CN112604506B - Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane - Google Patents
Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane Download PDFInfo
- Publication number
- CN112604506B CN112604506B CN202011138592.5A CN202011138592A CN112604506B CN 112604506 B CN112604506 B CN 112604506B CN 202011138592 A CN202011138592 A CN 202011138592A CN 112604506 B CN112604506 B CN 112604506B
- Authority
- CN
- China
- Prior art keywords
- membrane
- polytetrafluoroethylene
- catalytic
- solution
- polytetrafluoroethylene 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.)
- Active
Links
Classifications
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
- B01D2323/385—Graft polymerization involving radiation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to a preparation method of a polytetrafluoroethylene membrane for catalytic decoloration of dye and an application method of the polytetrafluoroethylene membrane, belonging to the technical field of water treatment. The preparation method of the polytetrafluoroethylene membrane for catalytic dye decolorization comprises the steps of grafting a 2-hydroxyethyl methacrylate (HEMA) solution to the surface of a polytetrafluoroethylene microporous membrane by adopting a gamma-ray irradiation method, then carrying out activation treatment and chelation treatment, and coupling the treated membrane with metal ions to obtain the polytetrafluoroethylene membrane for catalytic dye decolorization. The preparation method of the polytetrafluoroethylene membrane for catalytic dye decolorization is simple and easy to implement and low in cost, and the prepared membrane not only has excellent corrosion resistance, mechanical strength and low resistance, but also has excellent catalytic degradation performance, so that the dye decolorization efficiency is improved; the invention also provides a simple application method of the polytetrafluoroethylene membrane.
Description
Technical Field
The invention relates to a preparation method of a polytetrafluoroethylene membrane for catalytic decoloration of dye and an application method of the polytetrafluoroethylene membrane, belonging to the technical field of water treatment.
Background
Methylene Blue (MB) is a dye widely used in the printing and leather industries, as a fluorescent pigment for histological analysis, and as a sensitizer in semiconductors. Direct discharge of waste water from MB causes serious ecological problems. Due to the stability and complex aromatic structure of MB dyes, as well as antioxidant and antibacterial properties, biological methods are generally not capable of decolorizing MBs. Therefore, it is generally preferred that the metal nanoparticles eliminate these dyes by catalytic degradation.
The polytetrafluoroethylene microporous membrane is a porous material formed by the processes of rolling, multidirectional stretching, heat treatment and the like, has a large number of micropores, has the characteristics of high filtration precision, smooth surface, easy ash removal, corrosion resistance, low resistance and the like, has high porosity of more than 80 percent, can only play a role of physical interception due to the chemical inertia and extreme hydrophobicity of the polytetrafluoroethylene, cannot effectively remove harmful substances in water, and greatly limits the development and application of the polytetrafluoroethylene microporous membrane. Therefore, in order to make up for the deficiency in the performance of PTFE, the PTFE microporous membrane is chemically modified. For example, CN111530125A discloses an affinity chromatography device for separating a target protein or antibody from an aqueous mixture containing the target protein or antibody, the main components of the device being a polytetrafluoroethylene membrane containing inorganic particles, the polymer membrane and/or the inorganic particles having affinity ligands bound thereto. The affinity ligand may be a protein, antibody or polysaccharide that binds reversibly to the target protein or antibody. CN111135719A discloses a preparation method of a composite nanofiltration membrane for water purification. Carrying out hydrophilic modification on a polytetrafluoroethylene-based membrane, carrying out alkylation modification and quaternization modification on glass fiber, adding quaternization glass fiber into m-phenylenediamine solution to prepare suspension, adding trimesoyl chloride into n-hexane solution, stirring and dissolving, finally sequentially putting the hydrophilic polytetrafluoroethylene-based membrane into the m-phenylenediamine solution and the trimesoyl chloride solution, and drying to prepare the composite nanofiltration membrane with better pressure resistance. Seda Saki et al, incorporated Tetraethoxysilane (TEOS) functionalized sodium bentonite into polysulfone/polyethyleneimine (PSF/PEI) membranes and prepared sodium bentonite with high efficiency for methylene blue dye removal by a phase inversion method.
