CA2898815A1 - A preparation method of an oil-absorbing hollow fiber porous membrane - Google Patents
A preparation method of an oil-absorbing hollow fiber porous membrane Download PDFInfo
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- 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
- B01D69/08—Hollow fibre membranes
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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2323/00—Details relating to membrane preparation
- B01D2323/56—Use of ultrasound
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/32—Hydrocarbons, e.g. oil
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Abstract
This invention discloses a preparation method of an oil-absorbing hollow fiber porous membrane. The preparation method is implemented by taking graphene as a surface adsorption layer and taking a hollow fiber porous membrane as a matrix layer through the following preparation process: (1) preparation of graphene dispersion liquid:
mixing 0.1-1 g of graphene with 200-1000 ml of dispersant, and carrying out ultrasonic dispersion for 10-50 min; (2) preparation of an oil-absorbing hollow fiber porous membrane:
firstly, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1). Then pumping filtration is carried out from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 5-30 min, then the obtained product is naturally dried in the air until the graphene on the surface of the hollow fiber porous membrane falls off.
Finally, the obtained product is put in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room temperature for 6-12 h; and (3) enhancing the interface bonding strength between the graphene and the hollow fiber porous membrane by using 1) a solvent processing method or 2) a dilute solution processing method.
mixing 0.1-1 g of graphene with 200-1000 ml of dispersant, and carrying out ultrasonic dispersion for 10-50 min; (2) preparation of an oil-absorbing hollow fiber porous membrane:
firstly, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1). Then pumping filtration is carried out from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 5-30 min, then the obtained product is naturally dried in the air until the graphene on the surface of the hollow fiber porous membrane falls off.
Finally, the obtained product is put in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room temperature for 6-12 h; and (3) enhancing the interface bonding strength between the graphene and the hollow fiber porous membrane by using 1) a solvent processing method or 2) a dilute solution processing method.
Description
A PREPARATION METHOD OF AN OIL-ABSORBING HOLLOW FIBER POROUS
MEMBRANE
BACKGROUND OF THE INVENTION
[0001] Technical Field
MEMBRANE
BACKGROUND OF THE INVENTION
[0001] Technical Field
[0002] The invention relates to a technique for preparing a functional hollow fiber membrane, and specifically in the preparation method of an oil-absorbing hollow fiber porous membrane.
[0003] 2. Description of Related Art
[0004] In recent years, with increasing problems of water resource (such as river, ocean, etc.) and environment pollutions caused by oily organic compounds and its organic waste water, waste fluids and various accidents like oil tanker or oil leakages, traditional oil-absorbing materials (e.g. clay, paper pulp, wood, cotton, etc.) cannot meet the needs of oily waste water recycling and environmental management because of their low oil adsorption capacity, poor oil-water selectivity and unsatisfactory oil retaining ability.
[0005] Among various processing methods for oil pollutants, oil-absorbing fiber has been widely used because of its large specific surface area, fast oil adsorption rate, high efficiency, easy oil recycling and other advantages. Xiao et al. fabricated oil-absorbing copolymethacrylate fiber (CN 200710059780.7; CN 200410019338.8). Liu et al.
prepared superfine oil-absorbing fiber by using the electrospinning technology (CN
200710043566.2). However, these oil-absorbing fibers can only swell and absorb oil through the void between the fibers or polymer crosslinked networks. When the oil adsorption capacity reached at saturation, the adsorption function of the oil-absorbing fiber would be depleted and the fiber could not be continuously used, however, the oil-absorbing material needs to be desorbed and recycled. In fact, the desired oil-absorbing material has low service efficiency and high disposal cost, and it is difficult to meet the should meet the needs of continuous treatment, fast and efficient organic waste water disposal, pollution due to large area oil spill on water surface, environmental protection and the like.
prepared superfine oil-absorbing fiber by using the electrospinning technology (CN
200710043566.2). However, these oil-absorbing fibers can only swell and absorb oil through the void between the fibers or polymer crosslinked networks. When the oil adsorption capacity reached at saturation, the adsorption function of the oil-absorbing fiber would be depleted and the fiber could not be continuously used, however, the oil-absorbing material needs to be desorbed and recycled. In fact, the desired oil-absorbing material has low service efficiency and high disposal cost, and it is difficult to meet the should meet the needs of continuous treatment, fast and efficient organic waste water disposal, pollution due to large area oil spill on water surface, environmental protection and the like.
