CN114225708A - Super-hydrophilic oleophobic separation membrane for oil-water separation and preparation method thereof - Google Patents
Super-hydrophilic oleophobic separation membrane for oil-water separation and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000926 separation method Methods 0.000 title claims abstract description 97
- 239000012528 membrane Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012071 phase Substances 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 34
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000012695 Interfacial polymerization Methods 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 14
- 150000007519 polyprotic acids Polymers 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- -1 biphenyl anhydride Chemical class 0.000 claims description 4
- 238000010406 interfacial reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 61
- 239000004745 nonwoven fabric Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 229920000728 polyester Polymers 0.000 description 17
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000012466 permeate Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000001612 separation test Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
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- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical group ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a super-hydrophilic oleophobic separation membrane for oil-water separation and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of surface modification of separation membranes, and particularly relates to a super-hydrophilic oleophobic separation membrane for oil-water separation and a preparation method thereof.
Background
The oil-water mixture has wide sources, has serious influence on the ecological environment and the production process, and needs to be efficiently separated from the oil-water mixture in terms of environmental protection, resource recycling and safe production. The traditional oil-water separation technology comprises methods of air floatation, flocculation, adsorption, electric dehydration, chemical demulsification and the like. The technologies need to consume a large amount of energy, add chemical agents, increase the sludge amount and the like. The ultrafiltration membrane separation technology belongs to a physical method, does not need an additional medicament, has simple treatment process, can remove emulsified oil and dissolved oil which are difficult to treat, and is an ideal oil-water separation technology.
The traditional membrane separation technology mainly uses pore size screening as a separation mechanism, namely materials with the pore size smaller than that of a separation membrane can permeate the membrane, and materials with the pore size larger than that of the separation membrane are intercepted on the surface of the membrane, so that the separation process is completed. According to the sieving principle, if the dissolved oil and the emulsified oil need to be separated, the pore diameter of the separation membrane should be less than 0.1 μm, even less than 10nm, the pore diameter of the separation membrane is required to be small, the porosity is low, the filtration resistance is large, and the operation pressure needs to be increased. However, the increase in the operating pressure causes the oil droplets to deform and permeate the separation membrane, thereby reducing the oil-water separation efficiency of the separation membrane.
In recent years, with the development of bionic technology, researchers have conducted extensive and intensive research on the super-hydrophobic and super-hydrophilic phenomena of animals and plants in nature. The wettable surface has been widely used in daily life and industrial production, such as self-cleaning of building exterior walls and fabric surfaces, anti-fogging treatment of glasses and window surfaces, and the like. From the viewpoint of surface chemistry, when the surface tension of solid and liquid is close, a super-wet surface can be obtained. The surface tension of the oil substances is 20-40 mN/m, the surface tension of the water is 72mN/m, the difference of the surface tensions of the oil substances and the water is large, and a theoretical basis is provided for realizing an oil-water separation process by utilizing the wettability difference of a film material. Most of the current commercial membrane materials are hydrophobic engineering plastics, such as polysulfone, polyethersulfone, polyvinylidene fluoride, polypropylene and the like. The surface energy of the materials is positioned near hydrocarbon materials, the materials have certain lipophilicity, oil drops are easily spread on the surface of the membrane and inside membrane pores in the oil-water separation process, the surface of the membrane is seriously polluted and blocked, the flux of the separation membrane is further reduced, the filtration resistance is improved, the service life of the separation membrane is shortened, and the oil-water separation cost is increased. Therefore, the traditional separation membrane has great limitation in the oil-water separation process.
The super-wetting oil-water separation membrane utilizes the difference of the wettability of membrane materials to oil and water, but not the membrane aperture, because the surface tension difference between common water and oil is large, the selective adsorption of one phase on the surface with different wettability to water and oil and the repulsion of the other phase can be realized, the wettability of the surface is enhanced, and the separation efficiency can be improved. When oily sewage contacts the surface of the membrane, water can continuously permeate downwards, the surface always keeps super oleophobic property, oil is trapped on the surface to achieve the effect of oil-water separation, and the potential oil repellency of the membrane prevents the oil from polluting the surface of the membrane all the time, so that the membrane is suitable for occasions with much water and less oil, is a real anti-pollution, low-energy-consumption, long-service-life and high-efficiency separation membrane, and becomes the main development direction of the future oil-water separation membrane.
