CN113368711A - Preparation method of high-performance MABR hollow fiber composite membrane - Google Patents
Preparation method of high-performance MABR hollow fiber composite membrane Download PDFInfo
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- CN113368711A CN113368711A CN202110819895.1A CN202110819895A CN113368711A CN 113368711 A CN113368711 A CN 113368711A CN 202110819895 A CN202110819895 A CN 202110819895A CN 113368711 A CN113368711 A CN 113368711A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 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 30
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000767 polyaniline Polymers 0.000 claims abstract description 26
- 239000002033 PVDF binder Substances 0.000 claims abstract description 25
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 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 abstract description 7
- 239000000243 solution Substances 0.000 claims description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 60
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 25
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000008399 tap water Substances 0.000 claims description 15
- 235000020679 tap water Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000009940 knitting Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000009730 filament winding Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/102—Permeable membranes
-
- 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
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- 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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention relates to the technical field of membrane separation, and provides a preparation method of a high-performance MABR hollow fiber composite membrane. According to the invention, the strength of the hollow fiber membrane can be improved to a certain extent by taking the PET braided tube as the supporting layer and taking the PVDF modified by polyaniline as the casting membrane coating layer, and the service cycle and the service life of the membrane are prolonged, wherein the modified PVDF, PVP, LiCl and DMAC are mixed according to a certain proportion to prepare the casting membrane coating layer, so that the problem of poor hydrophilicity of the PVDF can be improved to a certain extent, and the performance of the hollow fiber composite membrane can be effectively enhanced.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of a high-performance MABR hollow fiber composite membrane.
Background
An aerated biofilm reactor (MABR) is an emerging technology for wastewater treatment, a new form of membrane bioreactor. MABR is based on a gas permeable membrane through which a gaseous substrate is provided to a biofilm formed outside the membrane. Because oxygen and pollutants enter the biomembrane from two sides of the biomembrane respectively, microorganisms in the MABR biomembrane have unique colony structures, and different layered microorganisms have different pollutant treatment capacities. The main advantages of MABR include high gas utilization efficiency, low energy consumption and small reactor footprint. The MABR has great technical advantages and wide application prospect in the aspect of strengthening the degradation of organic wastewater.
The hollow fiber membrane used for the MABR in the prior art has poor performance, low treatment efficiency and short service life in the wastewater treatment process, and increases the cost of wastewater treatment, so how to prepare the hollow fiber membrane with high performance and more suitable for the MABR becomes a technical problem to be solved by technical personnel in the field.
Disclosure of Invention
Solves the technical problem
Aiming at the defects of the prior art, the invention provides a preparation method of a high-performance MABR hollow fiber composite membrane, and solves the problems that the hollow fiber membrane used for MABR in the prior art has poor performance, low treatment efficiency and short service life in the wastewater treatment process, and the wastewater treatment cost is increased.
Technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a high-performance MABR hollow fiber composite membrane comprises the following preparation steps:
s1, adding a certain amount of aniline subjected to reduced pressure distillation into lmol/L hydrochloric acid deionized water solution at the temperature of 0-5 ℃, slowly dropwise adding a certain amount of ammonium persulfate hydrochloric acid solution, keeping the reaction temperature of the materials at 0-5 ℃ in the dropwise adding process, stirring for 4-5 hours after the dropwise adding is finished to obtain dark green polyaniline suspension, filtering the materials, washing with deionized water until the washing liquid is neutral, and drying to obtain hydrochloric acid in-situ doped polyaniline;
s2, adding polyaniline in S1 into a certain amount of N-methyl pyrrolidone, ball-milling for 24-26h by using a ball mill, and removing insoluble substances in the solution by using a high-degree centrifuge after the ball milling is finished to obtain a pre-composite solution;
s3, adding PVDF powder into the pre-composite solution in S2, adding a certain amount of tert-butyl hydroperoxide, stirring, ultrasonically dispersing the obtained mixed solution for 20-30min under the action of an ultrasonic oscillator after stirring is finished, and standing for 5-6h at 75-80 ℃ to obtain the PVDF composite solution;
s4, taking PET fiber filaments as raw materials, knitting by using a high-speed knitting machine to obtain a PET fiber knitted tube, immersing the PET fiber knitted tube in a NaOH aqueous solution at 80 ℃ for 30-40min, cleaning with deionized water after immersion, and drying for later use;
s5, adding 25-28 parts of PVDF composite solution, 6-8 parts of PVP, 4-5 parts of LiCl and 85-88 parts of DMAC into a stirring tank, dissolving at 40-45 ℃ for 11-12h, transferring into a defoaming tank, and standing and defoaming at 40-45 ℃ for 3-4h in the defoaming tank to obtain a casting composite solution;
s6, uniformly coating the casting film composite solution in the S5 on the outer surface of the PET fiber braided tube prepared by the S4 to obtain a composite film yarn;
and S7, carrying out phase conversion on the composite membrane filaments in the S6 in a tap water gel bath at 35 ℃ to form a membrane, collecting the membrane filaments after membrane formation by a filament winding wheel, and soaking the membrane filaments in tap water for 48 hours to obtain the high-performance MABR hollow fiber composite membrane.
