CN114367205A - Hydrophobic and oleophobic composite membrane and preparation method and application thereof - Google Patents
Hydrophobic and oleophobic composite membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 141
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000012982 microporous membrane Substances 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 230000033444 hydroxylation Effects 0.000 claims abstract description 9
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims description 36
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052681 coesite Inorganic materials 0.000 claims description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910052682 stishovite Inorganic materials 0.000 claims description 19
- 229910052905 tridymite Inorganic materials 0.000 claims description 19
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 239000001632 sodium acetate Substances 0.000 claims description 17
- 235000017281 sodium acetate Nutrition 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000007785 strong electrolyte Substances 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 238000002715 modification method Methods 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 17
- 230000004907 flux Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 7
- 230000003075 superhydrophobic effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000012025 fluorinating agent Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- 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
-
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- 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
- B01D71/26—Polyalkenes
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- 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
- B01D71/36—Polytetrafluoroethene
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- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Aiming at the problems of the existing super-amphiphobic modification method, the invention discloses a hydrophobic and oleophobic composite membrane and a preparation method and application thereof. The method realizes the functions of pollution resistance and wetting resistance by grafting nano particles on the surface of a membrane to construct a stable micro/nano coarse structure, and comprises the following specific steps: cleaning the hydrophobic microporous membrane with the surface subjected to hydroxylation modification, and soaking the hydrophobic microporous membrane into ether or alkane solution containing acyl chloride for soaking; fully contacting with the nano-particle suspension liquid after soaking; and cleaning and drying to obtain the hydrophobic and oleophobic composite membrane. The hydrophobic and oleophobic composite membrane prepared by the invention has stable structure, can realize double anti-wetting property to water drops and organic liquid drops without low surface energy modification, has simple preparation process and mild reaction condition, can be repeatedly used, and has certain economic feasibility.
Description
Technical Field
The invention relates to a composite membrane and a preparation method thereof, in particular to a hydrophobic and oleophobic composite membrane and a preparation method and application thereof.
Background
Membrane Distillation (MD) technology is a separation technology that combines membrane with distillation. In the membrane distillation process of the non-volatile aqueous solution, theoretically, only water vapor can permeate through membrane pores, and can achieve 100% interception of ions, macromolecules, colloids, cells and other non-volatile substances, so that the water quality similar to distilled water can be directly obtained. Based on the method, the membrane distillation is widely applied to the separation of salt water, and also shows unique advantages in the advanced treatment of organic wastewater of high-concentration degradation-resistant complex systems, such as chemical industry, printing and dyeing, radiation and the like. However, when the membrane distillation is used for treating wastewater with high salt and high organic matter concentration, inorganic pollutants in the wastewater are easy to crystallize and scale on the surface of the membrane, and organic pollutants are adhered and accumulated on the surface, which can cause membrane pollution and wetting, influence the membrane distillation effect and effluent quality, and the membrane surface is continuously subjected to flushing of pressurized wastewater in the treatment process, so that the membrane structure is easily damaged, cannot be reused after cleaning, and greatly increases the membrane distillation treatment cost. Therefore, the improvement of the stability, pollution resistance and anti-wettability of the membrane material is still the key point of the scale application of the membrane distillation technology.
The current research shows that the super-hydrophobic composite membrane prepared by grafting nano particles to form a micro-nano rough surface, preparing a coating with a special regular structure on the membrane, electrospinning nano fibers and the like has a stable structure, and can effectively reduce inorganic salt scaling. However, with the increase of the hydrophobicity of the membrane surface, some hydrophobic oil organic matters are easier to adsorb on the membrane surface, so that the super-hydrophobic structure is disabled. In order to solve the problem, Li and the like find that the super-hydrophobic oleophobic composite membrane obtained by adopting a micro-nano structure and low surface energy modification can make up the defect that the super-hydrophobic membrane is easy to adsorb oil pollutants, but a fluorinating agent used for low surface energy modification is high in price and has certain toxicity, and the membrane prepared by the method has the problem of low membrane distillation flux. In view of the above, there is a need to provide an economical and environment-friendly method for preparing a composite membrane with stable structure and hydrophobic and oleophobic properties without losing membrane distillation flux.
