CN111978856B - Super-hydrophilic/underwater super-oleophobic copper mesh, preparation method thereof and application of copper mesh in separation of emulsified oil-in-water - Google Patents
Super-hydrophilic/underwater super-oleophobic copper mesh, preparation method thereof and application of copper mesh in separation of emulsified oil-in-water Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000010949 copper Substances 0.000 title claims abstract description 158
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 158
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000000926 separation method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003618 dip coating Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 29
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 32
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 29
- 230000004907 flux Effects 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229960003638 dopamine Drugs 0.000 claims description 15
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001369 Brass Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000010951 brass Substances 0.000 claims description 4
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- 239000002131 composite material Substances 0.000 abstract 1
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- 238000004945 emulsification Methods 0.000 abstract 1
- 229920001690 polydopamine Polymers 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 53
- 239000000463 material Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 16
- 238000002791 soaking Methods 0.000 description 13
- 230000003075 superhydrophobic effect Effects 0.000 description 9
- LWXNQQIVUUSCSL-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol trihydrochloride Chemical compound Cl.Cl.Cl.OCC(N)(CO)CO LWXNQQIVUUSCSL-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 235000019476 oil-water mixture Nutrition 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000012466 permeate Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 238000001612 separation test Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 230000009545 invasion Effects 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
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- 229910052625 palygorskite Inorganic materials 0.000 description 1
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- 238000001259 photo etching Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/10—Thickening liquid suspensions by filtration with stationary filtering elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention discloses a super-hydrophilic/underwater super-oleophobic copper mesh, a preparation method thereof and application of the copper mesh in oil-in-water separation and emulsification. Firstly, ultrasonically cleaning a copper mesh by using acetone, ethanol and deionized water respectively, and drying; preparing a composite dip-coating solution of polydopamine, polyethyleneimine and aminated carbon nanotubes; immersing the whole pre-cleaned copper mesh into the dip-coating liquid; then putting the whole dip-coating liquid system with the copper mesh on a shaking table for horizontal-rotary coating operation; and taking out the copper mesh, cleaning the copper mesh with deionized water, and drying the copper mesh. The method has the advantages of simple preparation technology, low raw material consumption, mild reaction conditions and no harm to the environment, and the obtained super-hydrophilic/underwater super-oleophobic copper mesh has the advantages of physical wear resistance and chemical corrosion resistance, and has the function of quickly and efficiently separating various emulsified oil-in-water such as toluene, petroleum ether, isooctane, 1, 2-dichloroethane and the like.
Description
Technical Field
The invention relates to a super-hydrophilic/underwater super-oleophobic material, in particular to a preparation method of a super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water, belonging to the fields of chemical engineering and super-hydrophilic materials.
Background
The frequent occurrence of oil leakage accidents and the increase in the discharge of oily wastewater has undoubtedly posed a serious threat to both the ecological environment and human health over the past decade. Therefore, it is important to develop an advanced material for treating these oily wastewater, especially a highly stable surfactant-containing emulsified oil water. With the rapid development of special wetting property materials, the super-hydrophilic/underwater super-oleophobic material with the advantages of rapidness, high efficiency, low energy consumption and environmental protection becomes a hot door material for oil-water separation.
Superhydrophilic/underwater superoleophobic materials generally refer to a class of materials that have a contact angle for water in air of less than 5 and can be spread out rapidly across a surface while having an oil contact angle under water of greater than 150. The material has strong affinity to water and good repulsion to oil under water, so the wetting material has certain application prospect in the aspects of oil-water separation, pollution resistance, water transportation and the like.
The Chinese invention patent application CN109758789A discloses a method for preparing a super-hydrophilic/underwater super-oleophobic aluminum net by sequentially adopting a photoetching method and an electrochemical method. The Chinese patent application CN109821425A discloses a method for modifying a super-hydrophilic and super-oleophobic metal net by etching and illumination. The method successfully prepares the super-hydrophilic metal filter screen material, but can only be applied to separating immiscible oil-water mixtures, and cannot complete the separation of emulsified oil-water mixtures. The reason is that the two technologies only carry out wettability regulation, and the large pore diameter of the metal mesh material is neglected, so that small-size oil drops easily permeate from the large pores of the metal mesh together with the water phase, and finally, the emulsified oil-water mixture cannot be separated. It follows that the pore size of the separation material is important to be able to separate a wide range of sizes of emulsified oil and water mixtures.
Document 1(Xinjuan Zeng et al, A cross-linked modified mesh pre)A coated by brush-coating method for oil-in-water emulsions separation, Materials Chemistry and Physics) reported that an ultra-hydrophilic/underwater ultra-hydrophobic type stainless steel net prepared by brushing polyvinyl alcohol/glutaraldehyde/attapulgite/titanium dioxide showed a satisfactory effect of 97.5% in terms of small pore diameter, but exhibited a flux of less than 50 L.m.-2·h-1Ultra low flux of (2). Document 2(Yue Chen et al, A Co)3O4Nano-needle mesh for high-density effect, high-flux emission separation, Journal of Materials Chemistry A.) reported the deposition of nanosized needles of Co on stainless steel mesh3O4The prepared super-hydrophilic/underwater super-hydrophobic type stainless steel net has the separation efficiency of more than 99 percent, but the permeation flux is only 160--2·h-1. Document 3(Xinyu Chen et al, Durable and stable MnMoO)4-coated copper mesh for highly efficient oil-in-water emulsion separation and photodegradation of organic contaminants,ACS Applied Materials&Interfaces.) reported that a super-hydrophilic/underwater super-hydrophobic type copper mesh prepared by coating manganese molybdate had a separation efficiency as high as 99.9% at most, but the permeation flux showed less than 200 L.m-2·h-1. In the three prior arts, when pore size is controlled, the pore size is excessively reduced to increase the retention rate of the emulsified oil-water mixture, so that the permeation flux is correspondingly reduced. Moreover, the ultra-hydrophilic/underwater ultra-oleophobic materials that rely solely on "size sieving" to separate emulsions are limited in their flux due to the limited pore size. If a large pore size is maintained, the separation efficiency is greatly affected. Therefore, it is important to develop a super hydrophilic/super oleophobic underwater material with high efficiency and high flux.