[0006] The graphene-based porous polymer oil-absorbing material is a novel oil-absorbing material. In 2011, D. Zha et al. obtained superhydrophobic oleophylic PVDF/graphene porous material. The preparation process is as follows: firstly, the PVDF/graphene gel was formed by diffusion of methanol or water into PVDF/graphene suspension in N,N-dimethylformamide (DMF), and then replaced DMF in the gel with water, and followed by freeze-drying for the final product. (Zha D, Mei S.
Wang Z, et al.
Superhydrophobic polyvinylidene fluoride/graphene porous materials. Carbon, 2011, 49(15): 5166-5172.); in 2012, D. D. Nguyen et al. immersed a melamine sponge into an ethyl alcohol dispersion liquid of the graphene to obtain a graphene-coated sponge, and the graphene-coated sponge endured surface treatment by polydimethylsiloxane to prepare a superhydrophobic oleophylic sponge-based graphene material (Nguyen D D, Tai N H, Lee S B, et al.. Superhydrophobic and superoleophilic properties of graphene-based sponges fabricated using a facile dip coating method. Energy & Environmental Science, 2012, 5(7): 7908-7912.). The above-mentioned material has a strong absorption ability for oily organic compounds, showing the maximum adsorption capacity for trichloromethane up to 165 times its own weight. In 2013, Liu et al. immersed a polyurethane foam into the dispersion liquid of the graphene oxide, adjusted the pH of the dispersion liquid, and reduced the graphene oxide by using hydrazine to prepare a superhydrophobic oleophylic sponge-based graphene oil-absorbing material (Yue Liu, Junkui Ma, Tao Wu, et al..
Cost-effective reduced graphene oxide-coated polyurethane sponge as a highly efficient and reusable oil-absorbent. ACS Applied materials & interfaces, 2013, 5(20):10018-10026.). The maximum adsorption capacity of the as-prepared material for trichloromethane reaches 160 g/g. The above-mentioned polymer-based graphene oil-absorbing materials have attracted people's attention because of its good oil and water selectivity and high oil adsorption capacity far exceeding that of the conventional intrinsic synthetic oil-absorbing resin material. However, the oil adsorption process of these oil-absorbing materials still is intermittent operation, which cannot realize continuous efficient adsorption and separation of the oil-water system; as for they are limited in the industrial scale-up.
BRIEF SUMMARY OF THE INVENTION
Wang Z, et al.
Superhydrophobic polyvinylidene fluoride/graphene porous materials. Carbon, 2011, 49(15): 5166-5172.); in 2012, D. D. Nguyen et al. immersed a melamine sponge into an ethyl alcohol dispersion liquid of the graphene to obtain a graphene-coated sponge, and the graphene-coated sponge endured surface treatment by polydimethylsiloxane to prepare a superhydrophobic oleophylic sponge-based graphene material (Nguyen D D, Tai N H, Lee S B, et al.. Superhydrophobic and superoleophilic properties of graphene-based sponges fabricated using a facile dip coating method. Energy & Environmental Science, 2012, 5(7): 7908-7912.). The above-mentioned material has a strong absorption ability for oily organic compounds, showing the maximum adsorption capacity for trichloromethane up to 165 times its own weight. In 2013, Liu et al. immersed a polyurethane foam into the dispersion liquid of the graphene oxide, adjusted the pH of the dispersion liquid, and reduced the graphene oxide by using hydrazine to prepare a superhydrophobic oleophylic sponge-based graphene oil-absorbing material (Yue Liu, Junkui Ma, Tao Wu, et al..
Cost-effective reduced graphene oxide-coated polyurethane sponge as a highly efficient and reusable oil-absorbent. ACS Applied materials & interfaces, 2013, 5(20):10018-10026.). The maximum adsorption capacity of the as-prepared material for trichloromethane reaches 160 g/g. The above-mentioned polymer-based graphene oil-absorbing materials have attracted people's attention because of its good oil and water selectivity and high oil adsorption capacity far exceeding that of the conventional intrinsic synthetic oil-absorbing resin material. However, the oil adsorption process of these oil-absorbing materials still is intermittent operation, which cannot realize continuous efficient adsorption and separation of the oil-water system; as for they are limited in the industrial scale-up.
BRIEF SUMMARY OF THE INVENTION
[0007] For the shortage of the existing oil-absorbing material, the technical problem to be solved by the invention is to provide a preparation method of an oil-absorbing hollow fiber porous membrane. Starting from oil adsorption of the material, the preparation method is implemented by taking superhydrophobic oleophylic graphene as a surface adsorption layer and taking an oleophylic (non-swelling) hollow polymer fiber porous membrane as a matrix layer. The oil-absorbing hollow fiber porous membrane combines oil absorbents with the benefits of oil adsorption performance and oil-water separation function, and further the membrane can achieve the characteristics of continuous oil adsorption and water-repellency and continuous oil-water separation.