Although the prior art carries out a great deal of modification research on polytetrafluoroethylene membranes and methylene blue adsorbents respectively, the research on catalytic decolorization of dyes by using the polytetrafluoroethylene membranes is relatively lacked, and no relevant report on the polytetrafluoroethylene membranes for MB decolorization exists at present.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a preparation method of a polytetrafluoroethylene membrane for catalytic decoloration of dyes, which is simple and easy to implement and low in cost, and the prepared membrane not only has excellent corrosion resistance, mechanical strength and low resistance, but also has excellent catalytic degradation performance, so that the decoloration efficiency of the dyes is improved; the invention also provides a simple application method of the polytetrafluoroethylene membrane.
The preparation method of the polytetrafluoroethylene membrane for catalytic dye decolorization comprises the steps of grafting a 2-hydroxyethyl methacrylate (HEMA) solution to the surface of a polytetrafluoroethylene microporous membrane by adopting a gamma-ray irradiation method, then carrying out activation treatment and chelation treatment, and coupling the treated membrane with metal ions to obtain the polytetrafluoroethylene membrane for catalytic dye decolorization.
Preferably, the gamma radiation dose is 2-15kGy; the concentration of the 2-hydroxyethyl methacrylate (HEMA) solution is 5-10w/v%.
Preferably, the activating agent used in the activation treatment is NaOH or Na 2 CO 3 More preferably Na 2 CO 3 (ii) a The concentration is 0.5-2mol/L.
Preferably, the chelating agent used in the chelating treatment is Polyethyleneimine (PEI), ethylenediamine or iminodiacetic acid (IDA), more preferably PEI, which is a polycationic chelating agent capable of providing a highly branched hydrophilic three-dimensional matrix, and has a solution pH of 10.5 and a concentration of 1-15wt%.
Preferably, the polytetrafluoroethylene microporous membrane is prepared by the following steps:
mixing high molecular weight polytetrafluoroethylene dispersion resin with lubricating oil, mixing, blank making, extruding, rolling, degreasing, longitudinally stretching, transversely stretching, sintering and curing, and then processing by adopting a composite process.
Preferably, the high molecular weight polytetrafluoroethylene dispersion resin has an SSG of 2.145 to 2.155.
Preferably, the mass ratio of the lubricating oil to the high molecular weight polytetrafluoroethylene dispersion resin is 24-30:100.
preferably, the extrusion pressure is 10 to 15MPa under the condition that the compression ratio is 100; the degreasing temperature is 180-240 ℃; the stretching temperature is 180-240 ℃, and the sintering and curing temperature is 350-380 ℃; the sintering time is 8-15min.
Preferably, the metal ion is a divalent Ni ion, zn ion, co ion, or Cu ion, preferably a Cu ion, the metal ion concentration is 0.5 to 3mol/L, and pH =4.1.
The application method of the polytetrafluoroethylene membrane is to perform catalytic decoloration treatment on a methylene blue dye solution by using the polytetrafluoroethylene membrane in the presence of metal hydride, namely by the hydrolysis reaction of the metal hydride, and then measure the change of the absorption intensity of ultraviolet-visible light at a wavelength of 664.
Preferably, the metal hydride is LiAlH 4 、NH 3 BH 3 Or NaBH 4 . More preferably NaBH 4 It is cheaper and more convenient, has high hydrogen storage efficiency, good stability and easy acquisition.
The preparation method of the polytetrafluoroethylene membrane for catalytic dye decolorization specifically comprises the following steps:
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin and lubricating oil according to a certain proportion, mixing, blanking, extruding, calendering, degreasing, longitudinally stretching, transversely stretching, sintering and curing, and carrying out a composite process, wherein the composite process is to carry out composite without any medium on the basis that a base film is not influenced;
(2) Preparing HEMA solutions with different concentrations by adding Mohr's salt at room temperature, placing the membrane in monomer solution, sealing, and degassing with nitrogen for 5-30min;
(3) At 25 ℃ with gamma radiation, to 60 Co is used as a radiation source and at a certain speed of 1.5kGyh -1 Dynamic irradiation is carried out under different radiation doses, and the cleaning agent is used for cleaning and drying;
(4) Treating the membrane material obtained in the step (3) with an activating agent and a chelating agent solution for a period of time in sequence and cleaning;
(5) And (3) soaking the membrane obtained in the step (4) in a divalent metal ion solution with a certain concentration at room temperature for crosslinking for 10-60min, and cleaning and drying to obtain the target product polytetrafluoroethylene membrane.
