CN110523299A - A kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane - Google Patents
A kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane Download PDFInfo
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D67/0093—Chemical modification
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- 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
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- 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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a kind of preparation methods of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane, and the present invention is specifically includes the following steps: S1, PTFE/SiO2The preparation of composite hollow fiber membrane, the hydrophilic modifying of S2, PTFE/SiO2 hollow-fibre membrane, S3, modified film wire hydrophily attenuation test, the present invention relates to PTFE hollow-fibre membrane water-treatment technology fields.The preparation method of the hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane, the method being crosslinked by physical chemistry, pass through the effect of coupling agent and crosslinking agent, hydroxyl (- OH), which is introduced, in film surface prepares the PTFE microporous barrier with stable hydrophilic performance, significantly improve the hydrophilicity of composite micro porous film, and it ensure that the stabilization of PTFE hollow-fibre membrane hydrophilicity, modified film wire pure water flux can achieve 3500L/ ㎡ * h, water contact angle is 60 °, improve PTFE hollow-fibre membrane product advantage, make PTFE hollow fiber membrane surface that there is stable hydrophilicity, expand PTFE hollow-fibre membrane in UF membrane and the application range of water treatment field.
Description
Technical field
The present invention relates to PTFE hollow-fibre membrane water-treatment technology fields, specially a kind of hydrophilic polyfluortetraethylemicroporous hollow
The preparation method of tunica fibrosa.
Background technique
Membrane separation technique is a novel isolation technics developed in recent years, it is a kind of special manufacture of utilization
, film with selective penetrated property, the method separated under external force promotion to mixture, is to have on a molecular scale
The mixture of the molecule of different-grain diameter realizes the technology of Selective Separation, including hollow-fibre membrane, volume when passing through semi-permeable membrane
A variety of assembling modes such as film, plate membrane, wherein hollow-fibre membrane is big with unit volume loading density, it is high-efficient to be separated by filtration,
The advantages that equipment is small, structure is simple, easy to operate, and it is raw in micro-filtration (MF), ultrafiltration (UF) reverse osmosis (RO), nanofiltration (NF), film
Have and its be widely applied in the isolation technics such as object reactor (MBR), polytetrafluoroethylene (PTFE) (PTFE) be a kind of comprehensive performance very
Excellent separation membrane, have extremely excellent chemical stability, heat-resisting quantity, organic solvent-resistant and chemical corrosion resistance with
And good mechanical property, it is known as the good reputation of " King ", in addition, hollow-fibre membrane has compared to the seperation film of other structures pattern
Have: the effective area of film is big, water flux is big, membrane module structure is compact, packed density is high, occupied area is small, easy to clean etc. excellent
Point, therefore polytetrafluoroethylhollow hollow fiber membrane has broad application prospects in UF membrane field, still, due to its extremely low table
Face can cause the wetability of PTFE film very poor, pure water flux is very low, in MBR system actual moving process with superpower hydrophobicity
In, backwash can only often be restored to the 0.2%-1% of initial flux, it is necessary to could be restored by chemical cleaning, thus increased greatly
The expense for having added system to run and safeguard, therefore usually require to carry out it special modification when for water process, make
It is with hydrophily.
Currently, the hydrophilic modification method of PTFE film mainly has low-temperature plasma, wet chemical process, radiation grafting, filling
It is modified etc., although the chemically and physically method including including high-temperature melting method etc. makes film surface contact angle be down to 70 ° by 130 °
The level of left and right, makes the hydrophily of film be improved, but still the place that comes with some shortcomings.Wherein, high-temperature fusion treatment process
Middle PTFE can discharge a kind of noxious material perfluoroisobutylene, and be not easy to keep shape, method of chemical treatment treated PTFE film
Surface is obviously dimmed and influences the performance of material body, and treatment process can also generate a large amount of harmful waste liquid, seriously pollute environment,
Operational danger is higher；Hyperthermia radiation grafting can damage PTFE matrix, cause the reduction of its mechanical property.These modification sides
Method more or less exist destroy membrane body structure, modified effect not persistently, operating procedure is many and diverse and instrument and equipment is complicated etc. lacks
Point limits application of the PTFE film in water process.
Therefore, before film, inorganic nano-particle is equal the invention proposes a kind of modified thinking of new physical-chemical
It is even to be mixed into PTFE powder formulation, it is prepared after green compact, pushing, stretching, sintering in a large amount of nanoparticle insertion nodes
PTFE hollow-fibre membrane by the effect of coupling agent and crosslinking agent, is introduced with the nanoparticle of insertion for " ground " in film surface
Hydroxyl (- OH) prepares the PTFE hollow-fibre membrane with stable hydrophilic performance.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of preparation sides of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane
Method can make PTFE hollow fiber membrane surface have stable hydrophilicity, thus expand PTFE hollow-fibre membrane in UF membrane and
The application range of water treatment field, while can be applied to the advanced treating of heavy civil sanitary sewage, industrial wastewater.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs: during one kind is hydrophilic polyfluortetraethylemicroporous
The preparation method of empty fiber membrane, specifically includes the following steps:
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: the nanometer of 0.25-2% is added in the original formula of PTFE
SiO2Particle in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fibre
Film；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after being soaked for a period of time, so
It is soaked in the GA aqueous solution that concentration is 2% afterwards, film wire is taken out after a period of time and drying obtains hydrophily PTFE/SiO2It is hollow
Tunica fibrosa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
After swinging processing 8h, water contact angle and pure water flux are tested respectively.