Further, the preparation process of the hydrochloric acid solution of ammonium persulfate in S1 is as follows: adding a certain amount of ammonium persulfate powder into hydrochloric acid solution with the concentration of lmol/L for stirring for 30-40nim to obtain the hydrochloric acid solution of ammonium persulfate.
Furthermore, the volume ratio of the polyaniline to the N-methylpyrrolidone in S2 is 1: 10-15.
Further, the ultrasonic power of the ultrasonic dispersion in the S3 is 50-200W.
Further, the inner diameter of the PET fiber braided tube in S4 is 2.0mm, the number of the ingots is 24 ingots, and the mesh number is 40 meshes.
Further, the mass fraction of the NaOH aqueous solution in S4 is 5%.
Further, in S5, before the composite solution in the stirring tank is transferred to the defoaming tank, an amount of defoaming agent may be added to the composite solution in the stirring tank.
Further, the temperature of the tap water in S7 is normal temperature.
Advantageous effects
The invention provides a preparation method of a high-performance MABR hollow fiber composite membrane, which has the following beneficial effects compared with the prior art:
according to the invention, the PVDF is modified by the polyaniline, so that the hydrophilicity of the PVDF can be improved by polyaniline modification, the membrane hanging process of the MABR can be facilitated by the property of the polyaniline, and the pollution resistance and the biodegradability of the PVDF can be improved by modifying the PVDF by the polyaniline. According to the invention, the strength of the hollow fiber membrane can be improved to a certain extent by taking the PET braided tube as the supporting layer and taking the PVDF modified by polyaniline as the casting membrane coating layer, and the service cycle and the service life of the membrane are prolonged, wherein the modified PVDF, PVP, LiCl and DMAC are mixed according to a certain proportion to prepare the casting membrane coating layer, so that the problem of poor hydrophilicity of the PVDF can be improved to a certain extent, and the performance of the hollow fiber composite membrane can be effectively enhanced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the 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 invention.