Compared with the traditional separation membrane, the technology has the following advantages:
the separation membrane has large aperture and large unit area treatment capacity;
the separation membrane has strong anti-pollution capability, can be applied to high-viscosity and high-concentration feed liquid, and oil substances are not adhered to the surface of the membrane;
the phase change is not needed in the separation process, the structure of the modification equipment is simple, and the operation cost is low;
the separation membrane can be operated only by low pressure (0.1MPa), the pollution resistance is strong, and the operation cost is extremely low;
in conclusion, the super-hydrophilic oleophobic membrane has the advantages of high water flux and strong pollution resistance in the oil-water separation process, can be used for treating high-concentration oily sewage, and greatly reduces the membrane pollution problem in the subsequent ultrafiltration membrane separation process. The super-hydrophilic oleophobic membrane is mostly finished by hydrophilic or hydrophobic modification on the surface of a porous material, and the surface performance of the porous material can be modified by a surface modification technology, so that the oil/water wettability difference is realized.
The water contact angle of a flat material surface can be expressed by Young's equation:
γsg-γsl＝γlg·cosθ (1)
in the formula: gamma raysg、γsl、γlgRespectively represent the surface tension of solid-gas, solid-liquid and liquid-gas, and theta represents the water contact angle. However, young's equation only applies to the case that the surface of the material is flat, and the water contact angle of the rough surface cannot be expressed by young's equation. The water has two states on the surface of the rough material: one is the penetration of water into the interstices of the coarse structure, known as the Wenzel model; the other is that water does not penetrate into the coarse structure, water drops are suspended on the coarse structure, one part is in contact with the material, and the other part is in contact with air, and the model is called Cassie-Baxter. According to Wenzel theory:
cosθw＝R·cosθ (2)
in the formula: θ w represents the Wenzel theoretical water contact angle, θ represents the material flat surface water contact angle, R represents the material surface roughness factor, and R > 1. Thus, the higher the surface roughness of a hydrophobic material (the larger R), the larger the water contact angle (θ w > θ >90 °), and the higher the surface roughness of a hydrophilic material, the smaller the water contact angle (θ w < θ <90 °). The PVDF material belongs to a hydrophobic material, and the surface roughness R is obviously improved, so that the theta w is improved. Therefore, as for the hydrophilic material, the larger the surface roughness, the better the hydrophilicity. Conversely, for hydrophobic materials, the greater the surface roughness the more hydrophobic it is. Therefore, for the super-hydrophilic oleophobic membrane, the research direction for preparing the super-hydrophilic oleophobic membrane is to improve the roughness of the super-hydrophilic oleophobic membrane on the basis of keeping the surface hydrophilicity.
The interfacial polymerization method is derived from an interfacial polymerization principle proposed by Morgan, and utilizes two reaction monomers with high reaction activity to perform polymerization reaction at mutually incompatible oil-water two-phase interfaces, so that a layer of compact selective separation cortex is generated on the surface of a porous supporting layer, and the method is commonly used for preparing reverse osmosis or nanofiltration composite membranes. The interfacial reaction can be divided into three stages: (1) in the first stage of the reaction, the aqueous phase amine monomer and the oil phase acyl chloride monomer quickly form a loose initial polyamide film upon contact, and the film is formed before the reaction reaches the condition of limited diffusion; (2) since the initial polyamide film formed hinders the diffusion of the aqueous phase amine monomer into the oil phase reaction zone, the growth of the polyamide film begins to be controlled by limited diffusion; (3) when the resulting polyamide film reaches a certain thickness and density, the diffusion of the aqueous monomer stops, and interfacial polymerization and film growth are terminated. Due to the self-inhibition characteristic of the interfacial reaction, the generated polyamide membrane is uniform and compact, is very thin and is only 20-200 nm, and therefore, high flux and salt rejection rate can be obtained. From the above process, it was found that the process of interfacial polymerization formation of polyamide is affected by both reaction and diffusion processes. Wherein, the reaction speed of the water phase monomer and the oil phase monomer is the key to control the surface morphology of interfacial polymerization. When the interfacial polymerization reaction speed is too high, a stable interfacial layer is formed between the two phases, so that the subsequent diffusion process is prevented, and the polyamide layer is smooth. The addition of the additive into the water phase and the oil phase can regulate and control the reaction speed of the water phase monomer and the oil phase monomer, and effectively improve the roughness of the cross-linked layer.