Preferably, in the step S2 PTFE hollow-fibre membrane and water without hydrophilic modifying contact angle be 138 °-
139 °, while by the PTFE/SiO of hydrophilic modifying2The contact angle of hollow-fibre membrane and water is 60 ° -80 °, external pressure 0.1MPa item
Film wire pure water flux is 1200-3500L/ ㎡ * h under part.
Preferably, it is 65 ° -85 ° that water contact angle is tested in the step S3, film wire pure water flux under the conditions of external pressure 0.1MPa
For 840-2640L/ ㎡ * h, contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, illustrate film wire hydrophily compared with
Stablize, can effectively keep for a long time.
Preferably, in the step S1 batch mixer be NBD-QMJW-104 model ball mill mixing machine.
Preferably, the coupling agent in the step S2 is chromium complex coupling agent, silane coupling agent or titanate coupling agent
One of or a variety of combinations.
Preferably, drying is to carry out drying and processing using the air flow dryer of HG-4 model in the step S2.
Preferably, the ultrasonic cleaner in the step S3 is the supersonic wave cleaning machine for selecting TTL-120 model.
Preferably, in the step S3 test of water contact angle be using the water contact angle test machine of model PT-108 come
It is tested.
(3) beneficial effect
The present invention provides a kind of preparation methods of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane.Have compared with prior art
It is standby following the utility model has the advantages that the hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane preparation method, pass through and use physics-chemical modification
Inorganic nano-particle is uniformly blended into PTFE powder formulation by thinking before film, and a large amount of nanoparticle insertions are prepared in stretching
PTFE hollow-fibre membrane in node, with the nanoparticle of insertion for " ground ", by the effect of coupling agent and crosslinking agent, in film
Surface introduces hydroxyl (- OH) and prepares the PTFE hollow-fibre membrane with stable hydrophilic performance, passes through physics-chemical crosslinking
Method, inorganic nano-particle are embedded into inside film wire, and crosslinked hydrophilic layer is firmly adhered to PTFE by the effect of chemical bond
On micro- fibril and node, the hydrophilicity of composite micro porous film is improved significantly, and ensure that PTFE hollow-fibre membrane hydrophily
The stabilization of energy, modified film wire pure water flux can achieve 3500L/ ㎡ * h, and water contact angle is 60 °, improve PTFE well
Hollow-fibre membrane product advantage makes PTFE hollow fiber membrane surface have stable hydrophilicity, to expand the hollow fibre of PTFE
Film is tieed up in UF membrane and the application range of water treatment field.
Detailed description of the invention
Fig. 1 is flow chart of the invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the embodiment of the present invention provides a kind of seven kinds of technical solutions: hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane
Preparation method, specifically include following embodiment:
Embodiment 1
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 0.25% Nano-meter SiO_2 is added in the original formula of PTFE2
Particle in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 1h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 1h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 138 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 72 °, and film wire pure water flux is 2100L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 76 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 1460L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 2
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 0.5% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 1h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 1h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 138 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 68 °, and film wire pure water flux is 2500L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 75 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 1750L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 3
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 1% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 1h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 1h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 136 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 76 °, and film wire pure water flux is 1800L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 81 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 1300L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 4
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 1.5% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 1h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 1h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 138 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 77 °, and film wire pure water flux is 1500L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 82 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 970L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 5
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 2% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 1h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 1h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 139 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 80 °, and film wire pure water flux is 1200L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 85 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 840L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 6
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 0.5% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 2h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 2h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 135 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 60 °, and film wire pure water flux is 3500L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 65 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 2640L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
Embodiment 7
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: 0.5% Nano-meter SiO_2 is added in the original formula of PTFE2Grain
Son in batch mixer after mixing obtains PTFE/SiO after green compact, pushing, stretching, sintering2Composite hollow fiber membrane；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane impregnates
In the PVA aqueous solution that the concentration for being mixed with a certain amount of coupling agent is 1%, film wire is taken out and dried after impregnating 3h, is then impregnated
Film wire is taken out in the GA aqueous solution that concentration is 2%, after 3h and is dried obtains hydrophily PTFE/SiO2Hollow-fibre membrane, without
The PTFE hollow-fibre membrane of hydrophilic modifying and the contact angle of water are 135 °, the hydrophily PTFE/SiO obtained through this embodiment2In
The contact angle of empty fiber membrane and water is 66 °, and film wire pure water flux is 2900L/ ㎡ * h under the conditions of external pressure 0.1MPa；
S3, modified film wire hydrophily attenuation test: the modified film wire of step S2 is shaken through ultrasonic cleaner ultrasound
Water contact angle and pure water flux are tested respectively after swinging processing 8h, it is found that its contact angle is 73 °, film wire is pure under the conditions of external pressure 0.1MPa
Water flux is 2150L/ ㎡ * h.Contact angle does not obviously rise, and film wire pure water flux is not decreased obviously, and illustrates film wire hydrophily
It is more stable, it can effectively keep for a long time.
