CN112999874A - Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application - Google Patents
Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application Download PDFInfo
- Publication number
- CN112999874A CN112999874A CN202110208146.5A CN202110208146A CN112999874A CN 112999874 A CN112999874 A CN 112999874A CN 202110208146 A CN202110208146 A CN 202110208146A CN 112999874 A CN112999874 A CN 112999874A
- Authority
- CN
- China
- Prior art keywords
- pmia
- membrane
- mixed matrix
- preparing
- matrix membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 title claims abstract description 22
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 title claims description 80
- 239000012528 membrane Substances 0.000 claims abstract description 112
- 238000005266 casting Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002114 nanocomposite Substances 0.000 claims abstract description 18
- 238000005191 phase separation Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000007790 scraping Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 abstract description 20
- 239000011941 photocatalyst Substances 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- -1 polyisophthaloyl Polymers 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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
-
- 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
- C02F2101/30—Organic 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for preparing a photocatalytic performance polyisophthaloyl metaphenylene diamine mixed matrix membrane by blending and an application thereof, wherein the preparation method comprises the following steps: mixing a GO-ZnO-Ag nano composite material prepared by a hydrothermal synthesis method with polyisophthaloyl metaphenylene diamine (PMIA) and preparing to obtain a casting solution, and preparing a PMIA mixed matrix membrane by a non-solvent induced phase separation method; the mixed matrix membrane can be used for improving the organic pollution resistance of the ultrafiltration membrane. Compared with the prior art, the invention adds the photocatalysts GO-ZnO-Ag into the PMIA membrane casting solution in the form of additives, and the modified PMIA membrane is blended, so that the mechanical strength of the composite membrane is improved, the hydrophilicity is greatly enhanced, and the composite membrane has better methylene blue pollution resistance.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and relates to a method for preparing a PMIA mixed matrix membrane with photocatalytic performance by blending and application.
Background
The membrane separation technology is one of the preferable technologies in the field of water pollution control engineering, and is widely applied to drinking water purification and wastewater treatment and recycling due to low cost, good effluent quality, high intensification degree, simple equipment and convenient operation. However, the membrane pollution phenomenon, especially organic pollution, often causes the attenuation of membrane flux, the increase of operation cost and the shortening of membrane service life, thereby becoming a major obstacle for the wide application of membrane separation technology in drinking water, sewage and wastewater treatment.
The modification of the membrane material can be divided into chemical modification and blending modification of the membrane material, and the latter is convenient for large-scale popularization due to simple operation and difficult falling of hydrophilic groups, and is a hotspot of research in recent years.
The technology of photocatalysis and membrane separation is being gradually applied to the research of membrane separation, and Chinese patent CN103881122A discloses a preparation method of a polyvinyl chloride/nano tin dioxide composite membrane with high visible light catalytic activity. However, the membrane prepared by the method has insufficient pollution resistance to organic pollutant methylene blue and low interception efficiency. Chinese patent CN107158960A discloses a preparation method of a high-flux and anti-pollution polyisophthaloyl metaphenylene diamine nanofiltration membrane. According to the method disclosed by the invention, under the condition of keeping the rejection rate to be increased, the contact angle of the prepared nanofiltration membrane is reduced from about 78 degrees to about 45 degrees, so that the hydrophilicity and the pollution resistance of the membrane are greatly improved.
In the preparation method of the membrane disclosed in the above-mentioned chinese patent, the membrane has an anti-pollution capability by its own catalytic performance. But also has disadvantages in that the membrane material is clogged due to the accumulation of contaminants, and the anti-contamination capability is weakened.
Disclosure of Invention
The invention aims to provide a method for preparing a PMIA mixed matrix membrane with photocatalytic performance by blending and an application thereof, which are used for solving the pollution problem of the PMIA membrane.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to protect a method for preparing a PMIA mixed matrix membrane with photocatalytic performance by blending, which comprises the following steps:
s1: synthesizing a GO-ZnO-Ag nano composite material with photocatalytic performance by a hydrothermal method;
s2: mixing the GO-ZnO-Ag nano composite material obtained in the S1 with PMIA to prepare a casting solution;
s3: the casting solution obtained in S2 was subjected to a non-solvent phase separation method to prepare a PMIA mixed matrix membrane.