Disclosure of Invention
The invention aims to solve the contradiction between separation efficiency and permeation flux of the super-hydrophilic/underwater super-oleophobic copper mesh during the separation of emulsified oil and water, and provides a method for separating emulsified oil from water, which has the advantages of low raw material consumption, mild reaction conditions and good compatibilityHas no environmental pollution and good durability, and has penetration flux of 2978.4-3949.2 L.m-2·h-1The high-efficiency, high-flux and high-efficiency super-hydrophilic/underwater super-oleophobic copper mesh with high flux and separation efficiency reaching 99.12-99.85 percent and the preparation method thereof.
The invention also aims to provide application of the super-hydrophilic/underwater super-oleophobic copper mesh in separation of emulsified oil-in-water.
In order to enhance the durability of the super-hydrophilic/underwater super-oleophobic copper net and ensure that the performance of the copper net cannot be reduced due to certain physical and chemical wear, the super-hydrophilic/underwater super-oleophobic copper net is prepared by directly immersing the copper net into a solution for reaction; meanwhile, the aperture regulation and control of the invention utilizes the adhesion principle of mussel bionic chemistry, the durability and the aperture regulation and control are combined with each other, clusters which are connected with each other by chemical bonds are firmly filled in square holes of a copper net, the durability is excellent, the surface charge of the copper net can be recovered by simple acid treatment, and the circulating separation performance is stronger, the super-hydrophilic/underwater super-oleophobic copper net has proper aperture and rich positive charges, the high-efficiency and high-flux separation of emulsified oil-in-water can be ensured, the separation efficiency can be more than 99.5 percent, and the permeation flux can be more than 2900 L.m-2·h-1Therefore, the method has a very strong application prospect.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water comprises the following steps:
1) cleaning and drying the 200-plus-400-mesh copper net;
2) purifying multi-walled carbon nanotubes (MWCNTs) by using dilute hydrochloric acid, then performing oxidation treatment by using mixed acid consisting of nitric acid and sulfuric acid at the temperature of 60-180 ℃ to modify the MWCNTs-COOH (carboxylated carbon nanotubes), and adding water to prepare a carboxylated carbon nanotube aqueous solution; adding Polyethyleneimine (PEI), treating at 20-30 deg.C for 4-8h, and modifying into aminated carbon nanotube (MWCNTs-NH)2)；
3) The aminated carbon nano tube (MWCNTs-NH) obtained in the step 2)2) Ultrasonically mixing the solution with dopamine, Tris (hydroxymethyl) aminomethane (Tris-HCl) and Polyethyleneimine (PEI) at room temperature to prepare dip-coating solution;
4) immersing the copper mesh obtained in the step 1) into the dip-coating liquid obtained in the step 3), then carrying out horizontal-rotary oscillation on a shaking table for 6-10h, taking out, washing with deionized water, and drying to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
To further achieve the object of the present invention, preferably, in step 1), the copper mesh includes one of a red copper mesh, a brass mesh and a phosphor copper mesh; the washing is ultrasonic cleaning for 10-15min by acetone, absolute ethyl alcohol and deionized water respectively; the blow-drying is performed by using nitrogen.
Preferably, in the step 2), the diameter of the multi-wall carbon nano tube is 20-40nm, the length of the multi-wall carbon nano tube is 10-15 μm, and the purity of the multi-wall carbon nano tube is more than 97%; the concentration of the dilute hydrochloric acid is 0.1-10mol/L, and the purification time of the dilute hydrochloric acid is 6-12 h; the mass ratio of nitric acid to sulfuric acid in the mixed acid is 1:2-1: 4; the time of the oxidation treatment is 6-8 h.
Preferably, the molecular weight of the PEI described in steps 2) and 3) is 600-10000; the mass ratio of the polyethyleneimine to the carboxylated carbon nanotube in the step 2) is 150-100: 1; adding 15-25g of polyethyleneimine per liter of carboxylated carbon nanotube aqueous solution.
Preferably, in the preparation process of the dip-coating liquid in the step 3), Tris (Tris-HCl), dopamine, PEI and deionized water are added firstly, ultrasonic treatment is carried out for 5-10min, and then MWCNTs-NH is added2And continuing to perform ultrasonic treatment for 5-10 min.
Preferably, the concentration of the tris in the dip-coating solution in the step 3) is 0.55-0.75g/L, the concentration of the dopamine is 0.20-0.30g/L, the concentration of the polyethyleneimine is 0.75-0.85g/L, and the concentration of the aminated carbon nanotube is 0.15-0.25 g/L.