Disclosure of Invention
The invention provides a hydrophobic and oleophobic composite membrane and a preparation method and application thereof, aiming at the problems that the existing superhydrophobic composite membrane is easy to adsorb oil substances, low surface energy modification needs to be carried out, nano particles are unevenly dispersed in the superhydrophobic and oleophobic modification process, the pore structure of a base membrane is influenced, the flux is low, the cost of a fluorinating agent used for low surface energy modification is high, toxicity exists and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a hydrophobic and oleophobic composite membrane, which comprises the following steps:
step 1, carrying out surface hydroxylation treatment on a hydrophobic microporous membrane;
step 3, preparing a nanoparticle suspension;
and 4, immersing the hydrophobic microporous membrane soaked in the step 2 into the suspension liquid obtained in the step 3 to enable the membrane to be fully contacted with the suspension liquid, and then washing and airing the membrane by using water to obtain the hydrophobic and oleophobic composite membrane.
Further, the hydrophobic microporous membrane in the step 1 is a PVDF membrane, a PTFE membrane, a PP membrane, a PVC membrane or a PES membrane.
Further, the specific process of carrying out surface hydroxylation treatment on the hydrophobic microporous membrane comprises the following steps: firstly, putting a hydrophobic microporous membrane into a strong alkaline solution to heat in a water bath to hydroxylate the surface of the hydrophobic microporous membrane, and then washing the residual alkaline solution on the surface of the membrane with water.
Furthermore, the concentration of the strong alkali solution is 2-12 mol/L; the temperature of the water bath heating is 40-90 ℃, and the time is 1-6 h.
Further, the acyl chloride in the step 2 is terephthaloyl chloride or 1,3, 5-benzene trimethyl acyl chloride; the ether is diethyl ether, the alkane is n-hexane, and the mass fraction of the acyl chloride in the ether or alkane solution is 0.1-1%.
Further, the temperature of soaking the hydrophobic microporous membrane subjected to hydroxylation treatment in the step 1 in an ether or alkane solution containing acid chloride is room temperature, and the soaking time is 10-60 min.
Further, the step 3 is a process for preparing the suspension: and dispersing the nano particles in a strong electrolyte solution, and preparing the suspension after ultrasonic treatment.
Further, the nanoparticle is TiO2Or SiO2(ii) a The strong electrolyte is sodium acetate; the TiO is2Or SiO2The mass ratio of the sodium acetate to the sodium acetate is 1: 1-20: 1; the ultrasonic time is 1-5 h, and the concentration of the sodium acetate solution is 0.5-5 mmol/L.
Further, the temperature for fully contacting the membrane with the suspension in the step 4 is room temperature, and the time is 1-5 hours.
The invention also provides a hydrophobic and oleophobic composite membrane prepared based on any one of the methods, wherein the surface of the hydrophobic and oleophobic composite membrane has a uniformly dispersed nano structure, the surface roughness of the composite membrane is 0.06-0.15 mu m, the contact angle of water on the surface of the composite membrane is 130-140 degrees, and the contact angle of oil on the surface of the composite membrane is 110-130 degrees.
The invention also provides application of the hydrophobic and oleophobic composite membrane, which is used for resisting pollution on the surface of the membrane.
Compared with the prior art, the invention has the following advantages:
1. the method prepares the hydrophobic and oleophobic composite membrane with the surface roughness of 0.06-0.15 mu m, the water contact angle of 130-.
