CN112295419A - Preparation method of selective permeability MABR composite membrane - Google Patents
Preparation method of selective permeability MABR composite membrane Download PDFInfo
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- CN112295419A CN112295419A CN202011124384.XA CN202011124384A CN112295419A CN 112295419 A CN112295419 A CN 112295419A CN 202011124384 A CN202011124384 A CN 202011124384A CN 112295419 A CN112295419 A CN 112295419A
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- 239000012528 membrane Substances 0.000 title claims abstract description 63
- UEKDBDAWIKHROY-UHFFFAOYSA-L bis(4-bromo-2,6-ditert-butylphenoxy)-methylalumane Chemical compound [Al+2]C.CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-].CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-] UEKDBDAWIKHROY-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 230000035699 permeability Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000010413 mother solution Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002033 PVDF binder Substances 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
-
- 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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of sewage treatment, and particularly relates to a preparation method of a selective permeability MABR composite membrane. The invention comprises the following steps: (1) sequentially adding PVDF, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and performing negative pressure defoaming to obtain a viscous mother solution I; (2) sequentially adding PTFE, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and defoaming under negative pressure to obtain a viscous mother solution II; (3) coating the mother liquor I on non-woven fabric, then putting the non-woven fabric into a cleaning tank, rinsing out an organic solvent and a pore-forming agent, and drying to obtain an MABR initial membrane; (4) and (4) coating the mother liquor II on the MABR initial membrane in the step (3), and drying to obtain the selective permeability MABR composite membrane. The invention is simple and convenient, and the obtained membrane has simple structure, air permeability and water impermeability, high air permeability, high oxygen utilization rate and strong denitrification capability.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a preparation method of a selective permeability MABR composite membrane.
Background
The selective permeability MABR composite membrane is a novel sewage treatment technology combining a gas-liquid separation membrane technology and a biomembrane water treatment technology. The core part of the technology includes selectively permeable MABR composite membranes and biofilms. The biofilm grows and adheres to the outer surface of the MABR composite membrane, the compressed air provides oxygen for the biofilm through the MABR composite membrane, the oxygen utilization rate of the MABR is close to 100% (the oxygen utilization rate of the traditional process is only 10-20%), and a new development direction is provided for energy conservation and consumption reduction of sewage treatment. The MABR composite membrane has dominant flora with nitrogen and carbon removal and phosphorus removal functions in an external biomembrane, the structural composition and distribution of the top-level flora are dominated by working conditions, the distribution proportion of main flora can be effectively regulated and controlled by changing working condition parameters, and the operation efficiency is optimized. MABR composite membranes use gas permeable membranes to provide oxygen to a biofilm growing attached to the membrane surface.
MABR has several advantages over traditional biofilm technology:
(1) bubbleless aeration provides significantly higher oxygen utilization efficiency, thereby enabling energy savings. Furthermore, air stripping during biological treatment of volatile organic compounds can be reduced.
(2) The unique microbial populations stratify to enable simultaneous nitrification, denitrification, and COD removal at relatively high rates.
(3) Special degrading microorganisms such as anaerobic ammonium oxidation bacteria are attached to the biological membrane to realize synchronous nitrification and denitrification.
According to market research, the number of domestic MABR composite membrane production plants is very small, most domestic plants cooperate with foreign plants, and domestic membranes with independent intellectual property rights need to be researched and developed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a selective permeability MABR composite membrane, which is simple and convenient, and the obtained membrane has simple structure, air permeability, water impermeability, high air permeability, high oxygen utilization rate and strong denitrification capability.
The preparation method of the selective permeability MABR composite membrane comprises the following steps:
(1) preparing a first mother solution: sequentially adding PVDF, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and performing negative pressure defoaming to obtain a viscous mother solution I;
(2) preparing a mother solution II: sequentially adding PTFE, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and defoaming under negative pressure to obtain a viscous mother solution II;
(3) preparation of MABR primary film: coating the mother liquor I on non-woven fabric, then putting the non-woven fabric into a cleaning tank, rinsing out an organic solvent and a pore-forming agent, and drying to obtain an MABR initial membrane;
(4) preparing an MABR composite membrane: coating the mother solution II on the MABR initial membrane in the step (3), and drying to obtain a selective permeability MABR composite membrane;
wherein, the surface modifier in the step (1) is one or more of polyvinylpyrrolidone, triethyl phosphate and polymethyl methacrylate, so that the surface of the PVDF membrane is rough and is easier to be bonded with the PTFE membrane.
Wherein, the surface modifier in the step (2) is one or more of polyvinylpyrrolidone, triethyl phosphate and polymethyl methacrylate, so that the PVDF membrane has a rough surface and is easier to adhere to the biological membrane.
Preferably, the dissolution temperature in step (1) and step (2) is 60-90 ℃.
Preferably, the raw materials in the step (1) are proportioned as follows according to mass fraction: 5% -12% of PVDF; 60% -70% of organic solvent; 3% -8% of pore-foaming agent; 13 to 20 percent of surfactant.
