributor; 103. Adsorbent feeding port; 104. Support layer; 105. Electromagnetic coil array; 2. Bioelectrochemical reaction unit; 201. Reaction tank; 202. Ion exchange membrane; 203. Anodic chamber; 204. Cathodic chamber; 205. Baffle plate assembly; 3. Microalgae photocatalytic coupling unit; 301. Photobiological film carrier; 302. Photobioreactor; 303. Full-spectrum LED array; 304. UV LED array; 4. Wastewater collection tank; 5. Impurity treatment module; 501. Base; 502. Filter column; 503. First filter screen; 6. Coagulation treatment chamber; 601. Coagulation accumulation cavity; 602. Water filtration cavity; 603. Piston; 604. Limit rod; 605. Limit plate; 606. Sealing cover; 607. Spring; 608. Second filter screen; 7. Permanent magnet separation device; 701. Drum; 702. Support seat; 703. External gear; 704. Driving motor; 705. Driving gear; 706. Separation and conveying trough; 8. Desorption device. Detailed implementation manners

[0029] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0030] Please refer to the attached Figure 1 - attached Figure 8 , the embodiment of the present invention provides a Fructus Aurantii Immaturus pharmaceutical wastewater treatment system, including a pretreatment unit, a molecular imprinting treatment unit 1, a bioelectrochemical reaction unit 2 and a microalgae photocatalytic coupling unit 3. Through the mutual cooperation of the above units, a technical breakthrough of molecular recognition-bioelectrochemistry-photobiology synergy is achieved, and the core pain points such as poor selectivity, low efficiency, high cost and resource waste in pharmaceutical wastewater treatment are solved.

[0031] The specific descriptions of each unit are as follows:

[0032] Pretreatment unit. Wastewater enters the pretreatment unit, and colloidal proteins in the wastewater are removed through flocculation agglomeration, and the generated floc impurities form flocculation aggregates, and the impurities in the wastewater are filtered through the flocculation aggregates; the pretreatment unit includes a wastewater collection tank 4. The wastewater in the pharmaceutical process is discharged into the wastewater collection tank 4 for centralized storage. On one side of the wastewater collection tank 4, there is an impurity treatment module 5. The impurity treatment module 5 includes a base 501. A plurality of filter columns 502 are embedded and fixedly connected to the upper part of the base 501. The bottom water inlets of the plurality of filter columns 502 are connected in parallel and are internally connected to the wastewater collection tank 4 through a pumping device. A valve is independently arranged at the water inlet of each filter column 502. A stirring device is arranged in the center of the filter column 502, and a flocculant feeding port is arranged at the top. The flocculant uses a cationic flocculant. The stirring device stirs and mixes the wastewater and the flocculant in the filter column 502. A first filter screen 503 is covered and fixed in the upper part of the filter column 502, and a water outlet is opened above the first filter screen 503. The water outlets of the plurality of filter columns 502 are connected in parallel. The filtered wastewater flows into the molecular imprinting treatment unit 1 through the parallel connection of the water outlets. A sewage outlet is opened in the lower middle part of the filter column 502, and an independent valve is arranged at the sewage outlet. One side of the base 501 is fixedly connected with a floc treatment chamber 6. The interior of the floc treatment chamber 6 is divided into an inner floc accumulation chamber 601 and an outer water filtration chamber 602. Among them, the interior of the floc accumulation chamber 601 is communicated with the sewage outlet of the filter column 502, and a piston 603 is arranged in the floc accumulation chamber 601. A driving device is arranged at one end of the floc accumulation chamber 601 for driving the piston 603 to move in the floc accumulation chamber 601. The other end is of an open structure, and a plurality of limiting rods 604 are fixedly connected to the outer wall of the opening. The ends of the plurality of limiting rods 604 are fixedly connected with a limiting plate 605. A sealing cover 606 is sleeved and slidably connected to the outer wall of the limiting rod 604. The sealing cover 606 is connected with the limiting plate 605 through a spring 607. The sealing cover 606 is embedded and sealed at the opening of the floc accumulation chamber 601 through the elastic force of the spring 607. The water filtration chamber 602 is opened outside the opening of the floc accumulation chamber 601. The water filtration chamber 602 is communicated with the floc accumulation chamber 601, and a second filter screen 608 is arranged at the communication part between the two. The drainage port of the water filtration chamber 602 extends into the wastewater collection tank 4 through a pipeline. When the driving device pushes the piston 603 towards the opening of the floc accumulation chamber 601, the wastewater in the floc accumulation chamber 601 is filtered through the second filter screen 608 under the action of air pressure and then flows back into the wastewater collection tank 4 through the pipeline. At the same time, the floc impurities in the floc accumulation chamber 601 are compressed to discharge water and are located between the sealing cover 606 and the piston 603. When the thrust of the driving device exceeds the elastic force threshold of the spring 607, the sealing cover 606 is separated from the opening of the floc accumulation chamber 601, and the floc impurities are extruded to the outside.