2. The invention adopts a surface modification method, so that the nano particles exist only on the surface of the base membrane, and the influence on the porosity and flux of the base membrane is smaller compared with the existing super-amphiphobic modification method (the existing super-amphiphobic modification method causes the nano particles to exist on the surface of the base membrane and to be distributed in membrane pores), and the conclusion can be proved through the measurement results of SEM, FTIR, XPS and porosity. In addition, compared with the existing super-amphiphobic modification method, the pure water flux of the hydrophobic and oleophobic composite membrane prepared by the surface modification method is improved by 20%.
3. The method can solve the defect that the super-hydrophobic membrane is easy to absorb oil pollutants without using a fluorinating agent with high price and certain toxicity for low surface energy modification, avoids the use of the fluorinating agent with high price, has no toxicity brought by the using process of the fluorinating agent, improves the safety performance, simplifies the preparation method, reduces the cost and improves the preparation efficiency of the hydrophobic and oleophobic composite membrane to a great extent.
4. According to the invention, uniformly dispersed nanoparticles are grafted on the surface of the membrane through a coordination covalent bond by adopting the connecting agent acyl chloride, so that the binding force between the nanoparticles and the membrane is greatly enhanced, and the nanoparticles are not easy to fall off. The composite membrane can keep high sewage treatment efficiency for a long time and can be reused after being cleaned, and the cost is saved.
Drawings
FIG. 1 is SiO according to the present invention2SEM picture and EDS analysis picture of/PVDF complex film;
FIG. 2 is SiO according to the present invention2FTIR and XPS profiles for a/PVDF composite membrane;
FIG. 3 shows a PVDF raw film, SiO of the present invention2Porosity diagrams of the PVDF composite membrane and the existing super-amphiphobic composite membrane;
FIG. 4 shows a PVDF raw film and SiO in example 32The flux of 50mg/L HA 24h of the PVDF composite membrane distillation treatment is changed along with the time;
FIG. 5 shows a PVDF raw film and SiO in example 32The flux of 3.5 wt% NaCl treated by membrane distillation of PVDF composite membrane for 24h along with timeMelting;
FIG. 6 shows a PVDF raw film and SiO in example 32The flux of 50mg/L kerosene subjected to membrane distillation treatment by a PVDF composite membrane is changed along with time for 24 hours;
FIG. 7 shows a PVDF raw film and SiO in example 32The flux of 50mg/L SDBS 24h after the PVDF composite membrane distillation treatment is changed along with the time;
FIG. 8 shows SiO in example 32The contact angle of the PVDF composite film changes before and after abrasion.
Detailed Description
The technical solution of the present invention will be specifically and specifically described below with reference to the embodiments of the present invention and the accompanying drawings. It should be noted that variations and modifications can be made by those skilled in the art without departing from the principle of the present invention, and these should also be construed as falling within the scope of the present invention.
Example 1
This example provides a TiO2Preparation method of/PVC composite membrane
Step 1: the PVC membrane is treated by 2mol/L NaOH solution in water bath at 90 ℃ for 1h to hydroxylate the surface, and then the alkaline solution remained on the surface of the membrane is washed clean by ultrapure water.
Step 2: and (3) immediately putting the hydroxylated PVC membrane into a normal hexane solution of TMC (the mass fraction of TMC in the normal hexane solution is 0.1%), and soaking for 60min at room temperature.
And step 3: taking TiO2Dispersed in sodium acetate solution, TiO2The mass ratio of the sodium acetate to the substance is 20:1 (the concentration of the sodium acetate solution is 0.5mmol/L), and the suspension is prepared after 5 hours of ultrasonic treatment.
Example 2
The present embodiment provides a SiO2Preparation method of/PTFE composite membrane
Step 1: the PTFE membrane is treated by a KOH solution of 12mol/L for 6h in a water bath at 40 ℃ to hydroxylate the surface, and then the residual alkali solution on the membrane surface is washed clean by ultrapure water.