The lubricating oil is preferably Mobil isoparaffin solvent oil.
In the step (3), the cleaning agent is preferably methanol and deionized water at 40 ℃; the drying mode is vacuum drying or freeze drying, and more preferably vacuum drying; the drying temperature is 40-70 deg.C, and the drying time is 8-20h.
The chelating agent solution is prepared by dissolving chelating agent in 0.5-2mol/L Na 2 CO 3 Solution was made with chelator solution pH =10.5.
In the step (3), the cleaning agent is preferably deionized water.
In the step (5), the drying mode is vacuum drying or freeze drying, and more preferably vacuum drying; the drying temperature is 40-70 deg.C, and the drying time is 8-20h.
HEMA is a hydrophilic monomer, is nontoxic, and has excellent physical properties and compatibility, and the invention grafts HEMA on PTFE membrane by gamma-ray irradiation, thus enhancing the hydrophilicity of PTFE membrane; the chelating agent has two or more ligands, and can react with metal ions, ni (II), zn (II), co (II), cu (II) and the like to generate a chelate ring, so that a chelate compound with stable chemical properties is obtained, wherein the coordinating atoms are most common nitrogen and oxygen. And decolorizing the dye by using the membrane containing the metal nanoparticle catalyst under the condition of the existence of metal hydride.
Compared with the common granular adsorbents such as activated carbon, humic acid and the like and common membrane materials, the modified membrane prepared by the method has the advantages of higher and faster catalytic decolorization efficiency, better effect, simple adsorption and degradation process, more convenient and faster later-stage recovery treatment, better durability, high mechanical strength and low resistance. Therefore, the PTFE membrane is subjected to hydrophilic modification and then chelated with metal ions, so that the problem of dye decolorization can be effectively solved, and in addition, the PTFE membrane is very effective in degrading organic matters, and becomes an important research and development direction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The average pore diameter of the metal ion modified membrane prepared by the invention is 0.5 mu m, and the porosity is more than 87%;
(2) The metal ion modified membrane prepared by the invention has the advantages of corrosion resistance, high mechanical strength, low resistance, high precision and the like of a polytetrafluoroethylene membrane, can be used for catalytic decolorization of a dye MB in the presence of metal hydride besides conventional physical interception, so that a double bond is changed into a single bond, the structure of the dye is damaged, and a dye solution becomes colorless;
(3) The modified film prepared by the method disclosed by the invention is firm in chemical bond combination, environment pollution caused by metal ion leakage is not easy to cause, the modified film can be efficiently used for a long time, and the decolorizing efficiency reaches 99.42% to the maximum;
(4) The preparation method is simple and feasible and has low cost.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a proportion (100);
(2) Adding 0.02g Mohr's salt to 8w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing with nitrogen for 15min;
(3) At 25 ℃ with gamma radiation at a radiation dose of 10kGy at 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Treating the membrane material obtained in the step (3) with 1.5mol/L sodium carbonate solution and 15wt% PEI solution for 30min in sequence, and cleaning with deionized water;
(5) Dipping the (4) into 2mol/L divalent metal ion Cu (II) solution for crosslinking for 25min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L of metal hydride NaBH 4 In the presence of the inventive film pairs 1.7 x 10 -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution of mol/L. The change in uv-vis absorption intensity was measured at 664 wavelengths. The decolorization efficiency reaches 99.42 percent.
Example 2
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a proportion (100);
(2) Adding 0.02g Mohr's salt to 10w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing for 5min with nitrogen;
(3) At 25 ℃ with gamma radiation at a radiation dose of 15kGy and a dose of 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Sequentially treating the membrane material obtained in the step (3) by using a 0.5mol/L sodium carbonate solution and a 5wt% PEI solution for 30min, and cleaning by using deionized water;
(5) Dipping the (4) into 1mol/L divalent metal ion Cu (II) solution for crosslinking for 30min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L of metal hydride NaBH 4 In the presence of the inventive film pairs 1.7 x 10 -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution of mol/L. The change in uv-vis absorption intensity was measured at 664 wavelengths. The decolorization efficiency reaches 93.31 percent.