Example 1:
the preparation method of the high-performance MABR hollow fiber composite membrane of the embodiment comprises the following preparation steps:
s1, adding a certain amount of aniline subjected to reduced pressure distillation into lmol/L hydrochloric acid deionized water solution at the temperature of 0 ℃, slowly dropwise adding a certain amount of ammonium persulfate hydrochloric acid solution, keeping the reaction temperature of the materials at 3 ℃ in the dropwise adding process, stirring for 5 hours after the dropwise adding is finished to obtain dark green polyaniline suspension, filtering the materials, washing with deionized water until washing liquor is neutral, and drying to obtain hydrochloric acid in-situ doped polyaniline;
s2, adding polyaniline in S1 into a certain amount of N-methyl pyrrolidone, ball-milling for 26 hours by using a ball mill, and removing insoluble substances in the solution by using a high-degree centrifuge after the ball milling is finished to obtain a pre-composite solution;
s3, adding PVDF powder into the pre-composite solution in S2, adding a certain amount of tert-butyl hydroperoxide, stirring, ultrasonically dispersing the obtained mixed solution for 20min under the action of an ultrasonic oscillator after stirring is finished, and standing for 5h at 78 ℃ to obtain the PVDF composite solution;
s4, taking PET fiber filaments as raw materials, knitting by using a high-speed knitting machine to obtain a PET fiber knitted tube, immersing the PET fiber knitted tube in a NaOH aqueous solution at 80 ℃ for 30min, cleaning with deionized water after immersion, and drying for later use;
s5, adding 25 parts of PVDF composite solution, 7 parts of PVP, 4 parts of LiCl and 87 parts of DMAC into a stirring tank, dissolving for 11 hours at 45 ℃, transferring into a defoaming tank, and standing and defoaming for 3 hours at 40 ℃ in the defoaming tank to obtain the casting composite solution;
s6, uniformly coating the casting film composite solution in the S5 on the outer surface of the PET fiber braided tube prepared by the S4 to obtain a composite film yarn;
and S7, carrying out phase conversion on the composite membrane filaments in the S6 in a tap water gel bath at 35 ℃ to form a membrane, collecting the membrane filaments after membrane formation by a filament winding wheel, and soaking the membrane filaments in tap water for 48 hours to obtain the high-performance MABR hollow fiber composite membrane.
The preparation process of the hydrochloric acid solution of ammonium persulfate in S1 is as follows: adding a certain amount of ammonium persulfate powder into hydrochloric acid solution with the concentration of lmol/L, and stirring for 35nim to obtain the hydrochloric acid solution of ammonium persulfate.
The volume ratio of polyaniline to N-methylpyrrolidone in S2 is 1: 15.
the ultrasonic power of the ultrasonic dispersion in S3 was 50W.
In S4, the inner diameter of the PET fiber braided tube is 2.0mm, the number of the ingots is 24 ingots, and the mesh number is 40 meshes.
The mass fraction of the NaOH aqueous solution in S4 was 5%.
In S5, a predetermined amount of defoaming agent may be added to the composite solution in the stirring tank before the composite solution in the stirring tank is transferred to the defoaming tank.
The temperature of tap water in S7 was room temperature.
Example 2:
the preparation method of the high-performance MABR hollow fiber composite membrane of the embodiment comprises the following preparation steps:
s1, adding a certain amount of aniline subjected to reduced pressure distillation into lmol/L hydrochloric acid deionized water solution at the temperature of 3 ℃, slowly dropwise adding a certain amount of ammonium persulfate hydrochloric acid solution, keeping the reaction temperature of the materials at 5 ℃ in the dropwise adding process, stirring for 4 hours after the dropwise adding is finished to obtain dark green polyaniline suspension, filtering the materials, washing with deionized water until washing liquor is neutral, and drying to obtain hydrochloric acid in-situ doped polyaniline;
s2, adding polyaniline in S1 into a certain amount of N-methyl pyrrolidone, ball-milling for 25 hours by using a ball mill, and removing insoluble substances in the solution by using a high-degree centrifuge after the ball milling is finished to obtain a pre-composite solution;
s3, adding PVDF powder into the pre-composite solution in S2, adding a certain amount of tert-butyl hydroperoxide, stirring, ultrasonically dispersing the obtained mixed solution for 30min under the action of an ultrasonic oscillator after stirring is finished, and standing for 6h at 75 ℃ to obtain the PVDF composite solution;
s4, taking PET fiber filaments as raw materials, knitting by using a high-speed knitting machine to obtain a PET fiber knitted tube, immersing the PET fiber knitted tube in 80 ℃ NaOH aqueous solution for 35min, cleaning with deionized water after immersion, and drying for later use;
s5, adding 28 parts of PVDF composite solution, 8 parts of PVP, 4 parts of LiCl and 88 parts of DMAC into a stirring tank, dissolving at 40 ℃ for 12 hours, transferring into a defoaming tank, and standing and defoaming in the defoaming tank at 43 ℃ for 4 hours to obtain the casting composite solution;
s6, uniformly coating the casting film composite solution in the S5 on the outer surface of the PET fiber braided tube prepared by the S4 to obtain a composite film yarn;
and S7, carrying out phase conversion on the composite membrane filaments in the S6 in a tap water gel bath at 35 ℃ to form a membrane, collecting the membrane filaments after membrane formation by a filament winding wheel, and soaking the membrane filaments in tap water for 48 hours to obtain the high-performance MABR hollow fiber composite membrane.
