CN103801274B - Preparation method of oil-absorbing hollow fiber porous membrane - Google Patents
Preparation method of oil-absorbing hollow fiber porous membrane Download PDFInfo
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- CN103801274B CN103801274B CN201410070073.8A CN201410070073A CN103801274B CN 103801274 B CN103801274 B CN 103801274B CN 201410070073 A CN201410070073 A CN 201410070073A CN 103801274 B CN103801274 B CN 103801274B
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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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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Abstract
The 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) preparing graphene dispersion liquid; mixing 0.1-1g of graphene with 200-1000ml of a dispersant, and carrying out ultrasonic dispersion on the obtained mixture for 10-50 min; (2) preparing an oil-absorbing hollow membrane; firstly, preparing a polymer hollow fiber porous membrane into an assembly, immersing the assembly into the graphene dispersion liquid prepared in the step (1), and carrying out dead-end suction filtration on the obtained object for 5-30 min at negative pressure of 0.2-0.8 bar, then after the obtained object is naturally dried in the air until the graphene on the surface of the hollow fiber porous membrane falls off, putting the obtained product into a vacuum drying oven at negative pressure of 0.1 MPa to carry out room-temperature drying for 6-12 h; and (3) enhancing the interface binding strength between the graphene and the hollow fiber porous membrane by using a solvent processing method (1) or a dilute solution processing method (2).
Description
Technical field
The present invention relates to a kind of technology of preparing of function hollow-fibre membrane, be specially a kind of preparation method of oil suction hollow fiber porous film.
Background technology
In recent years, the water resource such as river, ocean that oiliness organic compound and organic wastewater, waste liquid and various accident cause as oil carrier, tank leakage and problem of environmental pollution are on the rise, tradition oil absorption material is as clay, paper pulp, wood silk floss etc., its oil suction multiplying power is low, oil-water selectivity is poor, oil-retaining is weak, cannot meet the requirement of oily waste water resource and environmental improvement.
In many oil pollution substance treating methods, oil suction fibre is widely adopted because of advantages such as its specific area are large, speed of oil absorption is fast, efficiency is high, oil product easily reclaims.About the research of oil suction fibre, Xiao Changfa etc. have prepared copolymethacrylate oil suction fibre (CN200710059780.7; CN200410019338.8), Liu Yanping etc. have prepared supertine oil absorption fibre (CN200710043566.2) by electrostatic spinning technique.But described oil suction fibre can only by the space between fiber or the swelling oil suction of semi-intercrossing network, after absorption oil product reaches capacity state, its adsorption function totally, can not use continuously, need change oil absorption material or regenerate, not only service efficiency reduces, cost of disposal improves, and be difficult to meet continuously, fast, efficiently dispose organic wastewater, large area spilled oil on water surface pollutes and the demand such as environmental protection.
Porous polymer matrix Graphene oil absorption material is a kind of novel oil absorption material.2011, D.Zha etc. adopt diffusion method to make water or methyl alcohol enter dimethyl formamide (DMF) dispersion liquid of Kynoar (PVDF)/Graphene, obtain PVDF/ Graphene gel, the DMF in gel is replaced again with water, super-hydrophobic lipophile PVDF/ Graphene porous material (Zha D is obtained after freeze-drying, Mei S, Wang Z, et al.Superhydrophobic polyvinylidene fluoride/graphene porousmaterials [J] .Carbon, 2011,49 (15): 5166-5172.), 2012, the D.D.Nguyen of Taiwan Tsing-Hua University etc. by melamine sponge impregnating in the alcohol dispersion liquid of Graphene, obtain graphene coated sponge, again through dimethyl silicone polymer surface process, obtained super-hydrophobic, lipophile sponge base grapheme material (Nguyen D D, Tai N H, Lee S B, et al.Superhydrophobic and superoleophilic properties of graphene-based sponges fabricated using afacile dip coating method [J] .Energy & Environmental Science, 2012, 5 (7): 7908-7912.).It has very strong adsorption capacity to oiliness organic compound, as can be reached 165 times of deadweight to the maximum saturation adsorbance of chloroform, 2013, polyurethane sponge is immersed in the dispersion liquid of graphene oxide by the Liu of University Of Tianjin etc., regulate dispersion liquid pH, and adopt hydrazine to reduce to graphene oxide, obtained super-hydrophobic, super-oleophilic sponge base Graphene oil absorption material (Yue Liu, Junkui Ma, Tao Wu, et al.Cost-effective reduced grapheme oxide-coated polyurethane sponge asa highly efficient and reusable oil-absorbent [J] .ACS Applied materials & interfaces, 2013, 5 (20): 10018-10026.).It reaches 160g/g to the maximum saturation adsorbance of chloroform.Above-mentioned Polymers Graphene oil absorption material oil-water selectivity is good, oil suction multiplying power is high, considerably beyond the intrinsic synthesis oil-absorbing resin material of routine, is subject to people and pays close attention to.But the oil-absorbing process of these oil absorption materials still belongs to interval feature operation, the continuous high-efficient that the method for there is no realizes profit system adsorbs and is separated, and industrial sizable application is restricted.