Disclosure of Invention
In view of the above, the invention provides a super-hydrophilic oleophobic separation membrane for oil-water separation and a preparation method thereof, the super-hydrophilic oleophobic separation membrane with hydrophilicity and high roughness is prepared by adding a water-soluble monomer with a polyhydroxy structure into a water-phase monomer, adding polybasic acid anhydride into an oil-phase monomer and carrying out interfacial polymerization on the surface of a porous material and the inside of a pore channel, the preparation process is simple, the reaction speed is high, and the obtained super-hydrophilic oleophobic separation membrane has the advantages of high water flux, good hydrophilicity and strong anti-pollution capacity, and has a good separation effect in the oily sewage treatment process.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a super-hydrophilic oleophobic separation membrane for oil-water separation comprises the following steps:
s1, preparation of an aqueous phase solution: mixing water-soluble monomers with a polyhydroxy structure with piperazine (PIP) or m-phenylenediamine (MPD) to prepare an aqueous phase solution;
s2, preparation of oil phase solution: mixing polybasic acid anhydride and trimesoyl chloride (TMC) to prepare an oil phase solution;
s3, interfacial polymerization: soaking the porous material in the water phase solution, taking out, drying, soaking in the oil phase solution after drying, and taking out for interface reaction;
s4, repeating the interfacial polymerization process of S3 for multiple times to obtain the super-hydrophilic oleophobic separation membrane.
Further, in the S1, the water-soluble monomer with a polyhydroxy structure is tritolyl, 3,4, 5-trihydroxybenzoic acid or 3,3' -dihydroxybenzidine.
Further, in the S1, mixing a water-soluble monomer with a polyhydroxy structure with piperazine or m-phenylenediamine to obtain an aqueous phase monomer, wherein the water-soluble monomer with a polyhydroxy structure accounts for 0.5-95 wt% of the total mass of the aqueous phase monomer; in the aqueous phase solution, the concentration of an aqueous phase monomer obtained by mixing a water-soluble monomer with a polyhydroxy structure and piperazine or m-phenylenediamine is 0.01-15 wt%.
Further, in S2, the polybasic acid anhydride is trimellitic anhydride chloride, phthalic anhydride, pyromellitic dianhydride, or biphenyl anhydride.
Further, in the S2, polybasic acid anhydride and trimesoyl chloride are mixed to obtain an oil phase monomer, wherein the polybasic acid anhydride accounts for 0.5-95 wt% of the total weight of the oil phase monomer; in the oil phase solution, the concentration of an oil phase monomer obtained by mixing polybasic acid anhydride and trimesoyl chloride is 0.01-15 wt%.
Further, in the aqueous phase solution, the solvent is water; in the oil phase solution, a solvent is n-hexane, ethyl acetate, butyl acetate, benzene or toluene.
Further, in the step S3, the porous material is soaked in the aqueous phase solution for 1min to 20 hours, and the porous material is soaked in the oil phase solution for 1min to 20 hours.
Further, in the S3, soaking the porous material in the aqueous phase solution, taking out and drying, wherein the drying temperature is 30 ℃; and soaking the mixture in the oil phase solution, taking out the mixture to perform an interfacial reaction at the temperature of 30-200 ℃ for 1 min-20 h.
Further, in the step S3, the pore diameter of the porous material is in the range of 0.5 to 50 μm, and the porous material is preferably a porous material such as a non-woven fabric or a metal screen.
Further, in the step S4, the number of repetitions is 2 to 10.
