Rotary type spherical light tree reaction device suitable for deep removal of antibiotics in sewage and use method of rotary type spherical light tree reaction device

Abstract

The invention discloses a rotary spherical light tree reaction device suitable for deep removal of antibiotics in sewage and a use method. The device comprises a shell, a reactor, a connecting pipe and a controller. The shell is a cuboid made of glass fiber reinforced plastics. The reactor is spherical, the three reactors are sequentially fixed on the shell, the inner wall of the reactor is conductive glass coated with modified TiO2, a spherical rotating shaft supported by a rod is positioned at the center of a circle, ultraviolet optical fibers are uniformly distributed on the spherical rotating shaft, a fiber core is made of high-purity synthetic quartz, a cladding is made of fluorine-doped quartz, and the outer layer of the spherical rotating shaft is coated with a graphite sleeve for protection; an outer battery is connected between the conductive glass on the inner wall and the optical fiber sleeve, the conductive glass is an anode, and the optical fiber sleeve is a cathode; the reactors are sequentially connected in series through the connecting pipes; the controller is fixed to the bottom of the shell. The ultraviolet light is transmitted to the reaction area through the optical fiber, the mass transfer efficiency and the treatment capacity are enhanced through fluidized operation and an outer battery, the antibiotics are deeply removed, and the device has the advantages of being high in efficiency, low in cost and the like.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and in particular to the photocatalytic treatment process for antibiotics. Background Technology

[0002] Currently, antibiotics are widely detected in environmental water and soil, mainly originating from medical, aquaculture, and pharmaceutical wastewater. Improperly treated antibiotics can harm the environment and even human health, posing a core challenge to the water treatment field. Traditional biological processes in wastewater treatment plants have limited removal efficiency for many antibiotics, making complete degradation difficult. While advanced treatment technologies such as advanced oxidation and adsorption are effective, they suffer from bottlenecks such as high cost, potential for generating toxic byproducts, or susceptibility to complex water quality interference.

[0003] The core advantage of photocatalytic technology in treating antibiotics lies in the fact that the highly reactive oxygen species it generates can non-selectively attack and mineralize various antibiotic molecules, resulting in thorough degradation and helping to inhibit the spread of antibiotic resistance genes. This process is mild, energy-efficient, and does not introduce secondary pollution, making it a promising method for advanced treatment. However, current photocatalytic treatment processes are still immature, and the following problems urgently need to be addressed:

[0004] 1. Poor uniformity of light energy distribution leads to low catalyst light energy absorption efficiency. In photocatalytic systems, significant spatial heterogeneity often exists when ultraviolet light irradiates the catalyst support surface. Poor uniformity of light energy distribution results in locally excessively high or low light intensities, causing significant differences in the light flux received by each reaction site of the catalyst. This uneven light absorption leads to inconsistent catalyst activation levels, local overheating or underactivation, resulting in severely uneven spatial catalytic reaction efficiency, ultimately reducing the overall catalytic activity and efficiency of the system.

[0005] 2. Rapid recombination of holes and electrons in oxidation processes leads to the easy annihilation of oxidatively active substances. Holes and electrons generated by photoexcitation recombine rapidly. This process dissipates most of the incident light energy in the form of heat or light energy, resulting in a significant reduction in quantum efficiency. Consequently, the number of effective charge carriers that can migrate to the catalyst surface and participate in redox reactions to generate active species such as hydroxyl radicals is severely insufficient, fundamentally limiting the overall efficiency of photocatalytic degradation of pollutants.

[0006] 3. Low contact efficiency between the target pollutant and the photocatalyst, resulting in poor system mass transfer efficiency. During photocatalytic degradation, the lifetime of active species such as hydroxyl radicals is extremely short, and the reaction is mainly confined to the catalyst surface. If the mass transfer rate of antibiotics from the liquid phase to the active sites of the catalyst is too slow, a large number of active intermediates will be quenched and ineffective before the target pollutant arrives, leading to the apparent reaction rate being limited by the mass transfer process, and a significant reduction in overall treatment capacity and energy efficiency.

[0007] Therefore, in response to the problems of existing technologies, this invention proposes a rotating spherical photocatalytic reactor and its usage method suitable for the deep removal of antibiotics from wastewater. This invention utilizes ultraviolet optical fiber and TiO2 in an electric field environment for photocatalysis to produce oxidative active substances to remove antibiotics. The main advantages of this invention include (1) high uniformity of photocatalyst reception and high light energy utilization efficiency. Ultraviolet light is transmitted through optical fiber, the direction of the light path is controlled to make it uniformly dispersed on the inner wall, and the light flux received at each point is balanced by rotating the optical fiber. (2) The battery separates holes and electrons, resulting in more oxidative active substances. The catalytic reaction is aided by an external battery, and the photogenerated electrons move towards the cathode under the action of voltage, away from holes, reducing the recombination probability and improving the efficiency of generating active oxygen species. (3) The combined effect of flow state and electric field results in good antibiotic mass transfer. The water inside the reactor is in a flowing state, and under the combined action of electric field force, antibiotics have a higher probability of contacting the TiO2 wall and completing the reaction, thus improving the mass transfer efficiency. The advantages and disadvantages of this equipment in removing antibiotics compared with traditional photocatalytic treatment processes are shown in Table 1.