Meanwhile, the membrane can be processed and formed into products of various types with simple process and low cost, so that it satisfies the requirement of industrial applicability.
Meanwhile, the membrane can be processed and formed into products of various types with simple process and low cost, so that it satisfies the requirement of industrial applicability.
[0008] The technical solution of the invention for solving the technical problem is to design a preparation method of an oil-absorbing hollow fiber porous membrane.
The preparation method is implemented by taking graphene as a surface adsorption layer and taking a hollow fiber porous membrane as a matrix layer through the following preparation process:
The preparation method is implemented by taking graphene as a surface adsorption layer and taking a hollow fiber porous membrane as a matrix layer through the following preparation process:
[0009] (1). Preparation graphene dispersion liquid: Mixing 0.1-1g of graphene with 200-1000 ml of dispersant, and carrying out ultrasonic dispersion for 10-50 min to prepare the graphene dispersion liquid, wherein the graphene has a thickness of less than 10 nm and a diameter of 0.1-5 1.1m; and the dispersant is one of absolute ethyl alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide or dimethylacetamide.
[0010] (2). Preparation of an oil-absorbing hollow fiber porous membrane:
First, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1), and carrying out dead-end pumping filtration under a negative pressure of 0.02-0.08 MPa for 5-30 min.
Then the membrane is naturally dried in the air until the excess graphene on the surface of the hollow fiber porous membrane falls off, and put it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room temperature for 6-12 h, wherein the polymer hollow fiber porous membrane is polyvinyl chloride hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polypropylene hollow fiber membrane or polyacrylonitrile filament braided hollow tube; and the temperature of the graphene dispersion liquid is 20-30 C.
First, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1), and carrying out dead-end pumping filtration under a negative pressure of 0.02-0.08 MPa for 5-30 min.
Then the membrane is naturally dried in the air until the excess graphene on the surface of the hollow fiber porous membrane falls off, and put it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room temperature for 6-12 h, wherein the polymer hollow fiber porous membrane is polyvinyl chloride hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polypropylene hollow fiber membrane or polyacrylonitrile filament braided hollow tube; and the temperature of the graphene dispersion liquid is 20-30 C.
[0011] (3). Enhancement of the interface bonding strength between the graphene and the hollow fiber porous membrane: Enhancing the interface bonding strength between the graphene and the hollow fiber porous membrane by using one of the following two processing methods, alternately: 1) a solvent processing method: first, prepare 20-100 wt% of an aqueous solution of a solvent, then immerse the oil-absorbing hollow fiber porous membrane prepared in step (2) into the aqueous solution of designated solvent for 1-20 s, and quickly take the membrane out and put it in a coagulation bath for solidifying, yielding the oil-absorbing hollow fiber porous membrane, wherein the solvent is one of dimethylformamide, dimethylacetamide, dimethyl sulfoxide or dimethylbenzene;
and the coagulation bath is water; 2) A dilute solution processing method: firstly, preparing a dilute solution, then immerse the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution, carry out pumping filtration under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly take the membrane out and put it in a coagulation bath for solidification. This yields the oil-absorbing hollow fiber porous membrane, wherein the dilute solution is composed of polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively. The polymer is polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is one of the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent one of is dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent.
and the coagulation bath is water; 2) A dilute solution processing method: firstly, preparing a dilute solution, then immerse the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution, carry out pumping filtration under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly take the membrane out and put it in a coagulation bath for solidification. This yields the oil-absorbing hollow fiber porous membrane, wherein the dilute solution is composed of polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively. The polymer is polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is one of the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent one of is dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent.
[0012] The invention proposed for the first time the design concept for realizing oil adsorption and separation function simultaneously by using the special form of the hollow fiber porous membrane. Compared to the prior art, the oil-absorbing hollow fiber porous membrane of the invention has continuous oil adsorption and separation function, large specific surface area for oil adsorption, fast oil adsorption rate, high efficiency and easy oil recycle. The oil-absorbing hollow fiber porous membrane of the invention can be processed into products of various types and purposes as you required. While treating water polluted by oily organic matters, the porous membrane can float on the surface of water, and oil adsorption occurs at the oil-water interface, which broadens the application range and area. Moreover, the invention has simple process, low cost, easy industrial implementation and good economic and social benefit prospect.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0013] Fig. 1 is the structural schematic diagram of a continuous test device of the oil-absorbing hollow fiber porous membrane prepared by a preparation method of the invention.
DETAILED DESCRIPTION OF THE INVENTION
DETAILED DESCRIPTION OF THE INVENTION
[0014] Hereinafter, the invention is described in further detail in conjunction with examples and drawing.
