CN107149883B - A kind of graphene modified PVDF hollow fiber ultrafilter membrane and preparation method - Google Patents
A kind of graphene modified PVDF hollow fiber ultrafilter membrane and preparation method Download PDFInfo
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- CN107149883B CN107149883B CN201710538596.4A CN201710538596A CN107149883B CN 107149883 B CN107149883 B CN 107149883B CN 201710538596 A CN201710538596 A CN 201710538596A CN 107149883 B CN107149883 B CN 107149883B
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Abstract
The invention discloses a kind of graphene modified PVDF hollow fiber ultrafilter membrane and preparation method, ultrafiltration membrane is made of the system of following mass ratio: Kynoar 20~45%, graphene 0.01~1%, graphite powder 1~5%, iron powder 0~1%, composite coupler 0.02~0.5%, hydrophilic agent 1~25%, diluent 30~70%, pore former 2~20%.The entirety of ultrafiltration membrane is the preparation method comprises the following steps: graphene and graphite powder premixing, microwave drying；Composite coupler, iron powder, Kynoar, mixed at high speed is added；Other raw materials are added and are fabricated to film material；Ultrafiltration membrane is prepared using thermotropic phase method.The present invention utilizes graphene or its property formed with iron powder, the ultrafiltration membrane with functions such as catalysis, microelectrode, antibacterials is produced, when being applied to sewage treatment, there is filtration, it can speed up the oxidative degradation of pollutant again, to greatly improve sewage treating efficiency and stain resistance.
Description
Technical field
The present invention relates to a kind of hollow fiber ultrafiltration membrane and preparation method more particularly to a kind of graphene modified polyvinilidene fluorine second
Alkene hollow fiber ultrafiltration membrane and preparation method, belong to technical field of membrane.
Background technique
Hollow fiber ultrafiltration membrane technique is a kind of purification for being widely used in water, and solution separation is concentrated, and mentions from waste water
Utility is taken, purification of waste water recycles the new and high technology in field.The preferable hollow fiber ultrafiltration membrane of industrialization at present prepares skill
Art is mainly solution spinning, melt spinning pulling method and thermally induced phase separation.Wherein, solution spinning due to need using
A large amount of solvent (account for film forming system 80% or more), needs to recycle solvent, is separated and be recycled, it is easy to cause
Environmental pollution simultaneously deteriorates working condition, therefore development is restricted；Melt spinning pulling method is not required to molten compared with solution spinning
Agent and its removal process, technique is relatively simple, production efficiency is higher, but since its drilling process is to as-spun fibre aggregated structure
Requirement it is more harsh, there is a problem of that the control difficulty of spinning, post-tensioning stretching process and tunica fibrosa microcellular structure is larger；It is thermotropic
Phase separation method is mutually separated by changing the different polymeric systems generations of system temperature control, to reach to form microcellular structure
Purpose, the method have the advantages that tunica fibrosa micropore size is smaller, mechanical property is strong compared with the former two, it has also become from theory to
The hot spot of study on the industrialization.But in the existing discussion to thermally induced phase separation preparation hollow fiber ultrafiltration membrane, most of scientific research people
Research emphasis has been placed on and how to have improved on the filter effect and mechanical strength of ultrafiltration membrane by member, also rarely has urge to having at present
The report of the graphene modified PVDF hollow fiber ultrafilter membrane of change, microelectrode and antibacterial action.
Summary of the invention
In order to solve shortcoming present in above-mentioned technology, the present invention provides a kind of graphene modified polyvinilidene fluorides
Hollow fiber ultrafiltration membrane and preparation method.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of graphene modified polyvinilidene fluoride
Hollow fiber ultrafiltration membrane is made of the film forming system of following mass ratio:
Wherein, the content of iron powder is not 0.
Wherein, composite coupler is mixed by the silane coupling agent and titanate coupling agent of equal mass ratioes.
Hydrophilic agent is polyvinylpyrrolidone or polyethylene glycol.
Diluent is dibutyl phthalate, dioctyl phthalate, paraxylene, tributyl phosphate, tetrahydro furan
It one of mutters or a variety of combinations.
Pore former is sodium chloride or lithium chloride or calcium chloride or calcium carbonate.
Graphite powder, iron powder are nanoscale.
A kind of preparation method of graphene modified PVDF hollow fiber ultrafilter membrane, specific steps are as follows:
By 0.01~1% graphene with 1~5% graphite powder premix merges microwave drying, then addition 0.02~
0.5% composite coupler, 0~1% and content are not 0 iron powder, 20~45% Kynoar, mixed at high speed；
1~25% hydrophilic agent, 2~20% pore former, 30 are sequentially added into the ingredient after above-mentioned mixed at high speed
~70% diluent is uniformly mixed and is fabricated to film material；
Film material is poured onto 200~400 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；Melting
Film material afterwards is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The present invention is mainly to utilize graphene or its property-catalysis formed with iron powder, antibacterial, microelectrode, pre-
The ultrafiltration membrane of property is manufactured that after mixing using thermotropic phase method.This product be applied to sewage disposal process in when,
There is filtration, and have the function of catalysis, microelectrode, antibacterial etc., it can speed up the oxidative degradation of pollutant, thus
Greatly improve sewage treating efficiency and stain resistance.
Specific embodiment
The present invention will be further described in detail with reference to the specific embodiments.
In the present invention, a kind of graphene modified polyvinilidene fluoride hollow-fibre membrane is passed through by the film forming system of following mass ratio
It is prepared after premixing by thermotropic phase method:
Wherein, the content of iron powder is not 0；
Wherein, composite coupler is mixed by the silane coupling agent and titanate coupling agent of equal mass ratioes.
Hydrophilic agent is polyvinylpyrrolidone or polyethylene glycol.
Diluent is high boiling organic diluent, such as dibutyl phthalate, dioctyl phthalate, to diformazan
One of benzene, tributyl phosphate, tetrahydrofuran or a variety of combinations.
Pore former is sodium chloride or lithium chloride or the inorganic salts such as calcium chloride or calcium carbonate.
Graphite powder, iron powder are nanoscale.
A kind of preparation method of graphene modified PVDF hollow fiber ultrafilter membrane, specific steps are as follows:
In order to enable graphene to be effectively dispersed in Kynoar, and also to reduce cost, first will
0.01~1% graphene merges microwave drying with 1~5% graphite powder premix, and 0.02~0.5% compound idol is then added
Join agent, 0~1% and content is not 0 iron powder, 20~45% Kynoar, mixed at high speed；
1~25% hydrophilic agent, 2~20% pore former, 30 are sequentially added into the ingredient after above-mentioned mixed at high speed
~70% diluent is uniformly mixed and is fabricated to film material；
Hollow fiber ultrafiltration membrane is prepared using thermotropic phase method, by film material be poured onto 200~400 DEG C of twin-screw extrusion at
In type machine, it is made to be heated to molten condition；Film material after melting is cooled to doughnut after hollow-fibre membrane die orifice extrusion
Pipe；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
This method can be such that graphene is effectively evenly dispersed in Kynoar, will not make graphene generate reunite and
Failure reduces effectiveness.
Graphene is added in Kynoar and graphene modified polyvinilidene fluoride doughnut is made by the present invention to be surpassed
Filter membrane, so that the film is provided with the functions such as catalysis, antibacterial functions and its microelectrode formed with iron powder of graphene, therefore,
The oxidative degradation for accelerating pollutant can be played in sewage disposal process, and bacterium can be effectively suppressed in the breeding of film surface,
To greatly improve film antifouling property and wastewater treatment efficiency.
The invention has the benefit that
The filtration of ultrafiltration membrane 1) can be played, while having the function of catalysis, microelectrode again etc., it can promote dirty in sewage
Contaminate object oxidative degradation, thus greatly improve with wastewater treatment efficiency and speed, have the advantages that a film is multi-functional；
2) antibiotic property is preferable, can prevent bacterium from being bred in film surface；Antifouling property is good, easy cleaning；
3) hollow fiber ultrafiltration membrane that this formula and method are prepared has stronger tensile strength, not fracture of wire；
4) it is produced using thermotropic phase method, therefore the range of selectable raw material, additive is also very wide, production technology is suitable
Answering property is good, and expansion is stronger.
Overall effect of the invention is further elaborated below by five specific embodiments.
Embodiment one,
0.2% graphene is merged into microwave drying with 5% graphite powder premix, 0.5% compound coupling is then added
Agent, 0% iron powder, 20% Kynoar, mixed at high speed；
10% hydrophilic agent, 2% pore former, 30~62.3% are sequentially added into the ingredient after above-mentioned mixed at high speed
Diluent, be uniformly mixed be fabricated to film material；
Film material is poured onto 200 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；System after melting
Coating materials is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The outer diameter of the resulting hollow fiber ultrafiltration membrane of the present embodiment is 1.3mm, internal diameter 0.6mm, porosity 56%, film
Separating aperture is 0.03 micron, in 0.1MPa, 25 DEG C of test condition (detection reference standard: People's Republic of China's ocean row
The requirement of industry standard HY/T112-2008 " ultrafiltration membrane and its component ") under, pure water water-flowing amount is 720L/m2*hr；For usual
Sanitary sewage disposal operate normally in, influent COD (COD) be 350mg/L, productions water COD be 60mg/L, COD remove
Rate is 82.9%.
Embodiment two,
1% graphene is merged into microwave drying with 2% graphite powder premix, 0.15% compound coupling is then added
Agent, 0.5% iron powder, 45% Kynoar, mixed at high speed；
5% hydrophilic agent, 16.35% pore former, 30% are sequentially added into the ingredient after above-mentioned mixed at high speed
Diluent is uniformly mixed and is fabricated to film material；
Film material is poured onto 400 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；System after melting
Coating materials is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The outer diameter of the resulting hollow fiber ultrafiltration membrane of the present embodiment is 1.3mm, internal diameter 0.6mm, porosity 53%, film
Separating aperture is 0.05 micron, and at 0.1MPa, 25 DEG C of test condition, pure water water-flowing amount is 700L/m2*hr；For leading to
During normal sanitary sewage disposal operates normally, influent COD (COD) is 350mg/L, and production water COD is 35mg/L, and COD is gone
Except rate is 90%.
Embodiment three,
0.01% graphene is merged into microwave drying with 0.1% graphite powder premix, then addition 0.02% is compound
Coupling agent, 1% iron powder, 21% Kynoar, mixed at high speed；
25% hydrophilic agent, 20% pore former, 31.97% are sequentially added into the ingredient after above-mentioned mixed at high speed
Diluent is uniformly mixed and is fabricated to film material；
Film material is poured onto 300 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；System after melting
Coating materials is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The outer diameter of the resulting hollow fiber ultrafiltration membrane of the present embodiment is 1.3mm, internal diameter 0.6mm, porosity 71%, film
Separating aperture is 0.05 micron, and at 0.1MPa, 25 DEG C of test condition, pure water water-flowing amount is 720L/m2*hr；For leading to
During normal sanitary sewage disposal operates normally, influent COD (COD) is 350mg/L, and production water COD is 50mg/L, and COD is gone
Except rate is 85.7%.
Example IV,
0.2% graphene is merged into microwave drying with 1.4% graphite powder premix, 0.3% compound idol is then added
Join agent, 0.1% iron powder, 25% Kynoar, mixed at high speed；
Sequentially added into the ingredient after above-mentioned mixed at high speed 1% hydrophilic agent, 2% pore former, 70% dilution
Agent is uniformly mixed and is fabricated to film material；
Film material is poured onto 350 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；System after melting
Coating materials is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The outer diameter of the resulting hollow fiber ultrafiltration membrane of the present embodiment is 1.3mm, internal diameter 0.6mm, porosity 67%, film
Separating aperture is 0.05 micron, and at 0.1MPa, 25 DEG C of test condition, pure water water-flowing amount is 680L/m2*hr；For leading to
During normal sanitary sewage disposal operates normally, influent COD (COD) is 350mg/L, and production water COD is 45mg/L, and COD is gone
Except rate is 87.1%.
Embodiment five,
0.5% graphene is merged into microwave drying with 3.5% graphite powder premix, 0.25% compound idol is then added
Join agent, 0.2% iron powder, 30% Kynoar, mixed at high speed；
25% hydrophilic agent, 5% pore former, 35.55% are sequentially added into the ingredient after above-mentioned mixed at high speed
Diluent is uniformly mixed and is fabricated to film material；
Film material is poured onto 250 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；System after melting
Coating materials is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, is then sent into hollow fiber conduit
In gas phase or liquid phase separation slot, diluent, the pore former in film material are separated, graphene modified polyvinilidene fluoride is obtained
Hollow fiber ultrafiltration membrane.
The outer diameter of the resulting hollow fiber ultrafiltration membrane of the present embodiment is 1.3mm, internal diameter 0.6mm, porosity 67%, film
Separating aperture is 0.05 micron, and at 0.1MPa, 25 DEG C of test condition, pure water water-flowing amount is 720L/m2*hr；For leading to
During normal sanitary sewage disposal operates normally, influent COD (COD) is 350mg/L, and production water COD is 40mg/L, and COD is gone
Except rate is 83%.
Graphene modified PVDF hollow fiber ultrafilter membrane obtained by above-described embodiment meets the People's Republic of China (PRC)
The requirement of ocean professional standard HY/T112-2008 " ultrafiltration membrane and its component ".
Above embodiment is not limitation of the present invention, and the present invention is also not limited to the example above, this technology neck
The variations, modifications, additions or substitutions that the technical staff in domain is made within the scope of technical solution of the present invention, also belong to this hair
Bright protection scope.
Claims (7)
1. a kind of graphene modified PVDF hollow fiber ultrafilter membrane, it is characterised in that: it by following mass ratio film forming
System composition:
Wherein, the content of iron powder is not O.
2. graphene modified PVDF hollow fiber ultrafilter membrane according to claim 1, it is characterised in that: described multiple
Coupling agent is closed to be mixed by the silane coupling agent and titanate coupling agent for waiting mass ratioes.
3. graphene modified PVDF hollow fiber ultrafilter membrane according to claim 1, it is characterised in that: the parent
Aqua is polyvinylpyrrolidone or polyethylene glycol.
4. graphene modified PVDF hollow fiber ultrafilter membrane according to claim 1, it is characterised in that: described dilute
Releasing agent is one of dibutyl phthalate, dioctyl phthalate, paraxylene, tributyl phosphate, tetrahydrofuran
Or a variety of combination.
5. graphene modified PVDF hollow fiber ultrafilter membrane according to claim 1, it is characterised in that: it is described at
Hole agent is sodium chloride or lithium chloride or calcium chloride or calcium carbonate.
6. graphene modified PVDF hollow fiber ultrafilter membrane according to claim 1, it is characterised in that: the stone
Ink powder, iron powder are nanoscale.
7. a kind of preparation method of graphene modified PVDF hollow fiber ultrafilter membrane, it is characterised in that: the method
Specific steps are as follows:
0.01~1% graphene is merged into microwave drying with 1~5% graphite powder premix, is then added 0.02~0.5%
Composite coupler, 0~1% and content are not 0 iron powder, 20~45% Kynoar, mixed at high speed；
Sequentially added into the ingredient after above-mentioned mixed at high speed 1~25% hydrophilic agent, 2~20% pore former, 30~
70% diluent is uniformly mixed and is fabricated to film material；
Film material is poured onto 200~400 DEG C of twin-screw extrusion molding machine, it is made to be heated to molten condition；After melting
Film material is cooled to hollow fiber conduit after hollow-fibre membrane die orifice extrusion；
It is passed through compressed air or higher boiling non-solvent into hollow fiber conduit as core liquid, hollow fiber conduit is then sent into gas phase
Or in liquid phase separation slot, diluent, the pore former in film material are separated, it is hollow to obtain graphene modified polyvinilidene fluoride
Fiber ultrafiltration membrane.
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| CN108786495A (en) * | 2018-06-13 | 2018-11-13 | 南通强生石墨烯科技有限公司 | A kind of antibacterial graphene oxide is modified PVDF hollow-fibre membranes and preparation method thereof |
| CN109395591A (en) * | 2018-10-12 | 2019-03-01 | 南京龙源环保有限公司 | A kind of preparation method of reinforced graphite alkene polyvinylidene fluoride microporous film |
| CN113600039B (en) * | 2021-07-23 | 2022-05-24 | 北京中电加美环保科技有限公司 | Polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
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| CN105482417A (en) * | 2015-12-20 | 2016-04-13 | 青岛科技大学 | Method for preparing graphene-containing polymer composite |
| CN105797599A (en) * | 2016-05-09 | 2016-07-27 | 四川久润环保科技有限公司 | Graphene modified hollow fiber membrane and preparation method thereof |
| CN106492644A (en) * | 2016-11-18 | 2017-03-15 | 北京建筑大学 | A kind of ultrafilter membrane process for purifying water based on microemulsion modified Nano Zero-valent Iron Carbon Materials precoated shet |
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| CN105482417A (en) * | 2015-12-20 | 2016-04-13 | 青岛科技大学 | Method for preparing graphene-containing polymer composite |
| CN105797599A (en) * | 2016-05-09 | 2016-07-27 | 四川久润环保科技有限公司 | Graphene modified hollow fiber membrane and preparation method thereof |
| CN106492644A (en) * | 2016-11-18 | 2017-03-15 | 北京建筑大学 | A kind of ultrafilter membrane process for purifying water based on microemulsion modified Nano Zero-valent Iron Carbon Materials precoated shet |
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