[0008] Table 1. Process Comparison

[0009] Summary of the Invention

[0010] To address the problems of existing technologies, this invention provides a rotary spherical photopolymerization reactor and its method of use for the deep removal of antibiotics from wastewater. This device transmits ultraviolet light to the reaction zone via optical fiber, and utilizes fluidized bed operation and an external power supply to enhance mass transfer efficiency and processing capacity, thereby achieving deep removal of antibiotics. This invention is suitable for small-scale wastewater treatment plants and various enterprises with related needs, offering advantages such as high efficiency and low cost.

[0011] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0012] A rotary spherical photoresist reactor suitable for deep removal of antibiotics from wastewater includes a housing, a reactor, connecting pipes, and a controller.

[0013] The outer shell is made of fiberglass, and its dimensions are 8m × 5m × 3m (length × width × height).

[0014] There are three reactors, fixed sequentially on the outer shell. They are spherical in shape with a radius of 1m, and the inner wall is made of conductive glass coated with modified TiO2. The inner wall is removable and replaceable. A spherical rotating shaft is located at the center of the shaft and supported by a rod. The rod has wires connected to the rotating shaft, which can control its rotation. Ultraviolet optical fibers are evenly distributed on the spherical rotating shaft. The ultraviolet optical fibers are 0.8m long, with a core made of high-purity synthetic quartz and a cladding made of fluorine-doped quartz. The outer layer is protected by a graphite tube. An external battery is connected between the conductive glass on the inner wall and the optical fiber tube. The conductive glass is the anode and the optical fiber tube is the cathode.

[0015] The reactors are connected in series by connecting pipes, with the inlet and outlet pipes extending out from both sides of the outer shell.

[0016] The controller is fixed to the bottom of the housing and is connected to the ultraviolet light source, the spherical rotating shaft, the inner wall of the reactor, and the fiber optic sleeve by wires. It can control the switching of the light source, the rotation speed of the rotating shaft, and the voltage of the external battery.

[0017] This invention has the following advantages:

[0018] 1. High light energy utilization. The ultraviolet light is guided by optical fibers, ensuring it is uniformly incident on the inner catalyst wall. Furthermore, the optical fibers rotate at a constant speed, guaranteeing that the catalyst receives light energy evenly throughout the entire process. In this mode, the catalyst activation level is consistent, maximizing light energy utilization.

[0019] 2. High yield of active species. To reduce carrier recombination, an external battery is used in the equipment. Photogenerated electrons are directed away from holes by the battery, reducing the recombination probability. This gives carriers more opportunities to come into contact with H2O and O2, improving the efficiency of generating active oxygen species and enhancing the removal of antibiotics.

[0020] 3. High mass transfer efficiency of antibiotics. Since strong oxidizing agents such as hydroxyl radicals are unstable in water, they need to come into contact with antibiotics promptly to complete the reaction; otherwise, they will be wasted. This equipment employs a fluidized bed operation mode, where antibiotics are constantly in motion, increasing the probability of contact with the oxidant. Furthermore, because antibiotics are often in a charged state, the presence of an electric field in this equipment also guides the movement of ions.

[0021] 4. No risk of secondary pollution. The treatment process requires no additional reagents and removes antibiotics thoroughly, converting them into H2O, CO2, and inorganic ions without producing byproducts. Furthermore, the reactor contains strong oxidants and ultraviolet light, which have a sterilizing effect, preventing the emergence of microorganisms containing resistance genes.

[0022] 5. Easy to use. The equipment has a small footprint, making it suitable for truck transportation. Once it arrives at its destination, no complicated installation process is required; it can be operated simply by connecting water pipes and electrical circuits. It is suitable for temporary treatment or emergency situations, and can also be used for upgrading and retrofitting sewage treatment plants.

[0023] 6. Low equipment construction and operation costs. Traditional photocatalytic reactors are complex in design, requiring matching light sources, mass transfer, and separation systems, resulting in high initial investment and operation and maintenance costs. In contrast, this equipment has a simple structure and can operate automatically, resulting in low construction and maintenance costs. Attached Figure Description

[0024] Figure 1 A schematic diagram of the internal structure of the outer casing of the present invention is shown.

[0025] Figure 2 A schematic diagram of the overall structure of the reactor after it is opened is shown.

[0026] Figure 3 A diagram showing the internal structure of the reactor is displayed.

[0027] Figure 4 The internal structure diagram of ultraviolet optical fiber is shown.

[0028] Figure 5 The operating mechanism diagram is shown.

[0029] Figure 6 This demonstrates the equipment's processing performance during long-term operation.

[0030] Among them are:

[0031] 1. Outer shell; 2. Controller; 3. Circuit; 4. Reactor; 5. Connecting pipe; 6. Ultraviolet optical fiber; 7. Spherical rotating shaft. Detailed Implementation

[0032] The invention will now be explained in detail with reference to the illustrations and specific implementation schemes.

[0033] The mechanism of action of the equipment in this invention is as follows:

[0034] Step 1: Wastewater containing antibiotics flows into the first reactor through the inlet pipe; turn on the ultraviolet lamp and the motor to make the spherical shaft rotate, and the optical fiber fixed on the shaft rotates along with it.

[0035] In step 1, the water flows in a fluidized state under the rotation of the shaft, which can promote the contact between the antibiotics and the generated active substances. The rotation speed of the shaft is set to 10 rpm. The material of the inner wall of the reactor is Pt-modified TiO2, which has been proven to effectively reduce the optical band gap, thereby reducing the probability of electron-hole recombination. Due to the total internal reflection of the optical fiber, the light path of the ultraviolet light will advance along the fiber's layout direction and accurately hit the inner wall of the reactor, exciting electrons and holes. The reaction formula is shown below.

[0036]

[0037] Step 2: An external power source connected between the ultraviolet fiber optic sleeve and the inner wall of the reactor energizes them, generating a large number of active species. At this time, the fluidized antibiotics come into contact with the active species and are oxidized into water, CO2, and environmentally harmless ions.

[0038] In step 2, an external power source is connected to the inner wall of the reactor (made of conductive glass and...). A chemical battery is formed by combining an optical fiber sleeve (made of graphite) and a water-based electrode. Electrons excited in step 1 move along the circuit to the optical fiber sleeve under voltage, avoiding recombination with holes. The generated holes react with water to form hydroxyl radicals, while the generated electrons react with oxygen to form hydrogen peroxide; both are strong oxidants that can scavenge antibiotics. Furthermore, the battery creates an electric field inside the reactor, and since antibiotics are typically charged in water, their movement is influenced by the electric field, making them more likely to come into contact with the generated active species. The reaction formulas at the cathode and anode of the battery are shown below:

[0039] cathode:

[0040] anode:

[0041] The voltage of the external power supply is calculated using the following formula:

[0042]

[0043] In the formula, U represents the external battery voltage (V); E represents the theoretical degradation potential, which is related to the redox properties of the antibiotic and can be taken as 0.5-1.8V; R represents the resistance, which can be taken as 30-100Ω; F represents the Faraday constant, 96485C / mol; n is the number of electrons transferred, which is related to the type of antibiotic and can be taken as 30-70; Q is the influent flow rate (L / s); and C is the influent antibiotic concentration (mg / L). The current efficiency can be 0.1-0.3%; M is the molar mass range of the antibiotic, which can be 200-600 g / mol.

[0044] Step 3: After the wastewater is treated by the first reactor, it passes through the remaining two reactors in sequence. The treatment process in these two reactors is the same as that in the first reactor, which enhances the treatment of the wastewater and ensures that the effluent quality meets the standards.

[0045] In step 3, the inner wall of the reactor in this equipment is removable. If the TiO2 fails, the reactor can be opened and the TiO2 removed for replacement. Additionally, if the ultraviolet fiber is damaged, it can be removed from the rotating shaft for replacement.

[0046] Example 1: Upgrading and renovation of wastewater treatment plants

[0047] To test the equipment's performance in a low-concentration antibiotic environment, influent from a wastewater treatment plant was used as the test sample. The antibiotic concentration in the influent was detected to be approximately 55 ng / L, and the influent flow rate was set at 50 m³ / L. 3 / d. Start the equipment and calculate the magnitude of the external voltage in each reactor using the following formula.

[0048]

[0049] In the formula, U represents the external battery voltage, V; E represents the theoretical degradation potential, 1V; R represents the resistance, 70Ω; F represents the Faraday constant, 96485C / mol; n is the number of electrons transferred, 60; Q is the influent flow rate, 0.58L / s; C is the antibiotic influent concentration, 55ng / L. The current efficiency is 0.1%; M is the molar mass range of the antibiotic, with a value of 400 g / mol.

