CN114367205B - Hydrophobic oleophobic composite membrane and preparation method and application thereof - Google Patents
Hydrophobic oleophobic composite membrane and preparation method and application thereof Download PDFInfo
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- CN114367205B CN114367205B CN202210106974.2A CN202210106974A CN114367205B CN 114367205 B CN114367205 B CN 114367205B CN 202210106974 A CN202210106974 A CN 202210106974A CN 114367205 B CN114367205 B CN 114367205B
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- 239000012528 membrane Substances 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 25
- 239000012982 microporous membrane Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 12
- 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 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002033 PVDF binder Substances 0.000 claims description 37
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 20
- 239000001632 sodium acetate Substances 0.000 claims description 20
- 235000017281 sodium acetate Nutrition 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 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
- 230000003746 surface roughness Effects 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 238000002715 modification method Methods 0.000 abstract description 7
- 238000009736 wetting Methods 0.000 abstract description 3
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 19
- 230000004907 flux Effects 0.000 description 13
- 230000003075 superhydrophobic effect Effects 0.000 description 7
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 6
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012025 fluorinating agent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000011148 porous material Substances 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
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010041 electrostatic spinning 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
- 125000000524 functional group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 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
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- 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 nanometer particles are grafted on the surface of the membrane to form a stable micro/nanometer coarse structure, so that the functions of pollution resistance and wetting resistance are realized, and the specific steps are as follows: washing the hydrophobic microporous membrane with the surface subjected to hydroxylation modification, and immersing the membrane in ether or alkane solution containing acyl chloride; fully contacting the soaked nano particles with nano particle suspension; 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 infiltration resistance to water drops and organic liquid drops without low surface energy modification, has simple preparation process and mild reaction conditions, 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 a membrane with distillation. In the membrane distillation process of the non-volatile aqueous solution, only water vapor can pass through the membrane pores theoretically, and can achieve 100% interception of ions, macromolecules, colloid, 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 brine separation, and has unique advantages in advanced treatment of chemical industry, printing and dyeing, radiation and other organic wastewater of a high-concentration difficult-degradation complex system. However, when the membrane distillation is used for treating the wastewater with high salt and high organic 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 the effluent quality, the membrane surface is continuously washed by the pressurized wastewater in the treatment process, the membrane structure is easy to be damaged, the membrane cannot be repeatedly used after being cleaned, and the membrane distillation treatment cost is greatly increased. Therefore, improving the stability and anti-pollution and anti-wetting properties of the membrane material is still an important point for the large-scale application of membrane distillation technology.
The current research shows that the super-hydrophobic composite membrane prepared by grafting nano particles to construct micro-nano rough surfaces, preparing a coating with a special regular structure on the membrane, electrostatic spinning nano fibers and other modes has a stable structure, and can effectively reduce inorganic salt scaling. However, as the hydrophobicity of the membrane surface is improved, some hydrophobic oil organic matters are more easily adsorbed on the membrane surface, so that the superhydrophobic structure is disabled. In order to solve the problem, li and the like find that the super-hydrophobic oleophobic composite membrane obtained by adopting the structure of the micro-nano structure and the modification of low surface energy can make up for the defect that the super-hydrophobic membrane is easy to adsorb oil pollutants, but the fluorinating agent used for the modification of low surface energy has higher price and certain toxicity, and the membrane prepared by the method has the problem of low membrane distillation flux. In view of the above, it is necessary to provide an economical and environment-friendly method for preparing a composite membrane with stable structure and both water and oil repellency without losing membrane distillation flux.
Disclosure of Invention
Aiming at the problems that the prior superhydrophobic composite membrane is easy to adsorb oil substances and needs to be subjected to low surface energy modification, nano particles are unevenly dispersed in the superhydrophobic oleophobic modification process, the pore structure of a base membrane is affected, the flux is low, the cost of a fluorinating agent used for modifying the low surface energy is high, toxicity exists and the like, the invention provides the hydrophobic oleophobic composite membrane and a preparation method and application thereof.
In order to achieve the above purpose, the present 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 2, immersing the hydrophobic microporous membrane subjected to hydroxylation treatment in the step 1 into ether or alkane solution containing acyl chloride;
step 3, preparing nanoparticle suspension;
and 4, immersing the hydrophobic microporous membrane immersed in the step 2 into the suspension in the step 3, enabling the membrane to be in full contact with the suspension, and then washing with water and airing to obtain the hydrophobic 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 is as follows: firstly, placing the hydrophobic microporous membrane in a strong alkali solution, heating the microporous membrane in a water bath to hydroxylate the surface of the microporous membrane, and then washing the residual alkali solution on the surface of the membrane with water.
Further, the concentration of the strong alkali solution is 2mol/L to 12mol/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 ether or alkane solution containing acyl chloride is room temperature, and the soaking time is 10-60 min.
Further, the suspension preparation process in the step 3 is as follows: dispersing nano particles in a strong electrolyte solution, and preparing the suspension after ultrasonic treatment.
Further, the nanoparticle is TiO 2 Or SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The strong electrolyte is sodium acetate; the TiO 2 Or SiO 2 The mass ratio of the sodium acetate to the sodium acetate is 1:1-20:1; the ultrasonic time is 1 h-5 h, and the concentration of the sodium acetate solution is 0.5-5mmol/L.
Further, the temperature at which the membrane is sufficiently contacted with the suspension in the step 4 is room temperature for 1 to 5 hours.
The invention also provides a hydrophobic and oleophobic composite membrane prepared based on any one of the above methods, wherein the surface of the hydrophobic and oleophobic composite membrane is provided with 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 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 of the invention prepares the hydrophobic oleophobic composite membrane with the surface roughness of 0.06-0.15 mu m, the water contact angle of 130-140 degrees and the oil contact angle of 110-130 degrees by forming the uniformly dispersed nano structure on the surface of the membrane through chemical grafting, realizes the dual infiltration resistance to water drops and organic liquid drops, and has stable wettability resistance and pollution resistance when being applied to membrane distillation.
2. Compared with the existing super-amphiphobic modification method, the method has less influence on the porosity and flux of the base film (the existing super-amphiphobic modification method ensures that the nano particles are not only on the surface of the base film but also distributed in film holes), and the conclusion can be proved by SEM, FTIR, XPS and the measurement result of the 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 adsorb oil pollutants without using a fluorinating agent with high price and certain toxicity to carry out low surface energy modification, avoids the use of the fluorinating agent with high price, improves the safety performance, simplifies the preparation method, reduces the cost and greatly improves the preparation efficiency of the hydrophobic and oleophobic composite membrane.
4. According to the invention, the uniformly dispersed nano particles are grafted on the surface of the membrane through the coordinate covalent bond by adopting the connector acyl chloride, so that the binding force of the nano particles and the membrane is greatly enhanced, and the nano particles are not easy to fall off. The composite membrane can keep higher sewage treatment efficiency for a long time and can be reused after being cleaned, so that the cost is saved.
Drawings
FIG. 1 is a diagram of the SiO of the present invention 2 SEM and EDS analysis of PVDF composite membrane;
FIG. 2 is a diagram of the SiO of the present invention 2 FTIR and XPS images of PVDF composite membrane;
FIG. 3 shows a PVDF precursor film, siO according to the invention 2 A porosity map of the PVDF composite membrane and the existing super-amphiphobic composite membrane;
FIG. 4 shows a PVDF raw film and SiO in example 3 2 The flux of 50mg/L HA for 24 hours of PVDF composite membrane distillation treatment changes with time;
FIG. 5 shows a PVDF raw film and SiO in example 3 2 The flux of the PVDF composite membrane distillation treatment 3.5wt% NaCl for 24 hours changes with time;
FIG. 6 shows PVDF raw film and solidSiO in example 3 2 The flux of 50mg/L kerosene for 24 hours after the PVDF composite membrane distillation treatment varies with time;
FIG. 7 shows a PVDF raw film and SiO in example 3 2 The flux of 50mg/L SDBS 24h is changed with time after the PVDF composite membrane distillation treatment;
FIG. 8 is SiO in example 3 2 Contact angle changes before and after abrasion of PVDF composite membrane.
Detailed Description
The technical scheme of the invention is specifically and specifically described below with reference to the embodiment of the invention and the attached drawings. It should be noted that variations and modifications can be made by those skilled in the art without departing from the principles of the present invention, which are also considered to be within the scope of the present invention.
Example 1
The present embodiment provides a TiO 2 Preparation method of PVC composite film
Step 1: the PVC film was treated with 2mol/L NaOH solution at 90℃in a water bath for 1h to hydroxylate the surface, and then the residual alkali solution on the film surface was rinsed clean with ultrapure water.
Step 2: the hydroxylated PVC film is then placed in TMC in n-hexane (TMC in 0.1% by mass) and immersed for 60min at room temperature.
Step 3: tiO is taken 2 Dispersed in sodium acetate solution, tiO 2 The mass ratio of the sodium acetate to the sodium acetate is 20:1 (the concentration of the sodium acetate solution is 0.5 mmol/L), and the suspension is prepared after 5 hours of ultrasonic treatment.
Step 4, modifying the surface of the PVC film and TiO 2 The suspension is fully contacted for 1h at room temperature, and is naturally dried after being washed by ultrapure water to obtain TiO 2 PVC composite film.
Example 2
The present embodiment provides a SiO 2 Preparation method of PTFE composite film
Step 1: PTFE film was treated with 12mol/L KOH solution at 40℃in a water bath for 6 hours to hydroxylate the surface, and then the residual alkali solution on the film surface was rinsed with ultrapure water.
Step 2: the hydroxylated PTFE membrane was immersed in an ether solution of terephthaloyl chloride (the mass fraction of terephthaloyl chloride in the ether solution is 1%), and immersed at room temperature for 10 minutes.
Step 3: taking SiO 2 Dispersing in sodium acetate solution, siO 2 The mass ratio of the sodium acetate to the sodium acetate is 1:1 (the concentration of the sodium acetate solution is 5 mmol/L), and the suspension is prepared after 1h of ultrasonic treatment.
Step 4: modified PTFE film surface and SiO 2 The suspension is fully contacted for 5 hours at room temperature, and naturally dried after being washed by ultrapure water to obtain SiO 2 PTFE composite membrane.
Example 3
The present embodiment provides a SiO 2 The preparation method of the PVDF composite film comprises the following specific steps:
step 1: the PVDF membrane was treated with 7mol/L NaOH solution at 70℃in a water bath for 3 hours to hydroxylate the surface, and then the residual alkali solution on the membrane surface was rinsed with ultrapure water.
Step 2: the hydroxylated PVDF membrane was then placed in TMC in n-hexane (TMC in 0.5% by mass) and immersed for 30min at room temperature.
Step 3: taking SiO 2 Dispersing in sodium acetate solution, siO 2 The mass ratio of the sodium acetate to the sodium acetate is 8:1 (the concentration of the sodium acetate solution is 1 mmol/L), and the suspension is prepared after 4 hours of ultrasonic treatment.
Step 4, the surface of the PVDF film after modification and SiO 2 The suspension is fully contacted for 3 hours at room temperature, and naturally dried after being washed by ultrapure water to obtain SiO 2 PVDF composite membrane.
In this example, siO was grafted chemically to the surface 2 The nano particles which are uniformly dispersed on the surface of the PVDF film can be SiO as shown in the SEM image of figure 1 and the result of element analysis 2 . FIG. 2FTIR Structure 1100cm -1 The characteristic peaks in the vicinity are changes due to stretching vibration of coordinate covalent bonds, and the absorption peaks of Si and O elements appearing in the XPS result diagram are due to covalently grafted SiO 2 The presence of Si-OH and Si-O-Si functional groups. FTI (optical fiber interface)The measurement results of R and XPS further demonstrate SiO 2 Chemically grafted to the PVDF membrane surface. Testing PVDF raw film, siO of the present invention 2 The results of the porosity of the PVDF composite membrane and the prior super-amphiphobic composite membrane are shown in figure 3, compared with the super-amphiphobic modification, the surface modification method has less influence on the porosity of the base membrane, and the SiO 2 The pure water flux of the PVDF composite membrane is 20% higher than that of the super-amphiphobic composite membrane. The porosity measurement again demonstrates that the surface modification method only works with SiO 2 Grafted on the surface of the film
Example 4
Testing of PVDF raw film and SiO in example 3 2 Membrane distillation anti-fouling performance of PVDF composite membrane. The results of 24h direct contact membrane distillation experiments were carried out on 2 membranes using 50mg/L HA, 3.5wt% NaCl, 50mg/L kerosene and 50mg/L SDBS as feed solutions, respectively, with the flux varying with time as shown in FIGS. 4 to 7. PVDF raw film and SiO 2 The initial flux of the PVDF composite membrane is not greatly different, which shows that the method has little influence on the porosity of the composite membrane. In the whole operation process of 24h membrane distillation of four feed liquids, siO 2 The water flux attenuation of 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 SiO 2 The PVDF composite film has good pollution resistance and wettability resistance.
Example 5
The SiO of example 3 was taken 2 The PVDF composite membrane was subjected to a composite membrane stability test. Fixing the composite film on the inner wall of a 1L beaker by using double faced adhesive tape, adding quartz sand with the average grain diameter of 1mm and tap water, wherein the proportion is m (quartz sand): m (water) =1:5. Stirring by adopting an intelligent dispersing stirrer, setting the rotating speed to 800r/min and the abrasion impact time to 4h. Fig. 8 is a comparison of static contact angles of composite film surfaces before and after abrasion experiments. SiO (SiO) 2 The contact angle of the PVDF composite membrane to water is larger than 138 degrees, the contact angle of the PVDF composite membrane to the glycol of an organic liquid drop can reach 130 degrees, the hydrophobic and oleophobic angles are not changed greatly after abrasion experiments, the bonding force of the nano particles and the PVDF film is proved to be strong, the PVDF composite membrane is not easy to fall off, the composite membrane has stable structure, the composite membrane can keep higher sewage treatment efficiency for a long time when being applied to membrane distillation and can be heavy after being cleanedAnd (5) reusing.
Claims (8)
1. The preparation method of the hydrophobic and oleophobic composite membrane is characterized by comprising the following steps of:
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 ether or alkane solution containing acyl chloride;
step 3, preparing nanoparticle suspension;
step 4, immersing the hydrophobic microporous membrane immersed in the step 2 into the suspension liquid in the step 3 to enable the membrane to be fully contacted with the suspension liquid, and then washing and airing the membrane with water to obtain the hydrophobic oleophobic composite membrane;
the specific process of carrying out surface hydroxylation treatment on the hydrophobic microporous membrane is as follows: firstly, placing a hydrophobic microporous membrane into a strong alkali solution, heating the surface of the microporous membrane in a water bath to enable the surface of the microporous membrane to be hydroxylated, and then washing the residual alkali solution on the surface of the membrane with water;
the suspension preparation process in the step 3 is as follows: dispersing nano particles in a strong electrolyte solution, and preparing the suspension after ultrasonic treatment;
the nano particles are TiO 2 Or SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The strong electrolyte is sodium acetate; the TiO 2 Or SiO 2 The 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 0.5-5mmol/L;
the acyl chloride in the step 2 is terephthaloyl chloride or 1,3, 5-benzene trimethyl acyl chloride.
2. The method for preparing the hydrophobic and oleophobic composite membrane according to claim 1, wherein: 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.
3. The method for preparing a 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 method for preparing the hydrophobic and oleophobic composite membrane according to claim 1, wherein: the ether in the step 2 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%.
5. The method for preparing the hydrophobic and oleophobic composite membrane according to claim 1, wherein: the temperature of soaking the hydrophobic microporous membrane subjected to hydroxylation treatment in ether or alkane solution containing acyl chloride is room temperature, and the soaking time is 10-60 min.
6. The method for preparing the hydrophobic and oleophobic composite membrane according to claim 1, wherein: and (3) the temperature of the film fully contacted with the suspension in the step (4) is room temperature, and the time is 1-5 h.
7. A hydrophobic oleophobic composite membrane prepared based on the method of any one of claims 1-6, characterized in that: the surface of the hydrophobic oleophobic composite membrane is provided with 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.
8. Use of the hydrophobic oleophobic composite membrane according to claim 7, wherein: used for anti-pollution of the surface of the film.
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