Preferably, the rotating speed of the shaker in the horizontal-rotary coating operation of step 4) is 120-130rpm, and the dipping temperature is 20-30 ℃; the drying is carried out in an oven, the drying temperature is 100-120 ℃, and the drying time is 10-30 min.
A super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water is prepared by the preparation method; after the copper mesh is filled with clusters, a curled aminated carbon nano tube with a nano-micron scale is formed in a pore channel, the copper mesh contains rich amino groups, the affinity of the copper mesh with water can be enhanced, positive charges can be provided, the water contact angle in the air is equal to 0 degree, the underwater oil contact angle is 158.9-164.7 degrees, and the copper mesh has super-hydrophilicity/super-oleophobicity in the air and can be applied to separation of emulsified oil-in-water.
The super-hydrophilic/underwater super-oleophobic copper net for separating the emulsified oil-in-water is used for separating oily sewage in daily life or industrial production with high efficiency and high flux.
A preparation mechanism of a super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water comprises the following steps:
1. the forming mechanism of the aminated carbon nanotube cluster with the nanometer and micrometer level is as follows: dopamine firstly undergoes an oxidative autopolymerization process to generate an intermediate with a quinoid structure; then, the reaction product and polyethyleneimine are subjected to chemical reaction, and two corresponding products are generated through Schiff base reaction and Michael addition reaction respectively; the carbonyl of the first Schiff base reaction product is chemically bonded with the amino of the aminated carbon nanotube, and the amino of the second Michael addition reaction product is chemically bonded with the carboxyl of the aminated carbon nanotube. The specific reaction equation is as follows:
2. the aminated carbon nanotube clusters with the micro-nano level are firmly filled in the square holes of the copper mesh by means of chemical bonding, so that the copper mesh presents submicron pore channels, and high permeation flux can be ensured; meanwhile, the copper mesh has a cluster layer with rich amino groups, so that the surface energy of the copper mesh is improved, and the copper mesh has super-hydrophilicity; these amine groups also carry a large positive charge. Therefore, the copper mesh has high separation efficiency and high permeation flux to the emulsified oil-in-water stabilized by the anionic surfactant under the synergistic demulsification of the combination of the super-hydrophilic wetting property and the 'size sieving' effect exerted by proper submicron pore diameter and the 'charge shielding' effect generated by a large amount of positive charges.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the super-hydrophilic/underwater super-oleophobic copper mesh obtained by the method has high water affinity and high repellency to oil phase underwater.
2. The super-hydrophilic/underwater super-oleophobic copper mesh obtained by the invention can realize high-efficiency and high-flux separation of emulsified oil-in-water. Under the synergistic demulsification of the 'size sieving' effect of submicron pore channels and the 'charge shielding' effect of positive charges of the copper mesh, the separation efficiency of the copper mesh on emulsified oil-in-water stabilized by four anionic surfactants can be more than 99.5 percent, and the permeation flux can be more than 2900 L.m-2·h-1The above.
3. The super-hydrophilic/underwater super-oleophobic copper mesh obtained by the invention has excellent durability. After the treatment means of 50 times of abrasive paper abrasion, 24 hours of heat treatment, 24 hours of cold treatment, 24 hours of acid solution soaking, 24 hours of alkali solution soaking, 24 hours of salt solution soaking and the like, the contact angle of the copper net to deionized water in the air is always kept at 0 degree, and the contact angle of the copper net to isooctane under water is still between 150.7 and 163.3 degrees.
4. The super-hydrophilic/underwater super-oleophobic copper mesh prepared by the method is simple to prepare, low in raw material consumption, mild in reaction condition and harmless to the environment.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a 300 mesh phosphor-copper mesh cleaned only in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the superhydrophilic/underwater superhydrophobic and oleophobic mesh prepared in example 1 of the invention;
FIG. 3 is a partially enlarged Scanning Electron Microscope (SEM) image of the superhydrophilic/underwater superhydrophobic screen prepared in example 1 of the invention;
FIG. 4 is a photograph of the contact angle of the superhydrophilic/underwater superhydrophobic-oleophobic mesh prepared in example 1 of the invention to deionized water;
FIG. 5 is a photograph of the underwater contact angle of the superhydrophilic/underwater superhydrophobic and oleophobic mesh prepared in example 1 of the present invention to n-hexane under water;
FIG. 6 is a photograph of the contact angle of the superhydrophilic/superhydrophobic and oleophobic underwater net prepared in example 1 of the present invention with isooctane under water;
FIG. 7 is a photograph of the contact angle of the superhydrophilic/underwater superhydrophobic and oleophobic net of example 1 of the invention with petroleum ether underwater;
FIG. 8 is a photograph of the contact angle of the superhydrophilic/superhydrophobic and oleophobic underwater net of example 1 of the invention with toluene underwater;
FIG. 9 is a photograph of the contact angle of the superhydrophilic/underwater superhydrophobic-oleophobic mesh prepared in example 1 of the invention with 1, 2-dichloroethane under water;
FIG. 10 is a photograph of the contact angle of the superhydrophilic/underwater superhydrophobic and oleophobic net of example 1 of the invention with trichloroethane under water;
FIG. 11 is an X-ray photoelectron spectrum of example 1 of the present invention;
FIG. 12 is a zeta potential map of example 1 of the present invention;
FIG. 13 is a Scanning Electron Microscope (SEM) image of a copper mesh of a control group prepared in example 8 of the present invention;
FIG. 14 is a Scanning Electron Microscope (SEM) image of a copper mesh of a control group prepared in example 9 of the invention;
FIG. 15 is a zeta potential map of examples 8 and 9 of the present invention;
FIG. 16 is an optical micrograph and an oil droplet size distribution of a toluene-in-water emulsion before and after separation, prepared in example 1 of the present invention;
FIG. 17 is an optical micrograph and an oil droplet size distribution of a petroleum ether-in-water emulsion before and after separation, prepared in example 1 of the present invention;
FIG. 18 is an optical micrograph and an oil droplet size distribution of an isooctane-in-water emulsion before and after separation, prepared according to example 1 of the present invention;
FIG. 19 is an optical micrograph and a distribution of oil droplet size of a 1, 2-dichloroethane-in-water emulsion before and after separation prepared in example 1 of the present invention.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples and the accompanying drawings, but the scope of the present invention is not limited to the examples.