[0033] To solve the problem of intermittent discharge of pharmaceutical wastewater and large fluctuations in water quality and quantity, a wastewater collection tank 4 is set up. The discharged wastewater is centrally introduced into the wastewater collection tank 4 for storage and then uniformly treated. The wastewater collection tank 4 has a large capacity, and by trading space for time, the problem of intermittent wastewater discharge is solved. At the same time, the wastewater is centrally mixed, achieving the effect of balanced wastewater quality.

[0034] Secondly, since the wastewater contains a large amount of colloidal proteins and impurities, which will cause physical blockage of the imprinting sites in the molecular imprinting treatment unit 1. To solve this problem, an additional impurity treatment module 5 is set up, which is distributed at the front end of the molecular imprinting treatment unit 1. The wastewater is pumped out from the wastewater collection tank 4 and injected from the bottom of the filter column 502. With the addition and stirring of flocculants, flocculation occurs to the impurities and colloidal proteins in the wastewater. Along with the continuous progress of this process, the generated flocculent impurities form agglomerated aggregates, which are suspended in the middle and lower parts of the filter column 502, and their volume gradually increases. As a result, the impurities in the wastewater are intercepted by the agglomerated aggregates, playing a filtering role. At this time, the wastewater in the filter column 502 shows a layering phenomenon, that is, the upper layer is the water body filtered by the agglomerated aggregates, which has removed most of the colloidal proteins and impurities. When it overflows, it enters the molecular imprinting treatment unit 1. The filter screen 503 plays a role in isolating suspended matter in the early stage.

[0035] At the same time, with the continuous progress of the treatment, the volume of the agglomerated aggregates becomes too large. At this time, the agglomerated aggregates are discharged into the flocculation treatment chamber 6. Specifically, the agglomerated aggregates and part of the water flow enter the flocculation accumulation cavity 601 together. When a certain quantity is reached, the driving device pushes the piston 603 towards the opening of the flocculation accumulation cavity 601. At this time, under the action of the piston 603, the effective space of the flocculation accumulation cavity 601 gradually decreases, and then the space formed by the flocculation accumulation cavity 601 and the water filtration cavity 602 is gradually compressed and reduced, and the pressure inside the space increases. The wastewater in the flocculation accumulation cavity 601 is filtered by the filter screen 608 under the action of air pressure and then flows back into the wastewater collection tank 4 through the pipeline. At the same time, the flocculent impurities in the flocculation accumulation cavity 601 are compressed to discharge water and are located between the sealing cover 606 and the piston 603. When the thrust of the driving device exceeds the elastic force threshold of the spring 607, the sealing cover 606 is separated from the opening of the flocculation accumulation cavity 601, and the flocculent impurities are extruded to the outside for further treatment.

[0036] The impurity treatment module 5 is provided with a plurality of filter columns 502. Both the water inlet and the water outlet of the filter columns adopt a parallel structure, and independent control valves are provided at the water inlet of each filter column 502. Such a solution greatly improves the dynamic adaptation function of the impurity treatment module 5. When the waste water volume is large, in order to reduce the storage pressure of the waste water collection tank 4, multiple filter columns 502 can be selected to be enabled simultaneously to increase the water outlet speed of the waste water collection tank 4. When the waste water volume is small, the corresponding number of filter columns 502 can be selectively enabled, which not only reduces the energy consumption but also is conducive to the rapid formation of agglomerated flocs. It should be noted that there is a limit to the water inlet rate that a single filter column 502 can withstand, and the total water inlet rate is regulated by the pumping equipment.