Example 3
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a proportion (100);
(2) Adding 0.02g Mohr's salt to 5w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing with nitrogen for 10min;
(3) At 25 ℃ with gamma radiation at a radiation dose of 5kGy at 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Sequentially treating the membrane material obtained in the step (3) by using a 3.0mol/L sodium carbonate solution and a 15wt% PEI solution for 60min, and cleaning by using deionized water;
(5) Dipping the (4) into 2mol/L divalent metal ion Cu (II) solution for crosslinking for 60min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L of metal hydride NH 3 BH 3 In the presence of the inventive film pairs 1.7 x 10 -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution of mol/L. The change in uv-visible absorption intensity was measured at a wavelength of 664. The decolorization efficiency reaches 85.61 percent.
Example 4
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a ratio (100);
(2) Adding 0.02g Mohr's salt to 7w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing with nitrogen for 10min;
(3) At 25 ℃ with gamma radiation at a radiation dose of 6kGy at 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Sequentially treating the membrane material obtained in the step (3) with 0.5mol/L sodium carbonate solution and 10wt% ethylene diamine solution for 30min, and cleaning with deionized water;
(5) Dipping the (4) in a 0.5mol/L divalent metal ion Cu (II) solution for crosslinking for 10min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L of metal hydride NaBH 4 In the presence, 1.7 x 10 pairs of films according to the invention -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution of mol/L. The change in uv-visible absorption intensity was measured at a wavelength of 664. The decolorization efficiency reaches 90 percent.
Example 5
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a ratio (100;
(2) Adding 0.02g Mohr's salt to 8w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing with nitrogen for 30min;
(3) At 25 ℃ with gamma radiation at a radiation dose of 2kGy and a radiation dose of 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Sequentially treating the membrane material obtained in the step (3) with 2mol/L of sodium hydroxide and 1wt% of IDA solution for 10min, and washing with deionized water;
(5) Dipping the (4) into a 2.5mol/L divalent metal ion Cu (II) solution for crosslinking for 15min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L of metal hydride NaBH 4 In the presence of the inventive film pairs 1.7 x 10 -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution of mol/L. The change in uv-vis absorption intensity was measured at 664 wavelengths. The decolorization efficiency reaches 80.2 percent.
Example 6
(1) Preparing a PTFE microporous membrane: mixing high molecular weight polytetrafluoroethylene dispersion resin Dongye DF206 with lubricating oil according to a ratio (100);
(2) Adding 0.02g Mohr's salt to 10w/v% HEMA solution at room temperature, placing the membrane in the monomer solution, sealing, and degassing with nitrogen for 10min;
(3) At 25 ℃ with gamma radiation at a radiation dose of 8kGy and a radiation dose of 1.5kGyh -1 The membrane is dynamically irradiated at the speed of (1), washed by methanol and deionized water at 40 ℃ in sequence and dried in a vacuum drying oven at 50 ℃;
(4) Sequentially treating the membrane material obtained in the step (3) with 0.5mol/L sodium hydroxide solution and 12wt% ethylene diamine solution for 30min, and cleaning with deionized water;
(5) Dipping the (4) into 1mol/L divalent metal ion Cu (II) solution for crosslinking for 15min, washing with deionized water, and drying at 40 ℃ in vacuum;
at 0.05mol/L metal hydride LiAlH 4 In the presence, 1.7 x 10 pairs of films according to the invention -4 And (3) carrying out catalytic decolorization treatment on the MB dye solution in mol/L. The change in uv-vis absorption intensity was measured at 664 wavelengths. The decolorization efficiency reaches 98.5 percent.
Comparative example 1
The procedure is the same as in example 1, except that different kinds of metal ions are chelated.
The decolorization efficiency of the modified membranes chelating different metal ions on MB was compared, and the results are shown in Table 1:
TABLE 1
| Species of metal ions | Cu ion | Ni ion | Co ion | Is free of |
| MB decolorization efficiency% | 99.42 | 88.59 | 79.56 | 23.40 |
Comparative example 2
The procedure is as in example 1, except that a different hydrophilic monomer is used to modify the membrane.
The decoloring efficiency of the Cu ion-modified membranes prepared by hydrophilic modification with different monomers was compared with MB, and the results are shown in table 2:
TABLE 2
Comparative example 3
The procedure is as in example 1, except that HEMA concentration is different and gamma radiation dose is 10kGy.