Preferably, the raw materials in the step (2) are proportioned as follows according to mass fraction: 12-25% of PTFE, 60-70% of organic solvent, 5-15% of pore-forming agent and 3-16% of surfactant.
Preferably, the organic solvent is DMAC; more preferably, the organic solvent is a mixture of DMAC and NMF.
Preferably, the pore-forming agent in step (1) is one or more of N-methyl pyrrolidone, propylene glycol, glycerol, polyethylene glycol, lithium chloride or magnesium chloride.
Preferably, the pore-forming agent in step (2) is one or more of N-methyl pyrrolidone, propylene glycol, glycerol or polyethylene glycol.
Preferably, the selectively permeable MABR composite membrane is processable in roll form or in flat form.
Compared with the prior art, the invention has the following beneficial effects:
(1) the selective permeability MABR composite membrane prepared by the invention can realize synchronous nitrification/denitrification and anaerobic ammonia oxidation;
(2) the selective permeability MABR composite membrane prepared by the invention can simultaneously remove COD, BOD, ammonia nitrogen, total nitrogen and total phosphorus, and has high removal efficiency;
(3) the selective permeability MABR composite membrane prepared by the invention has high oxygen utilization rate; the oxygen utilization rate of the MABR is close to 100 percent (the oxygen utilization rate of the traditional process is only 10-20 percent), and a new development direction is provided for energy conservation and consumption reduction of sewage treatment;
(4) the selective permeability MABR composite membrane prepared by the invention has stable oxygenation performance in unit area, and the COD removal rate is more than 90 percent between 10 and 13 g/square meter d; the TN removal rate is more than 85%; NH (NH)3The removal rate is more than 90%;
(5) the product prepared by the invention has simple structure and low operating cost, saves energy by more than 67 percent compared with the traditional process, and provides a new process for saving energy and reducing consumption for wastewater treatment in the industries of municipal wastewater upgrading and transformation, papermaking, chemical industry, coking, petroleum, slaughtering, beer, tanning, food, metallurgy, textile and the like.
Detailed Description
Example 1
Stirring 6 wt% of polyvinylidene fluoride, 69 wt% of DMAC (dimethylacetamide), 2 wt% of polymethyl methacrylate, 5 wt% of triethyl phosphate, 3 wt% of N-methyl pyrrolidone and 15% of polyvinylpyrrolidone at the temperature of 80 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquor 1;
coating the mother solution 1 on a PET non-woven fabric, wherein the coating film thickness is 50 mu m, the coating speed is 6m/min, and after the coating film stays in the air for 10s, the coating film is immersed in a phase separation tank of deionized water at the temperature of 10 ℃ for 10 min; continuously immersing in a pore-forming water bath of deionized water solution of lithium chloride with the mass fraction of 3 percent at the temperature of 20 ℃ for 20 min; then immersing the glass fiber in a curing water bath of a deionized water solution with the components of 21 wt% of glycerin, 1 wt% of propylene glycol and 5 wt% of sodium hypochlorite at the temperature of 20 ℃ for 45 min; and (5) drying the membrane in a tunnel type dryer with the drying temperature of 80 ℃ to obtain the MABR initial membrane.
Stirring 16 wt% of polyvinylidene fluoride, 69 wt% of DMAC (dimethylacetamide), 7 wt% of polymethyl methacrylate and 8 wt% of polyethylene glycol at the temperature of 80 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquor 2;
and coating the mother solution 2 on an MABR initial membrane, and drying in a tunnel dryer with the drying temperature of 120 ℃ to obtain the selectively permeable MABR composite membrane.
Example 2
Stirring 8 wt% of polyvinylidene fluoride, 67 wt% of DMAC (dimethylacetamide), 2 wt% of polymethyl methacrylate, 5 wt% of triethyl phosphate, 3 wt% of N-methyl pyrrolidone and 15% of polyvinylpyrrolidone at 83 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquid 1;
coating the mother solution 1 on a PET non-woven fabric, wherein the coating film thickness is 50 mu m, the coating speed is 6m/min, and after the coating film stays in the air for 10s, the coating film is immersed in a phase separation tank of deionized water at the temperature of 10 ℃ for 10 min; continuously immersing in a pore-forming water bath of deionized water solution of lithium chloride with the mass fraction of 3 percent at the temperature of 20 ℃ for 20 min; then immersing the glass fiber in a curing water bath of a deionized water solution with the components of 21 wt% of glycerin, 1 wt% of propylene glycol and 5 wt% of sodium hypochlorite at the temperature of 20 ℃ for 45 min; and (5) drying the membrane in a tunnel type dryer with the drying temperature of 80 ℃ to obtain the MABR initial membrane.
Stirring 20 wt% of polyvinylidene fluoride, 65 wt% of DMAC (dimethylacetamide), 7 wt% of polymethyl methacrylate and 8 wt% of polyethylene glycol at the temperature of 80 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquor 2;
and coating the mother solution 2 on an MABR initial membrane, and drying in a tunnel dryer with the drying temperature of 120 ℃ to obtain the selectively permeable MABR composite membrane.
Example 3
Stirring 11 wt% of polyvinylidene fluoride, 61 wt% of DMAC (dimethylacetamide), 2 wt% of polymethyl methacrylate, 5 wt% of triethyl phosphate, 3 wt% of N-methyl pyrrolidone and 18% of polyvinylpyrrolidone at the temperature of 85 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquor 1;
coating the mother solution 1 on a PET non-woven fabric, wherein the coating film thickness is 50 mu m, the coating speed is 6m/min, and after the coating film stays in the air for 10s, the coating film is immersed in a phase separation tank of deionized water at the temperature of 10 ℃ for 10 min; continuously immersing in a pore-forming water bath of deionized water solution of lithium chloride with the mass fraction of 3 percent at the temperature of 20 ℃ for 20 min; then immersing the glass fiber in a curing water bath of a deionized water solution with the components of 21 wt% of glycerin, 1 wt% of propylene glycol and 5 wt% of sodium hypochlorite at the temperature of 20 ℃ for 45 min; and (5) drying the membrane in a tunnel type dryer with the drying temperature of 80 ℃ to obtain the MABR initial membrane.
Stirring 23 wt% of polyvinylidene fluoride, 62 wt% of DMAC (dimethylacetamide), 7 wt% of polymethyl methacrylate and 8 wt% of polyethylene glycol at 80 ℃ for 8 hours, fully and uniformly mixing feed liquid, and defoaming under negative pressure for 3 hours to obtain mother liquor 2;
and coating the mother solution 2 on an MABR initial membrane, and drying in a tunnel dryer with the drying temperature of 120 ℃ to obtain the selectively permeable MABR composite membrane.
The results of the tests conducted on the products prepared in examples 1 to 3 are as follows.
TABLE 1
| Distinguishing | Flux of gas | Water contact angle | Oxygen utilization rate |
| Example 1 | 0.49mL/(cm2·s) | 92.2° | 99％ |
| Example 2 | 0.57mL/(cm2·s) | 95.9° | 99.4％ |
| Example 3 | 0.62mL/(cm2·s) | 99.8° | 99.9％ |
The results of the tests performed in examples 1 to 3 were as follows:
| flux of gas | Water contact angle | Oxygen utilization rate | |
| Example 1 | 0.49ml/(cm2·s) | 92.2° | 99％ |
| Examples2 | 0.57ml/(cm2·s) | 95.9° | 99.4％ |
| Example 3 | 0.62ml/(cm2·s) | 99.8° | 99.9％ |
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (8)
1. A preparation method of a selective permeability MABR composite membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a first mother solution: sequentially adding PVDF, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and performing negative pressure defoaming to obtain a viscous mother solution I;
(2) preparing a mother solution II: sequentially adding PTFE, an organic solvent, a pore-forming agent and a surface modifier into a stirring tank for dissolving and stirring, and defoaming under negative pressure to obtain a viscous mother solution II;
(3) preparation of MABR primary film: coating the mother liquor I on non-woven fabric, then putting the non-woven fabric into a cleaning tank, rinsing out an organic solvent and a pore-forming agent, and drying to obtain an MABR initial membrane;
(4) preparing an MABR composite membrane: coating the mother solution II on the MABR initial membrane in the step (3), and drying to obtain a selective permeability MABR composite membrane;
the surface modifier in the steps (1) and (2) is one or more of polyvinylpyrrolidone, triethyl phosphate and polymethyl methacrylate, so that the surface of the PVDF membrane is rough and is easier to adhere to the PTFE membrane;
the surface modifier is one or more of polyvinylpyrrolidone, triethyl phosphate or polymethyl methacrylate.
2. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: the dissolving temperature of the step (1) and the step (2) is 60-90 ℃.
3. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: the raw materials in the step (1) are proportioned as follows according to mass fraction: 5% -12% of PVDF; 60% -70% of organic solvent; 3% -8% of pore-foaming agent; 13 to 20 percent of surfactant.
4. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: the raw materials in the step (2) are proportioned as follows according to mass fraction: 12-25% of PTFE, 60-70% of organic solvent, 5-15% of pore-forming agent and 3-16% of surfactant.
5. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: the organic solvent is a mixture of DMAC and NMF.
6. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: in the step (1), the pore-forming agent is one or more of N-methyl pyrrolidone, propylene glycol, glycerol, polyethylene glycol, lithium chloride or magnesium chloride.
7. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: in the step (2), the pore-forming agent is one or more of N-methyl pyrrolidone, propylene glycol, glycerol or polyethylene glycol.
8. The method of preparing a selectively permeable MABR composite membrane according to claim 1, wherein: and processing the selective permeability MABR composite membrane into a roll type or a flat plate type.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120012521A1 (en) * | 2009-01-15 | 2012-01-19 | Takeo Takahashi | Vinylidene fluoride resin hollow fiber porous membrane and process for producing same |
| CN103182254A (en) * | 2013-02-06 | 2013-07-03 | 天津大学 | Composite film for MABR and preparation method |
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