The preparation process of the hydrochloric acid solution of ammonium persulfate in S1 is as follows: adding a certain amount of ammonium persulfate powder into hydrochloric acid solution with the concentration of lmol/L, and stirring for 40nim to obtain the hydrochloric acid solution of ammonium persulfate.
The volume ratio of polyaniline to N-methylpyrrolidone in S2 is 1: 10.
the ultrasonic power of the ultrasonic dispersion in S3 was 100W.
In S4, the inner diameter of the PET fiber braided tube is 2.0mm, the number of the ingots is 24 ingots, and the mesh number is 40 meshes.
The mass fraction of the NaOH aqueous solution in S4 was 5%.
In S5, a predetermined amount of defoaming agent may be added to the composite solution in the stirring tank before the composite solution in the stirring tank is transferred to the defoaming tank.
The temperature of tap water in S7 was room temperature.
Example 3:
the preparation method of the high-performance MABR hollow fiber composite membrane of the embodiment comprises the following preparation steps:
s1, adding a certain amount of aniline subjected to reduced pressure distillation into lmol/L hydrochloric acid deionized water solution at the temperature of 5 ℃, slowly dropwise adding a certain amount of ammonium persulfate hydrochloric acid solution, keeping the reaction temperature of the materials at 0 ℃ in the dropwise adding process, stirring for 5 hours after the dropwise adding is finished to obtain dark green polyaniline suspension, filtering the materials, washing with deionized water until washing liquor is neutral, and drying to obtain hydrochloric acid in-situ doped polyaniline;
s2, adding polyaniline in the S1 into a certain amount of N-methyl pyrrolidone, ball-milling for 24 hours by using a ball mill, and removing insoluble substances in the solution by using a high-degree centrifuge after the ball milling is finished to obtain a pre-composite solution;
s3, adding PVDF powder into the pre-composite solution in S2, adding a certain amount of tert-butyl hydroperoxide, stirring, ultrasonically dispersing the obtained mixed solution for 25min under the action of an ultrasonic oscillator after stirring, and standing for 5h at 80 ℃ to obtain the PVDF composite solution;
s4, taking PET fiber filaments as raw materials, knitting by using a high-speed knitting machine to obtain a PET fiber knitted tube, immersing the PET fiber knitted tube in a NaOH aqueous solution at 80 ℃ for 40min, cleaning with deionized water after immersion, and drying for later use;
s5, adding 27 parts of PVDF composite solution, 6 parts of PVP, 5 parts of LiCl and 85 parts of DMAC into a stirring tank, dissolving at 43 ℃ for 12 hours, transferring into a defoaming tank, and standing and defoaming in the defoaming tank at 45 ℃ for 3 hours to obtain the casting composite solution;
s6, uniformly coating the casting film composite solution in the S5 on the outer surface of the PET fiber braided tube prepared by the S4 to obtain a composite film yarn;
and S7, carrying out phase conversion on the composite membrane filaments in the S6 in a tap water gel bath at 35 ℃ to form a membrane, collecting the membrane filaments after membrane formation by a filament winding wheel, and soaking the membrane filaments in tap water for 48 hours to obtain the high-performance MABR hollow fiber composite membrane.
The preparation process of the hydrochloric acid solution of ammonium persulfate in S1 is as follows: adding a certain amount of ammonium persulfate powder into hydrochloric acid solution with the concentration of lmol/L, and stirring for 30nim to obtain the hydrochloric acid solution of ammonium persulfate.
The volume ratio of polyaniline to N-methylpyrrolidone in S2 is 1: 12.
the ultrasonic power of the ultrasonic dispersion in S3 was 200W.
In S4, the inner diameter of the PET fiber braided tube is 2.0mm, the number of the ingots is 24 ingots, and the mesh number is 40 meshes.