[0037] Through the setting of the impurity treatment module 5, it plays a synergistic effect on the whole system, and not only improves the effect of the subsequent units:

[0038] Agglomeration flocculation (micrometer level) and molecular imprinting (nanometer level) form a multi-level interception network, and the pollutant removal covers 1 nm (small molecule flavonoids) to 500 μm (colloidal particles). The cationic flocculant preferentially neutralizes the negatively charged colloid.

[0039] Verified by data:

[0040]

[0041] The molecular imprinting treatment unit 1 receives the waste water output by the pretreatment unit. By using the Fe 3 O 4 @SiO 2 core-shell adsorption material as an adsorbent, combined with the magnetic field fluidization effect, targetedly absorbs the flavonoid substances in the waste water, and combined with the magnet-assisted and regeneration processes, completes the recovery of the flavonoid substances and the regeneration of the adsorbent; Fe 3 O 4 @SiO 2 In the core-shell adsorption material, the Fe 3 O 4 magnetic core is ellipsoidal, the SiO 2 shell layer thickness is 6.5 - 7.5 nm, the mesopore diameter is 0.8 - 1.2 nm, and the imprinting site density ≥ 3.2×1015 sites / cm 2 .

[0042] Fe 3 O 4 @SiO 2 The preparation method of the core-shell adsorption material is: synthesize the Fe 3 O 4 magnetic core by the co-precipitation method, and by regulating the Fe 2+ / Fe 3+The molar ratio is 1:2.5, controlling its ellipsoidal morphology (major axis: 15 ± 2 nm, minor axis: 5 ± 1 nm). Mesoporous SiO 2 The shell layer is formed by the hydrolysis of tetraethyl orthosilicate (TEOS), with a thickness of 7 ± 0.5 nm and a pore diameter of 0.8–1.2 nm (matching the molecular size of hesperidin 1.12 × 0.82 nm). 3-Aminopropyltriethoxysilane (APTES) is used as the functional monomer for surface imprinting to generate imprinting sites with a density of 3.2×10 15 sites / cm 2 (quantified by BET and XPS).

[0043] The molecular imprinting treatment unit 1 includes an adsorption tank 101. The top of the adsorption tank 101 is open, and a porous plate water distributor 102 is embedded and fixed below the opening. An adsorbent feeding port 103 is provided on the tank body between the top opening and the porous plate water distributor 102. An alternating magnetic field fluidization device is arranged in the middle and lower part of the adsorption tank 101 for maintaining the adsorbent in a rotating and fluidized state. A support layer 104 is arranged in the adsorption tank 101, which is within the magnetic field coverage range of the alternating magnetic field fluidization device. The support layer 104 is composed of a conical porous sintered plate for intercepting the adsorbent. The bottom of the adsorption tank 101 is sequentially provided with a drainage end and a backwashing end. The drainage end is connected to the water inlet of the bioelectrochemical reaction unit 2 through a pipeline, and an ultraviolet sensor is arranged at the drainage end for detecting the concentration of hesperidin in the discharged wastewater. The backwashing end is connected to the output end of the backwashing device. An adsorbent discharge part is provided on the tank body above the support layer 104, and the discharge part extends into the permanent magnetic separation device 7. The adsorbent is discharged by the backwashing power, and the saturated adsorbent discharged from the adsorbent discharge part is collected by the permanent magnetic separation device 7 and input into the desorption device 8. The saturated adsorbent is regenerated by the desorption device 8 and reused. A differential pressure transmitter is also arranged at the support layer 104 for real-time monitoring of the differential pressure change of the support layer 104.

[0044] The alternating magnetic field fluidization device includes an electromagnetic coil array 105. The electromagnetic coil array 105 is composed of 12 groups of annular coils. The 12 groups of annular coils are annularly embedded and arranged in an annular array on the outer tank wall of the adsorption tank 101 with the central axis of the adsorption tank 101 as the center. By controlling the current injected into the electromagnetic coil array 105, a non-uniform alternating magnetic field is formed. A water cooling system is also arranged in the electromagnetic coil array 105 for cooling the electromagnetic coils.

[0045] The setting of the alternating magnetic field fluidization device uses the Lorentz force to induce the rotation of the adsorbent, avoiding particle aggregation and forming a laminar flow state, improving the adsorption effect.

[0046] The permanent magnet separation device 7 includes a drum 701. The inner wall of the drum 701 is a permanent magnet part, and the outer wall is rotatably connected to a support seat 702. An external gear 703 is inlaid and fixedly connected to the outer wall of the drum 701. A driving motor 704 is fixedly connected to the outer wall of the support seat 702. The output end of the driving motor 704 is fixedly connected to a driving gear 705. The tooth end of the driving gear 705 meshes with the tooth end of the external gear 703. The drum 701 is driven by the driving motor 704 to rotate along its central axis. A separation and conveying trough 706 is arranged above the drum 701. The separation and conveying trough 706 is obliquely placed. One end of the upper wall of the separation and conveying trough 706 is attached to the inner upper wall of the drum 701, and the outer wall of the other end is fixedly connected to the feeding port of the desorption device 8. When the drum 701 rotates, the adsorbent magnetically adsorbed on the inner wall of the drum 701 is shoveled out by the upper wall of the separation and conveying trough 706 and falls into the separation and conveying trough 706. Under the action of gravity, the adsorbent flows into the desorption device 8 along the separation and conveying trough 706.

[0047] In the desorption device 8, the composition of the desorbing liquid is ethanol: ammonia water = 4:1 (v / v), pH = 9.5, and the desorption efficiency can reach 92.3%.

[0048] Meanwhile, the conditions for starting the permanent magnet separation device 7 are as follows:

[0049] The differential pressure transmitter ΔP ≥ 0.12 MPa; automatic reverse blowing and pulse discharging every 30 minutes; the concentration of hesperidin in the effluent > 5 mg / L.

[0050] Through the treatment of the molecular imprinting treatment unit 1, its comparison with traditional activated carbon adsorption is as follows:

[0051]

[0052] The bioelectrochemical reaction unit 2 uses a graphene aerogel loaded with electroactive bacteria as the anode and a carbon fiber cloth loaded with Fe / N co-doped carbon quantum dots as the cathode. The surface of the graphene aerogel is modified with carboxylated carbon quantum dots, and the specific surface area ≥ 1500 m 2 / g, and the pore size distribution includes 0.8 - 2 nm micropores and 5 - 10 nm mesopores. Among them, the micropores are used to adsorb small molecule pollutants, and the mesopores are used to promote the colonization of bacteria. The wastewater is output from the molecular imprinting treatment unit 1 and enters the bioelectrochemical reaction unit 2. After removing the organic pollutants in the wastewater through the oxidation reaction at the anode, a reduction reaction occurs at the cathode and H 2 O 2 ;

[0053] The bioelectrochemical reaction unit 2 includes a reaction cell 201. An ion exchange membrane 202 is arranged in the reaction cell 201. The ion exchange membrane 202 is made of sulfonated polyether ether ketone and divides the inner cavity of the reaction cell 201 into an anode chamber 203 and a cathode chamber 204. The anode is arranged in the anode chamber 203, and a baffle plate assembly 205 is also arranged in the anode chamber 203 to form an S-shaped flow channel. The cathode is arranged in the cathode chamber 204. The wastewater discharged from the molecular imprinting treatment unit 1 enters the anode chamber 203. After the organic pollutants in the wastewater are removed through an oxidation reaction, it is injected into the microalgae photocatalytic coupling unit 3 by a suction device. At the same time, the H⁺ generated by the oxidation reaction migrates to the cathode chamber 204 through the ion exchange membrane 202 for an oxygen reduction reaction.

[0054] Comparison between the bioelectrochemical reaction unit 2 and the traditional activated sludge method:

[0055]

[0056] For the microalgae photocatalytic coupling unit 3, the wastewater discharged from the bioelectrochemical reaction unit 2 enters the microalgae photocatalytic coupling unit 3. The microalgae photocatalytic coupling unit 3 includes a photobiological membrane carrier 301. The substrate of the photobiological membrane carrier 301 is a carbon fiber woven cloth, and a TiO 2 nanowire array is densely arranged below it, and a dual-algae symbiotic membrane is arranged above it to absorb small molecular organic matters in the wastewater. And the H 2 O 2 generated by the cathode is input into the TiO 2 nanowire array through a diversion tube, and the reaction generates ·OH to degrade the refractory organic matters in the wastewater.

[0057] The microalgae photocatalytic coupling unit 3 includes a photobioreactor 302. The photobioreactor 302 is made of light-transmissive polymethyl methacrylate material. The photobiological membrane carrier 301 is arranged inside the photobioreactor 302. An all-spectrum LED array 303 is arranged around the outer wall of the photobioreactor 302 at the position of the dual-algae symbiotic membrane, and an ultraviolet LED array 304 is arranged around the outer wall of the photobioreactor 302 at the position of the TiO₂ nanowire array.

[0058] Among them, the porosity of the carbon fiber woven cloth is 85%, and the specific surface area is 320 m 2 / m 3 , the TiO nanowire array is grown by a hydrothermal method, with a length of 1.2 ± 0.3 μm, a diameter of 25 ± 5 nm, and a vertical arrangement density of 10 6 roots / cm 2 ,

[0059] The algae species ratio is 65:35 of Chlorella and Scenedesmus to improve the system stability.

[0060] Through actual operation:

[0061]

[0062] Meanwhile, H 2 O 2 The utilization rate reaches 92%.

[0063] Although embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A system for treating wastewater from pharmaceutical production of Citrus aurantium, characterized in that: include: Pretreatment unit: wastewater enters the pretreatment unit, where colloidal proteins in the wastewater are removed through agglomeration and flocculation, and the generated flocculated impurities are formed into agglomerates, and the impurities in the wastewater are filtered through the agglomerates; The molecular imprinting treatment unit (1) receives the wastewater outputted by the pretreatment unit, adopts Fe3O4@SiO2 core-shell adsorption material with hesperidin as template as adsorbent, cooperates with magnetic field fluidization, conducts targeted absorption of flavonoids in the wastewater, and cooperates with magnet assistance and regeneration process to complete the recovery of flavonoids and regeneration of adsorbent; The bioelectrochemical reaction unit (2) uses a graphene aerogel loaded with electroactive bacteria as an anode, a carbon fiber cloth loaded with Fe / N co-doped carbon quantum dots as a cathode, and the surface of the graphene aerogel is modified with carboxylated carbon quantum dots, with a specific surface area of ​​≥1500m 2 / g, the pore size distribution includes 0.8-2nm micropores and 5-10nm mesopores, wherein the micropores are used to adsorb small molecular pollutants, and the mesopores are used to promote bacterial colonization. The wastewater is output from the molecular imprinting treatment unit (1) and enters the bioelectrochemical reaction unit (2). After the organic pollutants in the wastewater are removed by oxidation reaction at the anode, a reduction reaction occurs at the cathode to generate H2O2; The microalgae photocatalytic coupling unit (3) is configured such that wastewater discharged from the bioelectrochemical reaction unit (2) enters the microalgae photocatalytic coupling unit (3). The microalgae photocatalytic coupling unit (3) comprises a photobiofilm carrier (301). The base of the photobiofilm carrier (301) is a carbon fiber woven cloth, a TiO2 nanowire array is densely arranged below the carrier, and a double algae symbiotic membrane is arranged above the carrier, which is used to absorb small molecular organic matter in the wastewater. H2O2 generated by the cathode is input into the TiO2 nanowire array through a flow guide pipe, and the OH generated by the reaction degrades the difficult-to-degrade organic matter in the wastewater.

2. A Citrus aurantium pharmaceutical wastewater treatment system according to claim 1, characterized in that: The pretreatment unit comprises a wastewater collection pool (4), wastewater in the pharmaceutical process is discharged into the wastewater collection pool (4) for centralized storage, an impurity treatment module (5) is arranged on one side of the wastewater collection pool (4), the impurity treatment module (5) comprises a base (501), a plurality of filter columns (502) are embedded and fixedly connected to the upper part of the base (501), the bottom water inlets of the plurality of filter columns (502) are connected in parallel and connected to the inside of the wastewater collection pool (4) through a pumping device, a valve is independently arranged at the water inlet of each filter column (502), a stirring device is arranged at the center of the filter column (502), a flocculant introduction port is arranged at the top, the flocculant adopts a cationic flocculant, and the stirring device is used to stir the wastewater in the filter column (502). The filter column (502) is covered with and fixed with a filter screen (503) on the upper part, and a water outlet is provided above the filter screen (503). The water outlets of the multiple filter columns (502) are connected in parallel, and the filtered wastewater flows into the molecular imprinting treatment unit (1) through the parallel connection of the water outlets. A sewage outlet is provided in the lower middle part of the filter column (502), and an independent valve is provided at the sewage outlet. A flocculation treatment chamber (6) is fixedly connected to one side of the base (501), and the flocculation treatment chamber (6) is divided into an inner flocculation accumulation chamber (601) and an outer water filtering chamber (602), wherein the flocculation accumulation chamber (601) is connected to the sewage outlet of the filter column (502), and a valve is provided in the flocculation accumulation chamber (601). The invention relates to a piston (603). A driving device is arranged at one end of the flocculation accumulation chamber (601) for driving the piston (603) to move in the flocculation accumulation chamber (601). The other end is an opening structure, and a plurality of limiting rods (604) are fixedly connected to the outer wall of the opening. The ends of the plurality of limiting rods (604) are fixedly connected to a limiting plate (605). A sealing cover (606) is sleeved on the outer wall of the limiting rod (604) and slidably connected. The sealing cover (606) is connected to the limiting plate (605) by a spring (607). The sealing cover (606) is embedded in the opening of the flocculation accumulation chamber (601) and sealed by the elastic force of the spring (607). The water filter chamber (602) is opened on the outer side of the opening of the flocculation accumulation chamber (601). The water chamber (602) is connected to the flocculation chamber (601), and a second filter screen (608) is provided at the connection point between the two. The drainage port of the water filter chamber (602) extends to the wastewater collection tank (4) through a pipeline. When the driving device pushes the piston (603) to move toward the opening of the flocculation chamber (601), the wastewater in the flocculation chamber (601) is filtered by the second filter screen (608) under the action of air pressure and then flows back into the wastewater collection tank (4) through the pipeline. At the same time, the flocculation impurities in the flocculation chamber (601) are compressed to discharge the water and are located between the sealing cover (606) and the piston (603). When the thrust of the driving device exceeds the elastic threshold of the spring (607), the sealing cover (606) is separated from the opening of the flocculation chamber (601).The flocculated impurities are squeezed out to the outside.

3. The system for treating wastewater from pharmaceutical production of Citrus aurantium according to claim 1, characterized in that: The molecular imprinting treatment unit (1) comprises an adsorption tank (101), the top of the adsorption tank (101) is open, and a porous plate type water distributor (102) is embedded and fixed below the opening, an adsorbent feeding port (103) is provided on the tank body between the top opening and the porous plate type water distributor (102), an alternating magnetic field fluidization device is provided in the lower part of the adsorption tank (101), which is used to keep the adsorbent in a rotating and fluidized state, a support layer (104) is provided in the adsorption tank (101), which is located within the magnetic field coverage of the alternating magnetic field fluidization device, the support layer (104) is composed of a conical porous sintered plate, which is used to intercept the adsorbent, and the bottom of the adsorption tank (101) is provided with A drainage end and a backflush end are provided. The drainage end is connected to the water inlet of the bioelectrochemical reaction unit (2) through a pipeline. An ultraviolet sensor is provided at the drainage end for detecting the concentration of hesperidin in the discharged wastewater. The backflush end is connected to the output end of the backflush device. An adsorbent discharge portion is provided on the tank body above the support layer (104). The discharge portion extends into the permanent magnetic separation device (7). The saturated adsorbent discharged from the adsorbent discharge portion is collected by the permanent magnetic separation device (7) and input into the desorption device (8). The saturated adsorbent is regenerated by the desorption device (8) and reused. A differential pressure transmitter is also provided at the support layer (104) for real-time monitoring of the differential pressure change of the support layer (104).

