CN109589803B - Microbial carrier hybrid MBfR membrane and preparation method thereof - Google Patents
Microbial carrier hybrid MBfR membrane and preparation method thereof Download PDFInfo
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- CN109589803B CN109589803B CN201910081942.XA CN201910081942A CN109589803B CN 109589803 B CN109589803 B CN 109589803B CN 201910081942 A CN201910081942 A CN 201910081942A CN 109589803 B CN109589803 B CN 109589803B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention relates to a microbial carrier hybrid MBfR membrane and a preparation method thereof, wherein the MBfR membrane comprises the following casting solution in percentage by weight: PVDF 12-35%, pore-forming agent 2-18%, microbial carrier 0.05-15% and solvent 45-86%; the microbial carrier is mainly one or a combination of two of nitric acid modified activated carbon powder or carbon nano tubes with the granularity of 300-2000 meshes. The microbial carrier hybrid MBfR membrane is a hollow fiber membrane, the inner and outer side aperture is distributed in a gradient manner, and the ratio of the inner and outer side aperture is 5-50; the hollow fiber membrane is a single-core membrane or a multi-core hole structure with concentric inner and outer circles. The activated carbon microparticles doped on the surface of the membrane provide a great specific surface area, and provide good microorganism attachment and growth conditions for the product; the multi-pore membrane structure has higher mechanical strength, so that the water power and steam impact resistance of the product is greatly enhanced.
Description
Technical Field
The application belongs to the technical field of ultrafiltration membrane preparation, and particularly relates to a multicore-structure-enhanced microbial carrier hybrid MBfR membrane which has the characteristic of excellent microbial load and takes PVDF as a main body, and a preparation method thereof.
Background
The Membrane Biofilm Reactor (MBfR) Membrane is a novel water pollution control technology combining Membrane aeration with traditional biological sewage treatment, can be applied to the treatment of drinking water items with over-standard nitrite due to excellent oxygen mass transfer characteristics, saves energy by 40-90% compared with a reverse osmosis treatment process and a nanofiltration treatment process, and has no concentrated water discharge; can also be applied to black and odorous river treatment and other nitrification and denitrification links, and is more and more widely applied to the fields of feed water purification, reclaimed water reuse, wastewater treatment and the like. At present, the existing marketized products at home and abroad basically adopt a sintered and stretched PTFE hydrophobic membrane as an MBfR membrane material, have no cortex, have consistent inside and outside pore diameters, have too low bubble point pressure, and the too small microorganism in the outer cortex pore diameter is extremely difficult to be filmed, and the microorganism can only be simply attached to the MBfR membrane surface through EPS, and the microorganism property is single, and is small in quantity, thereby bringing about the defects of extremely low oxygen mass transfer microorganism utilization rate, unstable COD and TN removal efficiency, and further being difficult to popularize marketized. Therefore, it is very important to find a membrane element production process which has a pore size gradient, ensures a proper bubble point pressure by a proper inner layer pore size, has a larger three-dimensional reticular pore structure and a huge specific surface area at an outer layer and is convenient for the growth and propagation of microorganisms.
Polyvinylidene fluoride (PVDF) is a high-end synthetic material widely used at present, has very excellent physical and chemical properties, can resist most inorganic acids (except fuming sulfuric acid and concentrated nitric acid), various strong bases, most organic solvents (such as alcohols, halogenated hydrocarbons, aliphatic hydrocarbons and aromatic hydrocarbons) and the like, and can be applied to various corrosive environments. However, for long-term use environments of water power and steam water impact, the unsupported PVDF hollow fiber membrane has the defect of easy filament breakage, and in order to solve the problem, the MBR membrane element in the market at present adopts a PET crocheted tube to coat PVDF to manufacture a filtering membrane, but the internal filtering membrane can only be used as external pressure, and the cortex can fall off due to internal pressure use, so that the product fails.
Therefore, it is necessary to develop an MBfR membrane having a smaller pore size in the inner layer, a larger three-dimensional reticular pore structure in the outer layer, and a larger specific surface area in the outer layer, and at the same time, the MBfR membrane is required to have higher mechanical strength to adapt to the use environment with higher hydraulic impact.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a microbial carrier hybrid MBfR membrane, and provides an MBfR hollow fiber membrane which is easy to attach microorganisms and has a proper bubble point and enhanced mechanical strength and takes a PVDF material as a main material, and also provides a preparation method of the membrane.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides a microbial carrier hybrid MBfR membrane, which is a hollow fiber membrane; the casting solution comprises the following components in percentage by weight: 12-35% of PVDF, 2-18% of pore-forming agent, 0.05-15% of microbial carrier and 45-86% of solvent, wherein the microbial carrier is one or a combination of two of nitric acid modified activated carbon powder or carbon nano tubes with the granularity of 300-2000 meshes.
Preferably, the present invention provides a microbial carrier hybrid MBfR membrane, which is a hollow fiber membrane; the casting film is prepared from the following components in percentage by weight: 12-35% of PVDF, 2-18% of pore-forming agent, 0.05-15% of microbial carrier and 45-86% of solvent, wherein the microbial carrier is one or a combination of two of nitric acid modified activated carbon powder or carbon nano tubes with the granularity of 300-2000 meshes.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, and PVDF is resin powder with the weight-average molecular weight of 10-80 ten thousand.
Further preferably, the PVDF is resin powder with the average weight average molecular weight of 20-60 ten thousand.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, and the main component of the pore-forming agent is one or more of polyethylene glycol, glycerol, tween, diethylene glycol and polyvinylpyrrolidone.
Further preferably, the polyethylene glycol has an average relative molecular weight of PEG200-PEG 2000.
Further preferably, the polyethylene glycol has an average relative molecular weight of PEG400-PEG 600.
Further preferably, the polyvinylpyrrolidone has a K value of K15-K120.
Further preferably, the polyvinylpyrrolidone has a K value of K60-K120.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, and the main component of the solvent is one or more mixed solvents of dimethylformamide, dimethylacetamide and butyrolactone phosphate.
In another preferred embodiment, the invention provides a microbial carrier hybrid MBfR membrane, wherein the membrane is an internal pressure type or external pressure type hollow fiber membrane.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, wherein the filtration pore diameter of the inner side of an internal pressure type hollow fiber membrane is between 0.02 and 1.5 micrometers, and the pore diameter of the outer side of the internal pressure type hollow fiber membrane is between 0.1 and 50 micrometers.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, wherein the inner pore diameter of the external pressure type hollow fiber membrane is between 0.1 and 50 micrometers, and the outer filtration pore diameter is between 0.02 and 1.5 micrometers.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, the support layer of the membrane structure being a sponge-like microstructure, but also a finger-like pore or bubble cavity structure. The sponge microporous structure is preferably selected for improving the strength and toughness of the product; for reducing energy consumption of the product, a finger-shaped hole single-skin structure is preferred.
Preferably, the invention provides a microbial carrier hybrid MBfR membrane, wherein the inside and outside pore diameters in the membrane are distributed in a gradient manner, and the ratio of the inside and outside pore diameters is 5-50, preferably 10-40, and more preferably 15-30.
In another preferred embodiment, the invention provides a microbial carrier hybrid MBfR membrane, wherein the hollow fiber can be a simple single-core membrane with inner and outer circles maintaining a certain concentricity; the structure can also be a larger outer circle, the structure with 1-11 core holes is arranged inside the structure, preferably 3-9 core holes, more preferably 5-7 core holes, and the number of the core holes is preferably odd.
The invention also provides a preparation method of the microbial carrier hybrid MBfR membrane, which adopts a dry-wet method or a wet method to prepare the membrane and comprises the following steps:
(1) preparing a casting solution according to the components in the weight ratio accurately;
(2) fully stirring and dissolving the casting solution at the temperature of 50-132 ℃;
(3) fully vacuumizing or standing and defoaming the dissolved casting solution;
(4) spinning and drying are carried out through a conventional spinning process.
Preferably, step 4 is specifically operative to: extruding the defoamed membrane casting solution into an insertion tube type spinning nozzle through nitrogen or a pump, introducing 15-80 ℃ water or an aqueous solution into the core solution, wherein the aqueous solution consists of 10-85 mass percent of DMAc or DMF and pure water, the distance between the outlet of the spinning nozzle and the liquid level of the gel bath is 20 cm below to 50 cm above, the temperature of the gel bath is constant at 10-70 ℃, and the membrane casting solution forms a membrane in the gel bath and is collected through a winding system.
Preferably, the winding speed of the MBfR film is 10-100m/min, preferably 15-45 m/min.
Compared with the prior art, the invention has the obvious beneficial effects that: the microbial carrier hybrid MBfR membrane provided by the invention has the following characteristics:
1. the modifier is nitric acid modified activated carbon powder with the granularity of 300-2000 meshes or one or two combinations of carbon nano tubes, wherein the modified activated carbon is treated by nitric acid to effectively remove the ash content in the product in the processing process of the activated carbon, and the problem that the quality of the product is uncontrollable due to the fact that the casting solution is unstable when the membrane is prepared because of too high ash content in the activated carbon product which is not treated by inorganic acid such as nitric acid, hydrochloric acid or phosphoric acid is solved; the surface of the activated carbon powder after nitric acid treatment is rich in hydroxyl groups, which is beneficial to the stability of the casting solution and the good combination of the activated carbon powder and PVDF in the final product.
2. The MBfR membrane produced by the method has the inner side filtering pore diameter of 0.08-0.5 micron, the outer side pore diameter of 0.15-30 micron, the bubble point pressure of N2 of 20-500 kpa, and the proper bubble point pressure ensures that the product has a simple process operation mode and more excellent oxygen (hydrogen) utilization rate.
3. The contact angle of the outer surface of the MBfR film produced by the method is 36-65 degrees, and the activated carbon microparticles doped on the surface of the film provide a great specific surface area, so that good microorganism attachment and growth conditions are provided for the product.
4. The multi-pore membrane structure greatly enhances the waterpower and steam-water impact resistance of the product, and has simple preparation method and simple and convenient operation.
The benefit can greatly expand the application range of the product of the invention, and can be applied to micro-polluted drinking water treatment, black and odorous river treatment, reclaimed water reuse and sewage treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a schematic structural view of a multi-pore enhanced water and vapor impact resistant MBfR membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The hollow fiber membrane is a membrane having a self-supporting function and a fibrous shape. The hollow fiber membrane is prepared by processing polysulfone and dimethylacetamide serving as raw materials into fiber filaments with hollow inner cavities, and then dividing the fiber filaments by a high-permeability polymer, and has a selective permeability characteristic.
The microbial carrier hybrid MBfR membrane is prepared by a dry-wet method or a wet method, and comprises the following steps:
1. preparing a casting solution according to the components with required weight ratio;
2. fully stirring and dissolving the casting solution at the temperature of 50-132 ℃;
3. fully vacuumizing or standing and defoaming the dissolved casting solution;
4. spinning and drying are carried out through a conventional spinning process.
Step 4, the specific operation process is as follows: and extruding the defoamed membrane casting solution into an insertion tube type spinning nozzle through nitrogen or a pump, introducing 15-80 ℃ water or 10-85% aqueous solution of a corresponding solvent into the core solution, keeping the outlet of the spinning nozzle at a distance of 20 cm below the liquid level of the gel bath to 50 cm above the liquid level, keeping the temperature of the gel bath at 10-70 ℃, forming a membrane by the membrane casting solution in the gel bath, and collecting the product by a winding system.
Example 1
Example 1 a casting solution for an MBfR membrane was prepared with the following components in the following weight ratios: 15 percent of PVDF resin powder with weight average molecular weight of 70 ten thousand, 12 percent of polyvinylpyrrolidone (PVP-K15) powder, 3 percent of polyethylene glycol (PEG-600) liquid, 2 percent of nitric acid modified activated carbon material with particle size of 200 meshes, 3 percent of carbon nano tube sold in the market and 65 percent of dimethylacetamide (DMAc) solvent, wherein the materials are added into a reaction kettle in a certain sequence (firstly, PVP-K15 and PEG-600 are added into DMAC solution, stirred for 20 minutes, then, the activated carbon and the carbon nano tube are added, stirred for 30 minutes to 2 hours, and finally, PVDF, activated carbon and the carbon nano tube can be added firstly, but cannot be added finally, or cause uneven mixing which can cause defects in the final product), the temperature of a jacket of the reaction kettle is constant at 60 ℃, stirred for 12 hours at the stirring speed of 150rpm, and kept standing for 12 hours to ensure that bubbles in the feed liquid are fully removed, and slowly cooling to 50 ℃, slowly heating a metering pump and a spinning nozzle to 50 ℃, wherein the spinning nozzle is 30mm away from the page of a gel bath, the gel bath is pure water with the conductivity of 10 Siemens, the temperature of the gel bath is 60 ℃, the temperature of core liquid is 50 ℃ (the core liquid is an aqueous solution with the mass percent of DMAc being 30%), spinning is carried out at the speed of 10m/min, and the inner diameter of the finished fiber is 0.5mm, and the outer diameter of the finished fiber is 1.0 mm. Fully soaking and rinsing the collected finished membrane fibers, removing residual solvent and pore-forming agent, testing the performance of the embodiment according to a known method, and detecting the tensile breaking strength of the fibers by using a hollow fiber membrane tensile tester (model: YM-065, brand: Yuanmao), wherein the larger the detected value is, the better the product performance is. The performance test results of this example are as follows: the tensile breaking elongation of the fiber is 132 percent, the tensile breaking strength of the fiber is 2.1N, the filtration pore diameter of the outer side of the hollow fiber membrane is 0.08 micrometer, and the filtration pore diameter of the inner side is 12 micrometers.
Example 2
Example 2 a casting solution for an MBfR membrane was prepared with the following components in the following weight ratios: 18% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 8% of polyvinylpyrrolidone (PVP-K15) powder, 0.5% of nitric acid modified activated carbon material with the particle size of 600 meshes, 4.5% of commercially available carbon nanotubes and 69% of dimethylacetamide (DMAc) solvent. The spinning process was the same as in example i, spinning at a speed of 15m/min and the measured properties of the finished product were as follows: the tensile breaking elongation of the fiber is 165 percent, the tensile breaking strength of the fiber is 3.6N, the outer side aperture of the hollow fiber membrane is 0.1 micron, and the inner side aperture is 22 microns.
Example 3
Example 3 a casting solution for an MBfR membrane was prepared with the following components in the following weight ratios: 25% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 15% of polyethylene glycol (PEG-600) liquid, 5% of carbon nano tube sold in the market and 55% of Dimethylformamide (DMF) solvent. The spinning process was the same as in example i, spinning at a speed of 45m/min and the measured properties of the finished product were as follows: the tensile breaking elongation of the fiber is 176%, the tensile breaking strength of the fiber is 4.2N, the outside pore diameter of the hollow fiber membrane is 0.05 micron, and the inside pore diameter is 15 micron.
Example 4
Example 4 a casting solution for an MBfR membrane was prepared with the following components in the following weight ratios: 25% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 15% of polyethylene glycol (PEG-600) liquid, 5% of nitric acid modified activated carbon material with the particle size of 300 meshes and 55% of Dimethylformamide (DMF) solvent. The temperature of a jacket of a reaction kettle is constant at 80 ℃, the stirring speed of 150rpm is kept for 12 hours, the reaction kettle is kept still for 12 hours to ensure that bubbles in feed liquid are fully removed, the temperature of a metering pump and a spinning nozzle is slowly reduced to 70 ℃, the distance between the spinning nozzle and the page of a gel bath is 100mm, the gel bath is 60% DMAc aqueous solution, the temperature of the gel bath is 60 ℃, the temperature of a core liquid is pure water with the conductivity of 10 Siemens, the temperature of the core liquid is 60 ℃, spinning is carried out at the speed of 30m/min, a 5-core MBfR membrane (figure 1) is spun, and a finished fiber has 5 internal channels with the diameter of 0.8mm and the outer diameter of 6.5 mm. FIG. 1 shows a schematic diagram of a multi-pore enhanced water and steam impact resistant MBfR film structure, and the multi-pore film structure greatly enhances the water and steam impact resistance of a product. The MBfR film produced by the invention is simple to prepare, low in cost and more convenient and faster to operate. Fully soaking and rinsing the collected finished membrane fibers, removing residual solvent and pore-forming agent, and testing the performance of the embodiment according to a known method as follows: the tensile breaking elongation of the fiber is 210 percent, the tensile breaking strength of the fiber is 22N, the filtration pore diameter at the outer side of the hollow fiber membrane is 32 micrometers, and the filtration pore diameter at the inner side is 0.15 micrometer.
Example 5
In example 5, a casting solution of an MBfR film is prepared from the following components in parts by weight: 25% of PVDF resin powder with weight average molecular weight of 70 ten thousand, 19.95% of polyethylene glycol (PEG-600) liquid, 0.05% of nitric acid modified activated carbon material with the particle size of 1500 meshes and 55% of Dimethylformamide (DMF) solvent. The temperature of a jacket of a reaction kettle is constant at 80 ℃, the stirring speed of 150rpm is kept for 12 hours, the reaction kettle is kept still for 12 hours to ensure that bubbles in feed liquid are fully removed, the temperature of the feed liquid is slowly reduced to 70 ℃, the temperature of a metering pump and a spinning nozzle is slowly heated to 70 ℃, the distance between the spinning nozzle and the page of a gel bath is 100mm, the gel bath is 60% DMAc aqueous solution, the temperature of the gel bath is 60 ℃, the temperature of core liquid is pure water with the conductivity of 10 Siemens, the temperature of the core liquid is 60 ℃, spinning is carried out at the speed of 100m/min, and a 7-core MBfR membrane is spun, wherein the finished fiber has 7 internal channels with the diameter of 0.6mm and the external diameter of 8.0 mm. Fully soaking and rinsing the collected finished membrane fibers, removing residual solvent and pore-forming agent, and testing the performance of the embodiment according to a known method as follows: the tensile breaking elongation of the fiber is 210 percent, the tensile breaking strength of the fiber is 28N, the filtration pore diameter at the outer side of the hollow fiber membrane is 32 micrometers, and the filtration pore diameter at the inner side is 0.15 micrometer.
Example 6
In example 6, a casting solution of an MBfR membrane was prepared from the following components in parts by weight: 25% of PVDF resin powder with weight-average molecular weight of 70 ten thousand, 10% of polyethylene glycol (PEG-600) liquid, 7% of nitric acid modified activated carbon material with particle size of 1500 meshes, 8% of commercially available carbon nanotubes and 50% of Dimethylformamide (DMF) solvent. The temperature of a jacket of a reaction kettle is constant at 80 ℃, the stirring speed of 150rpm is kept for 12 hours, the reaction kettle is kept still for 12 hours to ensure that bubbles in feed liquid are fully removed, the temperature is slowly reduced to 70 ℃, the temperature of a metering pump and a spinning nozzle is slowly heated to 70 ℃, the distance between the spinning nozzle and the page of a gel bath is 100mm, the gel bath is 60% DMAc aqueous solution, the temperature of the gel bath is 60 ℃, the temperature of core liquid is purified water with the conductivity of 10 Siemens, the temperature of the core liquid is 60 ℃, spinning is carried out at the speed of 80m/min, and a 9-core MBfR membrane is spun, wherein the finished fiber has 9 internal channels with the diameter of 0.45mm, and the external diameter of 8.0 mm. Fully soaking and rinsing the collected finished membrane fibers, removing residual solvent and pore-forming agent, and testing the performance of the embodiment according to a known method as follows: the tensile breaking elongation of the fiber is 210 percent, the tensile breaking strength of the fiber is 31N, the filtration pore diameter at the outer side of the hollow fiber membrane is 32 micrometers, and the filtration pore diameter at the inner side is 0.15 micrometer.