The mass fraction of the NaOH aqueous solution in S4 was 5%.
In S5, a predetermined amount of defoaming agent may be added to the composite solution in the stirring tank before the composite solution in the stirring tank is transferred to the defoaming tank.
The temperature of tap water in S7 was room temperature.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a high-performance MABR hollow fiber composite membrane is characterized by comprising the following preparation steps:
s1, adding a certain amount of aniline subjected to reduced pressure distillation into lmol/L hydrochloric acid deionized water solution at the temperature of 0-5 ℃, slowly dropwise adding a certain amount of ammonium persulfate hydrochloric acid solution, keeping the reaction temperature of the materials at 0-5 ℃ in the dropwise adding process, stirring for 4-5 hours after the dropwise adding is finished to obtain dark green polyaniline suspension, filtering the materials, washing with deionized water until the washing liquid is neutral, and drying to obtain hydrochloric acid in-situ doped polyaniline;
s2, adding polyaniline in S1 into a certain amount of N-methyl pyrrolidone, ball-milling for 24-26h by using a ball mill, and removing insoluble substances in the solution by using a high-degree centrifuge after the ball milling is finished to obtain a pre-composite solution;
s3, adding PVDF powder into the pre-composite solution in S2, adding a certain amount of tert-butyl hydroperoxide, stirring, ultrasonically dispersing the obtained mixed solution for 20-30min under the action of an ultrasonic oscillator after stirring is finished, and standing for 5-6h at 75-80 ℃ to obtain the PVDF composite solution;
s4, taking PET fiber filaments as raw materials, knitting by using a high-speed knitting machine to obtain a PET fiber knitted tube, immersing the PET fiber knitted tube in a NaOH aqueous solution at 80 ℃ for 30-40min, cleaning with deionized water after immersion, and drying for later use;
s5, adding 25-28 parts of PVDF composite solution, 6-8 parts of PVP, 4-5 parts of LiCl and 85-88 parts of DMAC into a stirring tank, dissolving at 40-45 ℃ for 11-12h, transferring into a defoaming tank, and standing and defoaming at 40-45 ℃ for 3-4h in the defoaming tank to obtain a casting composite solution;
s6, uniformly coating the casting film composite solution in the S5 on the outer surface of the PET fiber braided tube prepared by the S4 to obtain a composite film yarn;
and S7, carrying out phase conversion on the composite membrane filaments in the S6 in a tap water gel bath at 35 ℃ to form a membrane, collecting the membrane filaments after membrane formation by a filament winding wheel, and soaking the membrane filaments in tap water for 48 hours to obtain the high-performance MABR hollow fiber composite membrane.
2. The preparation method of the high-performance MABR hollow fiber composite membrane according to claim 1, wherein the preparation process of the hydrochloric acid solution of ammonium persulfate in S1 is as follows: adding a certain amount of ammonium persulfate powder into hydrochloric acid solution with the concentration of lmol/L for stirring for 30-40nim to obtain the hydrochloric acid solution of ammonium persulfate.
3. The method for preparing a high-performance MABR hollow fiber composite membrane according to claim 1, wherein the volume ratio of polyaniline to N-methylpyrrolidone in S2 is 1: 10-15.
4. The method for preparing a high-performance MABR hollow fiber composite membrane according to claim 1, wherein the ultrasonic power of ultrasonic dispersion in S3 is 50-200W.
5. The method of claim 1, wherein the inner diameter of the woven tube of PET fibers in S4 is 2.0mm, the number of ingots is 24 ingots, and the mesh number is 40.
6. The method for preparing a high-performance MABR hollow fiber composite membrane according to claim 1, wherein the mass fraction of NaOH aqueous solution in S4 is 5%.
7. The method of claim 1, wherein a defoaming agent is added to the composite solution in the stirring tank in a predetermined amount before the composite solution in the stirring tank is transferred to the defoaming tank in step S5.
8. The method for preparing a high-performance MABR hollow fiber composite membrane according to claim 1, wherein the temperature of tap water in S7 is normal temperature.
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