4. A Citrus aurantium pharmaceutical wastewater treatment system according to claim 3, characterized in that: In the Fe3O4@SiO2 core-shell adsorption material, the Fe3O4 magnetic core is ellipsoidal, the SiO2 shell thickness is 6.5-7.5nm, the mesopore diameter is 0.8-1.2nm, and the imprinting site density is ≥3.2×10 15 si tes / cm 2 .

5. The system for treating wastewater from pharmaceutical production of Citrus aurantium according to claim 3, characterized in that: The alternating magnetic field fluidization device comprises an electromagnetic coil array (105), wherein the electromagnetic coil array (105) is composed of 12 groups of annular coils, wherein the 12 groups of annular coils are embedded in the outer tank wall of the adsorption tank (101) with the central axis of the adsorption tank (101) as the center ring and are arranged in an annular array, and a non-uniform alternating magnetic field is formed by controlling the current injected into the electromagnetic coil array (105). A water cooling system is also provided in the electromagnetic coil array (105) for cooling the electromagnetic coils.

6. A Citrus aurantium pharmaceutical wastewater treatment system according to claim 3, characterized in that: The permanent magnetic separation device (7) comprises a drum (701), the inner wall of the drum (701) being a permanent magnetic part, the outer wall being rotatably connected to a support seat (702), the outer wall of the drum (701) being inlaid with and fixedly connected to an external gear (703), the outer wall of the support seat (702) being fixedly connected to a driving motor (704), the output end of the driving motor (704) being fixedly connected to a driving gear (705), the tooth end of the driving gear (705) being meshed with the tooth end of the external gear (703), and the drum (701) being driven by the driving motor (704) to rotate along its central axis. The roller (701) is rotated linearly, and a separation conveying trough (706) is arranged on the upper part of the roller (701). The separation conveying trough (706) is placed obliquely, and the upper wall of one end of the separation conveying trough (706) is in contact with the inner upper wall of the roller (701), and the outer wall of the other end is fixedly connected to the feed port of the desorption device (8). When the roller (701) rotates, the adsorbent magnetically attracted to the inner wall of the roller (701) is shoveled out by the upper wall of the separation conveying trough (706) and falls into the separation conveying trough (706). Under the action of gravity, the adsorbent flows into the desorption device (8) along the separation conveying trough (706).

7. The system for treating wastewater from pharmaceutical production of Citrus aurantium according to claim 1, characterized in that: The bioelectrochemical reaction unit (2) comprises a reaction pool (201), wherein an ion exchange membrane (202) is arranged in the reaction pool (201), wherein the ion exchange membrane (202) is made of sulfonated polyetheretherketone, and the inner cavity of the reaction pool (201) is divided into an anode chamber (203) and a cathode chamber (204), wherein the anode is arranged in the anode chamber (203), and a baffle assembly (205) is also arranged in the anode chamber (203) to form an S-shaped flow channel, and the cathode is arranged in the cathode chamber (204), and the wastewater discharged from the molecular imprinting treatment unit (1) enters the anode chamber (203), and after the organic pollutants in the wastewater are removed by oxidation reaction, the wastewater is injected into the microalgae photocatalytic coupling unit (3) by a suction device, and at the same time, H generated by the oxidation reaction is + It migrates through the ion exchange membrane (202) to the cathode chamber (204) to undergo an oxygen reduction reaction.

8. The system for treating wastewater from pharmaceutical production of Citrus aurantium according to claim 1, characterized in that: The microalgae photocatalytic coupling unit (3) comprises a photobioreactor (302), wherein the photobioreactor (302) is made of a light-transmitting polymethyl methacrylate material, a photobiofilm carrier (301) is arranged inside the photobioreactor (302), a full-spectrum LED array (303) is arranged around the outer wall of the photobioreactor (302) located at the double algae symbiotic film, and an ultraviolet LED array (304) is arranged around the outer wall of the photobioreactor (302) located at the TiO2 nanowire array.

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