[0015] The preparation method (hereinafter referred to as preparation method) of an oil-absorbing hollow fiber porous membrane designed in the invention is implemented by taking graphene as a surface adsorption layer and taking a hollow fiber porous membrane as a matrix layer through the following preparation process:
[0016] (1) Preparation of a graphene dispersion liquid: Mixing 0.1-1g of graphene with 200-1000m1 of a dispersant, and carrying out ultrasonic dispersion for 10-50 min to form the graphene dispersion liquid, wherein the graphene has a thickness of less than 10 nm and a diameter of 0.1-5 p.m; and the dispersant is one of absolute ethyl alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide or dimethylacetamide;
[0017] (2) Preparation of an oil-absorbing hollow fiber porous membrane:
First, preparing a polymer hollow fiber porous membrane into module, and immersing the module into the graphene dispersion liquid prepared in step (1); pumping filtration from a dead-end under a negative pressure of 0.02-0.08 MPa for 5-30 min. Then the membrane is naturally dried in the air until excess graphene on the surface of the hollow fiber porous membrane falls off, putting it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 6-12 h, wherein the temperature of the graphene dispersion liquid is 20-30 C;
First, preparing a polymer hollow fiber porous membrane into module, and immersing the module into the graphene dispersion liquid prepared in step (1); pumping filtration from a dead-end under a negative pressure of 0.02-0.08 MPa for 5-30 min. Then the membrane is naturally dried in the air until excess graphene on the surface of the hollow fiber porous membrane falls off, putting it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 6-12 h, wherein the temperature of the graphene dispersion liquid is 20-30 C;
[0018] (3) Enhancement of the interface bonding strength between the graphene and the hollow fiber porous membrane: Enhancing the interface bonding strength between the graphene and the hollow fiber porous (based) membrane by using one of two processing methods, alternately: 1) a solvent processing: preparing 20-100 wt% of an aqueous solution of a solvent, then immersing the oil-absorbing hollow membrane prepared in step (2) into the solvent aqueous solution for 1-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidification. This yields the oil-absorbing hollow membrane, wherein the solvent is one of dimethylformamide, dimethylacetamide, dimethyl sulfoxide or dimethylbenzene; and the medium of the coagulation bath is water;
and 2) a dilute solution processing method: firstly, preparing a dilute solution, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution, carrying out pumping filtration under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidification. This will yield the oil-absorbing hollow membrane, wherein the dilute solution is prepared by polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively.
The polymer material is one of polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is one of the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent is one of dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent, or water.
and 2) a dilute solution processing method: firstly, preparing a dilute solution, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution, carrying out pumping filtration under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidification. This will yield the oil-absorbing hollow membrane, wherein the dilute solution is prepared by polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively.
The polymer material is one of polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is one of the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent is one of dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent, or water.
[0019] The dispersant for dispersing the graphene in the preparation method of the invention comprises absolute ethyl alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide or dimethylacetamide, etc.; and the dispersant is preferably absolute ethyl alcohol.
[0020] In order to guarantee efficient oil adsorption and separation, the preparation method of the invention is further characterized in that the specification of the hollow fiber porous membrane comprises pore size range of 0.1-10 [tm, and more than 50%
porosity; and the specification of the filament braided hollow tube comprises a braiding pitch of 400-600
porosity; and the specification of the filament braided hollow tube comprises a braiding pitch of 400-600
[0021] The oil-absorbing hollow fiber porous membrane of the invention can be prepared according to the preparation method of the invention. The oil-absorbing hollow fiber porous membrane not only has a high oil adsorption function, but also has a continuous oil adsorption function, as well as an oil-water separation function. The hollow fiber porous membrane prepared by the preparation method of the invention can be applied to oil adsorption and separation, herein the hollow fiber porous membrane is guaranteed for non-swelling in the oils. As for the oils, toluene, trichloromethane and other oil low-molecular organic liquids, or kerosene, diesel and other partial hydrocarbon mixtures are mainly included.
[0022] The first principle that the oil-absorbing hollow fiber porous membrane prepared by the preparation method of the invention has a continuous oil adsorption function is that when the surface of the oil-absorbing hollow fiber porous membrane prepared in step (2) is processed by using an aqueous solution of a solvent, the hollow fiber membrane is swelled and dissolved by the good solvent for the polymer material of the hollow fiber porous membrane, and further re-solidifying in a coagulation bath, the graphene can be embedded into the hollow fiber membrane surface, thereby enhancing the interface bonding strength between the graphene and the hollow fiber membrane.
[0023] The second principle that the oil-absorbing hollow membrane prepared by the preparation method of the invention has a continuous oil adsorption function is that when the surface of the oil-absorbing hollow fiber porous membrane prepared in step (2) is processed by using a dilute solution, the graphene can be firmly anchored to the surface of the oil-absorbing hollow membrane while making sure that the graphene is exposed to the surface of the matrix layer as a dilute polymer solution with a certain viscosity, thereby enhancing the interface bonding strength between the graphene and the oil-absorbing hollow membrane.
[0024] The oil-absorbing hollow fiber porous membrane prepared by the preparation method of the invention takes hydrophobic graphene as an adsorption layer and takes an oleophylic (non-swelling) hollow polymer fiber porous membrane as a matrix layer. The membrane is prepared into a membrane assembly and put into an oil/water solution with one end being sealed and the other end being provided with an appropriate negative pressure, wherein the graphene adsorption layer has a function of oil adsorption and water-repellency, and the negative pressure provides power for continuous oil adsorption-desorption. The mass transfer mechanism of continuous oil adsorption and separation is that the oil can be absorbed preferentially by the graphene on the outer surface of the oil-absorbing hollow fiber membrane, and then the oil passes through the hollow fiber porous membrane wall through negative pressure pumping and is transported to an oil storage device along the hollow pipeline, which achieves simultaneous oil adsorption and desorption.
[0025] Those not described in the invention are suitable for the prior art.
Hereinafter, the invention is described in further detail by providing specific examples, but the protection range of the claims of the application is not limited by the specific examples.
Hereinafter, the invention is described in further detail by providing specific examples, but the protection range of the claims of the application is not limited by the specific examples.
[0026] EXAMPLE 1
[0027] (1) Preparation of the graphene dispersion liquid: 800 ml of dispersant dimethylacetamide and 0.24 g of graphene are added into a container, and ultrasonic dispersion is carried out on the obtained mixture for 30 min to obtain homogenous graphene dispersion.
[0028] (2) Preparation of the oil-absorbing hollow fiber porous membrane: the polyacrylonitrile filaments braided hollow tube is prepared into an assembly and immersed into the graphene dispersion liquid at a temperature of 25 C, pumping filtration is carried out from a dead-end of hollow fiber porous membrane under a negative pressure of 0.08 MPa for 10 min, and then the membrane is placed in the air for naturally drying until excess graphene on the surface of the hollow fiber porous membrane falls off, finally, the membrane is put in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 10 h.
[0029] (3) Processing of the surface of the oil-absorbing hollow fiber porous membrane:
first, a dilute solution is prepared, polyacrylonitrile which is 1% of the total mass of the dilute solution, polyvinylpyrrolidone which is 6% of the total mass of the dilute solution and dimethylacetamide which is 93% of the total mass of the dilute solution are mixed and stirred at 70 C for 1 h to form a uniform transparent solution, then the oil-absorbing hollow membrane prepared in step (2) is immersed into the dilute solution, filtration is carried out at a negative pressure of 0.8 bar for 7 s, and the membrane is quickly taken out and put into water for solidification to obtain the final product.
first, a dilute solution is prepared, polyacrylonitrile which is 1% of the total mass of the dilute solution, polyvinylpyrrolidone which is 6% of the total mass of the dilute solution and dimethylacetamide which is 93% of the total mass of the dilute solution are mixed and stirred at 70 C for 1 h to form a uniform transparent solution, then the oil-absorbing hollow membrane prepared in step (2) is immersed into the dilute solution, filtration is carried out at a negative pressure of 0.8 bar for 7 s, and the membrane is quickly taken out and put into water for solidification to obtain the final product.
[0030] Performance examination: the water intake pressure of the product hollow fiber membrane is 0.016 MPa , and the kerosene flux measured under 0.01 MPa is 12733 L/m2. h.
[0031] EXAMPLE 2
[0032] (1) Preparation of the graphene dispersion liquid: 600 ml of dispersant absolute ethyl alcohol and 0.3 g of graphene are added into a container, and ultrasonic dispersion is carried out on the obtained mixture for 30 min to obtain homogenous graphene dispersion.
[0033] (2) Preparation of the oil-absorbing hollow fiber porous membrane: the polyvinyl chloride hollow fiber membrane is prepared into an assembly and immersed into the graphene dispersion liquid at a temperature of 20 C, pumping filtration is carried out from a dead-end of hollow fiber porous membrane under a negative pressure of 0.06 MPa for 30 min, and then the membrane is placed in the air for naturally drying until excess graphene on the surface of the hollow fiber porous membrane falls off, finally the membrane is put in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room temperature for 12 h.
[0034] (3) Processing of the surface of the oil-absorbing hollow fiber porous membrane:
the oil-absorbing hollow membrane prepared in step (2) is immersed into 80 wt%
of toluenedimethylbenzene aqueous solution and taken out after 3 s and then immediately put into water for solidification to obtain the final product.
the oil-absorbing hollow membrane prepared in step (2) is immersed into 80 wt%
of toluenedimethylbenzene aqueous solution and taken out after 3 s and then immediately put into water for solidification to obtain the final product.
[0035] Performance examination: the water intake pressure of the product hollow fiber membrane is 0.065 MPa, and the kerosene flux measured under 0.056 MPa is 126.32 L/m2. h.
[0036] EXAMPLE 3
[0037] (1) Preparation of the graphene dispersion liquid: 800 -ml of dispersant absolute ethyl alcohol and 0.32 g of graphene are added into a container, and ultrasonic dispersion is carried out on the obtained mixture for 35 min to obtain homogenous graphene dispersion.
[0038] (2) Preparation of the oil-absorbing hollow fiber porous membrane: the polyvinylidene fluoride hollow fiber membrane is prepared into an assembly and immersed into the graphene dispersion liquid at a temperature of 20 C, pumping filtration is carried out from a dead-end of hollow fiber porous membrane under a negative pressure of 0.08 MPa for 20 min, and then the membrane is placed in the air for naturally drying until excess graphene on the surface of the hollow fiber porous membrane falls off, finally, the membrane is put in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 12 h.
[0039] (3) Processing of the surface of the oil-absorbing hollow membrane: the oil-absorbing hollow membrane prepared in step (2) is immersed into 100 wt% of dimethylacetamide solution and taken out after 1 s and then immediately put into water for solidifying to obtain the final product.
[0040] Performance examination: the water intake pressure of the product hollow fiber membrane is 0.06 MPa, and the kerosene flux measured under 0.044 MPa is 88.24 L/m2.h.
[0041] EXAMPLE 4
[0042] (1) Preparation of the graphene dispersion liquid: 500 ml of dispersant absolute ethyl alcohol and 0.20 g of graphene are added into a container, and ultrasonic dispersion is carried out on the obtained mixture for 20 min to obtain homogenous graphene dispersion liquid.
[0043] (2) Preparation of the oil-absorbing hollow fiber porous membrane: the polypropylene hollow fiber membrane is prepared into an assembly and immersed into the graphene dispersion liquid at a temperature of 20 C, pumping filtration is carried out from a dead-end of hollow fiber porous membrane under a negative pressure of 0.08 MPa for 20 min, and the membrane is placed in the air for naturally drying.
[0044] (3) Processing of the surface of the oil-absorbing hollow fiber porous membrane:
first, a dilute solution is prepared, polypropylene which is 1% of the total mass of the dilute solution and decahydronaphthalene which is 99% of the total mass of the dilute solution are mixed and stirred at 180 C for 1h to form a uniform transparent solution.
Then, the oil-absorbing hollow fiber porous membrane prepared in step (2) is immersed into the dilute solution, filtration is carried out at a negative pressure of 0.08 MPa for 7 s, and the membrane is quickly taken out and put into ethyl alcohol for solidification to obtain the final product.
first, a dilute solution is prepared, polypropylene which is 1% of the total mass of the dilute solution and decahydronaphthalene which is 99% of the total mass of the dilute solution are mixed and stirred at 180 C for 1h to form a uniform transparent solution.
Then, the oil-absorbing hollow fiber porous membrane prepared in step (2) is immersed into the dilute solution, filtration is carried out at a negative pressure of 0.08 MPa for 7 s, and the membrane is quickly taken out and put into ethyl alcohol for solidification to obtain the final product.
[0045] Performance examination: the water intake pressure of the product hollow fiber membrane is 1.3 bar, and the kerosene flux measured under 0.084 MPa is 1398.86 L/m2.h.
[0046] The continuous oil adsorption and oil-water separation performance tests are carried out on the oil-absorbing hollow fiber porous membrane prepared in examples 1-4 in the invention: the continuous oil adsorption device being used is a well-known common membrane filtration device (referring to Fig. 1). Firstly, the oil-absorbing hollow fiber porous membrane is prepared into a membrane assembly 3 and suspends at the interface of the kerosene 2 and water 1. A circulating water vacuum pump 7 provides an appropriate negative pressure for pumping oil and water. The oil is preferentially absorbed by the graphene on the outer surface of the oil-absorbing hollow fiber membrane and is desorbed through negative pressure pumping. Meanwhile, the oil passes through the hollow fiber porous membrane wall and is transported to a liquid storage tank 6 along the hollow pipeline orderly through a pressure gauge 4 and a valve 5. The liquid storage tank 6 is connected with the circulating water vacuum pump 7 through a pipeline.
[0047] Before measuring the kerosene flux of the oil-absorbing hollow fiber membrane, the critical water intake pressure is measured, and then under a condition of below the critical pressure, the measurement for kerosene flux can be carried out in guarantee that the oil-absorbing hollow fiber porous membrane only absorbs oil but not water.
The test results are shown in Table 1. The continuous oil adsorption device test shows that the oil-absorbing hollow fiber porous membrane can simultaneously carry out continuous oil adsorption and oil-water separation, and the continuous oil adsorption of the oil-absorbing hollow membrane can be realized. The kerosene flux table (table 1) of the oil-absorbing hollow membrane means that the oil-absorbing hollow fiber porous membrane has a continuous oil adsorption function.
The test results are shown in Table 1. The continuous oil adsorption device test shows that the oil-absorbing hollow fiber porous membrane can simultaneously carry out continuous oil adsorption and oil-water separation, and the continuous oil adsorption of the oil-absorbing hollow membrane can be realized. The kerosene flux table (table 1) of the oil-absorbing hollow membrane means that the oil-absorbing hollow fiber porous membrane has a continuous oil adsorption function.
[0048] Table 1. Kerosene Flux of the Oil-Absorbing Hollow Membrane Prepared In the Examples Test Time (min) pressu ________________________________________________________________________ Examples re (bar) Example I
kerosene 0.1 12733 12233 12103 11973 11687 11478 flux (L/m2.h ) Example 2 kerosene 0.56 126.32 116.24 109.78 95.54 93.23 90.38 88.76 86.21 86.13 flux (L/m2.h) Example 3 kerosene 0.44 88.24 82.75 80.65 78.59 71.78 66.57 60.63 55.75 51.43 flux (L/m2.h ) Example 4 kerosene 0.84 1398.86 1391.73 1388.39 1385.94 1382.78 1380.64 1378.67 1377.85 1377.70 flux (L/m2.h )
kerosene 0.1 12733 12233 12103 11973 11687 11478 flux (L/m2.h ) Example 2 kerosene 0.56 126.32 116.24 109.78 95.54 93.23 90.38 88.76 86.21 86.13 flux (L/m2.h) Example 3 kerosene 0.44 88.24 82.75 80.65 78.59 71.78 66.57 60.63 55.75 51.43 flux (L/m2.h ) Example 4 kerosene 0.84 1398.86 1391.73 1388.39 1385.94 1382.78 1380.64 1378.67 1377.85 1377.70 flux (L/m2.h )
Claims (4)
1. A preparation method of an oil-absorbing hollow fiber porous membrane, the preparation method being implemented by taking graphene as a surface adsorption layer and taking a hollow fiber porous membrane as a matrix layer through the following preparation process:
(1). Preparation of graphene dispersion liquid: mixing 0.1-1g of graphene with 200-1000ml of a dispersant, and carrying out ultrasonic dispersion for 10-50 min to prepare the graphene dispersion liquid, wherein the graphene has a thickness of less than nm and a diameter of 0.1-5 µm; and the dispersant is one of absolute ethyl alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide or dimethylacetamide;
(2). Preparation an oil-absorbing hollow fiber porous membrane: firstly, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1), and pumping filtration from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 5-30 min.
Then the membrane is naturally dried in the air until excess graphene on the surface of the hollow fiber porous membrane falls off, putting it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 6-12 h, wherein the polymer hollow fiber porous membrane becomes a polyvinyl chloride hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polypropylene hollow fiber membrane or polyacrylonitrile filament braided hollow tube ; and the temperature of the graphene dispersion liquid is 20-30 °C;
(3). Enhancement of the interface bonding strength between the graphene and the hollow fiber porous membrane: enhancing the interface bonding strength between the graphene and the hollow fiber porous membrane by using one of the following two processing methods, alternately: 1) a solvent processing method: first, preparing 20-100 wt% of an aqueous solution of a solvent, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the solvent aqueous solution for 1-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidifying, yielding the oil-absorbing hollow fiber porous membrane, wherein the solvent is dimethylformamide, dimethylacetamide, dimethyl sulfoxide or dimethylbenzene; and the medium of the coagulation bath is water. 2) a dilute solution processing method: firstly, preparing a dilute solution, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution. Then pumping filtration is carried out from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidifying, yielding the oil-absorbing hollow fiber porous membrane, wherein the dilute solution is prepared by polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively; the polymer is polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent is dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent, or water.
(1). Preparation of graphene dispersion liquid: mixing 0.1-1g of graphene with 200-1000ml of a dispersant, and carrying out ultrasonic dispersion for 10-50 min to prepare the graphene dispersion liquid, wherein the graphene has a thickness of less than nm and a diameter of 0.1-5 µm; and the dispersant is one of absolute ethyl alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide or dimethylacetamide;
(2). Preparation an oil-absorbing hollow fiber porous membrane: firstly, preparing a polymer hollow fiber porous membrane into module, immersing the module into the graphene dispersion liquid prepared in step (1), and pumping filtration from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 5-30 min.
Then the membrane is naturally dried in the air until excess graphene on the surface of the hollow fiber porous membrane falls off, putting it in a vacuum oven under a negative pressure of 0.1 MPa for drying at a room-temperature for 6-12 h, wherein the polymer hollow fiber porous membrane becomes a polyvinyl chloride hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polypropylene hollow fiber membrane or polyacrylonitrile filament braided hollow tube ; and the temperature of the graphene dispersion liquid is 20-30 °C;
(3). Enhancement of the interface bonding strength between the graphene and the hollow fiber porous membrane: enhancing the interface bonding strength between the graphene and the hollow fiber porous membrane by using one of the following two processing methods, alternately: 1) a solvent processing method: first, preparing 20-100 wt% of an aqueous solution of a solvent, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the solvent aqueous solution for 1-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidifying, yielding the oil-absorbing hollow fiber porous membrane, wherein the solvent is dimethylformamide, dimethylacetamide, dimethyl sulfoxide or dimethylbenzene; and the medium of the coagulation bath is water. 2) a dilute solution processing method: firstly, preparing a dilute solution, then immersing the oil-absorbing hollow fiber porous membrane prepared in step (2) into the dilute solution. Then pumping filtration is carried out from dead-end of hollow fiber porous membrane under a negative pressure of 0.02-0.08 MPa for 3-20 s, and quickly taking the membrane out and putting it in a coagulation bath for solidifying, yielding the oil-absorbing hollow fiber porous membrane, wherein the dilute solution is prepared by polymer material, additives and solvents, as each constituent percentage of total quantity is 0.5-6wt%, 0-12wt% and 82-99wt%, respectively; the polymer is polyvinyl chloride, polyvinylidene fluoride, polypropylene or polyacrylonitrile; the additive is the distilled water, anhydrous lithium chloride, polyvinylpyrrolidone or polyethylene glycol; the solvent is dimethylformamide, dimethylacetamide, tetrahydrofuran or decahydronaphthalene; and the medium of the coagulation bath is the aqueous solution of the solvent, or water.
2. The preparation method of an oil-absorbing hollow fiber porous membrane according to claim 1, characterized in that, the specification of the hollow fiber porous membrane comprises an pore size range of 0.1-10 µm, and more than 50% porosity ; and the specification of the filament braided hollow tube comprises a braiding pitch of 400-600 µm.
3. An oil-absorbing hollow fiber porous membrane, wherein the hollow fiber porous membrane is prepared by the preparation method of an oil-absorbing hollow fiber porous membrane according to claim 1 or 2.
4. The oil-absorbing hollow fiber porous membrane according to claim 3, characterized in that, the hollow fiber porous membrane is non-swelling in an oil to be processed, such as toluene, trichloromethane, kerosene or diesel.
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| CN201410070073.8A CN103801274B (en) | 2014-02-28 | 2014-02-28 | Preparation method of oil-absorbing hollow fiber porous membrane |
| CN201410070073.8 | 2014-02-28 | ||
| PCT/CN2014/089681 WO2015127792A1 (en) | 2014-02-28 | 2014-10-28 | Method for preparing oil-absorbing hollow fiber porous membrane |
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| CN103801274B (en) * | 2014-02-28 | 2015-07-08 | 天津工业大学 | Preparation method of oil-absorbing hollow fiber porous membrane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113856244A (en) * | 2021-10-21 | 2021-12-31 | 国网浙江省电力有限公司检修分公司 | Porous composite material with gradient structure and preparation method and application thereof |
| CN113975978A (en) * | 2021-12-10 | 2022-01-28 | 江苏巨之澜科技有限公司 | Graphene-enhanced photo-thermal evaporation membrane, membrane assembly and sewage concentration treatment device |
| CN113975978B (en) * | 2021-12-10 | 2023-05-26 | 江苏巨之澜科技有限公司 | Graphene-enhanced photo-thermal evaporation membrane, membrane module and sewage concentration treatment device |
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| JP2016515933A (en) | 2016-06-02 |
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