TABLE 3
| HEMA concentration w/v% | 2 | 5 | 8 | 10 | 15 |
| MB decolorization efficiency% | 75.3 | 94.05 | 99.42 | 91 | Poor film properties |
Claims (6)
1. A preparation method of a polytetrafluoroethylene membrane for catalytic decoloration of dye is characterized by comprising the following steps: grafting a 2-hydroxyethyl methacrylate solution on the surface of a polytetrafluoroethylene microporous membrane by adopting a gamma-ray irradiation method, then carrying out activation treatment and chelation treatment, and coupling the treated membrane with metal ions to obtain the polytetrafluoroethylene membrane for catalytic dye decolorization;
the activating agent used for the activating treatment is NaOH or Na 2 CO 3 The concentration is 0.5-2mol/L;
the chelating agent used for chelating treatment is polyethyleneimine, ethylenediamine or iminodiacetic acid, the pH of the solution is 10.5, and the mass concentration is 1-15wt%;
the preparation process of the polytetrafluoroethylene microporous membrane comprises the following steps:
mixing high molecular weight polytetrafluoroethylene dispersion resin with lubricating oil, mixing, blank making, extruding, rolling, degreasing, longitudinally stretching, transversely stretching, sintering and curing, and then processing by adopting a composite process;
the extrusion pressure is 10-15MPa under the condition that the compression ratio is 100; the degreasing temperature is 180-240 ℃; the stretching temperature is 180-240 ℃, and the sintering and curing temperature is 350-380 ℃; the sintering time is 8-15min;
the metal ions are bivalent Ni ions, zn ions, co ions or Cu ions, the concentration of the metal ions is 0.5-3mol/L, and the pH =4.1;
the 2-hydroxyethyl methacrylate solution is HEMA solution with different concentrations prepared by adding 0.02g Mohr's salt at room temperature(ii) a The gamma ray irradiation method is to use gamma rays at 25 ℃ to 60 Co is used as a radiation source and at a certain speed of 1.5kGyh -1 And dynamic irradiation at different radiation doses.
2. The method for preparing a polytetrafluoroethylene membrane for the catalytic decolorization of dyes according to claim 1, wherein: the radiation dose of gamma ray is 2-15kGy; the concentration of the 2-hydroxyethyl methacrylate solution is 5-10w/v%.
3. The method for preparing a polytetrafluoroethylene membrane for the catalytic decolorization of dyes according to claim 1, wherein: the SSG of the high molecular weight polytetrafluoroethylene dispersion resin is from 2.145 to 2.155.
4. The method for preparing a polytetrafluoroethylene membrane for the catalytic decolorization of dyes according to claim 1, wherein: the mass ratio of the lubricating oil to the high molecular weight polytetrafluoroethylene dispersion resin is 24-30:100.
5. a method for using a polytetrafluoroethylene membrane prepared by the preparation method according to any one of claims 1 to 4, wherein the polytetrafluoroethylene membrane is prepared by: the catalytic decolorization treatment of the methylene blue dye solution was performed with the teflon membrane in the presence of metal hydride, and then the change in the uv-vis absorption intensity was measured at 664 wavelengths.