The super-hydrophilic oleophobic separation membrane for oil-water separation is prepared by the preparation method of the super-hydrophilic oleophobic separation membrane for oil-water separation.
The invention applies the interfacial polymerization process to the surface modification process of the porous material, the aperture of the bottom membrane of the original reverse osmosis or nanofiltration membrane is about 10nm, and the polyamide layer can be supported to form a stable separation layer on the surface of the membrane. In the invention, the porous material is used as the bottom membrane, the aperture is 0.5-50 μm, a compact separation layer cannot be formed under the condition, and the interface crosslinking layer adheres to the pore channel and the surface of the membrane, thereby modifying the wettability of the separation membrane.
In the traditional interfacial polymerization, piperazine or m-phenylenediamine is used as a water phase monomer, trimesoyl chloride is used as an oil phase monomer, and the water phase monomer and the oil phase monomer quickly form a compact cross-linked layer in the process of oil-water interface contact. Researches show that the process of the separation membrane can be delayed and the roughness of a cross-linked layer can be increased by adding groups with lower reactivity into water-phase monomers and oil-phase monomers. Meanwhile, part of unreacted groups such as hydroxyl or carboxyl and the like can be remained on the surface of the membrane, and the hydrophilicity of the separation membrane is improved. Researches show that compared with PIP, hydroxyl in the functional monomer with the polyhydroxy structure has low reaction activity, partial hydroxyl and carboxyl are remained on the surface of polyamide along with the addition of the functional monomer with the polyhydroxy structure in a water phase, the roughness of the surface of the nanofiltration membrane is increased, the hydrophilicity is improved, the retention rate of inorganic salt is reduced, and the water flux is improved. Similarly, the reactivity of the polybasic acid anhydride is lowered compared to TMC, and as the polybasic acid anhydride is added to the oil phase, a part of carboxyl groups remain on the surface of the polyamide layer, increasing the roughness and improving the hydrophilicity.
Compared with the prior art, the super-hydrophilic oleophobic separation membrane for oil-water separation and the preparation method thereof have the following advantages:
(1) according to the preparation method, the water-soluble monomer with the polyhydroxy structure is added into the water-phase monomer, the polybasic acid anhydride is added into the oil-phase monomer, the reaction process of interfacial polymerization is adjusted, and the cross-linking layer with the hydrophilicity and the rough structure is formed on the surface of the porous material and in the pore canal, so that the super-hydrophilic oleophobic membrane is obtained, and the preparation method is simple, the conditions are easy to control, and continuous production can be realized;
(2) the super-hydrophilic oleophobic separation membrane has the advantages of high water flux, high oil-water separation efficiency, good hydrophilicity and strong pollution resistance; the method has wide application range, not only has good separation effect in the process of oily sewage treatment, but also can be applied to the fields of sewage treatment, material separation and the like, and has good industrial application value.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
An aqueous solution was prepared by dissolving 4g of tritolyl and 6g of PIP in 490g of deionized water, and an oil solution was prepared by dissolving 0.5g of phthalic anhydride and 0.5g of TMC in 199g of n-hexane. And (2) soaking a polyester non-woven fabric (with the thickness of 100 mu m and the average pore diameter of 10 mu m) in the aqueous phase solution for 10min, taking out the polyester non-woven fabric, drying the polyester non-woven fabric in a 30 ℃ oven for 1h, soaking the dried non-woven fabric in the oil phase solution for 10min, taking out the polyester non-woven fabric, heating the polyester non-woven fabric in a 55 ℃ oven for 20min, and finishing the interfacial polymerization process to obtain the super-hydrophilic oleophobic membrane.
The detection shows that the water contact angle of the non-woven fabric before modification is 75 degrees, the water contact angle of the separation membrane after modification is 15 degrees, and the water contact angle completely disappears within 3 seconds.
Oil-water separation test is carried out on the produced water of the oil field, the oil content in the produced water of the oil field before the test is 200ppm, the suspended particle content is 60ppm, and the median of the particle size is 8 μm. The water flux of the super-hydrophilic oleophobic membrane in the oily wastewater is 500 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 94%. The oil content in the permeate was less than 20ppm, the suspended particle content was 25ppm, and the median particle size was less than 5 μm.
Example 2
2g of 3,4, 5-trihydroxybenzoic acid and 8g of PIP are dissolved in 490g of deionized water to prepare an aqueous phase solution, and 0.2g of pyromellitic dianhydride and 0.8g of TMC are dissolved in 199g of n-hexane to prepare an oil phase solution. And (2) soaking a polyester non-woven fabric (with the thickness of 100 mu m and the average pore diameter of 10 mu m) in the aqueous phase solution for 10min, taking out the polyester non-woven fabric, drying the polyester non-woven fabric in a 30 ℃ oven for 1h, soaking the dried non-woven fabric in the oil phase solution for 15min, taking out the polyester non-woven fabric, heating the polyester non-woven fabric in a 55 ℃ oven for 10min to complete the interfacial polymerization process, and obtaining the super-hydrophilic oleophobic membrane.
Through detection, the water contact angle of the non-woven fabric before modification is 75 degrees, and after modification, the water contact angle of the super-hydrophilic oleophobic membrane is 26 degrees and completely disappears within 5 seconds.
Oil-water separation test is carried out by adopting the produced water of the oil field, and the oil content in the produced water of the oil field before the test is120ppm, a suspended particle content of 65ppm and a median particle diameter of 8 μm. The water flux of the super-hydrophilic oleophobic membrane in the oily wastewater is 400 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 89%. The oil content in the permeate was less than 12ppm, the suspended particle content was 25ppm, and the median particle size was less than 5 μm.
Example 3
8g of 3,3' -dihydroxybenzidine and 2g of PIP were dissolved in 490g of deionized water to prepare an aqueous solution, and 0.8g of benzidine anhydride and 0.2g of TMC were dissolved in 199g of n-hexane to prepare an oil phase solution. And (2) soaking a polyester non-woven fabric (with the thickness of 200 mu m and the average pore diameter of 8 mu m) in the aqueous phase solution for 10min, taking out the polyester non-woven fabric, drying the polyester non-woven fabric in a 30 ℃ oven for 1h, soaking the dried non-woven fabric in the oil phase solution for 20min, taking out the polyester non-woven fabric, heating the polyester non-woven fabric in a 55 ℃ oven for 30min to complete the interfacial polymerization process, and obtaining the super-hydrophilic oleophobic membrane.
Through detection, the water contact angle of the non-woven fabric before modification is 75 degrees, and after modification, the water contact angle of the super-hydrophilic oleophobic membrane is 5 degrees and completely disappears within 1 second.
Oil-water separation test is carried out on the oil field produced water, the oil content in the oil field produced water before the test is 300ppm, the suspended particle content is 60ppm, and the median of particle size is 8 μm. The water flux of the super-hydrophilic oleophobic membrane in the oily wastewater is 400 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 93%. The oil content in the permeate was less than 35ppm, the suspended particle content was 25ppm, and the median particle size was less than 5 μm.
Comparative example 1
Taking a polyester non-woven fabric (with the thickness of 100 mu m and the average pore diameter of 10 mu m), and carrying out an oil-water separation test on the produced water of the oil field, wherein the oil content in the produced water of the oil field before the test is 120ppm, the suspended particle content is 60ppm, and the median of the particle size is 7 mu m.
After the nonwoven fabric filtration, the oil content in the permeate was about 40ppm, the suspended particle content was 25ppm, and the median particle size was less than 5 μm. The water flux of the separation membrane in the oily sewage is 80 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 35%.
Comparative example 2
Taking a polyester non-woven fabric (with the thickness of 200 mu m and the average pore diameter of 8 mu m), and carrying out an oil-water separation test on the produced water of the oil field, wherein the oil content in the produced water of the oil field before the test is 300ppm, the suspended particle content is 60ppm, and the median of the particle size is 6 mu m.
After the non-woven fabric filtration, the oil content in the permeation liquid is about 90ppm, the content of suspended particles is 25ppm, and the median particle size is less than 7 μm. The water flux of the separation membrane in the oily sewage is 60 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 20%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a super-hydrophilic oleophobic separation membrane for oil-water separation is characterized by comprising the following steps:
s1, preparation of an aqueous phase solution: mixing water-soluble monomers with a polyhydroxy structure with piperazine or m-phenylenediamine to prepare an aqueous solution;
s2, preparation of oil phase solution: mixing polybasic acid anhydride and trimesoyl chloride to prepare an oil phase solution;
s3, interfacial polymerization: soaking the porous material in the water phase solution, taking out, drying, soaking in the oil phase solution after drying, and taking out for interface reaction;
s4, repeating the interfacial polymerization process of S3 for multiple times to obtain the super-hydrophilic oleophobic separation membrane.
2. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the S1, the water-soluble monomer with the polyhydroxy structure is tritolyl, 3,4, 5-trihydroxybenzoic acid or 3,3' -dihydroxy benzidine.
3. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the S1, mixing a water-soluble monomer with a polyhydroxy structure with piperazine or m-phenylenediamine to obtain an aqueous phase monomer, wherein the water-soluble monomer with the polyhydroxy structure accounts for 0.5-95 wt% of the total mass of the aqueous phase monomer; in the aqueous phase solution, the concentration of an aqueous phase monomer obtained by mixing a water-soluble monomer with a polyhydroxy structure and piperazine or m-phenylenediamine is 0.01-15 wt%.
4. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the S2, the polybasic acid anhydride is chlorinated trimellitic anhydride, phthalic anhydride, pyromellitic dianhydride or biphenyl anhydride.
5. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the S2, mixing polybasic acid anhydride and trimesoyl chloride to obtain an oil phase monomer, wherein the polybasic acid anhydride accounts for 0.5-95 wt% of the total weight of the oil phase monomer; in the oil phase solution, the concentration of an oil phase monomer obtained by mixing polybasic acid anhydride and trimesoyl chloride is 0.01-15 wt%.
6. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the aqueous phase solution, the solvent is water; in the oil phase solution, a solvent is n-hexane, ethyl acetate, butyl acetate, benzene or toluene.
7. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in the step S3, the porous material is soaked in the aqueous phase solution for 1 min-20 h, and the porous material is soaked in the oil phase solution for 1 min-20 h.
8. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 7, characterized in that: in the S3, the porous material is soaked in the water phase solution and is taken out and dried, and the drying temperature is 30 ℃; and soaking the mixture in the oil phase solution, taking out the mixture to perform an interfacial reaction at the temperature of 30-200 ℃ for 1 min-20 h.
9. The method for producing a superhydrophilic oleophobic separation membrane for oil-water separation according to claim 1, characterized in that: in S3, the pore diameter range of the porous material is 0.5-50 μm.
10. The utility model provides a super hydrophilic oleophobic separation membrane for water oil separating which characterized in that: the super-hydrophilic oleophobic separation membrane for oil-water separation is prepared by the preparation method of the super-hydrophilic oleophobic separation membrane for oil-water separation of any one of claims 1 to 9.
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| WO1995001219A1 (en) * | 1993-06-29 | 1995-01-12 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
| CN110433667A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling seperation film and preparation method thereof |
| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN113117530A (en) * | 2020-01-15 | 2021-07-16 | 中国科学院大连化学物理研究所 | Composite membrane for improving permselectivity of polyamide nanofiltration composite membrane and preparation method thereof |
| CN113634133A (en) * | 2021-08-05 | 2021-11-12 | 宁波水艺膜科技发展有限公司 | High-yield semipermeable membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1995001219A1 (en) * | 1993-06-29 | 1995-01-12 | Minnesota Mining And Manufacturing Company | Interfacial polymerization in a porous substrate and substrates functionalized with photochemical groups |
| CN111686592A (en) * | 2019-03-11 | 2020-09-22 | 湖州欧美新材料有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN110433667A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling seperation film and preparation method thereof |
| CN113117530A (en) * | 2020-01-15 | 2021-07-16 | 中国科学院大连化学物理研究所 | Composite membrane for improving permselectivity of polyamide nanofiltration composite membrane and preparation method thereof |
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