In the embodiment of the invention, PVDF is resin powder with the weight average molecular weight of 10-80 ten thousand, and preferably the resin powder with the average weight average molecular weight of 20-60 ten thousand. One or more mixtures of polyethylene glycol, glycerol, tween, diethylene glycol and polyvinylpyrrolidone may be used as the main component of the pore-forming agent of the MBfR film of the present invention. One or more of dimethylformamide, dimethylacetamide and butyrolactone phosphate can be used as the main component of the MBfR membrane solvent of the present invention.
In embodiments of the invention, the support layer of the microbial carrier hybrid MBfR membrane may be a sponge-like microstructure, but also a finger-like pore or bubble cavity structure. The sponge microporous structure is preferably selected for improving the strength and toughness of the product; for reducing energy consumption of the product, a finger-shaped hole single-skin structure is preferred.
Comparative example
Experimental group 1: preparing a casting solution of the MBfR film from the following components in percentage by weight: 25% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 15% of polyethylene glycol (PEG-600) liquid, 5% of titanium dioxide particles with the particle size of 5000 meshes and 55% of Dimethylformamide (DMF) solvent. The spinning process was the same as in example l, spinning at a speed of 25 m/min.
Experimental group 2: preparing a casting solution of the MBfR film from the following components in percentage by weight: 25% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 15% of polyethylene glycol (PEG-600) liquid, 5% of nitric acid modified activated carbon material with the particle size of 300 meshes and 55% of Dimethylformamide (DMF) solvent. The spinning process was the same as in example l, spinning at a speed of 25 m/min.
Experimental group 3: preparing a casting solution of the MBfR film from the following components in percentage by weight: 25% of PVDF resin powder with the weight-average molecular weight of 70 ten thousand, 15% of polyethylene glycol (PEG-600) liquid, 20% of nitric acid modified activated carbon material with the particle size of 300 meshes and 55% of Dimethylformamide (DMF) solvent. The spinning process was the same as in example l, spinning at a speed of 25 m/min.
The performance of the finished product is detected according to the detection method in the prior art, and the specific result is as follows:
end product performance for experimental group 1: the tensile breaking elongation of the fiber is 108 percent, the tensile breaking strength of the fiber is 2.1N, the outside aperture of the hollow fiber membrane is 0.15 micron, and the inside aperture is 12 micron.
End product performance for experimental group 2: the tensile breaking elongation of the fiber is 170 percent, the tensile breaking strength of the fiber is 3.8N, the outside aperture of the hollow fiber membrane is 0.08 micrometer, and the inside aperture is 32 micrometers.
End product performance for experimental group 3: the tensile breaking elongation of the fiber is 152%, the tensile breaking strength of the fiber is 4.2N, the outside pore diameter of the hollow fiber membrane is 0.05 micron, and the inside pore diameter is 37 micron.
According to result analysis, the effect of the nitric acid modified activated carbon material adopted by the invention as a microorganism carrier is better than that of titanium dioxide particles with 5000-mesh granularity commonly adopted in the prior art, and the optimal selection range of the nitric acid modified activated carbon material is 0.05-15%.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The microbial carrier hybrid MBfR membrane is characterized by being a hollow fiber membrane, wherein the inner and outer side pore diameters of the hollow fiber membrane are distributed in a gradient manner, the ratio of the inner and outer side pore diameters is 5-50, and the hollow fiber membrane is of a structure with a circular outer part and 3-9 core pores in the inner part; the casting solution comprises the following components in percentage by weight:
the microbial carrier is nitric acid modified activated carbon powder with the granularity of 300-2000 meshes;
the pore-forming agent is polyvinylpyrrolidone or polyethylene glycol.
2. The microbial carrier hybrid MBfR membrane is characterized by being a hollow fiber membrane, wherein the inner and outer side pore diameters of the hollow fiber membrane are distributed in a gradient manner, the ratio of the inner and outer side pore diameters is 5-50, and the hollow fiber membrane is of a structure with a circular outer part and 3-9 core pores in the inner part; the casting film is prepared from the following components in percentage by weight:
the microbial carrier is nitric acid modified activated carbon powder with the granularity of 300-2000 meshes;
the pore-forming agent is polyvinylpyrrolidone or polyethylene glycol.
3. The microcarrier hybrid MBfR membrane of claim 1 or 2, wherein the support layer of the hollow fiber membrane is a sponge-like microstructure, a finger-like pore or a bubble-cavity structure.
4. The microbial carrier hybrid MBfR membrane according to claim 1 or 2, wherein the hollow fiber membrane is an internal pressure type hollow fiber membrane, the filtration pore diameter of the inner side of the internal pressure type hollow fiber membrane is between 0.02 and 5 micrometers, and the pore diameter of the outer side of the internal pressure type hollow fiber membrane is between 0.1 and 50 micrometers.
5. The microbial carrier hybrid MBfR membrane according to claim 1 or 2, wherein the hollow fiber membrane is an external pressure type hollow fiber membrane, the inner side pore diameter of the external pressure type hollow fiber membrane is between 0.1 and 50 micrometers, and the outer side filtration pore diameter is between 0.02 and 5 micrometers.
6. A preparation method of a microbial carrier hybrid MBfR membrane adopts a dry-wet method or a wet method to prepare the membrane, and comprises the following steps:
(1) preparing a casting solution by exactly following the components of the weight ratio of the microbial carrier hybrid MBfR membrane according to the claim 1 or 2;
(2) fully stirring and dissolving the casting solution prepared in the step (1) at the temperature of 50-132 ℃;
(3) carrying out vacuum or standing defoaming on the dissolved casting solution;
(4) extruding the defoamed membrane casting solution into an insertion tube type spinning nozzle through nitrogen or a pump, introducing water or an aqueous solution at 15-80 ℃ into the core solution, wherein the aqueous solution consists of 10-85% by mass of DMAc or DMF and pure water, the distance between the outlet of the spinning nozzle and the liquid level of the gel bath is 20 cm below to 50 cm above, the temperature of the gel bath is constant at 10-70 ℃, and the membrane casting solution forms a membrane in the gel bath and is collected through a winding system.
7. The method for preparing the microbial carrier hybrid MBfR membrane according to claim 6, wherein the coiling speed of the microbial carrier hybrid MBfR membrane is 10-100 m/min.
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| CN110064309B (en) * | 2019-04-15 | 2021-06-15 | 沈阳环境科学研究院 | Composite membrane for MABR and preparation method thereof |
| CN110124531B (en) * | 2019-05-21 | 2020-12-11 | 大连理工大学 | Preparation method of porous carbon-carbon nanotube hollow fiber membrane capable of generating hydroxyl radicals under electrochemical reinforcement |
| CN113563631B (en) * | 2021-07-29 | 2023-04-18 | 湖南时远新材料科技有限公司 | Acetalized polyvinyl alcohol MBBR biological filler and preparation method thereof |
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| JPH07232042A (en) * | 1994-02-25 | 1995-09-05 | Tokuyama Corp | Micro porous membrane |
| CN101596420A (en) * | 2009-06-19 | 2009-12-09 | 河海大学 | Active carbon doughnut PS membrane and preparation method thereof |
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