6. The method of applying a polytetrafluoroethylene membrane according to claim 5, wherein: the metal hydride is LiAlH 4 、NH 3 BH 3 Or NaBH 4 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011138592.5A CN112604506B (en) | 2020-10-22 | 2020-10-22 | Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011138592.5A CN112604506B (en) | 2020-10-22 | 2020-10-22 | Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112604506A CN112604506A (en) | 2021-04-06 |
| CN112604506B true CN112604506B (en) | 2022-11-25 |
Family
ID=75224387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011138592.5A Active CN112604506B (en) | 2020-10-22 | 2020-10-22 | Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112604506B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2262087A1 (en) * | 1996-07-29 | 1998-02-05 | K.K. Vayu | Modified polymers containing poly(2-hydroxyethyl(meth)acrylate) segment in the molecule |
| CN105504319A (en) * | 2015-12-23 | 2016-04-20 | 厦门理工学院 | Anthraquinone functionalized polyvinylidene fluoride membrane as well as preparation method and application thereof |
| CN105749981A (en) * | 2016-04-01 | 2016-07-13 | 河海大学 | Carbon nanotube/zinc oxide PTFE film and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817707A (en) * | 1996-05-06 | 1998-10-06 | Montell North America Inc. | Process for making propylene graft copolymers using a redox initiator system |
| CN105131329B (en) * | 2015-10-16 | 2018-03-30 | 武汉科技大学 | A kind of preparation method and application of the polyvinyl alcohol crosslinked affinity membrane of macropore chitosan of chelated metal ions |
| CN105664944B (en) * | 2016-02-19 | 2018-03-27 | 中国环境科学研究院 | A kind of Cu catalyst, Preparation method and use based on metal organic frame |
| US11008425B1 (en) * | 2019-11-13 | 2021-05-18 | King Abdulaziz University | Method of producing metal nanoparticle-loaded biopolymer microgels |
-
2020
- 2020-10-22 CN CN202011138592.5A patent/CN112604506B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2262087A1 (en) * | 1996-07-29 | 1998-02-05 | K.K. Vayu | Modified polymers containing poly(2-hydroxyethyl(meth)acrylate) segment in the molecule |
| CN105504319A (en) * | 2015-12-23 | 2016-04-20 | 厦门理工学院 | Anthraquinone functionalized polyvinylidene fluoride membrane as well as preparation method and application thereof |
| CN105749981A (en) * | 2016-04-01 | 2016-07-13 | 河海大学 | Carbon nanotube/zinc oxide PTFE film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112604506A (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Godiya et al. | Silk fibroin/polyethylenimine functional hydrogel for metal ion adsorption and upcycling utilization | |
| EP2274081B1 (en) | Cellulose hydrate membrane, method for the production thereof, and use thereof | |
| US9174194B2 (en) | Adsorbent containing chelating polymer | |
| CN105504166A (en) | Sodium alginate-acrylamide composite aquagel, and preparation method and application thereof | |
| US20090120879A1 (en) | Material For Transfer Of Substance In Liquid Comprising Polymer Blend | |
| CN110882631B (en) | Polyamide composite nanofiltration membrane and preparation method thereof | |
| CN110787644B (en) | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof | |
| Mei et al. | Conjugating hyaluronic acid with porous biomass to construct anti-adhesive sponges for rapid uranium extraction from seawater | |
| CN107824057A (en) | A kind of dissaving polymer modifying polymer film and preparation method and application | |
| Marques et al. | Removal of aqueous copper (II) by using crosslinked chitosan films | |
| CN113101815B (en) | BILP-101 x-based composite membrane and preparation method and application thereof | |
| Liu et al. | One-pot fabrication of antibacterial β-cyclodextrin-based nanoparticles and their superfast, broad-spectrum adsorption towards pollutants | |
| CN110947370A (en) | Preparation method of chitosan-cyclodextrin-based sponge for dye adsorption | |
| CN114108314B (en) | Preparation method and application of fluorescent viscose fiber | |
| CN109627765A (en) | A kind of biodegradation type composite hydrogel and its preparation method and application | |
| CN112604506B (en) | Preparation method of polytetrafluoroethylene membrane for catalytic dye decolorization and application method of polytetrafluoroethylene membrane | |
| Bardajee et al. | Nanoporous hydrogel absorbent based on salep: Swelling behavior and methyl orange adsorption capacity | |
| Perju et al. | Removal of azo dyes from aqueous solutions using chitosan based composite hydrogels | |
| CN114539562B (en) | Green synthesis method of antibacterial super-large porous hydrogel, product thereof and application of antibacterial super-large porous hydrogel in wastewater treatment for degrading various pollutants | |
| Jia et al. | Upgraded β-cyclodextrin-based broad-spectrum adsorbents with enhanced antibacterial property for high-efficient dyeing wastewater remediation | |
| CN108126678B (en) | Renewable carbon nanomaterial coated fiber adsorbent and preparation method thereof | |
| CN113000034B (en) | Preparation method of uranium ion affinity membrane based on natural plant polyphenol composite coating | |
| CN109971043B (en) | Preparation method and application of chitosan-polyvinyl alcohol-iron composite membrane | |
| Tian et al. | Dialdehyde cellulose nanocrystal cross-linked chitosan foam with high adsorption capacity for removal of acid red 134 | |
| CN112844080A (en) | Method for modifying polymer membrane material by electron beam irradiation |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |