CN103801274A - Preparation method of oil-absorbing hollow fiber porous membrane - Google Patents
Preparation method of oil-absorbing hollow fiber porous membrane Download PDFInfo
- Publication number
- CN103801274A CN103801274A CN201410070073.8A CN201410070073A CN103801274A CN 103801274 A CN103801274 A CN 103801274A CN 201410070073 A CN201410070073 A CN 201410070073A CN 103801274 A CN103801274 A CN 103801274A
- Authority
- CN
- China
- Prior art keywords
- hollow fiber
- graphene
- fiber porous
- porous film
- oil suction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- 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
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Carbon And Carbon Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Water Treatment By Sorption (AREA)
- Artificial Filaments (AREA)
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, oiliness organic compound and organic wastewater thereof, waste liquid and various accident are on the rise as the water resource such as river, ocean and problem of environmental pollution that oil carrier, tank leakage cause, tradition oil absorption material is as clay, paper pulp, wood silk floss etc., its oil suction multiplying power is low, a little less than profit poor selectivity, oil-retaining, cannot meet the requirement of oily waste water resource and environmental improvement.
In many oil pollution substance treating methods, oil suction fibre because its specific area is large, speed of oil absorption is fast, efficiency is high, oil product easily the advantage such as recovery be widely adopted.About the research of oil suction fibre, Xiao Changfa etc. have prepared copolymethacrylate oil suction fibre (CN200710059780.7; CN200410019338.8), Liu Yanping etc. has prepared supertine oil absorption fibre (CN200710043566.2) by electrostatic spinning technique.But described oil suction fibre can only be by space or the swelling oil suction of semi-intercrossing network between fiber, when absorption oil product reaches capacity after state, its adsorption function totally, can not use continuously, need oil absorption material be changed or be regenerated, not only service efficiency reduces, cost of disposal improves, and is difficult to the satisfied demands such as organic wastewater, the pollution of large area spilled oil on water surface and environmental protection of continuously, fast, efficiently disposing.
Porous polymer matrix Graphene oil absorption material is a kind of novel oil absorption material.2011, the employing diffusion methods such as D.Zha make water or methyl alcohol enter dimethyl formamide (DMF) dispersion liquid of Kynoar (PVDF)/Graphene, obtain PVDF/ Graphene gel, water is replaced the DMF in gel again, after freeze-drying, obtain super-hydrophobic lipophile PVDF/ Graphene porous material (Zha D, Mei S, Wang Z, et al.Superhydrophobic polyvinylidene fluoride/graphene porous materials[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 processing, make 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 a facile dip coating method[J] .Energy & Environmental Science, 2012, 5 (7): 7908-7912.).It has very strong adsorption capacity to oiliness organic compound, as the maximum saturation adsorbance to chloroform can reach 165 times of deadweight, 2013, the Liu of University Of Tianjin etc. is immersed in polyurethane sponge in the dispersion liquid of graphene oxide, regulate dispersion liquid pH, and adopt hydrazine to reduce to graphene oxide, make 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 as a highly efficient and reusable oil-absorbent[J] .ACS Applied materials & interfaces, 2013, 5 (20): 10018-10026.).Its maximum saturation adsorbance to chloroform reaches 160g/g.Above-mentioned Polymers Graphene oil absorption material profit selectively good, oil suction multiplying power is high, considerably beyond the synthetic oil-absorbing resin material of conventional intrinsic, be subject to people and pay close attention to.But the oil-absorbing process of these oil absorption materials still belongs to intermittently feature operation, the continuous high-efficient that the method for there is no realizes profit system adsorbs and separates, 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 that a kind of preparation method of oil suction hollow fiber porous film is provided.This preparation method is from material oil-absorbing process, take super-hydrophobic, lipophile Graphene as surface absorbed layer, take oleophylic (non-swelling) property polymer hollow fiber multihole film as 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: design a kind of preparation method of oil suction hollow fiber porous film, this preparation method is take Graphene as surface absorbed layer, and take hollow fiber porous film as hypothallus, and employing is prepared as follows technique:
(1). configuration graphene dispersing solution; By 0.1-1g Graphene and 200-1000ml dispersant, ultrasonic wave disperses 10-50min, is mixed with graphene dispersing solution; Wherein, the thickness of Graphene is less than 10nm, and diameter is 0.1-5 μ m; Dispersant is the one in absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2). preparation oil suction hollow membrane; First polymer hollow fiber multihole film is made to assembly, be immersed in the graphene dispersing solution that (1) step configured, under 0.2-0.8bar negative pressure, dead end suction filtration 5-30min, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 6-12h under normal temperature; Described polymer hollow fiber multihole film refers to PVC hollow fiber membrane, Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane or polyacrylonitrile hollow braided tube; Described graphene dispersing solution temperature is 20-30 ℃;
(3). binding strength strengthening in interface between Graphene and hollow fiber porous film; Strengthen Graphene and hollow fiber porous film interface binding strength between the two by one of two kinds of factures: 1. solvent treatment method, first configure the solvent aqueous solution of 20-100wt%, then by step (2) prepared oil suction hollow fiber porous film be immersed in 1-20s in this solvent aqueous solution, it is curing that coagulating bath is put in taking-up rapidly, makes 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 by step (2) prepared oil suction hollow fiber porous film be immersed in this weak solution, suction filtration 3-20s under 0.2-0.8bar negative pressure, it is curing that coagulating bath is put in taking-up rapidly, makes 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; The aqueous solution or water that described coagulating bath medium is described solvent.
The present invention has proposed the specific form by hollow fiber porous film first, performance 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 forms and purposes as required, in the time that improvement is subject to the waters of oiliness Organic Pollution, can be suspended in the oil suction of oil-water interfaces place, 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
Fig. 1 is the continuous oil absorption test apparatus structure of the prepared oil suction hollow fiber porous film of preparation method of the present invention schematic diagram.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment and accompanying drawing:
The preparation method (hereinafter to be referred as preparation method) of the oil suction hollow fiber porous film (hereinafter to be referred as hollow membrane) of the present invention's design, take Graphene as surface absorbed layer, take hollow fiber porous film as hypothallus, adopts following technical process preparation:
(1) configure graphene dispersing solution; By 0.1-1g Graphene and 200-1000ml dispersant, ultrasonic wave disperses 10-50min, is mixed with graphene dispersing solution; Wherein, the thickness of described Graphene is less than 10nm, and diameter is 0.1-5 μ m; Described dispersant is absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2) prepare oil suction hollow membrane; First polymer hollow fiber multihole film is made to assembly, be immersed in the graphene dispersing solution that (1) step configured, dead end suction filtration 5-30min under 0.2-0.8bar negative pressure, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 6-12h under normal temperature; Described graphene dispersing solution temperature is 20-30 ℃;
(3) binding strength strengthening in interface between Graphene and doughnut porous basement membrane; Strengthen Graphene and doughnut porous (base) film interface binding strength between the two by one of two kinds of factures: 1. solvent treatment method, first configure the solvent aqueous solution of 20-100wt%, then by step (2) prepared oil suction hollow membrane be immersed in 1-20s in solvent aqueous solution, it is curing that coagulating bath is put in taking-up rapidly, makes 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, then by step (2) prepared oil suction hollow membrane be immersed in this weak solution, suction filtration 3-20s under 0.2-0.8bar negative pressure, takes out rapidly, puts into coagulating bath and solidifies, and makes 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, the aqueous solution or water that described coagulating bath medium is described solvent.
In preparation method of the present invention, comprise absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide etc. for the dispersant of dispersed graphite alkene; The preferred absolute ethyl alcohol of described dispersant.
For guaranteeing efficient oil suction and separating, preparation method's of the present invention further feature is that described hollow fiber porous film specification is: pore diameter range 0.1-10 μ m, and porosity is greater than 50%; Described woven hollow fiber pipe specification is: lay of braiding 400-600 μ m.
Can make oil suction hollow membrane of the present invention according to preparation method of the present invention.This oil suction hollow membrane not only has the function that oil absorbency is high, 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 processed oil product.Described processing oil product is mainly the part hydrocarbon mixtures such as the low molecule organic liquid of the oiliness such as toluene, chloroform or kerosene, diesel oil.
The prepared oil suction hollow membrane of preparation method of the present invention has one of principle of continuous oil absorptive function and is: adopt solvent aqueous solution treatment step (2) when prepared oil suction hollow membrane surface, because described solvent is the good solvent of hollow fiber porous film polymeric material, when oil suction hollow membrane contacts with solvent aqueous solution, solvent can be to the swelling dissolving of hollow-fibre membrane surface holes, again in curing in coagulating bath, Graphene can be embedded in doughnut fenestra, thereby improve the interface binding strength between Graphene and hollow-fibre membrane.
The prepared oil suction hollow membrane of preparation method of the present invention have continuous oil absorptive function principle two be: adopt weak solution treatment step (2) when prepared oil suction hollow membrane surface, because described weak solution is rare polymer solution, there is certain viscosity, Graphene can be bonded in securely to oil suction hollow membrane surface, guarantee that Graphene is exposed on the surface of hypothallus simultaneously, thereby improved the interface binding strength between Graphene and oil suction hollow membrane.
The prepared oil suction hollow membrane of preparation method of the present invention is take hydrophobicity Graphene as 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 sealing, the other end provides suitable negative pressure, Graphene adsorption layer plays oil suction and refuses water, the continuous conveying that negative pressure is oil product provides power, its continuous oil suction is that oil product is preferentially adsorbed by the Graphene of oil suction doughnut film outer surface with the mechanism of mass transfer separating, aspirate and make oil product pass hollow fiber porous film wall by negative pressure, be delivered to Fuel Tanking Unit along its hollow pipeline, its absorption and desorption to oil product is carried out simultaneously.
The present invention does not address part and is applicable to prior art.Provide specific embodiment below, describe the present invention in detail with further concrete, but the application's claim protection domain be not subject to the restriction of specific embodiment:
Embodiment 1
(1) configuration graphene dispersing solution: add 800mL dispersant dimethylacetylamide and 0.24g Graphene in container, ultrasonic wave dispersion treatment 30min, makes uniform graphene dispersing solution.
(2) prepare oil suction hollow membrane: polyacrylonitrile hollow knitted tubing is become to assembly, be immersed in temperature and be in the graphene dispersing solution of 25 ℃, dead-end filtration 10min under 0.8bar negative pressure, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface 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, to account for weak solution gross mass 1% polyacrylonitrile, account for weak solution gross mass 6% additive, account for the 93% dimethylacetylamide mixing of weak solution gross mass, stir 1h at 70 ℃, form the solution of transparent and homogeneous, then the oil suction hollow membrane of (2) step being 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, under 0.1bar, recording its kerosene flux is 12733L/m
2h.
Embodiment 2
(1) configuration graphene dispersing solution: add 600mL dispersant absolute ethyl alcohol and 0.3g Graphene in container, ultrasonic wave dispersion treatment 30min, makes uniform graphene dispersing solution.
(2) prepare oil suction hollow membrane: PVC hollow fiber membrane is made to assembly, be immersed in temperature and be in the graphene dispersing solution of 20 ℃, dead-end filtration 30min under 0.6bar negative pressure, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 12h under normal temperature.
(3) oil suction hollow membrane surface treatment: the oil suction hollow membrane that (2) step is prepared immerses in the 80wt% dimethylbenzene aqueous solution, takes out after 3s, puts into immediately water and solidifies and get final product.
Service check: it is 0.65bar that the water of this finished product hollow-fibre membrane enters pressure, under 0.56bar, recording its kerosene flux is 126.32L/m
2h.
(1) configuration graphene dispersing solution: add 800mL dispersant absolute ethyl alcohol and 0.32g Graphene in container, ultrasonic wave dispersion treatment 35min, makes uniform graphene dispersing solution.
(2) prepare oil suction hollow membrane: Pvdf Microporous Hollow Fiber Membrane is made to assembly, be immersed in temperature and be in the graphene dispersing solution of 20 ℃, dead-end filtration 20min under 0.8bar negative pressure, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface comes off, put into negative pressure 0.1MPa vacuum drying oven, dry 12h under normal temperature.
(3) oil suction hollow membrane surface treatment: the oil suction hollow membrane that (2) step is prepared immerses in 100wt% dimethylacetamide solution, takes out after 1s, puts into immediately water and solidifies and get final product.
Service check: it is 0.6bar that the water of this finished product hollow-fibre membrane enters pressure, under 0.44bar, recording its kerosene flux is 88.24L/m
2h.
Embodiment 4
(1) configuration graphene dispersing solution: add 500mL dispersant absolute ethyl alcohol and 0.20g Graphene in container, ultrasonic wave dispersion treatment 20min, makes uniform graphene dispersing solution.
(2) prepare oil suction hollow membrane: polypropylene hollow fiber membrane is made to assembly, be immersed in temperature and be in the graphene dispersing solution of 20 ℃, dead-end filtration 20min under 0.8bar negative pressure, is placed in air natural drying 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 99% decahydronaphthalene mixing of weak solution gross mass, stir 1h at 180 ℃, form the solution of transparent and homogeneous.Then the oil suction hollow membrane (2) step prepared immerses in weak solution, and suction filtration 7s under 0.8bar negative pressure takes out rapidly and puts 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, under 0.84bar, recording its kerosene flux 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 prepared oil suction hollow membrane of embodiment 1-4: continuous Oil sucking device used is known common film filter (referring to Fig. 1).First oil suction hollow membrane is made to membrane module 3 and be suspended in the interface of kerosene 2 and water 1, provide suitable negative pressure to aspirate profit by circulating water type vavuum pump 7; Oil product is preferentially adsorbed by the Graphene of oil suction doughnut film outer surface, and negative pressure suction makes its desorption, through hollow fiber porous film wall, it is carried along hollow pipeline, then pass through successively Pressure gauge 4 and valve 5 simultaneously, is delivered in fluid reservoir 6.Fluid reservoir 6 is connected with circulating water type vavuum pump 7 pipelines.
Before measuring oil suction hollow-fibre membrane kerosene flux, first to measure the critical pressure that its water enters, then under lower than critical pressure condition, measure its kerosene flux, to guarantee that the oil suction of oil suction hollow membrane does not absorb water.Test result as shown in table 1 (described continuous Oil sucking device test specification oil suction hollow membrane can in continuous adsorption oil product, carry out water-oil separating, it can realize the continuous oil suction of oil suction hollow membrane; And having characterized oil suction hollow membrane, oil suction hollow membrane kerosene flux table (table 1) there is continuous oil absorptive function.
The kerosene flux of the prepared oil suction hollow membrane of table 1 embodiment
Claims (4)
1. a preparation method for oil suction hollow fiber porous film, this preparation method is take Graphene as surface absorbed layer, and take hollow fiber porous film as hypothallus, and employing is prepared as follows technique:
(1) configuration graphene dispersing solution; By 0.1-1 g Graphene and 200-1000 ml dispersant, ultrasonic wave disperses 10-50 min, is mixed with graphene dispersing solution; Wherein, the thickness of Graphene is less than 10 nm, and diameter is 0.1-5 μ m; Dispersant is the one in absolute ethyl alcohol, 1-METHYLPYRROLIDONE, oxolane, dimethyl formamide or dimethylacetylamide;
(2) prepare oil suction hollow membrane; First polymer hollow fiber multihole film is made to assembly, be immersed in the graphene dispersing solution that (1) step configured, under 0.2-0.8 bar negative pressure, dead end suction filtration 5-30 min, then this film is placed in air natural drying, after the unnecessary Graphene in hollow fiber porous film surface comes off, put into negative pressure 0.1 MPa vacuum drying oven, dry 6-12 h under normal temperature; Described polymer hollow fiber multihole film refers to PVC hollow fiber membrane, Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane or polyacrylonitrile hollow braided tube; Described graphene dispersing solution temperature is 20-30 ℃;
(3) binding strength strengthening in interface between Graphene and hollow fiber porous film; Strengthen Graphene and hollow fiber porous film interface binding strength between the two by one of following two kinds of factures: 1. solvent treatment method, first configure the solvent aqueous solution of 20-100 wt%, then by step (2) prepared oil suction hollow fiber porous film be immersed in 1-20 s in this solvent aqueous solution, it is curing that coagulating bath is put in taking-up rapidly, makes 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 by step (2) prepared oil suction hollow fiber porous film be immersed in this weak solution, suction filtration 3-20 s under 0.2-0.8 bar negative pressure, it is curing that coagulating bath is put in taking-up rapidly, makes 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; The aqueous solution or water that described coagulating bath medium is 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 μ m, and porosity is greater than 50%; Described woven hollow fiber pipe specification is: lay of braiding 400-600 μ m.
3. an oil suction hollow fiber porous film, this hollow fiber porous film obtains according to preparation method's preparation of oil suction hollow fiber porous film described in claim 1 or 2.
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; The oil product of processing is toluene, chloroform, kerosene or diesel oil.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410070073.8A CN103801274B (en) | 2014-02-28 | 2014-02-28 | Preparation method of 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 |
| JP2016504481A JP6076536B2 (en) | 2014-02-28 | 2014-10-28 | Method for producing 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410070073.8A CN103801274B (en) | 2014-02-28 | 2014-02-28 | Preparation method of oil-absorbing hollow fiber porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103801274A true CN103801274A (en) | 2014-05-21 |
| CN103801274B CN103801274B (en) | 2015-07-08 |
Family
ID=50698948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410070073.8A Active CN103801274B (en) | 2014-02-28 | 2014-02-28 | Preparation method of oil-absorbing hollow fiber porous membrane |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6076536B2 (en) |
| CN (1) | CN103801274B (en) |
| CA (1) | CA2898815A1 (en) |
| WO (1) | WO2015127792A1 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128166A (en) * | 2014-07-22 | 2014-11-05 | 天津工业大学 | Hollow tubular oil suction 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 |
| WO2015127792A1 (en) * | 2014-02-28 | 2015-09-03 | 天津工业大学 | Method for preparing oil-absorbing hollow fiber porous membrane |
| CN105080356A (en) * | 2015-08-04 | 2015-11-25 | 天津工业大学 | Hydrophobic oleophylic hollow fiber composite film and preparation method thereof |
| CN105251459A (en) * | 2015-11-05 | 2016-01-20 | 南京理工大学 | Preparation method of graphene composite material having high oil absorption performance |
| CN105544019A (en) * | 2015-12-16 | 2016-05-04 | 华南理工大学 | High oil-absorbing polyacrylonitrile hollow activated carbon fiber and preparation method thereof |
| CN106757531A (en) * | 2016-12-08 | 2017-05-31 | 东南大学 | A kind of method using the filtering graphene-based doughnut of film preparation |
| CN107349802A (en) * | 2017-07-04 | 2017-11-17 | 联合环境技术（厦门）有限公司 | A kind of reinforced graphene is modified PVDF hollow-fibre membranes and preparation method thereof |
| CN108179732A (en) * | 2017-12-18 | 2018-06-19 | 天津膜天膜科技股份有限公司 | Fast and efficiently sea oil spill recovery system and its application method |
| CN109095550A (en) * | 2018-07-25 | 2018-12-28 | 深圳全钰环保科技有限公司 | Leachate treatment process and leachate processing system |
| CN110182898A (en) * | 2019-07-03 | 2019-08-30 | 青岛科技大学 | A kind of water-oil separating experimental provision |
| CN112221478A (en) * | 2020-10-09 | 2021-01-15 | 哈尔滨工程大学 | Graphene oil-absorbing fiber with efficient oil-water separation performance and preparation method thereof |
| CN113318611A (en) * | 2021-05-31 | 2021-08-31 | 天津工业大学 | Hollow fiber ultrafiltration membrane with lasting high pollution resistance and preparation method thereof |
| CN114824342A (en) * | 2021-01-28 | 2022-07-29 | 上海神力科技有限公司 | Preparation method of graphite polar plate, fuel cell and vehicle |
| CN114870632A (en) * | 2022-05-12 | 2022-08-09 | 浙江师范大学 | Coupling film for improving decoloration rate of printing and dyeing wastewater and preparation method thereof |
| CN115779700A (en) * | 2023-02-07 | 2023-03-14 | 天津膜天膜科技股份有限公司 | Rapid oil absorption hollow fiber membrane and preparation method and application thereof |
| CN117019118A (en) * | 2023-10-08 | 2023-11-10 | 西安金沃泰环保科技有限公司 | Filtering material for benzene series waste gas and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106759198A (en) * | 2017-03-02 | 2017-05-31 | 中国科学技术大学 | Spilled-oil recovery unit and method |
| CN210528841U (en) * | 2019-08-09 | 2020-05-15 | 河南烯力新材料科技有限公司 | Adhesive structure and electronic device |
| 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 |
| CN113363668A (en) * | 2021-06-08 | 2021-09-07 | 浙江理工大学 | Graphene-loaded glass fiber membrane with excimer ultraviolet irradiation modification and preparation method thereof |
| CN113856244B (en) * | 2021-10-21 | 2023-03-21 | 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 |
| 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 |
| CN114990683A (en) * | 2022-06-06 | 2022-09-02 | 华北电力大学（保定） | Graphene coating stainless steel array microporous fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580571A (en) * | 2012-03-15 | 2012-07-18 | 上海交通大学 | Method for preparing ultra high molecular weight polyethylene micro-filtration membrane |
| CN102600734A (en) * | 2012-03-27 | 2012-07-25 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| WO2013062373A1 (en) * | 2011-10-26 | 2013-05-02 | Idt International Co., Ltd. | Mixture of multi-layered graphene for adsorbing organic material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 JP JP2016504481A patent/JP6076536B2/en not_active Expired - Fee Related
- 2014-10-28 CA CA2898815A patent/CA2898815A1/en not_active Abandoned
- 2014-10-28 WO PCT/CN2014/089681 patent/WO2015127792A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013062373A1 (en) * | 2011-10-26 | 2013-05-02 | Idt International Co., Ltd. | Mixture of multi-layered graphene for adsorbing organic material |
| CN102580571A (en) * | 2012-03-15 | 2012-07-18 | 上海交通大学 | Method for preparing ultra high molecular weight polyethylene micro-filtration membrane |
| CN102600734A (en) * | 2012-03-27 | 2012-07-25 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015127792A1 (en) * | 2014-02-28 | 2015-09-03 | 天津工业大学 | Method for preparing oil-absorbing hollow fiber porous membrane |
| CN104128166A (en) * | 2014-07-22 | 2014-11-05 | 天津工业大学 | Hollow tubular oil suction 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 |
| CN105080356A (en) * | 2015-08-04 | 2015-11-25 | 天津工业大学 | Hydrophobic oleophylic hollow fiber composite film and preparation method thereof |
| WO2017020436A1 (en) * | 2015-08-04 | 2017-02-09 | 天津工业大学 | Hydrophobic and lipophilic hollow fiber composite film and preparation method thereof |
| CN105251459A (en) * | 2015-11-05 | 2016-01-20 | 南京理工大学 | Preparation method of graphene composite material having high oil absorption performance |
| CN105544019A (en) * | 2015-12-16 | 2016-05-04 | 华南理工大学 | High oil-absorbing polyacrylonitrile hollow activated carbon fiber and preparation method thereof |
| CN106757531B (en) * | 2016-12-08 | 2019-10-11 | 东南大学 | A method of using the filtering graphene-based doughnut of film preparation |
| CN106757531A (en) * | 2016-12-08 | 2017-05-31 | 东南大学 | A kind of method using the filtering graphene-based doughnut of film preparation |
| CN107349802A (en) * | 2017-07-04 | 2017-11-17 | 联合环境技术（厦门）有限公司 | A kind of reinforced graphene is modified PVDF hollow-fibre membranes and preparation method thereof |
| CN108179732A (en) * | 2017-12-18 | 2018-06-19 | 天津膜天膜科技股份有限公司 | Fast and efficiently sea oil spill recovery system and its application method |
| CN109095550A (en) * | 2018-07-25 | 2018-12-28 | 深圳全钰环保科技有限公司 | Leachate treatment process and leachate processing system |
| CN110182898A (en) * | 2019-07-03 | 2019-08-30 | 青岛科技大学 | A kind of water-oil separating experimental provision |
| CN112221478A (en) * | 2020-10-09 | 2021-01-15 | 哈尔滨工程大学 | Graphene oil-absorbing fiber with efficient oil-water separation performance and preparation method thereof |
| CN114824342A (en) * | 2021-01-28 | 2022-07-29 | 上海神力科技有限公司 | Preparation method of graphite polar plate, fuel cell and vehicle |
| CN113318611A (en) * | 2021-05-31 | 2021-08-31 | 天津工业大学 | Hollow fiber ultrafiltration membrane with lasting high pollution resistance and preparation method thereof |