The present invention, batch mixer is the ball mill mixing machine of NBD-QMJW-104 model in step S1.
The present invention, the coupling agent in step S2 are in chromium complex coupling agent, silane coupling agent or titanate coupling agent
One or more combinations.
The present invention, drying is to carry out drying and processing using the air flow dryer of HG-4 model in step S2.
The present invention, the ultrasonic cleaner in step S3 are the supersonic wave cleaning machines for selecting TTL-120 model.
The present invention, the test of water contact angle is carried out using the water contact angle test machine of model PT-108 in step S3
Test.
1-7 can see that best Nano-meter SiO_2 based on the above embodiments2The solid content of particle is 0.5%, with PTFE resin
On the basis of amount；Best film wire a length of 2h when impregnating, film wire contact angle is 60 ° under this condition, and pure water flux is 3500L/ ㎡ * h.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane, it is characterised in that: specifically includes the following steps:
S1、PTFE/SiO2The preparation of composite hollow fiber membrane: the nanosized SiO_2 grain of 0.25-2% is added in the original formula of PTFE
Son in batch mixer after mixing obtains PTFE/SiO2 composite hollow fiber membrane after green compact, pushing, stretching, sintering；
S2、PTFE/SiO2The hydrophilic modifying of hollow-fibre membrane: the PTFE/SiO that step S1 is obtained2Hollow-fibre membrane is soaked in mixed
Have in the PVA aqueous solution that the concentration of a certain amount of coupling agent is 1%, film wire is taken out and dried after a certain period of time by immersion, then soaks
It steeps in the GA aqueous solution that concentration is 2%, takes out film wire after a certain period of time and drying obtains hydrophily PTFE/SiO2Doughnut
Film；
S3, modified film wire hydrophily attenuation test: by the modified film wire of step S2 through ultrasonic cleaner sonic oscillation at
After managing 8h, water contact angle and pure water flux are tested respectively.
2. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
The contact angle of PTFE hollow-fibre membrane and water in the step S2 without hydrophilic modifying is 138 ° -139 °, while by hydrophilic
Modified PTFE/SiO2The contact angle of hollow-fibre membrane and water is 60 ° -80 °, and film wire pure water flux is under the conditions of external pressure 0.1MPa
1200-3500L/㎡*h。
3. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
It is 65 ° -85 ° that water contact angle is tested in the step S3, and film wire pure water flux is 840-2640L/ ㎡ * under the conditions of external pressure 0.1MPa
h。
4. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
Batch mixer is the ball mill mixing machine of NBD-QMJW-104 model in the step S1.
5. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
Coupling agent in the step S2 is one of chromium complex coupling agent, silane coupling agent or titanate coupling agent or a variety of
Combination.
6. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
Drying is to carry out drying and processing using the air flow dryer of HG-4 model in the step S2.
7. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
Ultrasonic cleaner in the step S3 is the supersonic wave cleaning machine for selecting TTL-120 model.
8. a kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane according to claim 1, it is characterised in that:
The test of water contact angle is tested using the water contact angle test machine of model PT-108 in the step S3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910869114.2A CN110523299A (en) | 2019-09-16 | 2019-09-16 | A kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane |
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| CN112604516A (en) * | 2020-12-17 | 2021-04-06 | 德蓝水技术股份有限公司 | Polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN112999895A (en) * | 2021-03-05 | 2021-06-22 | 浙江理工大学 | Preparation method of polyvinylidene fluoride hydrophilic stretched film |
| CN115414801A (en) * | 2022-08-31 | 2022-12-02 | 浙江大学 | Method for preparing lasting hydrophilic polytetrafluoroethylene separation membrane by one-step method |
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| CN112999895B (en) * | 2021-03-05 | 2022-07-22 | 浙江理工大学 | Preparation method of polyvinylidene fluoride hydrophilic stretch film |
| CN115414801A (en) * | 2022-08-31 | 2022-12-02 | 浙江大学 | Method for preparing lasting hydrophilic polytetrafluoroethylene separation membrane by one-step method |
| CN115414801B (en) * | 2022-08-31 | 2024-03-19 | 浙江大学 | Method for preparing durable hydrophilic polytetrafluoroethylene separation membrane by one-step method |
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