Step 2: the hydroxylated PTFE membrane is immersed in an ether solution of terephthaloyl chloride (the mass fraction of the terephthaloyl chloride in the ether solution is 1%) and is immersed for 10min at room temperature.
And step 3: taking SiO2Dispersed in sodium acetate solution, SiO2The mass ratio of the sodium acetate to the substance is 1:1 (the concentration of the sodium acetate solution is 5mmol/L), and the suspension is prepared after ultrasonic treatment for 1 h.
And 4, step 4: modified PTFE membrane surface and SiO2The suspension is fully contacted for 5h at room temperature, and is naturally aired after being washed by ultrapure water to obtain SiO2A PTFE composite membrane.
Example 3
The present embodiment provides a SiO2The preparation method of the PVDF composite membrane comprises the following specific steps:
step 1: the PVDF membrane is treated by 7mol/L NaOH solution for 3h in 70 ℃ water bath to hydroxylate the surface, and then the residual alkaline solution on the membrane surface is washed clean by ultrapure water.
Step 2: the hydroxylated PVDF membrane is immediately placed into a normal hexane solution of TMC (the mass fraction of TMC in the normal hexane solution is 0.5 percent) and soaked for 30min at room temperature.
And step 3: taking SiO2Dispersed in sodium acetate solution, SiO2The mass ratio of the sodium acetate to the substance is 8:1 (the concentration of the sodium acetate solution is 1mmol/L), and the suspension is prepared after 4 hours of ultrasonic treatment.
This example uses surface chemical grafting to form SiO2The nano particles are loaded on the surface of the PVDF membrane, and the SEM picture and the element analysis result of FIG. 1 show that the nano particles uniformly dispersed on the surface of the PVDF membrane can be SiO2. FIG. 2FTIR Structure 1100cm-1The nearby characteristic peak is the change caused by the stretching vibration of the coordinate covalent bond, and the absorption peaks of Si and O elements appearing in the XPS result chart are due to covalent graftingSiO2The presence of Si-OH and Si-O-Si functional groups. FTIR and XPS measurements further demonstrate SiO2Chemically grafted on the surface of the PVDF membrane. Testing of PVDF Primary film, SiO of the invention2The porosity of the PVDF composite membrane and the existing super-amphiphobic composite membrane is shown in FIG. 3, the surface modification method has less influence on the porosity of the base membrane compared with the super-amphiphobic modification method, and the SiO is modified2The pure water flux of the PVDF composite membrane is 20 percent higher than that of the super-amphiphobic composite membrane. Porosity measurements also again demonstrate that the surface modification method only uses SiO2Grafted on the surface of the membrane
Example 4
PVDF raw film and SiO in example 3 were tested2The PVDF composite membrane has membrane distillation pollution resistance. The results of flux changes with time are shown in FIGS. 4 to 7, where 2 membranes were subjected to a 24-hour direct contact membrane distillation experiment using 50mg/L HA, 3.5 wt% NaCl, 50mg/L kerosene and 50mg/L SDBS as feed solutions, respectively. PVDF raw film and SiO2The initial flux difference of the PVDF composite membrane is not large, which shows that the method has small influence on the porosity of the composite membrane. SiO in the whole operation process of 24h membrane distillation of four kinds of feed liquid2The attenuation condition of the water flux produced by the PVDF composite membrane is obviously improved compared with that of the PVDF original membrane, and no obvious pollutant residue is found on the surface of the composite membrane after the experiment is finished, which shows that the SiO composite membrane has the advantages of high water flux attenuation, high water resistance and high water resistance2The PVDF composite membrane has good pollution resistance and wettability resistance.