[0050] The calculated external voltage was 32V. The effluent quality after sequential treatment by the reactor is shown in Table 2, proving that this equipment has a good removal effect on low concentrations of antibiotics and has the advantages of short start-up time and stable effluent.

[0051] Table 2 Wastewater Treatment Data of Wastewater Treatment Plant

[0052]

[0053] Example 2: Wastewater from a Pharmaceutical Industrial Park

[0054] To test the equipment's performance in handling high-concentration antibiotic environments, wastewater was collected from a pharmaceutical industrial park. This wastewater contained antibiotics such as ciprofloxacin at concentrations as high as 350 ng / L, with an influent flow rate of 50 m³ / L. 3 / d. Start the equipment; the external power supply voltage is calculated using the following formula:

[0055]

[0056] In the formula, U represents the external battery voltage, V; E represents the theoretical degradation potential, 1V; R represents the resistance, 100Ω; F represents the Faraday constant, 96485C / mol; n is the number of electrons transferred, 60; Q is the influent flow rate, 0.58L / s; and C is the antibiotic influent concentration, 350ng / L. The current efficiency is 0.3%; M is the molar mass range of the antibiotic, with a value of 600 g / mol.

[0057] The calculated external voltage was 66V. The equipment ran continuously for one week, and the results are shown in Table 3. The results show that this equipment still has a good treatment effect in the treatment of high concentrations of antibiotics, and the effluent is stable and meets the treatment requirements.

[0058] Table 3 Reactor performance parameters and treatment effects

[0059]

[0060] Example 3: Long-term effectiveness assessment and maintenance performance verification

[0061] To evaluate the long-term economic efficiency and stability of the reactor, it is necessary to systematically test the performance degradation pattern of its core components during long-term operation, and examine the system performance through maintenance operations such as replacement.

[0062] The influent from a wastewater treatment plant in Example 1 was used as the test sample, and the influent flow rate was still set at 50 m³ / s. 3 / d, external power supply voltage 32V. Start the equipment and run continuously for 90 days, during which the inner wall and damaged optical fibers are replaced when the removal rate is below 80%. The operating results are as follows: Figure 5 As shown in Table 4, the operating parameters are as follows. The results show that this equipment has low operating costs and high cost-effectiveness.

[0063] Table 4 Reactor operating parameters

[0064]

[0065] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various equivalent transformations can be made to the technical solutions of the present invention, and these equivalent transformations all fall within the protection scope of the present invention.

Claims

1. A rotary spherical photoresist reactor suitable for deep removal of antibiotics from wastewater, characterized in that: Includes the outer shell, reactor, connecting pipes, and controller.

2. The reactor according to claim 1, characterized in that: There are three reactors in total, fixed sequentially on the outer shell. They are spherical in shape, with the inner wall coated with conductive glass containing modified TiO2. The inner wall is removable and replaceable. A spherical rotating shaft is located at the center, supported by a rod. The rod contains wires that connect to the rotating shaft, allowing its rotation to be controlled. Ultraviolet optical fibers are evenly distributed on the spherical rotating shaft. The core of the ultraviolet optical fiber is made of high-purity synthetic quartz, the cladding material is fluorine-doped quartz, and the outer layer is protected by a graphite sheath. An external battery is connected between the conductive glass on the inner wall and the optical fiber sheath, with the conductive glass acting as the anode and the optical fiber sheath as the cathode.

3. The method of using the rotary spherical photoresist reactor for deep removal of antibiotics from wastewater according to any one of claims 1 to 2, characterized in that, The specific steps include the following: Step 1: Wastewater containing antibiotics flows into the first reactor through the inlet pipe; turn on the ultraviolet lamp and the motor to rotate the spherical shaft, and the optical fiber fixed on the shaft rotates along with it. Step 2: An external power source connected between the ultraviolet fiber optic sleeve and the reactor inner wall energizes them, generating a large number of active species. At this point, the fluidized antibiotics come into contact with the active species and are oxidized into water, CO2, and environmentally harmless ions. The voltage of the external power source is calculated using the following formula: In the formula, U represents the external battery voltage, in V; E represents the theoretical degradation potential, which is related to the redox properties of the antibiotic and can be 0.5-1.8V; R represents the resistance, which can be 30-100Ω; F represents the Faraday constant, 96485C / mol; n is the number of electrons transferred, which is related to the type of antibiotic and can be 30-70; Q is the influent flow rate, L / s; C is the influent antibiotic concentration, mg / L. The current efficiency can be 0.1-0.3%; M is the molar mass range of the antibiotic, which can be 200-600 g / mol. Step 3: After the wastewater is treated by the first reactor, it passes through the remaining two reactors in sequence. The treatment process in these two reactors is the same as that in the first reactor, which enhances the treatment of the wastewater and ensures that the effluent quality meets the standards.

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