Environment-friendly low-carbon membrane reactor

Abstract

The invention discloses an environment-friendly low-carbon membrane reactor which comprises a reaction base body, a treatment membrane and a liquid guide block, the reaction base body is provided with an upper base cylinder and a lower base cylinder which are detachably connected together up and down, and the treatment membrane is horizontally arranged and clamped between the upper base cylinder and the lower base cylinder; the liquid guide block is located above the treatment film and is sequentially provided with a plurality of first guide holes with consistent upper and lower hole diameters, second guide holes with gradually reduced hole diameters from top to bottom and third guide holes with gradually increased hole diameters from top to bottom from the center to the outer edge, and the carbon emission is relatively low.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage treatment, particularly to the technical field of membrane reactors. Background Art

[0002] With the increasingly severe global climate change problem, reducing carbon emissions and achieving sustainable development have become the common goals of governments and enterprises around the world. The sewage treatment industry, due to its special "energy - environment" dual attributes, is facing huge transformation pressure.

[0003] Membrane reactors are key equipment for sewage treatment, capable of effectively removing impurities and pollutants in sewage by using membranes, such as the easily disassembled ceramic membrane device for sewage treatment with the publication number CN119215666A. However, the core components of membrane reactors mostly rely on high - energy - consuming materials (the equipment matrix is usually prepared from metal alloy materials) and high - energy - consuming processes (the sintering temperature of ceramic membranes often exceeds 1000°C, such as the nano - ceramic membrane with the publication number CN109516777B), and generally require an additional transmembrane pressure (i.e., using power components such as water pumps to apply an external pressure to drive sewage across the membrane), resulting in a high carbon footprint throughout their life cycle. Summary of the Invention

[0004] The purpose of the present invention is to solve the problems in the prior art and propose a green and environment - friendly low - carbon membrane reactor with relatively low carbon emissions.

[0005] To achieve the above - mentioned purpose, the present invention proposes a green and environment - friendly low - carbon membrane reactor, which includes a reaction matrix, a treatment membrane, and a liquid guide block. The reaction matrix has an upper base cylinder and a lower base cylinder that are detachably connected together up and down. The treatment membrane is horizontally arranged and clamped between the upper base cylinder and the lower base cylinder. The liquid guide block is located above the treatment membrane and is successively provided with a number of first guide holes with the same upper and lower apertures, second guide holes with gradually decreasing apertures from top to bottom, and third guide holes with gradually increasing apertures from top to bottom from the center to the outer edge.

[0006] Preferably, both the reaction matrix and the liquid guide block are made of recycled glass.

[0007] Preferably, the treatment membrane is a low - temperature calcined polyacrylonitrile - based composite membrane.

[0008] Preferably, the preparation method of the low - temperature calcined polyacrylonitrile - based composite membrane is as follows: a) Solution preparation: Dissolve 10 - 15 parts by weight of polyacrylonitrile in 80 - 85 parts by weight of N,N - dimethylformamide to form a homogeneous solution. Add 20 - 30% of the weight of polyacrylonitrile of urea and 5 - 10% of the weight of polyacrylonitrile of ferric nitrate nonahydrate into the homogeneous solution and stir until evenly dispersed. Then, dropwise add an acid solution to adjust the pH to 2 - 3 to obtain a film - forming solution; b) Film formation: After defoaming the film-forming solution, pour it onto a flat plate and scrape it to the required thickness, and then immerse it in a coagulation bath to form a nascent film; c) Low-temperature calcination: First, vacuum pre-dry the nascent film at 50-70 °C for 10-15 h, and then under the protection of inert gas, heat it up to 250-400 °C at a temperature rise rate of 2-5 °C / min and keep it warm for 1-3 h to obtain the finished product.

[0009] Preferably, a filtrate tank is further arranged below the reaction matrix.

[0010] Preferably, the adjacent ends of the upper base cylinder and the lower base cylinder are respectively provided with an upper ring wing and a lower ring wing extending horizontally outwards, and the outer edge of the treatment film extends into the space between the upper ring wing and the lower ring wing and separates the upper cylinder channel from the lower cylinder channel.

[0011] Preferably, the reaction matrix further has a hydraulic extrusion mechanism that can support the treatment film to keep the treatment film in a tightly supported state.

[0012] Preferably, the hydraulic extrusion mechanism includes a piston, a top bar, a pressing plate, a spring and a cover plate. The top surface of the upper ring wing is provided with a blind groove, the top opening of the blind groove is closed by the cover plate and is provided with a plurality of through holes penetrating downwards to the bottom surface. The piston is located in the blind groove and a top bar extending into each through hole is installed at the bottom. The top surface of the lower ring wing is provided with blind holes corresponding to each through hole respectively, and pressing plates supported upwards by springs are respectively arranged in each blind hole. The cover plate is connected to a hydraulic system to inject or suck out hydraulic oil into the hydraulic cavity jointly formed by the upper ring wing, the piston and the cover plate.

[0013] Preferably, the upper ring wing is respectively screwed to the lower ring wing and the cover plate through fasteners.

[0014] Preferably, sealing rings are further respectively installed between the upper ring wing and the lower ring wing and between the upper ring wing and the cover plate.

[0015] Advantages of the present invention: 1) By arranging the reaction matrix to horizontally clamp the treatment film, and adding a liquid guide block with uniformly sized through holes, reduced-diameter through holes and enlarged-diameter through holes designed layer by layer from the inner circle to the outer circle above the treatment film to divert sewage, on the one hand, gravity can be used to drive wastewater across the membrane (no additional transmembrane pressure is required), greatly reducing energy consumption (environmentally friendly and green), and on the other hand, the liquid guide block can make anti-pollution and high flux coexist (the reduced-diameter through holes in the middle circle can inhibit pollution through high shear force, and the through holes in the center and outer edge can share the flow pressure to avoid overload in a single area, achieving a dynamic balance between anti-pollution and high flux) and optimize the pressure distribution (the high pressure in the reduced-diameter area drives osmosis, the low pressure in the enlarged-diameter area extends the reaction time, combined with the stable flow in the central uniformly sized area, making the pressure gradient on the membrane surface more uniform and reducing the risk of structural fatigue); 2) By using a low-temperature calcined polyacrylonitrile-based composite membrane as the treatment membrane, not only can physical filtration and catalytic degradation be utilized to effectively achieve sewage treatment, but also the problem of a significant increase in carbon footprint caused by high-temperature roasting can be avoided; 3) By adding a hydraulic extrusion mechanism composed of a piston, a top bar, a pressing plate, a spring, and a cover plate in the reaction matrix, when the treatment membrane is used for a period of time and loosening occurs, the piston with the top bar can be evenly pressed down by hydraulic action, so that the top bar cooperates with the pressing plate equipped with a spring to jointly tighten the treatment membrane, thereby stabilizing the transmembrane pressure difference (the tightened state enables the membrane material to maintain stable deformation under pressure, ensuring uniform pressure distribution and avoiding flow fluctuations caused by local collapse of the loose membrane) and extending the service life of the membrane (the loose membrane is prone to local collapse due to pollutant accumulation or pressure changes during long-term operation, resulting in irreversible pore closure, while the tightened membrane can avoid this problem, thereby further reducing carbon emissions), and the treatment membrane does not need to be frequently adjusted or replaced manually (which not only reduces the operating cost but also improves the treatment efficiency).

[0016] The features and advantages of the present invention will be described in detail through embodiments in conjunction with the accompanying drawings. Description of the Drawings

[0017] Figure 1 is a cross-sectional view of Embodiment 1; Figure 2 is a cross-sectional view of the reaction matrix of Embodiment 1; Figure 3 is Figure 2 an enlarged schematic view of part A of Figure 4 is Figure 3 a working schematic view during pressurization; Figure 5 is a cross-sectional view of the liquid guide block of Embodiment 1; Figure 6 is an effect diagram of the degradation of wastewater by the low-temperature calcined polyacrylonitrile-based composite membrane of Embodiment 2; Figure 7 is an effect diagram of the recycled water of the low-temperature calcined polyacrylonitrile-based composite membrane of Embodiment 2.

[0018] In the figures: 1 - reaction matrix, 11 - upper base cylinder, 111 - upper cylinder channel, 112 - blind groove, 113 - through hole, 12 - lower base cylinder, 121 - lower cylinder channel, 122 - blind hole, 13 - hydraulic extrusion mechanism, 131 - piston, 132 - top bar, 133 - pressing plate, 134 - spring, 135 - cover plate, 2 - treatment membrane, 3 - liquid guide block, 31 - first guide hole, 32 - second guide hole, 33 - third guide hole, 4 - filtrate tank. Detailed Embodiments

[0019] Embodiment 1: Referring to Figures 1 to 5 , the green and environment-friendly low-carbon membrane reactor of the present invention includes a reaction matrix 1, a treatment membrane 2, and a liquid guide block 3. The reaction matrix 1 has an upper base cylinder 11 and a lower base cylinder 12 that are detachably connected together up and down. The treatment membrane 2 is horizontally arranged and clamped between the upper base cylinder 11 and the lower base cylinder 12. The liquid guide block 3 is located above the treatment membrane 2 and is successively provided with a number of first guide holes 31 with the same upper and lower pore diameters, second guide holes 32 with gradually decreasing pore diameters from top to bottom, and third guide holes 33 with gradually increasing pore diameters from top to bottom from the center to the outer edge; among them, the central average diameter through hole (the inner diameter of the first guide hole 31 is uniform up and down) can stabilize the main flow rate (as the main flow passage, maintaining the basic flow rate and pressure balance, and avoiding excessive overall pressure drop caused by changes in the peripheral structure) and ensure the minimum flux (even if the peripheral through holes are temporarily ineffective due to pollution or blockage, the central channel can still maintain the basic filtration ability, improving the system reliability), the middle ring reduced-diameter through hole (the inner diameter of the second guide hole 32 decreases from top to bottom) can prevent pollution with high shear (using the reduced diameter to accelerate the fluid, generating a strong shear force to scour the membrane surface and delaying membrane pollution), strengthen the local driving force (using the Venturi effect to increase the transmembrane pressure difference and enhance the permeation flux), and promote turbulent mixing (by enhancing fluid disturbance to improve the contact efficiency between pollutants and the catalytic active sites on the membrane surface), while the outer edge enlarged-diameter through hole (the inner diameter of the third guide hole 33 increases from top to bottom) is mainly used to disperse the fluid pressure (enlarging the cross-sectional area to reduce the local pressure drop, protecting the membrane material from high-pressure impact, preventing the membrane material from being washed loose, and extending the service life of the membrane).

[0020] Both the reaction matrix 1 and the liquid guide block 3 are made of recycled glass as raw materials; in addition, natural ores such as pyrophyllite, quartz sand, limestone, and dolomite can also be added as raw materials, and then the finished product can be made through processes such as grinding, melting, drawing, and post-processing; the reaction matrix 1 and the liquid guide block 3 prepared from the above low-carbon materials can reduce energy consumption and resource waste in raw material production.

[0021] A filtrate tank 4 is also arranged below the reaction matrix 1.

[0022] The adjacent ends of the upper base cylinder 11 and the lower base cylinder 12 are respectively provided with an upper ring wing and a lower ring wing extending horizontally outwards. The outer edge of the treatment membrane 2 extends between the upper ring wing and the lower ring wing and separates the upper cylinder channel 111 from the lower cylinder channel 121.

[0023] The reaction matrix 1 also has a hydraulic extrusion mechanism 13 that can support the treatment membrane 2 to keep the treatment membrane 2 in a tightly supported state.

[0024] The hydraulic extrusion mechanism 13 includes a piston 131, a top bar 132, a pressing plate 133, a spring 134 and a cover plate 135. A blind groove 112 is provided on the top surface of the upper ring wing. The top opening of the blind groove 112 is closed by the cover plate 135, and a plurality of through holes 113 penetrating downward to the bottom surface are provided. The piston 131 is located in the blind groove 112, and a top bar 132 extending into each through hole 113 is installed at the bottom. The top surface of the lower ring wing is provided with blind holes 122 corresponding to each through hole 113 one by one, and a pressing plate 133 supported upward by a spring 134 is provided in each blind hole 122. The cover plate 135 is connected to a hydraulic system to inject or suck hydraulic oil into the hydraulic cavity jointly formed by the upper ring wing, the piston 131 and the cover plate 135.

[0025] The upper ring wing is respectively screwed to the lower ring wing and the cover plate 135 through fasteners.

[0026] Sealing rings are respectively installed between the upper ring wing and the lower ring wing and between the upper ring wing and the cover plate 135.

[0027] Working process of the present invention: During use, sewage is poured into the upper base cylinder 11 along the upper cylinder channel 111, so that the sewage is separated by the treatment membrane 2 to remove dirt and then enters the filtrate tank 4 along the lower cylinder channel 121. If the treatment membrane 2 becomes loose, the hydraulic system can be made to inject hydraulic oil into the hydraulic cavity, so as to use the hydraulic oil to push the piston 131 and make each top bar 132 squeeze the treatment membrane 2 into the corresponding blind hole 122 along the through hole 113 where it is located until the treatment membrane 2 is tightened.

[0028] In addition, in this embodiment, the carbon footprint accounting can be divided into the carbon footprint calculation in the acquisition stage of chemical raw materials and auxiliary materials, the carbon footprint calculation in the transportation stage, and the carbon footprint calculation in the synthesis stage, specifically as follows: The quantification of the carbon footprint in the acquisition stage of chemical raw materials and auxiliary materials is shown in formula (1); C 原料获取 =∑(M i ×EF i ) (1); In the formula, i is the type of raw materials and auxiliary materials added in the acquisition stage of chemical raw materials and auxiliary materials; M i is the total mass of the materials added in the acquisition stage of chemical raw materials and auxiliary materials; EF i is the carbon emission factor of the added product (i.e., the amount of carbon dioxide emitted per unit material consumption); The quantification of the carbon footprint in the transportation stage is shown in formula (2); C 运输 =∑(T i ×D i ×EFi ) (2); Wherein, i is the type of raw materials and auxiliary materials added in the acquisition stage of chemical raw and auxiliary materials; T i represents the energy consumed per kilometer by the average of the i-th type of vehicle, in kilograms (kg); D i represents the transportation distance of the i-th type of vehicle, in kilometers (km); EF i represents the greenhouse gas emission factor in the production process of the i-th type of energy, in kilograms of carbon dioxide equivalent per kilogram of energy (kg CO2eq / kg); For the quantification of the carbon footprint in the synthesis stage, see Formula (3); C 合成 = ∑(E i × EF i ) (3); Wherein, i is the energy such as electricity and natural gas consumed in the synthesis stage, and E i represents the activity level of the i-th type of energy consumed in the synthesis process, in kilograms (kg); EF i represents the greenhouse gas emission factor in the production process of the i-th type of energy, and its unit is expressed as kilograms of carbon dioxide equivalent per kilogram of energy (kg CO2eq / kg).

[0029] Example 2: The treatment membrane 2 is a low-temperature calcined polyacrylonitrile-based composite membrane, and the low-temperature calcined polyacrylonitrile-based composite membrane is prepared by the following method: Solution preparation: Dissolve 12 parts by weight of polyacrylonitrile (PAN) in 82 parts of N,N-dimethylformamide (DMF) to form a homogeneous solution (slowly add PAN powder to DMF and stir at 65 °C until completely dissolved), add 25% of the weight of PAN of urea and 7% of the weight of PAN of ferric nitrate nonahydrate to the homogeneous solution and stir until evenly dispersed, and then add concentrated sulfuric acid to adjust the pH to 2.5 to obtain a film-forming solution; among them, PAN is the film-forming matrix, which is used to provide mechanical strength and pore structure; DMF is the solvent, which is used to dissolve PAN and form a homogeneous solution; urea is the pore-forming agent, which can decompose to generate gas and form a porous structure during calcination; ferric nitrate nonahydrate is the iron source and can generate catalytically active substances such as Fe2O3 after calcination; concentrated sulfuric acid is used to adjust the acidity of the solution to promote the complexation and dispersion of iron ions; Film formation: After defoaming the film-forming solution, pour it onto a flat plate (such as a clean glass plate or a polytetrafluoroethylene plate) and scrape it to the required thickness, and then immerse it in a coagulation bath (water or ethanol / water mixture) to induce phase separation to form a nascent membrane (residual solvent can be removed by washing with absolute ethanol); Low-temperature calcination: First, transfer the nascent membrane to a vacuum drying oven for vacuum pre-drying at 60 °C for 12 h, and then transfer it to a tubular furnace. Under the protection of an inert gas, heat it up to 300 °C at a temperature rise rate of 3 °C / min and hold for 2 h to obtain the finished product (the treated membrane 2 presents a porous network structure, and Fe2O3 nanoparticles are uniformly loaded in the PAN matrix); this low-temperature calcination method not only has a lower carbon footprint compared to traditional ceramic membranes, but also can avoid the complete carbonization of PAN (the treated membrane 2 presents semi-rigid characteristics, and its flexibility after swelling is improved to a certain extent and can withstand a certain degree of bending).

[0030] Other parts are the same as in Example 1.

[0031] Next, use the principle of gravity-driven osmosis to pass 1 L of wastewater containing pollutants through this low-temperature calcined polyacrylonitrile-based composite membrane; at the beginning of the experiment, place the membrane material in 1 L of wastewater containing pollutants and undergo an adsorption process for 30 minutes to ensure that a stable adsorption / desorption equilibrium is established between the pollutant solution and the membrane surface at room temperature; then, introduce 0.8 mM of peroxymonosulfate (PMS) into the reaction system as the starting point of catalytic degradation (marking the official start of the degradation reaction); within the preset degradation time period, use a pipette to accurately extract 1 mL of reaction solution samples at strict time intervals (-30 minutes, 0 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 60 minutes); in addition, to terminate the reaction activity in a timely manner, 1 mL of methanol needs to be quickly added to each sample for quenching treatment and sealed in a liquid phase vial (for subsequent high performance liquid chromatography analysis to obtain the degradation effect of antibiotic wastewater).

[0032] This low-temperature calcined polyacrylonitrile-based composite membrane can achieve sewage treatment through physical filtration (retaining suspended particles and macromolecular pollutants through its own pores) and catalytic degradation (Fe2O3 can generate reactive free radicals when contacting PMS to degrade organic matter); as Figure 6 shown, the low-temperature calcined polyacrylonitrile-based composite membrane achieves a 100% degradation effect on the wastewater containing pollutants within 60 min; referring to Figure 3 , the low-temperature calcined polyacrylonitrile-based composite membrane can still maintain a 100% degradation effect after 10 cycles.

[0033] The above embodiments are illustrative of the present invention, not limiting of the present invention. Any simple transformation of the present invention belongs to the protection scope of the present invention.

Claims

1. Green environmental protection and low-carbon membrane reactor, characterized in that: It includes a reaction matrix (1), a treatment membrane (2) and a liquid guiding block (3). The reaction matrix (1) has an upper base cylinder (11) and a lower base cylinder (12) which are detachably connected together in an upper and lower manner. The treatment membrane (2) is horizontally arranged and is clamped between the upper base cylinder (11) and the lower base cylinder (12). The liquid guiding block (3) is located above the treatment membrane (2) and is successively provided with a number of first guiding holes (31) with the same upper and lower apertures, second guiding holes (32) with gradually decreasing apertures from top to bottom, and third guiding holes (33) with gradually increasing apertures from top to bottom from the center to the outer edge.

2. The green and environment-friendly low-carbon membrane reactor according to claim 1, wherein: Both the reaction matrix (1) and the liquid guiding block (3) are made of recycled glass.

3. The green and environment-friendly low-carbon membrane reactor according to claim 1, characterized in that: The treatment membrane (2) is a low-temperature calcined polyacrylonitrile-based composite membrane.

4. The green and environment-friendly low-carbon membrane reactor according to claim 3, wherein, The preparation method of the low-temperature calcined polyacrylonitrile-based composite membrane is as follows: a) Solution preparation: Dissolve 10 - 15 parts by weight of polyacrylonitrile into 80 - 85 parts of N,N-dimethylformamide to form a homogeneous solution. Add 20 - 30% of the weight of polyacrylonitrile of urea and 5 - 10% of the weight of polyacrylonitrile of ferric nitrate nonahydrate into the homogeneous solution and stir until evenly dispersed. Then add acid solution to adjust the PH to 2 - 3 to obtain a film-forming solution. b) Film formation: After defoaming the film-forming solution, pour it onto a flat plate and scrape it to the required thickness, and then immerse it in a coagulation bath to form a nascent membrane. c) Low-temperature calcination: First, vacuum pre-dry the nascent membrane at 50 - 70 °C for 10 - 15 h, and then under the protection of inert gas, heat it up to 250 - 400 °C at a temperature rise rate of 2 - 5 °C / min and keep it warm for 1 - 3 h to obtain the finished product.

5. The green environmental protection and low-carbon membrane reactor according to claim 1, wherein: A filtrate tank (4) is also arranged below the reaction matrix (1).

6. The green and environment-friendly low-carbon membrane reactor according to any one of claims 1 to 5, characterized in that: The adjacent ends of the upper base cylinder (11) and the lower base cylinder (12) are respectively provided with an upper ring wing and a lower ring wing extending horizontally outwards. The outer edge of the treatment membrane (2) extends between the upper ring wing and the lower ring wing and separates the upper cylinder channel (111) from the lower cylinder channel (121).

7. The green environmental protection and low-carbon membrane reactor according to claim 6, characterized in that: The reaction matrix (1) also has a hydraulic extrusion mechanism (13) that can support the treatment membrane (2) to keep the treatment membrane (2) in a tightly stretched state.

8. The green environmental protection and low-carbon membrane reactor according to claim 7, characterized in that: The hydraulic extrusion mechanism (13) includes a piston (131), a top bar (132), a pressing plate (133), a spring (134) and a cover plate (135). The top surface of the upper ring wing is provided with a blind groove (112). The top opening of the blind groove (112) is closed by the cover plate (135) and is provided with a number of through holes (113) penetrating downwards to the bottom surface. The piston (131) is located in the blind groove (112) and a top bar (132) extending into each through hole (113) is installed at the bottom. The top surface of the lower ring wing is provided with blind holes (122) corresponding to each through hole (113) one by one, and pressing plates (133) supported upwards by springs (134) are respectively arranged in each blind hole (122). The cover plate (135) is connected to the hydraulic system to inject or suck hydraulic oil into the hydraulic cavity jointly formed by the upper ring wing, the piston (131) and the cover plate (135).

9. The green and environmentally friendly low-carbon membrane reactor according to claim 8, characterized in that: The upper ring wing is respectively threadedly connected to the lower ring wing and the cover plate (135) through fasteners.

10. The green and environment-friendly low-carbon membrane reactor according to claim 8, wherein: Sealing rings are also respectively installed between the upper ring wing and the lower ring wing and between the upper ring wing and the cover plate (135).

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