| CN114870632A (en) * | 2022-05-12 | 2022-08-09 | 浙江师范大学 | Coupling film for improving decoloration rate of printing and dyeing wastewater and preparation method thereof |
| CN114870632B (en) * | 2022-05-12 | 2024-02-20 | 浙江师范大学 | Coupling film for improving decoloration rate of printing and dyeing wastewater and preparation method thereof |
| CN115779700A (en) * | 2023-02-07 | 2023-03-14 | 天津膜天膜科技股份有限公司 | Rapid oil absorption hollow fiber membrane and preparation method and application thereof |
| CN117019118A (en) * | 2023-10-08 | 2023-11-10 | 西安金沃泰环保科技有限公司 | Filtering material for benzene series waste gas and preparation method thereof |
| CN117019118B (en) * | 2023-10-08 | 2024-01-05 | 西安金沃泰环保科技有限公司 | Filtering material for benzene series waste gas and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016515933A (en) | 2016-06-02 |
| WO2015127792A1 (en) | 2015-09-03 |
| CA2898815A1 (en) | 2015-08-28 |
| JP6076536B2 (en) | 2017-02-08 |
| CN103801274B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103801274B (en) | Preparation method of oil-absorbing hollow fiber porous membrane | |
| CN103521199B (en) | A kind of preparation method of hollow tubular composite oil absorption material | |
| US10710027B2 (en) | Reinforced oil-absorptive membrane material, unit and preparation method thereof | |
| CN104324524B (en) | The preparation method of the ultralight sponge of a kind of super-hydrophobic super-oleophylic | |
| Lin et al. | Facile synthesis of electrospun carbon nanofiber/graphene oxide composite aerogels for high efficiency oils absorption | |
| CN106268355B (en) | A kind of super close/hydrophobic double property polymer films of asymmetry and preparation method thereof | |
| Ge et al. | Pumping through porous hydrophobic/oleophilic materials: an alternative technology for oil spill remediation | |
| CN103756006B (en) | A kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency | |
| CN105080356A (en) | Hydrophobic oleophylic hollow fiber composite film and preparation method thereof | |
| CN108854596B (en) | Preparation method of hollow fiber membrane for continuous oil-water separation | |
| Zhuo et al. | Methylcellulose strengthened polyimide aerogels with excellent oil/water separation performance | |
| CN108043243B (en) | Performance regulation and control method of carbon membrane for purifying oily wastewater | |
| CN104086798B (en) | Polypropylene modified polyurethane sponge as well as preparation method and application thereof | |
| CN106700121B (en) | A kind of high efficiency oil-water separation chitosan sponge and preparation method thereof | |
| CN110755887A (en) | Preparation method and application of super-infiltrated Janus material | |
| Zhu et al. | Preparation of high strength ultrafine polyvinyl chloride fibrous membrane and its adsorption of cationic dye | |
| CN105797431A (en) | Method for preparing efficient hydrophobic oil-absorbing sponge | |
| CN110394068A (en) | A kind of Janus polytetrafluoroethylhollow hollow fiber membrane and preparation method thereof | |
| Zhang et al. | Graphite powder coated polyurethane sponge hollow tube as a high‐efficiency and cost‐effective oil‐removal materials for continuous oil collection from water surface | |
| CN106283894B (en) | A kind of graphene oxide is modified filter paper and preparation method and application | |
| Zhang et al. | Continuous separation of oil from water surface by a novel tubular unit based on graphene coated polyurethane sponge | |
| CN105544019A (en) | High oil-absorbing polyacrylonitrile hollow activated carbon fiber and preparation method thereof | |
| CN107675360B (en) | Polystyrene nano fiber and preparation method thereof | |
| CN107511141A (en) | A kind of composite cellulosic membrane for adsorbing heavy metal and preparation method thereof | |
| CN107433192B (en) | A kind of composite fibre sorbing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |