CN113457463B - Biodegradable inorganic-organic composite membrane and preparation method thereof - Google Patents
Biodegradable inorganic-organic composite membrane and preparation method thereof Download PDFInfo
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- CN113457463B CN113457463B CN202110863598.7A CN202110863598A CN113457463B CN 113457463 B CN113457463 B CN 113457463B CN 202110863598 A CN202110863598 A CN 202110863598A CN 113457463 B CN113457463 B CN 113457463B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a biodegradable inorganic-organic composite membrane and a preparation method thereof, relating to the technical field of composite membranes and comprising a ceramic base membrane and a degradable crosslinked polylactic acid interception layer; the degradable crosslinked polylactic acid interception layer is arranged on the surface of the ceramic base film; the degradable crosslinked polylactic acid interception layer is prepared from a membrane casting solution, and the membrane casting solution comprises the following components in percentage by weight: 12-22% of polylactic acid, 3-12% of pore-forming agent, 1-6% of toughening agent and 60-84% of solvent. The ceramic microporous tubular membrane is used as a base membrane, a compact degradable interception layer is formed on the surface of the base membrane through an NIPS (NIPS) process, and chemical crosslinking is performed, so that the composite membrane has the effect of no degradation or slight degradation within the service life of 3-5 years, and the requirements of sewage treatment application scenes are met.
Description
Technical Field
The invention relates to the technical field of composite membranes, in particular to a biodegradable inorganic-organic composite membrane and a preparation method thereof.
Background
The Membrane Bioreactor (MBR) technology is a new technology combining biological treatment technology and membrane separation technology, replaces the secondary sedimentation tank in the traditional technology, and can efficiently carry out solid-liquid separation to obtain stable reclaimed water which can be directly used. But also can maintain high-concentration microorganism biomass in the biological tank, the process has less excess sludge, effectively removes ammonia nitrogen, has effluent suspended matters and turbidity close to zero, greatly removes bacteria and viruses in the effluent, and has low energy consumption and small occupied area. At present, the existing market products at home and abroad mainly take ceramic membranes and PVDF membranes with PET lining pipes as main materials, the ceramic membranes have long service life and good environmental friendliness, but membrane elements with small apertures and large flux are difficult to prepare by the ceramic membranes, and due to the pore-forming characteristic, although some ceramic membranes can also realize the gradient distribution of the apertures along the wall thickness direction, the ceramic membranes with compact retention layers on the filtering surfaces are still not seen, the products easily cause deep pollution during operation, namely pollutants easily enter the deep inside of membrane pores along the edges to block the pore passages, a large amount of strong acid and strong base is needed to clean and recover at the moment, secondary pollution is caused, and even the filtering surfaces are sometimes needed to be polished by abrasive paper type grinding materials to effectively recover the filtering flux. The PVDF membrane filtering surface with the PET lining pipe generally has a compact interception layer, pollutants generally form a filter cake on the membrane surface and rarely enter deep pore channels, the operation flux is reduced and then is recovered simply, but the membrane of the type after operation for many years is required to be replaced due to reasons of material aging, hydrophilicity reduction, deep pollutant accumulation and the like, the replaced old membrane is extremely difficult to treat, the PVDF membrane has almost no biodegradability and can only be subjected to dangerous waste treatment generally, and great environmental pollution is brought. Therefore, it is very important to find an MBR membrane product that is biodegradable and has a dense rejection layer.
Disclosure of Invention
Aiming at the defects and the defects of the prior art, the invention provides a biodegradable inorganic-organic composite membrane and a preparation method thereof, wherein a ceramic microporous tubular membrane is taken as a base membrane, a compact degradable interception layer is formed on the surface of the base membrane through an NIPS (NIPS) process, and chemical crosslinking is carried out simultaneously, so that the composite membrane has the effect of no degradation or slight degradation within the service life of 3-5 years, and the requirements of sewage treatment application scenes are met.
In order to achieve the above objects, the present invention provides a biodegradable inorganic-organic composite membrane comprising a ceramic-based membrane and a degradable crosslinked polylactic acid cut-off layer; the degradable crosslinked polylactic acid interception layer is arranged on the surface of the ceramic base membrane; the degradable crosslinked polylactic acid interception layer is prepared from a casting solution, and the casting solution comprises the following components in percentage by weight: 12-22% of polylactic acid, 3-12% of pore-forming agent, 1-6% of toughening agent and 60-84% of solvent.
Preferably, the biodegradable inorganic-organic composite membrane is a hollow fiber membrane and has a single-channel or multi-channel structure with concentric inner and outer circles.
Preferably, the ceramic base membrane is a hollow tubular membrane, the outer diameter of the ceramic base membrane is 12-25mm, the inner diameter of the ceramic base membrane is 8-16mm, and the filtering pore diameter is 0.5-1.2 mu m.
Preferably, the degradable crosslinked polylactic acid interception layer can be in a spongy microstructure, and also can be in a finger-shaped hole or bubble cavity structure; in order to optimize the filtering performance and the organic-inorganic composite strength, a spongy microporous structure is preferably selected; in order to reduce energy consumption of the product, a finger-shaped pore single-skin layer structure is preferred, and the filtering pore diameter of the degradable crosslinked polylactic acid interception layer is 0.03-0.22 mu m.
Preferably, the pore-forming agent is one or more of polyethylene glycol with the number-average relative molecular mass of 8000-20000, polyvinylpyrrolidone with the number-average relative molecular mass of 8000-58000, tween or diethylene glycol.
Preferably, the toughening agent is vinyl pyrrolidone vinyl acetate copolymer, and VP/VA is 7/3 or 6/4.
Preferably, the solvent is one or a mixture of more of dimethylformamide, dimethylacetamide and butyrolactone phosphate.
The preparation method of the biodegradable inorganic-organic composite membrane comprises the following operation steps:
step one, producing a customized single-hole or porous ceramic base membrane;
step two, weighing 12-22% of polylactic acid, 3-12% of pore-forming agent, 1-6% of toughening agent and 60-84% of solvent according to weight percentage, and fully stirring and dissolving at the temperature of 30-95 ℃ to form a casting solution;
step three, carrying out vacuum or standing defoaming on the casting solution;
extruding the defoamed membrane casting solution by nitrogen or a pump, coating the membrane casting solution on a hollow tubular ceramic base membrane 1 by a coating device according to different requirements, immersing the coated ceramic base membrane 1 into a non-solvent, performing phase separation for 10-120 seconds to obtain a nascent membrane, and taking out the ceramic base membrane 1 with the nascent membrane and washing the nascent membrane by clean water;
and step five, immersing the ceramic base film 1 prepared in the step four into a 60-95 ℃ aqueous solution of 0.2-5% of potassium persulfate, sodium persulfate or ammonium persulfate, taking out after 1-30min of crosslinking, washing by using clear water, and drying.
Preferably, the non-solvent in the fourth step is water, or a mixture of solvent and water in different proportions at a temperature of 20-80 ℃, or a mixture of inorganic salt and water, and the phase separation is adjusted to obtain the degradable crosslinked polylactic acid interception layer 2 with different pore diameters, the specific solvent is dimethylacetamide, dimethylformamide, ethanol, acetone, and the like, and the specific inorganic salt is sodium chloride, sodium carbonate, sodium sulfate, calcium chloride, and the like.
Preferably, the crosslinking in the fifth step comprises the following specific steps: and (3) immersing the ceramic base membrane 1 prepared in the fourth step into an initiator, namely a 0.2-5% normal-temperature aqueous solution of potassium persulfate, sodium persulfate or ammonium persulfate, for 30 minutes to 4 hours, transferring the nascent state membrane immersed with the initiator into a normal-pressure steam tank, and carrying out chemical crosslinking for 30 seconds to 30 minutes in a 100-DEG steam environment.
Preferably, the drying temperature in the fifth step is below 60 ℃, or naturally airing.
Compared with the prior art, the invention has the beneficial effects that:
1. an inorganic ceramic membrane is taken as a base membrane, a degradable compact interception layer is arranged on the surface of the base membrane, and the aperture of the interception layer is adjustable between 0.03 and 0.22 mu m according to project requirements; the PVDF membrane has the characteristics of high pollution resistance and easy recovery of filtration performance;
2. the biodegradable inorganic-organic composite membrane produced by the invention can conveniently adjust the degradation speed of the degradable interception layer of the product by necessary chemical crosslinking and adjusting the weight ratio and the crosslinking temperature of the initiator in the crosslinking solution so as to meet the requirements of different application scenes;
3. the biodegradable inorganic-organic composite membrane produced by the invention is a single-flow or multi-flow hollow tubular membrane, has high unit volume filling density and high structural strength, can be applied to a high hydraulic impact landfill leachate project, and can also be applied to various municipal sewage and industrial wastewater projects.
Description of the drawings:
fig. 1 is a schematic structural view of the present invention.
Description of reference numerals:
the ceramic-based film comprises a ceramic-based film 1 and a degradable crosslinked polylactic acid interception layer 2.
The specific implementation mode is as follows:
the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings, and the preferred embodiments in the description are only examples, and all other embodiments obtained by those skilled in the art without any inventive work belong to the protection scope of the present invention.
As shown in fig. 1, the following technical solutions are adopted in the present embodiment (example one):
in the embodiment, the membrane casting solution of the biodegradable inorganic-organic composite membrane is prepared from the following components in percentage by weight: 22% of polylactic resin powder with weight-average molecular weight of 55 ten thousand, 3% of polyvinylpyrrolidone (PVP-K60) powder, 6% of polyethylene glycol (PEG-10000) liquid, 2% of vinyl pyrrolidone vinyl acetate copolymer with VP/VA of 7/3 and 67% of dimethylacetamide (DMAc) solvent;
firstly, adding PVP-K60 and PEG-10000 into a DMAC solution, stirring for 60 minutes, then adding a vinyl pyrrolidone vinyl acetate copolymer, stirring for 2 hours, and finally adding polylactic acid; the temperature of a jacket of a reaction kettle is constant at 70 ℃, the stirring speed of 120rpm is adopted for 6 hours, the reaction kettle is kept still for more than 8 hours to ensure that bubbles in the feed liquid are fully removed, the temperature is slowly reduced to 45 ℃, the temperature of a metering pump and a coating die is slowly heated to 45 ℃, the metering pump is started, the casting film liquid is uniformly coated on the outer wall of a self-made ceramic membrane with the average pore diameter of 1.0 micron, the inner diameter of 8mm and the outer diameter of 12mm, the ceramic membrane is placed into DMA (direct memory access) to carry out phase separation from a 50 ℃ aqueous solution with the concentration of 35% after staying in the air for 5 seconds, and the time is 90 seconds; taking out, soaking and rinsing for 4 hours by using municipal tap water; completing the preparation of the nascent state biodegradable inorganic-organic composite membrane; preparing 1.5% of sodium persulfate as an aqueous solution of an initiator, adding the aqueous solution, heating to 92 ℃, transferring the nascent biodegradable inorganic-organic composite membrane into the aqueous solution for crosslinking for 60 minutes, taking out the crosslinked composite membrane, soaking and cleaning for 12 hours by municipal tap water, and removing residual pore-forming agent and the initiator to finish the preparation of the biodegradable inorganic-organic composite membrane;
the performance of this example was then tested according to known methods, and the results of the performance testing of this example are as follows: the filtering aperture of the degradable crosslinked polylactic acid interception layer 2 is 0.05 micron, the thickness of the degradable crosslinked polylactic acid interception layer 2 is 0.06mm, the adhesion strength of the degradable crosslinked polylactic acid interception layer 2 and the ceramic base film 1 is tested for 30 times according to standard hundred-grid tests without peeling defects, the hydrophilic contact angle of the coating layer is 56 degrees, the water flux is 1800LMH, and the section microstructure of the degradable crosslinked polylactic acid interception layer 2 is a spongy porous structure.