Further, the preparation method of the casting solution comprises the following steps:
s2-1: adding the GO-ZnO-Ag nano composite material, the cosolvent and the PMIA into N, N-dimethylacetamide, and uniformly stirring to obtain a mixed solution;
s2-2: and standing and defoaming the mixed solution to obtain the membrane casting solution.
Further, the co-solvent comprises LiCl and/or PVP.
In S2, the mass ratio of the GO-ZnO-Ag nano composite material to the cosolvent to the PMIA is (0.2-1.8) to 4.5 (12-20).
Further, in S2-1, the stirring temperature is 50-100 ℃, and the stirring time is 8-18 h.
Further, the non-solvent induced phase separation method in S3 includes:
s3-1: coating the casting solution on a substrate by scraping;
s3-2: and (3) placing the substrate with the membrane casting solution in a gel bath for phase separation to obtain the PMIA mixed matrix membrane.
Further, the casting solution in S3-1 is coated to be 100-250 μm in a blade coating manner;
the gel bath is deionized water, and the temperature of the gel bath is 15-30 ℃.
Further, the standing time in the standing and defoaming process in S2-2 is 5-12 h.
The second purpose of the invention is to protect a PMIA mixed matrix membrane with photocatalytic performance, which is prepared by adopting the method.
The third purpose of the invention is to protect the application of the PMIA mixed matrix membrane in the catalytic degradation of methylene blue.
The photocatalytic PMIA mixed matrix membrane prepared by the method can be used for resisting organic pollutants, and particularly can be used for improving the organic pollutant resistance of a catalytic membrane reactor device.
The GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane can be used for catalyzing a membrane reactor device, and organic pollutants on the surface of the membrane can be degraded under the irradiation of a visible light lamp, so that the membrane pollution phenomenon is inhibited. The method for realizing pollution resistance of the PMIA ultrafiltration membrane modified by the GO-ZnO-Ag photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device, fixing a polluted GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane on a membrane component, fixing an LED visible light lamp at a position which is 10cm away from the surface of the membrane, continuously using the GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane for a water flux experiment, filtering for 30min in the dark, opening the visible light lamp for filtering and simultaneously carrying out photocatalysis, realizing photocatalytic degradation on organic matters under the irradiation of the LED visible light lamp, and enhancing the flux. The organic contaminants include Methylene Blue (MB).
The GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane can activate the GO-ZnO-Ag photocatalyst on the surface of the membrane to generate active oxygen free radicals with oxidability under the irradiation of visible light, and the active oxygen free radicals can perform degradation reaction with organic pollutants to catalyze the pollutants into CO2And H2O。
The PMIA mixed matrix membrane of the present invention exhibits excellent contamination resistance and significantly improved rejection rate when treated with Methylene Blue (MB) solution. This is because the inorganic nanomaterial is embedded into the concave surface of the hybrid membrane surface during the phase separation process, which results in a smoother membrane surface that is less prone to contaminant accumulation. On the other hand, as hydrophilicity increases, the "hydrated layer" of the membrane surface effectively prevents the access of foulants, making fouling accumulation in the membrane pores more difficult and exhibiting higher anti-fouling performance.
The preparation method comprises the steps of adding the prepared GO-ZnO-Ag into the PMIA membrane casting solution in the form of an additive, and introducing the inorganic nanoparticle blending modified PMIA membrane to improve the mechanical strength of the composite membrane, greatly improve the hydrophilicity, and have better pollution resistance and interception performance, wherein the blending is the simplest and most common membrane modification method. Compared with other methods, the blending modification has the following advantages: the modification and the film formation are carried out synchronously, the process is simple, and complicated post-treatment steps are not needed; the additive can cover the membrane surface and the inner wall of the membrane hole at the same time and can not cause the damage of the membrane structure.