Summary of the invention
For the deficiency of existing oil absorption material, the technical problem that quasi-solution of the present invention is determined is, provides a kind of preparation method of oil suction hollow fiber porous film.This preparation method is from material oil-absorbing process, with super-hydrophobic, lipophilic graphene for surface absorbed layer, with oleophylic (non-swelling) property polymeric hollow fibre perforated membrane for hypothallus, the oil suction hollow fiber porous film oil-collecting product absorption property of preparation and oil-water separating function are in one, there is continuous oil suction and refuse water and continuous water-oil separating feature, also can be processed into the goods of variform, and technical process is simple simultaneously, cost is low, meets industrial applicibility requirement.
The technical scheme that the present invention solve the technical problem is: the preparation method designing a kind of oil suction hollow fiber porous film, and this preparation method is surface absorbed layer with Graphene, take hollow fiber porous film as hypothallus, and adopts following preparation technology:
(1). configuration graphene dispersing solution; By 0.1-1g Graphene and 200-1000ml dispersant, ultrasonic wave dispersion 10-50min, is mixed with graphene dispersing solution; Wherein, the thickness of Graphene is less than 10nm, and diameter is 0.1-5 μm; Dispersant is the one in absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2). preparation oil suction hollow membrane; First polymeric hollow fibre perforated membrane is made assembly, be immersed in (1) the configured graphene dispersing solution of step, under 0.2-0.8bar negative pressure, dead end suction filtration 5-30min, then this film is placed natural drying in atmosphere, after the Graphene of hollow fiber porous film excess surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 6-12h under normal temperature; Described polymeric hollow fibre perforated membrane refers to PVC hollow fiber membrane, Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane or polyacrylonitrile hollow woven tube; Described graphene dispersion liquid temp is 20-30 DEG C;
(3). interface cohesion fastness strengthening between Graphene and hollow fiber porous film; By one of two kinds of factures strengthening Graphene and hollow fiber porous film interface cohesion fastness between the two: 1. solvent treatment method, first the solvent aqueous solution of 20-100wt% is configured, then the oil suction hollow fiber porous film that step is (2) prepared is immersed in 1-20s in this solvent aqueous solution, rapid taking-up is put into coagulating bath and is solidified, i.e. obtained described oil suction hollow fiber porous film; Described solvent is dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or dimethylbenzene; Described coagulating bath medium is water; 2. weak solution facture, first configure weak solution, then the oil suction hollow fiber porous film that step is (2) prepared is immersed in this weak solution, suction filtration 3-20s under 0.2-0.8bar negative pressure, rapid taking-up is put into coagulating bath and is solidified, i.e. obtained described oil suction hollow fiber porous film; Described weak solution is rare polymer solution, and polymeric material quality accounts for the 0.5-6% of weak solution gross mass, and additive quality accounts for the 0-12% of weak solution gross mass, and solvent quality accounts for the 82-99% of weak solution gross mass, and each component sum is 100%; Described polymer is polyvinyl chloride, Kynoar, polypropylene or polyacrylonitrile; Described solvent is dimethyl formamide, dimethylacetylamide, oxolane or decahydronaphthalene; Described coagulating bath medium is the aqueous solution or the water of described solvent.
The present invention proposes the specific form by hollow fiber porous film first, plays oil suction and the synergistic design concept of separation function.Compared with prior art, oil suction hollow fiber porous film of the present invention has continuous oil suction and separation function, and its oil suction specific area is large, and speed of oil absorption is fast, efficiency is high, and oil product easily reclaims; Oil suction hollow fiber porous film of the present invention can be processed into the goods of various form and purposes as required, when administering the waters by oiliness Organic Pollution, the oil suction of oil-water interfaces place can be suspended in, its range of application and field are widened, and the inventive method technique is simple, with low cost, industrializing implementation is easy, has good economic and social benefit prospect.
Accompanying drawing explanation
The oil suction hollow fiber porous film continuous oil absorption test apparatus structure schematic diagram of Fig. 1 obtained by preparation method of the present invention.
Detailed description of the invention
The present invention is described further below in conjunction with embodiment and accompanying drawing:
The preparation method (hereinafter referred to as preparation method) of oil suction hollow fiber porous film (hereinafter referred to as hollow membrane) of the present invention's design is surface absorbed layer with Graphene, be hypothallus with hollow fiber porous film, adopt following technical process to prepare:
(1) configure graphene dispersing solution; By 0.1-1g Graphene and 200-1000ml dispersant, ultrasonic wave dispersion 10-50min, is mixed with graphene dispersing solution; Wherein, the thickness of described Graphene is less than 10nm, and diameter is 0.1-5 μm; Described dispersant is absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2) prepare oil suction hollow membrane; First polymeric hollow fibre perforated membrane is made assembly, be immersed in (1) the configured graphene dispersing solution of step, dead end suction filtration 5-30min under 0.2-0.8bar negative pressure, then this film is placed natural drying in atmosphere, after the Graphene of hollow fiber porous film excess surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 6-12h under normal temperature; Described graphene dispersion liquid temp is 20-30 DEG C;
(3) between Graphene and doughnut porous basement membrane, interface cohesion fastness is strengthened; Graphene and doughnut porous (base) film interface cohesion fastness is between the two strengthened: 1. solvent treatment method by one of two kinds of factures, first the solvent aqueous solution of 20-100wt% is configured, then the oil suction hollow membrane that step is (2) prepared is immersed in 1-20s in solvent aqueous solution, rapid taking-up is put into coagulating bath and is solidified, i.e. obtained described oil suction hollow membrane; Wherein, described solvent is the one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or dimethylbenzene; Described coagulating bath medium is water; 2. weak solution facture, first configures weak solution, and be then immersed in this weak solution by the oil suction hollow membrane that step is (2) prepared, under 0.2-0.8bar negative pressure, suction filtration 3-20s, takes out rapidly, puts into coagulating bath and solidifies, i.e. obtained described oil suction hollow membrane; Described weak solution is rare polymer solution, and wherein, polymeric material quality accounts for the 0.5-6% of weak solution gross mass, and additive quality accounts for the 0-12% of weak solution gross mass, and solvent quality accounts for the 82-99% of weak solution gross mass, and each component sum is 100%; Described polymeric material is polyvinyl chloride, Kynoar, polypropylene or polyacrylonitrile; Described solvent is the one in dimethyl formamide, dimethylacetylamide, oxolane or decahydronaphthalene, and described coagulating bath medium is the aqueous solution or the water of described solvent.
Absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide etc. are comprised for the dispersant of dispersed graphite alkene in preparation method of the present invention; The preferred absolute ethyl alcohol of described dispersant.
For ensureing efficient oil suction and being separated, the further feature of preparation method of the present invention is, described hollow fiber porous film specification is: pore diameter range 0.1-10 μm, and porosity is greater than 50%; Described woven hollow fiber pipe specification is: lay of braiding 400-600 μm.
Oil suction hollow membrane of the present invention can be obtained according to preparation method of the present invention.This oil suction hollow membrane not only has the high function of oil absorbency, and has continuous oil absorptive function, also has oil-water separating function simultaneously.Preparation method's gained hollow fiber porous film of the present invention is not swelling in handled oil product.Described process oil product is mainly the oiliness such as toluene, chloroform low molecule organic liquid or the some hydrocarbon such as kerosene, diesel oil mixture.
Oil suction hollow membrane obtained by preparation method of the present invention has one of principle of continuous oil absorptive function: during the oil suction hollow membrane surface adopting solvent aqueous solution treatment step (2) obtained, due to the good solvent that described solvent is hollow fiber porous film polymeric material, when oil suction hollow membrane contacts with solvent aqueous solution, solvent can to the swelling dissolving of hollow-fibre membrane surface holes, again while solidifying in coagulating bath, Graphene can be embedded in doughnut fenestra, thus improve the interface cohesion fastness between Graphene and hollow-fibre membrane.
Oil suction hollow membrane obtained by preparation method of the present invention has two of the principle of continuous oil absorptive function: during the oil suction hollow membrane surface adopting weak solution treatment step (2) obtained, due to the polymer solution that described weak solution is rare, there is certain viscosity, Graphene can be bonded in securely oil suction hollow membrane surface, ensure the exposed surface at hypothallus of Graphene simultaneously, thus improve the interface cohesion fastness between Graphene and oil suction hollow membrane.
Oil suction hollow membrane obtained by preparation method of the present invention with hydrophobicity Graphene for adsorption layer, oleophylic (non-swelling) property hollow fiber porous film is hypothallus, be made into membrane module and put into oil/water solution, one end seals, the other end provides suitable negative pressure, Graphene adsorption layer plays oil suction and refuses water, the continus convergence that negative pressure is oil product provides power, its continuous oil suction and the mechanism of mass transfer be separated are that oil product is by the Graphene Preferential adsorption of oil suction doughnut film outer surface, oil product is made to pass hollow fiber porous film wall by negative-pressure ward, Fuel Tanking Unit is delivered to along its hollow pipeline, make it carry out the absorption of oil product and desorption simultaneously.
The present invention does not address part and is applicable to prior art.Provide specific embodiment below, specifically to describe the present invention in detail further, but the application's claims is not by the restriction of specific embodiment:
Embodiment 1
(1) graphene dispersing solution is configured: add 800mL dispersant dimethylacetylamide and 0.24g Graphene in a reservoir, ultrasonic wave dispersion treatment 30min, obtained uniform graphene dispersing solution.
(2) oil suction hollow membrane is prepared: polyacrylonitrile hollow knitted tubing is become assembly, being immersed in temperature is in the graphene dispersing solution of 25 DEG C, dead-end filtration 10min under 0.8bar negative pressure, then this film is placed natural drying in atmosphere, after hollow fiber porous film excess surface Graphene comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 10h under normal temperature.
(3) oil suction hollow membrane surface treatment: first configure weak solution, weak solution gross mass 1% polyacrylonitrile will be accounted for, account for weak solution gross mass 6% additive, account for the mixing of weak solution gross mass 93% dimethylacetylamide, 1h is stirred at 70 DEG C, form the solution of transparent and homogeneous, then oil suction hollow membrane step (2) prepared immerses in weak solution, suction filtration 7s under 0.8bar negative pressure, takes out rapidly and puts into water and solidify and get final product.
Service check: it is 0.16bar that the water of this finished product hollow-fibre membrane enters pressure, and recording its kerosene flux under 0.1bar is 12733L/m
2h.
Embodiment 2
(1) graphene dispersing solution is configured: add 600mL dispersant absolute ethyl alcohol and 0.3g Graphene in a reservoir, ultrasonic wave dispersion treatment 30min, obtained uniform graphene dispersing solution.
(2) oil suction hollow membrane is prepared: PVC hollow fiber membrane is made assembly, being immersed in temperature is in the graphene dispersing solution of 20 DEG C, dead-end filtration 30min under 0.6bar negative pressure, then this film is placed natural drying in atmosphere, after hollow fiber porous film excess surface Graphene comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 12h under normal temperature.
(3) oil suction hollow membrane surface treatment: oil suction hollow membrane step (2) prepared immerses in the 80wt% dimethylbenzene aqueous solution, takes out, put into water immediately and solidify and get final product after 3s.
Service check: it is 0.65bar that the water of this finished product hollow-fibre membrane enters pressure, and recording its kerosene flux under 0.56bar is 126.32L/m
2h.
Embodiment 3
(1) graphene dispersing solution is configured: add 800mL dispersant absolute ethyl alcohol and 0.32g Graphene in a reservoir, ultrasonic wave dispersion treatment 35min, obtained uniform graphene dispersing solution.
(2) oil suction hollow membrane is prepared: Pvdf Microporous Hollow Fiber Membrane is made assembly, being immersed in temperature is in the graphene dispersing solution of 20 DEG C, dead-end filtration 20min under 0.8bar negative pressure, then this film is placed natural drying in atmosphere, after hollow fiber porous film excess surface Graphene comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 12h under normal temperature.
(3) oil suction hollow membrane surface treatment: oil suction hollow membrane step (2) prepared immerses in 100wt% dimethylacetamide solution, takes out, put into water immediately and solidify and get final product after 1s.
Service check: it is 0.6bar that the water of this finished product hollow-fibre membrane enters pressure, and recording its kerosene flux under 0.44bar is 88.24L/m
2h.
Embodiment 4
(1) graphene dispersing solution is configured: add 500mL dispersant absolute ethyl alcohol and 0.20g Graphene in a reservoir, ultrasonic wave dispersion treatment 20min, obtained uniform graphene dispersing solution.
(2) prepare oil suction hollow membrane: polypropylene hollow fiber membrane is made assembly, being immersed in temperature is in the graphene dispersing solution of 20 DEG C, and dead-end filtration 20min under 0.8bar negative pressure, places natural drying in atmosphere by film.
(3) oil suction hollow membrane surface treatment: first configure weak solution, will account for weak solution gross mass 1% polypropylene, account for the mixing of weak solution gross mass 99% decahydronaphthalene, and stir 1h, form the solution of transparent and homogeneous at 180 DEG C.Then the oil suction hollow membrane step (2) prepared immerses in weak solution, suction filtration 7s under 0.8bar negative pressure, takes out rapidly to put into ethanol and solidify and get final product.
Service check: it is 1.3bar that the water of this finished product hollow-fibre membrane enters pressure, and recording its kerosene flux under 0.84bar is 1398.86L/m
2h.
The present invention has carried out continuous adsorption oil product and the test of water-oil separating performance to the oil suction hollow membrane obtained by embodiment 1-4: continuous Oil sucking device used is known common film filter (see Fig. 1).First oil suction hollow membrane is made membrane module 3 and be suspended in kerosene 2 and the interface of water 1, provide suitable negative pressure to aspirate profit by circulating water type vavuum pump 7; Oil product is by the Graphene Preferential adsorption of oil suction doughnut film outer surface, and negative-pressure ward makes its desorption, simultaneously through hollow fiber porous film wall, makes it carry along hollow pipeline, more successively through Pressure gauge 4 and valve 5, is delivered in fluid reservoir 6.Fluid reservoir 6 is connected with circulating water type vavuum pump 7 pipeline.
Before measuring oil suction hollow-fibre membrane kerosene flux, first to measure the critical pressure that its water enters, then lower than under critical pressure condition, measure its kerosene flux, to ensure that the oil suction of oil suction hollow membrane does not absorb water.Test result is as shown in table 1, and (described continuous Oil sucking device test specification oil suction hollow membrane can carry out water-oil separating while continuous adsorption oil product, and it can realize the continuous oil suction of oil suction hollow membrane; And oil suction hollow membrane kerosene flux table (table 1) characterizes oil suction hollow membrane has continuous oil absorptive function.
The kerosene flux of the oil suction hollow membrane obtained by table 1 embodiment
Claims (4)
1. a preparation method for oil suction hollow fiber porous film, this preparation method is surface absorbed layer with Graphene, is hypothallus, and adopts following preparation technology with hollow fiber porous film:
(1). configuration graphene dispersing solution; By 0.1-1g Graphene and 200-1000ml dispersant, ultrasonic wave dispersion 10-50min, is mixed with graphene dispersing solution; Wherein, the thickness of Graphene is less than 10nm, and diameter is 0.1-5 μm; Dispersant is the one in absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2). preparation oil suction hollow fiber porous film; First polymeric hollow fibre perforated membrane is made assembly, be immersed in (1) the configured graphene dispersing solution of step, under 0.2-0.8bar negative pressure, dead end suction filtration 5-30min, then this film is placed natural drying in atmosphere, after the Graphene of hollow fiber porous film excess surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 6-12h under normal temperature, i.e. obtained described oil suction hollow fiber porous film; Described polymeric hollow fibre perforated membrane refers to PVC hollow fiber membrane, Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane or polyacrylonitrile hollow woven tube; Described graphene dispersion liquid temp is 20-30 DEG C;
(3). between Graphene and oil suction hollow fiber porous film, interface cohesion fastness is strengthened; By one of following two kinds of factures strengthening Graphene and oil suction hollow fiber porous film interface cohesion fastness between the two: 1. solvent treatment method, first the solvent aqueous solution of 20-100wt% is configured, then the oil suction hollow fiber porous film that step is (2) prepared is immersed in 1-20s in this solvent aqueous solution, rapid taking-up is put into coagulating bath and is solidified, i.e. the oil suction hollow fiber porous film of obtained binding strength strengthening; Described solvent is dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or dimethylbenzene; Described coagulating bath medium is water; 2. weak solution facture, first configure weak solution, then the oil suction hollow fiber porous film that step is (2) prepared is immersed in this weak solution, suction filtration 3-20s under 0.2-0.8bar negative pressure, rapid taking-up is put into coagulating bath and is solidified, i.e. the oil suction hollow fiber porous film of obtained binding strength strengthening; Described weak solution is rare polymer solution, and polymeric material quality accounts for the 0.5-6% of weak solution gross mass, and solvent quality accounts for the 82-99% of weak solution gross mass, and each component sum is 100%; Described polymer is polyvinyl chloride, Kynoar, polypropylene or polyacrylonitrile; Described solvent is dimethyl formamide, dimethylacetylamide, oxolane or decahydronaphthalene; Described coagulating bath medium is the aqueous solution or the water of described solvent.
2. the preparation method of oil suction hollow fiber porous film according to claim 1, is characterized in that described hollow fiber porous film specification is: pore diameter range is 0.1-10 μm, and porosity is greater than 50%; Described woven hollow fiber pipe specification is: lay of braiding 400-600 μm.
3. an oil suction hollow fiber porous film, the preparation method of this hollow fiber porous film oil suction hollow fiber porous film according to claim 1 or 2 prepares and obtains.
4. oil suction hollow fiber porous film according to claim 3, is characterized in that described hollow fiber porous film is not swelling in handled oil product; Handled oil product is toluene, chloroform, kerosene or diesel oil.
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| CN201410070073.8A CN103801274B (en) | 2014-02-28 | 2014-02-28 | Preparation method of oil-absorbing hollow fiber porous membrane |
| JP2016504481A JP6076536B2 (en) | 2014-02-28 | 2014-10-28 | Method for producing oil-absorbing hollow fiber porous membrane |
| PCT/CN2014/089681 WO2015127792A1 (en) | 2014-02-28 | 2014-10-28 | Method for preparing oil-absorbing hollow fiber porous membrane |
| CA2898815A CA2898815A1 (en) | 2014-02-28 | 2014-10-28 | A preparation method of an 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 |
| CN104128166B (en) * | 2014-07-22 | 2016-04-06 | 天津工业大学 | A kind of hollow tubular oil absorption material and preparation method thereof |
| CN104313552A (en) * | 2014-10-22 | 2015-01-28 | 湖南元素密码石墨烯研究院（有限合伙） | Preparation method of chemical nickel-graphene antirust coating |
| CN104525098A (en) * | 2014-12-04 | 2015-04-22 | 常州大学 | Preparation method of hollow aluminum-silicon sphere adsorption material |
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| WO2021255758A1 (en) * | 2020-06-15 | 2021-12-23 | Log 9 Materials Scientific Private Limited | High gravimetric sorption capacity oil/chemical/dye sorbent pads and a method of manufacturing the same |
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| CN115779700B (en) * | 2023-02-07 | 2023-06-27 | 天津膜天膜科技股份有限公司 | Rapid oil-absorbing hollow fiber membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101337969B1 (en) * | 2011-10-26 | 2013-12-06 | 주식회사 아이디티인터내셔널 | mixture of multi-layered graphene for adsorbing organic material |
| CN102580571B (en) * | 2012-03-15 | 2014-04-16 | 上海交通大学 | Method for preparing ultra high molecular weight polyethylene micro-filtration membrane |
| CN102600734B (en) * | 2012-03-27 | 2014-12-10 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| CN102617853B (en) * | 2012-03-27 | 2013-08-07 | 大连理工大学 | Preparation method of foamed porous graphene/polypyrrole composite oil absorption material |
| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| GB201214565D0 (en) * | 2012-08-15 | 2012-09-26 | Univ Manchester | Membrane |
| CN103521199B (en) * | 2013-10-26 | 2015-08-26 | 天津工业大学 | A kind of preparation method of hollow tubular composite oil absorption material |
| CN103801274B (en) * | 2014-02-28 | 2015-07-08 | 天津工业大学 | Preparation method of oil-absorbing hollow fiber porous membrane |
-
2014
- 2014-02-28 CN CN201410070073.8A patent/CN103801274B/en active Active
- 2014-10-28 WO PCT/CN2014/089681 patent/WO2015127792A1/en active Application Filing
- 2014-10-28 JP JP2016504481A patent/JP6076536B2/en not_active Expired - Fee Related
- 2014-10-28 CA CA2898815A patent/CA2898815A1/en not_active Abandoned
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|---|---|
| CN103801274A (en) | 2014-05-21 |
| JP6076536B2 (en) | 2017-02-08 |
| CA2898815A1 (en) | 2015-08-28 |
| JP2016515933A (en) | 2016-06-02 |
| WO2015127792A1 (en) | 2015-09-03 |
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