Compared with the prior art, the beneficial effects of the embodiment are as follows:
1. an inorganic ceramic membrane is taken as a base membrane, a degradable compact interception layer is arranged on the surface of the base membrane, and the aperture of the interception layer is adjustable between 0.03 and 0.22 mu m according to project requirements; the PVDF membrane has the characteristics of environmental friendliness of the traditional ceramic membrane, high pollution resistance and easiness in recovery of filtration performance;
2. the biodegradable inorganic-organic composite membrane produced by the invention can conveniently adjust the degradation speed of the degradable interception layer of the product by necessary chemical crosslinking and adjusting the weight ratio and the crosslinking temperature of the initiator in the crosslinking solution so as to meet the requirements of different application scenes;
3. the biodegradable inorganic-organic composite membrane produced by the invention is a single-flow or multi-flow hollow tubular membrane, has high unit volume filling density and high structural strength, can be applied to a high hydraulic impact landfill leachate project, and can also be applied to various municipal sewage and industrial wastewater projects.
The second embodiment:
in the embodiment, the membrane casting solution of the biodegradable inorganic-organic composite membrane is prepared from the following components in parts by weight: 12% of polylactic resin powder with weight-average molecular weight of 55 ten thousand, 5% of polyvinylpyrrolidone (PVP-K60) powder, 6% of polyethylene glycol (PEG-10000) liquid, 3% of vinyl pyrrolidone vinyl acetate copolymer with VP/VA of 7/3, and 74% of dimethylacetamide (DMAc) solvent; the coating process and the cross-linking process of the present embodiment are the same as those of the first embodiment;
the performance of this example was tested according to known methods, and the results of the performance test of this example are as follows: the filtering aperture of the degradable crosslinked polylactic acid interception layer 2 is 0.2 micron, the thickness of the degradable crosslinked polylactic acid interception layer 2 is 0.03mm, the adhesion strength of the degradable crosslinked polylactic acid interception layer 2 and the ceramic base film 1 is tested for 30 times according to standard hundred-grid test without peeling defect, the hydrophilic contact angle of the coating layer is considered to be 52 degrees, the water flux is 3200LMH, and the microstructure of the section of the degradable crosslinked polylactic acid interception layer 2 is a finger-shaped hole and bubble cavity comprehensive structure.
Example three:
the components in the embodiment are the same as the first embodiment in terms of the following weight ratio and process, and the initiator in the embodiment adopts a cross-linking process for industrial production, and the specific operation is as follows: preparing a normal-temperature 3% potassium persulfate aqueous solution, soaking the nascent biodegradable inorganic-organic composite membrane for 2 hours at normal temperature by using the solution, and then putting the inorganic-organic composite membrane soaked with the initiator potassium persulfate into a normal-pressure steam tank for crosslinking for 10 minutes; after the crosslinking is finished, the raw materials are soaked and cleaned for 12 hours by municipal tap water to remove residual pore-foaming agents and initiators, and for better cleaning effect, fresh water is replaced for one time within 2 hours during the cleaning period;
the performance of this example was tested according to known methods, and the results of the performance test of this example are as follows: the filtering aperture of the degradable crosslinked polylactic acid interception layer 2 is 0.05 micrometer, the thickness of the degradable crosslinked polylactic acid interception layer 2 is 0.05mm, the adhesion strength of the degradable crosslinked polylactic acid interception layer 2 and the ceramic base film 1 is tested for 30 times according to standard hundred-grid tests without peeling defects, the hydrophilic contact angle of the coating layer is 55 degrees, the water flux is 1200LMH, and the section microstructure of the degradable crosslinked polylactic acid interception layer 2 is a spongy porous structure.
It will be appreciated by those skilled in the art that modifications and equivalents may be made to the embodiments described above, and that various modifications, equivalents, improvements and the like may be made without departing from the spirit and scope of the invention.
Claims (1)
1. A biodegradable inorganic-organic composite film characterized by: the material comprises a ceramic basement membrane (1) and a degradable crosslinked polylactic acid interception layer (2); the degradable crosslinked polylactic acid interception layer (2) is arranged on the surface of the ceramic base membrane (1); the degradable crosslinked polylactic acid interception layer (2) is prepared from a casting solution, and the casting solution comprises the following components in percentage by weight: 12-22% of polylactic acid, 3-12% of pore-forming agent, 1-6% of toughening agent and 60-84% of solvent; the composite membrane is a hollow fiber membrane and has a structure of a single channel or a multi-channel with concentric inner and outer circles; the ceramic base membrane (1) is a hollow tubular membrane, the outer diameter of the ceramic base membrane (1) is 12-25mm, the inner diameter of the ceramic base membrane (1) is 8-16mm, and the filtering aperture is 0.5-1.2 mu m; the filtering pore size of the degradable crosslinked polylactic acid interception layer (2) is 0.03-0.22 mu m; the pore-forming agent is formed by mixing one or more of polyethylene glycol with the number-average relative molecular mass of 8000-20000, polyvinylpyrrolidone with the number-average relative molecular mass of 8000-58000, tween or diethylene glycol; the toughening agent is vinyl pyrrolidone-vinyl acetate copolymer, and VP/VA is 7/3 or 6/4; the solvent is formed by mixing one or more of dimethylformamide, dimethylacetamide or butyrolactone phosphate;
producing a customized single-hole or porous ceramic-based membrane;
weighing 12-22% of polylactic acid, 3-12% of pore-forming agent, 1-6% of toughening agent and 60-84% of solvent according to weight percentage, and fully stirring and dissolving at the temperature of 30-95 ℃ to form a casting solution;
carrying out vacuum or standing defoaming on the casting solution;
extruding the defoamed membrane casting solution by nitrogen or a pump, coating the membrane casting solution on a hollow tubular ceramic base membrane (1) by a coating device according to different requirements, soaking the coated ceramic base membrane (1) into a non-solvent, performing phase splitting for 10-120 seconds to obtain a nascent membrane, taking out the ceramic base membrane (1) with the nascent membrane, and washing the nascent membrane with clear water; the non-solvent is water, or a mixture of solvent and water with different proportions at the temperature of 20-80 ℃, or a mixture of inorganic salt and water, and the phase separation is adjusted to obtain the degradable crosslinked polylactic acid interception layer (2) with different pore diameters, the specific solvent is one or more of dimethylacetamide, dimethylformamide, ethanol and acetone, and the specific inorganic salt is one or more of sodium chloride, sodium carbonate, sodium sulfate and calcium chloride;
immersing the ceramic base membrane (1) into an initiator, namely a 0.2-5% normal-temperature aqueous solution of potassium persulfate, sodium persulfate or ammonium persulfate, for 30 minutes to 4 hours, then transferring the nascent-state membrane immersed with the initiator into a normal-pressure steam tank, carrying out chemical crosslinking for 30 seconds to 30 minutes in a steam environment at 100 ℃, then taking out the nascent-state membrane after crosslinking, washing the nascent-state membrane clean by using clear water, and drying the nascent-state membrane.
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| CN104437130A (en) * | 2014-11-06 | 2015-03-25 | 沈鹏 | Degradable hollow fiber membrane and preparation method thereof |
| CN110170250A (en) * | 2019-06-27 | 2019-08-27 | 长春工业大学 | A kind of degradable poly lactic acid/cellulose-acetafolic and preparation method thereof |
| CN112023725A (en) * | 2020-07-29 | 2020-12-04 | 广州大学 | A kind of preparation method of polylactic acid microporous membrane |
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| CN103861468B (en) * | 2014-04-09 | 2017-02-01 | 天津工业大学 | Compound nanofiltration membrane for dye desalination and treatment of waste water during dye desalination, as well as preparation method of compound nanofiltration membrane |
| EP3147024A1 (en) * | 2015-09-25 | 2017-03-29 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Hollow-fibre polymer membrane |
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| CN110170250A (en) * | 2019-06-27 | 2019-08-27 | 长春工业大学 | A kind of degradable poly lactic acid/cellulose-acetafolic and preparation method thereof |
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Effective date of registration: 20230331 Address after: 415000 No. 106, Qianming Road, Changde economic and Technological Development Zone, Hunan Province (floors 3-4, building 4, electronic information Industrial Park) Patentee after: Hunan Shiyuan New Material Technology Co.,Ltd. Patentee after: Beijing Shiyuan Technology Co.,Ltd. Address before: 415000 No. 106, Qianming Road, Changde economic and Technological Development Zone, Hunan Province (floors 3-4, building 4, electronic information Industrial Park) Patentee before: Hunan Shiyuan New Material Technology Co.,Ltd. |
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