Example 1
Ultrasonically cleaning a 400-mesh phosphorus-copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the phosphorus-copper net with nitrogen for later use; preparing 0.60g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.25g/L dopamine and 0.78g/L PEI, ultrasonically oscillating in water bath for 5min, and adding 0.2g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 5min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 120rpm, dip-coating time to be 6h, and dip-coating temperature to be 25 ℃; taking out and drying in an oven at 100 ℃ for 10min to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a 400 mesh phosphor copper mesh cleaned only according to the present invention. As can be seen in FIG. 1, the pore size of the unmodified copper mesh is large, and the range is 30-50 μm.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water prepared in example 1. As shown in fig. 2, the copper mesh prepared in this example 1 is filled with fine clusters, and the pore diameter ranges from 0.01 μm to 0.58 μm. FIG. 3 shows that the clusters are structures formed by disordered winding after the aminated carbon nanotubes react with dopamine and PEI, have the size of nanometer level and high surface energy and positive charges brought by abundant amino groups, and finally the super-hydrophilic/underwater super-oleophobic copper net for separating emulsified oil-in-water is prepared.
Fig. 4 to 10 are contact angle photographs of the superhydrophilic/underwater superoleophobic copper mesh for separating emulsified oil-in-water prepared in this example 1 on deionized water in air and on n-hexane, iso-octane, petroleum ether, toluene, 1, 2-dichloroethane and chloroform in water, respectively, and it can be seen from the photographs in fig. 4 to 10 that the contact angle of deionized water in air on the surface of the copper mesh is 0 °, the contact angle of underwater n-hexane on the surface of the copper mesh is 164 °, the contact angle of iso-octane on the surface of the copper mesh is 161 °, the contact angle of petroleum ether on the surface of the copper mesh is 162 °, the contact angle of toluene on the surface of the copper mesh is 164 °, the contact angle of 1, 2-dichloroethane on the surface of the copper mesh is 164 °, and the contact angle of chloroform on the surface of the copper mesh is 163 °, which indicates the superhydrophilic/underwater superoleophobic characteristic of the copper mesh.
FIG. 11 is an XPS surface elemental analysis chart of a superhydrophilic/underwater superoleophobic copper mesh for separating emulsified oil-in-water prepared in this example 1, which contains a large amount of N elements; thus indicating the presence of a large number of amine groups in the copper network.
FIG. 12 is Zeta potential diagrams of the super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water prepared in this example 1 under different pH values, and it can be seen from the analysis that the surface of the copper mesh exhibits positive charge, and the positive charge slightly decreases but keeps stronger positive charge with the increase of pH value; thus indicating that a large amount of positive charge can be present in the copper mesh.
Example 2
Ultrasonically cleaning a 400-mesh phosphorus-copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the phosphorus-copper net with nitrogen for later use; preparing 0.60g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.25g/L dopamine and 0.78g/L PEI, ultrasonically oscillating in water bath for 5min, and adding 0.25g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 5min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 120rpm, setting the dip-coating time to be 8h, and setting the dip-coating temperature to be 25 ℃; taking out and drying in an oven at 100 ℃ for 10min to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
Example 3
Ultrasonically cleaning a 400-mesh phosphorus-copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the phosphorus-copper net with nitrogen for later use; preparing 0.75g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.30g/L dopamine and 0.85g/L PEI, ultrasonically shaking in water bath for 5min, and adding 0.25g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 5min to obtain a dip-coating solution; soaking the cleaned copper net in the above dip-coating solution, transferring the whole system to a shaking table with a rotation speed of 130rpm, a dip-coating time of 10h and a dip-coating temperature of30 ℃; taking out and drying in an oven at the drying temperature of 120 ℃ for 30min to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
Example 4
Ultrasonically cleaning a 200-mesh red copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the red copper net with nitrogen for later use; preparing 0.60g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.25g/L dopamine and 0.78g/L PEI, ultrasonically oscillating in water bath for 10min, and adding 0.2g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 10min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 120rpm, setting the dip-coating time to be 8h, and setting the dip-coating temperature to be 25 ℃; taking out and drying in an oven at the drying temperature of 120 ℃ for 10min to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
Example 5
Ultrasonically cleaning a 200-mesh brass net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the brass net with nitrogen for later use; preparing 0.60g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.30g/L dopamine and 0.85g/L PEI, ultrasonically oscillating in water bath for 10min, and adding 0.25g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 10min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 130rpm, the dip-coating time to be 10 hours, and the dip-coating temperature to be 25 ℃; taking out and drying in an oven at 100 ℃ for 10min to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
Example 6
Contact angle measurements including contact angle experiments of water in air and contact angle experiments of oil in water were performed on the superhydrophilic/underwater superoleophobic copper mesh for separating emulsified oil-in-water prepared in examples 1-5 at room temperature by using a JC2000C1 contact angle measuring instrument of the morning digital technology equipment ltd in shanghai, and specific results are shown in table 1.
TABLE 1
As can be seen from Table 1, the contact angles of the super-hydrophilic/underwater super-oleophobic copper net prepared by the method disclosed by the invention to water in the air are all 0 degrees, and the contact angles to various kinds of oil in the water are between 158.6 and 164.7 degrees, which indicates that the super-hydrophilic/underwater super-oleophobic copper net has the super-hydrophilic/underwater super-oleophobic performance, probably because positively charged clusters are filled in square holes of the copper net, the roughness of the copper net is increased, and the surface energy of the copper net is increased by adding high-surface-energy amino groups, carboxyl groups, hydroxyl groups and other groups, so that the super-hydrophilic/underwater super-oleophobic copper net is prepared.
Example 7
Stability test of super-hydrophilic/underwater super-oleophobic copper mesh
After the surface is damaged by mechanical abrasion, cold and hot treatment and acid-base salt soaking, the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper mesh for separating the emulsified oil-in-water to deionized water in the air and the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper mesh for separating the emulsified oil-in-water to isooctane in the water are measured.
Mechanical wear resistance test of super hydrophilic/underwater super oleophobic copper net: the super-hydrophilic/underwater super-oleophobic copper net for separating the emulsified oil-in-water prepared in examples 1 to 5 was adhered to a glass sheet by a double-sided adhesive tape, then the glass sheet was placed on 1000-mesh sandpaper with the copper net surface facing the sandpaper, then a 50g weight was placed above the glass sheet, and the glass sheet was dragged at a speed of 4cm/s with a dragging distance of 20cm, and one horizontal dragging and one longitudinal dragging was referred to as one cycle. The test was performed once every 5 cycles of the drag test to test the change in contact angle of the superhydrophilic/underwater superoleophobic copper mesh used to separate the emulsified oil-in-water to deionized water in air and to isooctane in water. The result shows that after 50 times of circulating drag test, the contact angle of the copper net in air to deionized water is always kept 0 degrees, and the contact angle of the copper net underwater to isooctane is still larger than 150 degrees, which shows that the super-hydrophilic/underwater super-oleophobic copper net has better mechanical abrasion resistance.
And (3) testing the cold and heat resistance of the super-hydrophilic/underwater super-oleophobic copper mesh: the super-hydrophilic/underwater super-oleophobic copper mesh for separating the emulsified oil-in-water prepared in the examples 1 to 5 is respectively placed in an oven at 300 ℃ and a refrigerator at-30 ℃ for 24h, and the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper mesh for separating the emulsified oil-in-water to deionized water in the air and the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper mesh for separating the emulsified oil-in-water to isooctane in the water are tested. The result shows that after the cold and hot treatment, the contact angle of the copper net to deionized water in the air is always kept to be 0 degrees, and the contact angle of the copper net to isooctane under water is still larger than 150 degrees, which shows that the super-hydrophilic/underwater super-oleophobic copper net has better cold and hot resistance.
And (3) testing acid and alkali resistance of the super-hydrophilic/underwater super-oleophobic copper mesh: the super-hydrophilic/underwater super-oleophobic copper net for separating the emulsified oil-in-water prepared in the embodiment 1-5 is respectively placed in 1mol/L sulfuric acid, sodium hydroxide and sodium chloride solution for 24h, and the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper net for separating the emulsified oil-in-water to deionized water in the air and the change of the contact angle of the super-hydrophilic/underwater super-oleophobic copper net for separating the emulsified oil-in-water to isooctane in the water are tested. The result shows that after the soaking treatment of the three high-concentration acid, alkali and salt solutions, the contact angle of the copper net to deionized water in the air is always kept 0 degrees, and the contact angle of the copper net to isooctane underwater is still larger than 150 degrees, which shows that the super-hydrophilic/underwater super-oleophobic copper net has better acid and alkali salt resistance.
The above stability test results are shown in table 2.
TABLE 2
From the above examples, it can be seen from table 2 that the super-hydrophilic/underwater super-oleophobic copper mesh prepared by the method of the present invention has strong physical and chemical stability, and can withstand mechanical abrasion, heat and cold treatment and attack of corrosive solvents such as acid, alkali and salt, and thus it has a strong application prospect in actual oil-water separation.
Example 8 (comparative example 1)
Ultrasonically cleaning a 400-mesh phosphorus-copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the phosphorus-copper net with nitrogen for later use; preparing 0.60g/L Tris (hydroxymethyl) aminomethane (Tris-HCl) solution, adding 0.25g/L dopamine and 0.78g/L PEI, ultrasonically oscillating in water bath for 5min, and adding 0.2g/L MWCNTs-NH2Continuing to perform ultrasonic treatment for 5min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 120rpm, dip-coating time to be 6h, and dip-coating temperature to be 25 ℃; and then, soaking the copper mesh in a 1% PAA solution for 10min, taking out the copper mesh, and drying the copper mesh in an oven at the drying temperature of 100 ℃ for 10min to obtain the copper mesh with the charges eliminated as a comparison group.
Fig. 13 is a Scanning Electron Microscope (SEM) image of the charge-depleted copper mesh prepared in example 8. As can be seen from fig. 13, the copper mesh prepared in this example 8 is still filled with fine clusters. The pore size ranges between 0.01 and 0.57 μm.
Example 9 (comparative example 2)
Ultrasonically cleaning a 400-mesh phosphorus-copper net (with the size of 3cm multiplied by 3cm) with acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying the phosphorus-copper net with nitrogen for later use; preparing 0.60g/L Tris (Tris-HCl) solution, adding 0.25g/L dopamine and 0.78g/L PEI, unlike example 1, this procedure did not add MWCNTs-NH2Continuing to perform ultrasonic treatment for 5min to obtain a dip-coating solution; soaking a cleaned copper net in the dip-coating solution, transferring the whole system to a shaking table, setting the rotation speed of the shaking table to be 120rpm, dip-coating time to be 6h, and dip-coating temperature to be 25 ℃; taking out and drying in an oven at 100 ℃ for 10min to obtain a copper mesh with an unreasonably controlled aperture as a comparison group.
Fig. 14 is a Scanning Electron Microscope (SEM) image of the copper mesh prepared in example 9, whose pore size is not reasonably controlled. As can be seen in fig. 14, the copper mesh prepared in this example 9 has no clusters in the square pores due to the absence of carbon nanotube clusters, and only has a fragile and irregular PDA/PEI coating. The pore size ranges between 30-50 μm.
FIG. 15 is a Zeta potential diagram of the copper mesh prepared in examples 8 and 9 at pH 6. it can be seen from the analysis that the copper mesh of example 8 exhibits a slight negative charge after treatment with a 1% by volume polyacrylic acid solution, and the Zeta potential of the initial copper mesh surface is also slightly negative, which is practical. In example 9, MWCNTs-NH is not added to the copper mesh during modification2So that no cluster structure exists in the pores and the pore diameter is still larger. But the charge is positively charged due to the presence of a large number of amine groups on the PEI.
Example 10
Separation test of emulsified oil-in-water
The following oil-water separation test was performed on the super-hydrophilic/underwater super-oleophobic copper mesh for separating emulsified oil-in-water prepared in examples 1 to 5: the prepared super-hydrophilic/underwater super-oleophobic copper mesh is cut into a disc shape with the radius of 2.5cm, the disc shape is placed in the middle of a sand core filtering device and is clamped and sealed, a glass tube with a scale capacity is arranged at the upper end of a clamp, a 200mL conical bottle device is arranged at the lower end of the clamp and is kept vertically placed, emulsified water oil is poured into the disc shape, a water phase can rapidly pass through the copper mesh, and emulsified oil drops in water can be blocked in the glass tube at the upper end after the steps of demulsification, coalescence, combination and the like. The separation efficiency is the ratio of the oil content in the filtrate after separation and the mother liquor before separation. Permeate flux is the ratio of the volume of filtrate passing per unit area and per unit time. Specific results of separation efficiency and permeation flux are shown in table 3.
TABLE 3
Note: "-" indicates that the emulsified oil-water mixture could not be separated.
The results show that the separation efficiency in the embodiments 1-5 is more than 99.5%, and the emulsified oil-water separation performance is very high; the permeation flux in examples 1 to 5 was more than 2900 L.m-2·h-1Has high oil-water permeability.
Example 8 (comparative example 1) and example 1 were prepared under exactly the same conditions except that example 8 was finally subjected to the "charge elimination" step, and since the substrate did not carry a positive charge, the separation efficiency for various emulsified oil-in-water solutions decreased from 99.51-99.82% to 95.87-97.45% and the comparison showed an oil content in water that increased from 20ppm to 30-160 ppm, compared to example 1 and examples 2-5. According to the emission standard of the pollutants in the petrochemical industry of GB 31571-2015 and the emission standard of the pollutants in the petroleum refining industry of GB 31570-2015, the emission standard is met when the content of organic carbon is not more than 20 ppm; this shows that the surface charge plays a critical role in breaking the emulsion. That is, the emulsified oil water treated by the copper mesh prepared by the invention can be directly discharged; the emulsified oil water treated by the copper mesh after the positive charge is eliminated obviously does not meet the requirement. Once the positive charges on the surface of the copper mesh are eliminated, even if the pore size range is kept the same, the separation efficiency of the four emulsified oil-in-water separation methods is obviously reduced, which indicates that small-sized oil drops in the emulsified oil-in-water cannot be broken on the surface of the copper mesh in time after the 'charge shielding' effect is lost, and the small oil drops cannot be intercepted only by 'size screening'.
Analytical example 9 (comparative example 2) found that when the pore size of the copper mesh is 30-50 microns, although the surface has positive charges, the "charge shielding" effect can destabilize the surfactant on the outer surface of the oil droplets, but after the basic guarantee of the "size sieving" effect is lost, the oil phase has too low an intrusion pressure, and the oil droplets have too much time to coalesce and directly permeate, resulting in the failure of the separation process. Therefore, "size screening" is a basic guarantee that the oil-water separation material can realize high-efficiency separation. At present, the research of performing high-efficiency and high-flux separation by using other demulsification means and 'size screening' synergistic demulsification is not seen yet. The industry commonly uses conventional treatment means for oily sewage treatment, such as chemical demulsification, physical demulsification, biological demulsification or electric demulsification. The measures are time-consuming and energy-consuming, cannot be completed in one step, and usually fine treatment by other measures, such as microfiltration and ultrafiltration membrane filtration, is carried out after the coarse treatment, although the final treatment can also reach the emission standard, secondary pollution is easily caused, so that special oil recovery work cannot be carried out. The ionic material has low cost, high efficiency, obvious emulsion breaking strengthening effect, convenient modification and easy realization on various base materials. Compared with other demulsification means, the method can ensure that the standard of discharging the filtrate is preferentially realized at lower cost. The impartation of "ionic" type surfaces is a promising means of modification for separation materials that are sought after for industrial applications. Therefore, the invention utilizes the technology of combining 'size screening' and 'charge shielding', can complete the demulsification material of filtration and separation in one step, and has wide prospect in the future oil-water separation field.
The treatment of emulsified oil and water is generally carried out in large batch, and if only the separation efficiency is high, the flux is small, the energy consumption and the time consumption are low, the industrial requirements are obviously not met, so that the higher the flux is, the better the flux is on the premise of ensuring the qualified separation efficiency. As can be seen from Table 3, the super-hydrophilic/underwater super-oleophobic copper mesh prepared by the method disclosed by the invention can simultaneously ensure high-efficiency separation efficiency and high permeation flux when various emulsified oil-in-water are separated, and overcomes the problem that the prior art is difficult to realize both the high-efficiency separation efficiency and the high permeation flux. The super-hydrophilic/underwater super-oleophobic copper net prepared by the method has the separation efficiency of more than 99 percent for four emulsified oil-in-water, and the permeation flux is 2900 L.m-2·h-1The oil-water separator has outstanding oil-water separation performance.
Compared with the common oil-water separation material, the high-efficiency material can be used for intercepting oil drops with wide size range just because of the capability of capturing the oil drops with small size, thereby ensuring the ultrahigh purity of the osmotic filtrate. The charge shielding effect in the invention is an effective means for helping destabilization of small-size oil drops to be captured, and the demulsification capability in the whole separation process is enhanced. The common oil-water separation material only depends on a single demulsification means, cannot break through the bottleneck of high-efficiency separation, has the separation efficiency of emulsified oil-water lower than 99 percent, and is the difficult point of achieving high-efficiency separation.
The size-sieving effect is that the size of the separating material is smaller than the size of the emulsified oil droplets, so that from a filtration point of view, the emulsified oil droplets cannot pass through the pores of the separating material at all and are thus trapped above the material. Taking example 1 of the present invention as an example, the pore size of the separation layer of example 1 in Table 3 is in the range of 0.01-0.58 μm, and the pore size of the 4 emulsified oil-in-water emulsions prepared by the present invention after dynamic light scattering analysis (left panels of FIGS. 16-19) is in the range of 0.1-10.0, 0.1-13.0, 0.1-11.0 and 0.1-14.0 μm in sequence, and the large size oil droplets are clearly visible. While the right graphs in fig. 16-19 are the particle size graphs of the filtrate separated in example 1, it is obvious that the particle size distribution of oil droplets of the four types of emulsified oil-in-water after separation is less than 15nm, which is at the normal level of dischargeable filtrate, and no obvious oil droplets appear in the graphs, which fully proves the efficient separation effect. Furthermore, the size of the emulsified oil droplets in the initial emulsion is for the most part larger than the pore size of the separating layer of example 1. Thus, the submicron pore size of example 1 acts as a key gating barrier throughout the separation process, preventing the passage of a significant portion of the large oil droplets through the permeation pathway, while the small oil droplets coalesce into large droplets with the assistance of charge demulsification. As can be seen from table 3, the Zeta potential of example 1 is 55.3mV, and when negatively charged emulsified oil droplets approach the copper mesh surface, strong electrostatic interactions are generated between the strongly positively charged oil droplets and example 1. In the embodiment, strong electrostatic attraction is generated between hydrophilic ends of the cationic surfactant and the anionic surfactant in the emulsified oil-in-water, and after the outer surfaces of oil drops are unstable, adjacent oil drops can be combined only through simple contact, so that small-size oil drops are gradually combined into larger oil drops.
Under the synergistic effect of 'size screening' effect interception of large oil drops and 'charge shielding' effect destabilization of small oil drops, the submicron pore canal can ensure that the oil phase has large invasion pressure and strong affinity with a water phase, and can obtain high permeability; meanwhile, the positive charges of the copper mesh can damage the surfactant on the outer surface of the oil drops, so that the attraction among the oil drops is increased, particularly the instability of the small-size oil drops can be coalesced and enlarged after collision contact, and finally an immiscible oil-water two-phase mixture is formed. Particularly, the method of the invention meets the discharge standards of GB 31571-2015 petrochemical industry pollutants and GB 31570-2015 petroleum refining industry pollutants for the separation of four emulsified water and oil, realizes direct discharge, and breaks through the bottleneck of the prior art.
The embodiments of the present invention are not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (8)
1. The application of the super-hydrophilic/underwater super-oleophobic copper mesh in separation of emulsified oil-in-water is characterized in that: the oil-in-water efficiency of the separation emulsion reaches 99.12-99.85%, and the permeation flux is 2978.4-3949.2 L.m-2·h-1(ii) a After the copper mesh is filled with clusters, a curled aminated carbon nanotube with a nano-micron scale is formed in a pore channel, the water contact angle in the air is equal to 0 degree, and the underwater oil contact angle is 158.9-164.7 degrees; the super-hydrophilic/underwater super-oleophobic copper mesh is prepared by the following steps:
1) cleaning and drying the 200-plus-400-mesh copper net;
2) purifying multi-wall carbon nano-tubes by using dilute hydrochloric acid, then carrying out oxidation treatment on the multi-wall carbon nano-tubes by using mixed acid consisting of nitric acid and sulfuric acid at the temperature of 60-180 ℃, modifying the multi-wall carbon nano-tubes into carboxylated carbon nano-tubes, and adding water to prepare a carboxylated carbon nano-tube aqueous solution; then adding polyethyleneimine, and treating for 4-8h at 20-30 ℃ to modify into an aminated carbon nanotube;
3) ultrasonically mixing the aminated carbon nanotube obtained in the step 2) with dopamine, tris (hydroxymethyl) aminomethane and polyethyleneimine at room temperature to prepare dip-coating liquid;
4) immersing the copper mesh obtained in the step 1) into the dip-coating liquid obtained in the step 3), then carrying out horizontal-rotary oscillation on a shaking table for 6-10h, taking out, washing with deionized water, and drying to obtain the super-hydrophilic/underwater super-oleophobic copper mesh.
2. The use of the superhydrophilic/underwater superoleophobic copper mesh of claim 1 for separating emulsified oil-in-water, characterized in that: step 1), the copper mesh comprises one of a red copper mesh, a brass mesh and a phosphor copper mesh; the cleaning is ultrasonic cleaning for 10-15min by acetone, absolute ethyl alcohol and deionized water respectively; the blow-drying is performed by using nitrogen.
3. The application of the super-hydrophilic/underwater super-oleophobic copper net in the separation of emulsified oil-in-water according to claim 1, characterized in that in step 2), the multi-walled carbon nanotubes have the diameter of 20-40nm, the length of 10-15 μm and the purity of more than 97%; the concentration of the dilute hydrochloric acid is 0.1-10mol/L, and the purification time of the dilute hydrochloric acid is 6-12 h; the mass ratio of nitric acid to sulfuric acid in the mixed acid is 1:2-1: 4; the time of the oxidation treatment is 6-8 h.
4. The application of the super-hydrophilic/underwater super-oleophobic copper net in the separation of emulsified oil-in-water according to claim 1, characterized in that the molecular weight of PEI in steps 2) and 3) is 600-10000; the mass ratio of the polyethyleneimine to the carboxylated carbon nanotube in the step 2) is 150-100: 1; adding 15-25g of polyethyleneimine per liter of carboxylated carbon nanotube aqueous solution.
5. The use of the superhydrophilic/underwater superoleophobic copper mesh of claim 1 for separating emulsified oil-in-water, characterized in that: adding the tris (hydroxymethyl) aminomethane, dopamine, polyethyleneimine and deionized water in the preparation process of the dip-coating solution in the step 3), performing ultrasonic treatment for 5-10min, then adding the aminated carbon nanotube, and continuing performing ultrasonic treatment for 5-10 min.
6. The use of the superhydrophilic/underwater superoleophobic copper mesh of claim 1 for separating emulsified oil-in-water, characterized in that: the concentration of the tris (hydroxymethyl) aminomethane in the dip-coating liquid in the step 3) is 0.55-0.75g/L, the concentration of the dopamine is 0.20-0.30g/L, the concentration of the polyethyleneimine is 0.75-0.85g/L, and the concentration of the aminated carbon nanotube is 0.15-0.25 g/L.
7. The use of the superhydrophilic/underwater superoleophobic copper mesh of claim 1 for separating emulsified oil-in-water, characterized in that: in the step 4), the rotation speed of the shaking table in the horizontal-rotation oscillation is 120-130rpm, and the dip-coating temperature is 20-30 ℃; the drying is carried out in an oven, the drying temperature is 100-120 ℃, and the drying time is 10-30 min.
8. The use of the superhydrophilic/underwater superoleophobic copper mesh of claim 1 for separating emulsified oil-in-water, characterized in that: the emulsified oil-in-water is oily sewage in daily life or industrial production; the oil phase in the emulsified oil-in-water is selected from one or more of toluene, petroleum ether, isooctane and 1, 2-dichloroethane.
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| CN113082853B (en) * | 2021-03-31 | 2022-05-24 | 华南理工大学 | Three-dimensional Janus stainless steel mesh capable of separating emulsified oil and water and preparation method thereof |
| CN115703684B (en) * | 2021-08-16 | 2023-06-13 | 宝山钢铁股份有限公司 | Super-wettability material for oil-water separation and preparation method and application thereof |
| CN114505061B (en) * | 2022-01-24 | 2023-01-06 | 华南理工大学 | Super-hydrophilic/underwater super-oleophobic copper mesh and preparation method and application thereof |
| CN114504950B (en) * | 2022-01-24 | 2023-04-21 | 华南理工大学 | Super-hydrophilic and underwater super-oleophobic oil-water separation copper mesh membrane and preparation method thereof |
| CN114733499B (en) * | 2022-01-28 | 2024-06-14 | 华南理工大学 | Janus positive and negative charge type super-hydrophilic/underwater super-oleophobic foam copper group and preparation method and application thereof |
| CN115785990B (en) * | 2022-12-22 | 2024-05-17 | 南阳腾远石油工程技术服务有限公司 | Crude oil demulsifier and preparation method thereof |
| CN117001796B (en) * | 2023-07-03 | 2024-05-28 | 东莞理工学院 | Super-hydrophobic wood with demulsification capability and preparation method and application thereof |
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