Compared with the prior art, the invention has the following characteristics:
1) compared with the traditional PMIA ultrafiltration membrane, the GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane provided by the invention has higher hydrophilicity and obvious photocatalytic performance; in the GO-ZnO-Ag photocatalyst, GO with electron transfer performance is used as a carrier, and nano silver particles (AgNPs) are used as an electron carrier, so that the recombination rate of excited electrons and holes on ZnO under ultraviolet light is delayed, the visible light response capability of GO-ZnO-Ag is effectively promoted, a good anti-pollution effect is achieved under the irradiation of visible light, the membrane pollution phenomenon can be effectively reduced, and the reduction rate of membrane flux is slowed down;
2) the invention provides a GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane and an ultraviolet photocatalyst (such as TiO)2) Compared with the modified PMIA membrane, the catalytic degradation efficiency is obviously improved;
3) the method for preparing the GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane is simple and easy to operate, the used equipment is conventional instruments in the field, the process period is short, the requirement on the process environment is low, the cost is low, and the method can be widely applied to preparation of photocatalyst modified PMIA membranes;
4) the method for preparing the GO-ZnO-Ag photocatalyst modified PMIA ultrafiltration membrane is a blending modification method, the photocatalyst GO-ZnO-Ag in the modified membrane is not easy to dissolve out along with water flow in the using process, the poisoning and potential secondary pollution to a water body are avoided, and the durability and the stability of the membrane structure are ensured.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a PMIA film prepared in example 1;
FIG. 2 is a comparison of water flux of the photocatalyst-modified PMIA films (M1-M5) prepared in examples 1-5 and the PMIA raw film M0;
FIG. 3 is a graph comparing the photocatalytic efficiency of GO-ZnO-Ag photocatalyst-modified PMIA films (M1-M5) prepared in examples 1-5 with that of PMIA original film M0.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As a part of the technical scheme, the photocatalysis technology is a novel, efficient and environment-friendly technical means in the field of water treatment in recent years, and the technology utilizes renewable light energy to generate active group superoxide radical to degrade organic pollutants in water. Therefore, the technical scheme combines the photocatalysis technology with the membrane modification technology to form the composite photocatalysis separation modified membrane, and can effectively improve the self-cleaning capability, the hydrophilic performance and the interception characteristic of the membrane.
As part of the concept of the present embodiment, the PMIA used in the present embodiment has a hydrogen bond network structure, so that it has excellent mechanical properties and good thermal stability (Tg 558K). More importantly, the PMIA has good hydrophilicity due to a large number of aramid fiber groups and hydrogen bond networks contained in the main chain of the PMIA, so that the PMIA membrane has good permeability and anti-pollution capability. In addition, the material is easy to dissolve in a common organic solvent DMAc, so that the PMIA ultrafiltration membrane is prepared by adopting a non-solvent induced phase inversion (NIPS) method in the technical scheme, and the possibility is provided for industrial production.
The preparation method of the PMIA mixed matrix membrane with the blended photocatalytic performance in the technical scheme comprises the following steps:
1) preparing a casting solution: adding the GO-ZnO-Ag nano composite material, a cosolvent LiCl and PMIA into N, N-dimethylacetamide (DMAc), stirring for 8-18 h at 50-100 ℃, standing and defoaming to obtain a casting solution, wherein the GO-ZnO-Ag nano composite material in the technical scheme can be prepared by referring to the existing literature;
wherein the mass ratio of the GO-ZnO-Ag nano composite material to the cosolvent to the PMIA is (0.2-1.8) to 4.5 (12-20);
2) non-solvent induced phase separation method PMIA mixed matrix membrane preparation: and (3) coating the casting film liquid on a glass plate in a scraping thickness of 100-250 mu m, and placing the glass plate in a 15-30 ℃ hydrogel bath for phase separation to obtain the PMIA mixed matrix film.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
In the invention, the photocatalyst is added into the film, the conductive Graphene Oxide (GO) with good ductility is used as a carrier, ZnO particles are loaded to ensure that the ZnO particles are uniformly dispersed, the reduction of catalytic efficiency caused by agglomeration is avoided, and excited electrons generated by ZnO under the irradiation of an ultraviolet lamp are combined with dissolved oxygen in a solution to generate superoxide radical (O.O)2 -) The Ag-ZnO composite film has catalytic reduction performance, can degrade organic matters in water, can delay the recombination of excited electrons and electron hole pairs by compounding Ag on ZnO, enables the electrons to have more combined oxygen, has a self-cleaning function, prevents pollutants from accumulating on the film, and prolongs the service life of the film.