Example 5
Take the SiO in example 32And carrying out composite membrane stability test on the PVDF composite membrane. Fixing the composite membrane on the inner wall of a 1L beaker by using a double-sided adhesive tape, adding quartz sand with the average particle size of 1mm and tap water, and matching m (quartz sand): m (water) ═ 1: 5. Stirring by adopting an intelligent dispersion stirrer, wherein the set rotating speed is 800r/min, and the abrasion impact time is 4 h. FIG. 8 is a comparison of static contact angles of composite film surfaces before and after abrasion experiments. SiO 22The PVDF composite membrane has a contact angle to water larger than 138 degrees, a contact angle to organic liquid drop ethylene glycol up to 130 degrees, and is characterized by hydrophobic and oleophobic properties, the change of the hydrophobic and oleophobic angle after a wear test is not large, and the composite membrane proves that the nano particles are strong in binding force with the PVDF membrane, not easy to fall off, stable in structure and applicable to membrane distillationCan maintain high sewage treatment efficiency for a long time and can be reused after being cleaned.
Claims (10)
1. A preparation method of a hydrophobic and oleophobic composite membrane is characterized by comprising the following steps:
step 1, carrying out surface hydroxylation treatment on a hydrophobic microporous membrane;
step 2, immersing the hydrophobic microporous membrane subjected to hydroxylation treatment in the step 1 into an ether or alkane solution containing acyl chloride;
step 3, preparing a nanoparticle suspension;
and 4, immersing the hydrophobic microporous membrane soaked in the step 2 into the suspension liquid obtained in the step 3 to enable the membrane to be fully contacted with the suspension liquid, and then washing and airing the membrane by using water to obtain the hydrophobic and oleophobic composite membrane.
2. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 1, characterized in that: the hydrophobic microporous membrane in the step 1 is a PVDF membrane, a PTFE membrane, a PP membrane, a PVC membrane or a PES membrane; the specific process of carrying out surface hydroxylation treatment on the hydrophobic microporous membrane comprises the following steps: firstly, putting a hydrophobic microporous membrane into a strong alkaline solution to heat in a water bath to hydroxylate the surface of the hydrophobic microporous membrane, and then washing the residual alkaline solution on the surface of the membrane with water.
3. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 2, wherein the concentration of the strong alkali solution is 2-12 mol/L; the temperature of the water bath heating is 40-90 ℃, and the time is 1-6 h.
4. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 1, characterized in that: the acyl chloride in the step 2 is terephthaloyl chloride or 1,3, 5-benzene trimethyl acyl chloride; the ether is diethyl ether, the alkane is n-hexane, and the mass fraction of acyl chloride in the ether or alkane solution is 0.1-1%.
5. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 1, characterized in that: and (2) soaking the hydrophobic microporous membrane subjected to hydroxylation treatment in the step (1) in an ether or alkane solution containing acid chloride at room temperature for 10-60 min.
6. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 1, characterized in that: the process for preparing the suspension in the step 3 comprises the following steps: and dispersing the nano particles in a strong electrolyte solution, and preparing the suspension after ultrasonic treatment.
7. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 6, characterized in that: the nano-particles are TiO2Or SiO2(ii) a The strong electrolyte is sodium acetate; the TiO is2Or SiO2The mass ratio of the sodium acetate to the sodium acetate is 1: 1-20: 1; the ultrasonic time is 1-5 h, and the concentration of the sodium acetate solution is 0.5-5 mmol/L.
8. The preparation method of the hydrophobic and oleophobic composite membrane according to claim 1, characterized in that: and in the step 4, the temperature for fully contacting the membrane with the suspension is room temperature, and the time is 1-5 h.
9. A hydrophobic and oleophobic composite membrane prepared based on the method of any one of claims 1-8, characterized in that: the surface of the hydrophobic and oleophobic composite membrane has a uniformly dispersed nano structure, the surface roughness of the composite membrane is 0.06-0.15 mu m, the contact angle of water on the surface of the composite membrane is 130-ion 140 degrees, and the contact angle of oil on the surface of the composite membrane is 110-ion 130 degrees.
10. The application of the hydrophobic and oleophobic composite membrane of any one of claims 1-9, characterized in that: is used for resisting pollution on the surface of the membrane.
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