Example 1:
this example was used to prepare a PMIA mixed matrix membrane, the specific preparation method being as follows:
1) dissolving a GO-ZnO-Ag nano composite material, LiCl and PMIA in DMAc according to the mass ratio of 0.2:4.5:18, stirring for 8 hours at 50 ℃ until the materials are fully dissolved, and standing and defoaming for 5 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 250 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a PMIA mixed matrix membrane which is marked as an M1 ultrafiltration membrane.
The obtained M1 ultrafiltration membrane was characterized by scanning electron microscopy, and the results are shown in fig. 1. As can be seen from the figure, the membrane cross-section is dense in surface but has large membrane pores.
Example 2:
this example was used to prepare a PMIA mixed matrix membrane, the specific preparation method being as follows:
1) dissolving a GO-ZnO-Ag nano composite material, LiCl and PMIA in DMAc according to the mass ratio of 0.5:4.5:15, stirring for 10 hours at 70 ℃ until the materials are fully dissolved, and standing and defoaming for 10 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 150 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a PMIA mixed matrix membrane which is marked as an M2 ultrafiltration membrane.
Example 3:
this example was used to prepare a PMIA mixed matrix membrane, the specific preparation method being as follows:
1) dissolving a GO-ZnO-Ag nano composite material, LiCl and PMIA in DMAc according to the mass ratio of 1.0:4.5:17, stirring for 15 hours at 80 ℃ until the materials are fully dissolved, and standing and defoaming for 12 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 130 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a PMIA mixed matrix membrane which is marked as an M3 ultrafiltration membrane.
Example 4:
this example was used to prepare a PMIA mixed matrix membrane, the specific preparation method being as follows:
1) dissolving a GO-ZnO-Ag nano composite material, LiCl and PMIA in DMAc according to the mass ratio of 1.5:4.5:14, stirring for 18 hours at 50 ℃ until the materials are fully dissolved, and standing and defoaming for 5 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 100 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a PMIA mixed matrix membrane which is marked as an M4 ultrafiltration membrane.
Example 5:
this example was used to prepare a PMIA mixed matrix membrane, the specific preparation method being as follows:
1) dissolving a GO-ZnO-Ag nano composite material, LiCl and PMIA in DMAc according to the mass ratio of 1.8:4.5:20, stirring for 18 hours at 100 ℃ until the materials are fully dissolved, and standing and defoaming for 12 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 250 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain a PMIA mixed matrix membrane which is marked as an M5 ultrafiltration membrane.
Comparative example 1:
the PMIA flat membrane without the GO-ZnO-Ag nano composite material is prepared by adopting an NIPS method in the comparative example, and the specific preparation method is as follows:
1) dissolving LiCl and PMIA in DMAc in a mass ratio of 4:15, stirring for 10 hours at 60 ℃ until the LiCl and the PMIA are fully dissolved, and standing and defoaming for 6 hours to obtain a casting solution;
2) coating the casting solution on a glass plate in a scraping way, wherein the thickness of the scraped film is 250 mu m;
3) immersing the glass plate with the membrane liquid into deionized water for phase splitting;
4) and transferring the membrane after phase separation into deionized water to be soaked so as to remove redundant solvent, and then putting the membrane into clean deionized water for storage to obtain an unmodified PMIA flat membrane which is marked as an M0 ultrafiltration membrane.
The ultrafiltration membranes of examples 1-5 and comparative example were tested for water flux and methylene blue rejection, wherein the water flux and methylene blue rejection test methods are described in the following references: wang, Gui-E Chen, Hai-Ling Wu, publication of GO-Ag/PMIA/F127 modified membrane IPA coaggulant bath for catalytic reduction of 4-nitrophenol, Sep, purify, technol.235(2020) 116143.
The results are shown in FIGS. 2 and 3, respectively, from which it can be seen that each of the membranes with added nanoparticles exhibited superior permeability and better separation performance compared to the original PMIA membrane. The permeability increase may be due to the influence of two main factors: 1) the addition of nanoparticles will impart hydrophilicity to the membrane, thereby increasing the rate of water passage through the membrane. 2) The pore size and porosity of the modified membrane is enlarged compared to the original membrane, which undoubtedly favors permeability. The improvement in separation performance can be illustrated by three reasons: 1) the pore size of the membrane is smaller than the size of the contaminants. 2) The methylene blue molecules can be effectively intercepted by the complex structure of the sponge pores formed by delayed phase separation. 3) The theory of increased hydrophilicity with an interfacial hydration layer is used to reduce the contact between the contaminants and the membrane surface, thereby preventing the contaminants from penetrating the modified membrane. Meanwhile, compared with the method for simply cleaning the polluted membrane by water, the method can effectively catalyze and decompose methylene blue attached to the membrane pores after the membrane is exposed to visible light, thereby bringing higher flux recovery rate.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for preparing a PMIA mixed matrix membrane with photocatalytic performance by blending is characterized by comprising the following steps:
s1: synthesizing a GO-ZnO-Ag nano composite material with photocatalytic performance by a hydrothermal method;
s2: mixing the GO-ZnO-Ag nano composite material obtained in the S1 with PMIA to prepare a casting solution;
s3: the casting solution obtained in S2 was subjected to a non-solvent phase separation method to prepare a PMIA mixed matrix membrane.
2. The method for preparing the PMIA mixed matrix membrane with photocatalytic performance by blending according to claim 1, wherein the preparation method of the membrane casting solution comprises the following steps:
s2-1: adding the GO-ZnO-Ag nano composite material, the cosolvent and the PMIA into N, N-dimethylacetamide, and uniformly stirring to obtain a mixed solution;
s2-2: and standing and defoaming the mixed solution to obtain the membrane casting solution.
3. The method of blending to produce a PMIA mixed matrix membrane with photocatalytic properties according to claim 1, wherein the co-solvent comprises LiCl and/or PVP.
4. The method for preparing the PMIA mixed matrix membrane with photocatalytic performance by blending according to claim 1, wherein in S2, the mass ratio of the GO-ZnO-Ag nano composite material to the cosolvent to the PMIA is (0.2-1.8) to 4.5 (12-20).
5. The method for preparing the PMIA mixed matrix membrane with photocatalytic performance by blending according to claim 2, wherein in S2-1, the stirring temperature is 50-100 ℃ and the stirring time is 8-18 h.
6. The method for preparing a photocatalytic PMIA mixed matrix membrane by blending according to claim 1, wherein the non-solvent induced phase separation process in S3 comprises:
s3-1: coating the casting solution on a substrate by scraping;
s3-2: and (3) placing the substrate with the membrane casting solution in a gel bath for phase separation to obtain the PMIA mixed matrix membrane.
7. The method for preparing the PMIA mixed matrix membrane with photocatalytic performance by blending according to claim 6, wherein the coating of the casting solution in S3-1 is 100-250 μm;
the gel bath is deionized water, and the temperature of the gel bath is 15-30 ℃.
8. The method for preparing the PMIA mixed matrix membrane with photocatalytic performance by blending according to claim 2, wherein the standing time of the standing and defoaming process in S2-2 is 5-12 h.
9. A PMIA mixed matrix membrane with photocatalytic performance prepared by the method according to any one of claims 1 to 8.
10. Use of a PMIA mixed matrix membrane according to claim 9 for the catalytic degradation of methylene blue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110208146.5A CN112999874A (en) | 2021-02-25 | 2021-02-25 | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110208146.5A CN112999874A (en) | 2021-02-25 | 2021-02-25 | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112999874A true CN112999874A (en) | 2021-06-22 |
Family
ID=76385838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110208146.5A Pending CN112999874A (en) | 2021-02-25 | 2021-02-25 | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112999874A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522036A (en) * | 2021-07-06 | 2021-10-22 | 上海应用技术大学 | Polyphenylenediamine mixed matrix ultrafiltration membrane with photocatalysis effect and preparation application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
| CN103127844A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院生态环境研究中心 | Method for improving polyisophthaloyl metaphenylene diamine hollow fiber nanofiltration membrane hydrophilism and pollution resistant performance |
| RO133334A2 (en) * | 2017-09-18 | 2019-05-30 | Universitatea Politehnică Din Bucureşti | Process for manufacturing a photocatalyst uniform film as nanothread array based on zinc oxide hybridized with graphene oxide by double-pulse electrodeposition |
| CN110227453A (en) * | 2019-04-17 | 2019-09-13 | 江苏省农业科学院 | A kind of preparation method of Ag/ZnO/GO composite visible light catalyst |
| CN112121642A (en) * | 2020-09-14 | 2020-12-25 | 上海应用技术大学 | Poly (m-phenylene isophthalamide) water treatment membrane with photocatalytic self-cleaning performance and preparation method and application thereof |
| CN112121648A (en) * | 2020-09-14 | 2020-12-25 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof |
-
2021
- 2021-02-25 CN CN202110208146.5A patent/CN112999874A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127844A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院生态环境研究中心 | Method for improving polyisophthaloyl metaphenylene diamine hollow fiber nanofiltration membrane hydrophilism and pollution resistant performance |
| CN102921416A (en) * | 2012-11-05 | 2013-02-13 | 江苏大学 | Nano composite photocatalytic material and method for preparing same |
| RO133334A2 (en) * | 2017-09-18 | 2019-05-30 | Universitatea Politehnică Din Bucureşti | Process for manufacturing a photocatalyst uniform film as nanothread array based on zinc oxide hybridized with graphene oxide by double-pulse electrodeposition |
| CN110227453A (en) * | 2019-04-17 | 2019-09-13 | 江苏省农业科学院 | A kind of preparation method of Ag/ZnO/GO composite visible light catalyst |
| CN112121642A (en) * | 2020-09-14 | 2020-12-25 | 上海应用技术大学 | Poly (m-phenylene isophthalamide) water treatment membrane with photocatalytic self-cleaning performance and preparation method and application thereof |
| CN112121648A (en) * | 2020-09-14 | 2020-12-25 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522036A (en) * | 2021-07-06 | 2021-10-22 | 上海应用技术大学 | Polyphenylenediamine mixed matrix ultrafiltration membrane with photocatalysis effect and preparation application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shi et al. | Photocatalytic membrane in water purification: is it stepping closer to be driven by visible light? | |
| Yan et al. | In situ chemical oxidation: peroxide or persulfate coupled with membrane technology for wastewater treatment | |
| Xu et al. | Nitrogen–doped GO/TiO2 nanocomposite ultrafiltration membranes for improved photocatalytic performance | |
| Luo et al. | Fabrication of hierarchical layer-by-layer membrane as the photocatalytic degradation of foulants and effective mitigation of membrane fouling for wastewater treatment | |
| CN108842304B (en) | Porous supported electrostatic spinning nano photocatalytic fiber membrane and preparation method thereof | |
| CN108159888B (en) | Preparation method of super-hydrophilic ultrafiltration membrane with photocatalytic performance | |
| CN111760461B (en) | Preparation method of polyvinylidene fluoride mixed matrix membrane | |
| Chen et al. | Membrane-catalysis integrated system for contaminants degradation and membrane fouling mitigation: A review | |
| Miao et al. | Continuous and complete conversion of high concentration p‐nitrophenol in a flow‐through membrane reactor | |
| US10843138B1 (en) | Cellulose acetate V/ZN photocatalytic material | |
| Ahmad et al. | Effect of polymer template on structure and membrane fouling of TiO2/Al2O3 composite membranes for wastewater treatment | |
| CN110787645A (en) | Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof | |
| CN112121642A (en) | Poly (m-phenylene isophthalamide) water treatment membrane with photocatalytic self-cleaning performance and preparation method and application thereof | |
| Zhang et al. | Preparation of reusable UHMWPE/TiO2 photocatalytic microporous membrane reactors for efficient degradation of organic pollutants in water | |
| CN113058443A (en) | Preparation method of hollow fiber inorganic membrane | |
| CN115283013A (en) | Preparation method of nano manganese dioxide organic catalytic membrane | |
| CN112517071B (en) | Carbon nitride nanosheet-based photocatalytic composite membrane and preparation method and application thereof | |
| CN112999874A (en) | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by blending and application | |
| CN112121648A (en) | Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof | |
| Xu et al. | Ag@ SnS/PVDF membranes with self-cleaning ability driven by photocatalysis process | |
| CN112569807A (en) | Polyvinylidene fluoride mixed matrix membrane with photocatalytic performance and preparation and application thereof | |
| CN112225382A (en) | Method for removing traditional Chinese medicine and personal care product in wastewater | |
| CN109046307B (en) | Preparation method of photocatalyst for degrading emerging pollutants | |
| CN112569812A (en) | Poly (m-phenylene isophthalamide) mixed matrix membrane with photocatalytic performance and preparation and application thereof | |
| CN112999889A (en) | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by self-adhesion and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210622 |