CN106975367A - Ethylene tetrafluoroethylene copolymerized macromolecule microporous barrier and preparation method thereof - Google Patents
Ethylene tetrafluoroethylene copolymerized macromolecule microporous barrier and preparation method thereof Download PDFInfo
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- CN106975367A CN106975367A CN201710350124.6A CN201710350124A CN106975367A CN 106975367 A CN106975367 A CN 106975367A CN 201710350124 A CN201710350124 A CN 201710350124A CN 106975367 A CN106975367 A CN 106975367A
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- etfe
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- caco
- high temperature
- calcium carbonate
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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
-
- 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
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of ethylene tetrafluoroethylene copolymerized macromolecule（ETFE）Microporous barrier and preparation method thereof.The ETFE microporous barriers preparation process is：（1）ETFE pellets and calcium carbonate CaCO3Powder high-temperature blending is extruded, cut-out granulation；（2）ETFE/CaCO3Pellet high temperature press mold is blended；（3）Extraction process is by ETFE/CaCO3CaCO in diaphragm is blended3Dissolving is removed；（4）Wash drying to obtain ETFE microporous barriers.ETFE microporous barriers prepared by the present invention can be by selecting the CaCO of different-grain diameter3Powder, regulates and controls ETFE micropore sizes.ETFE microporous barriers prepared by the present invention have the advantages that high temperature resistant, resistance to organic matter, antipollution, acid and alkali-resistance, can be complicated for water quality treatment, intractable oil field reinjection water etc..
Description
Technical field
The present invention relates to the research field of microporous barrier, more particularly, to a kind of ethylene-tetrafluoroethylene copolymerized macromolecule micropore
Film and preparation method thereof.
Background technology
Oil is the most important energy of the mankind, in the recovery process of oil, in order to improve oil recovery factor, need to be to oil well
The middle substantial amounts of water of injection；Stratum associated water generation is also had during the generation of oil simultaneously.In order to obtain qualified oil
Product, it is necessary to associated water and water filling are separated with oil, in the water produced by separation still containing a certain amount of oily, gas with
And other solids or liquid impurity, these water for containing certain gauging, gas and other impurities are referred to as oil-polluted water, wherein
Impurity have suspended solid, oil, dissolving material (low molecule quality organic matter and inorganic salts, solution gas) etc..Due to water resource
Lack, re-injection underground after oil field is generally handled oil extraction-generated waste water, but it has higher oil reservoir nocuity, stronger corrosion
Property and certain fouling tendency, therefore, the problem of a key during water flooding recovery be：Prevent injection water from causing wound to stratum
Evil.
The technology that membrane separation technique is separated and purified using the selective penetrated property of film, the motive force of process is mainly film
The pressure difference of both sides；Mild condition, separation accuracy is high, optimal isolation technics；Membrane separation technique is extremely potential contains
Oily sewage disposal method.
Oil extraction-generated waste water feature is：Oil content is high, and COD is high, and salinity is high, and easy fouling is micro- containing a large amount of suspensions
Biology, water temperature is high, and water quality is complicated, difficult.Therefore, requirement of the processing oil extraction-generated waste water to film, especially membrane material is higher：It is resistance to
High temperature, resistance to organic matter, antipollution, acid and alkali-resistance etc..
ETFE, ethylene-tetrafluoroethylene copolymerized macromolecule, most tough fluoroplastics, it is maintaining polytetrafluoroethylene PTFE
While good heat-resisting, chemical-resistance and electrical insulation capability, radiation hardness and mechanical performance, which also have, significantly to be improved, its
Erosion-resisting characteristics, hardness, resistance to cold flow and creep resistant all go with FEP than PTFE, and can be processed with the forming method of thermoplastic,
Product dimensional stability can compare favourably with nylon or polyformaldehyde.ETFE films are the superior transparent construction materials of quality, from ETFE materials
Since material comes out, the application of ETFE materials is expanded in the state such as the U.S. and Japan Devoting Major Efforts To Developing ETFE application study.In recent years
Come, ETFE films grafting acidic-group/basic group prepares PEM/anion-exchange membrane, is used as the replacement of Nafion membrane
Product are used for fuel cell or vanadium flow battery, have attracted the attention of some scholars.The research report on ETFE domestic at present compared with
Few, only the paper of Tongji University and Deng Jisuo colleges and universities of Shanghai University is reported, in starting state.
ETFE is a kind of Crystalline plastics, crystallinity 50% ~ 60%；Good thermal stability, can be at -60 DEG C ~ 150 DEG C
It is used for a long time, short-period used temperature is up to 230 DEG C, more than 300 DEG C of decomposition temperature；Burning can self-extinguishment；In addition, ETFE mechanicalness
Can good, excellent dielectric properties, rub resistance, resistant to chemical etching.From material property, ETFE is very potential microporous barrier
Material, but ETFE solubility parameters is very low, only 13.8 MPa1/2, difficulty has suitable solvent, and ETFE fusing point is higher, leads
Cause the film preparation of ETFE micropores difficult, so nobody shows any interest in so far.
The present invention prepares ETFE microporous barriers using a kind of new method, and it has a high temperature resistant, automatically cleaning, and resistance to organic matter etc. is excellent
Point, is applicable to the complicated sewage disposal of the water quality such as oil extraction-generated waste water.
The content of the invention
The purpose of the present invention is to disclose a kind of ethylene-tetrafluoroethylene copolymerized macromolecule（ETFE）Microporous barrier and preparation method,
Be using high temperature resistant, resistance to organic matter, antipollution, acid and alkali-resistance ETFE as membrane material, prepare microporous barrier, can be multiple for water quality treatment
It is miscellaneous, intractable oil field reinjection water etc..
The method of the present invention adopts the following technical scheme that realization：
（1）By ETFE resins and calcium carbonate CaCO3Powder is blended in extruder, and extruder high temperature extrudes continuous fiber, will
Obtained fiber cuts off granulation using comminutor；（2）By step（1）Obtained blending pellet high temperature press mold；（3）By step（2）
Obtained film removes CaCO by concentrated hydrochloric acid extraction process3；（4）By step（3）Obtained film washing drying.
The weight average molecular weight of described ETFE resins is between 2 × 105~3 × 1,060,000.The content of ETFE resins be 50~
95wt%；Calcium carbonate content is 5~50wt%；
The particle size range of described calcium carbonate is 0.01 ~ 3 μm；
Blending temperature is in described extruder：200~280℃；
The temperature of described high temperature press mold is 170 ~ 250 DEG C；
The aperture of obtained ethylene-tetrafluoroethylene copolymerized macromolecule (ETFE) microporous barrier be 0.1~10 μm, film thickness be 40 ~
100μm。
Embodiment
Technical scheme is further detailed with reference to embodiment, but the embodiment is illustrated
It is not construed as limiting the invention.
Embodiment 1
By 70wt% ETFE (weight average molecular weight 2.5 × 106), 30wt% calcium carbonate（1.2 ten thousand mesh）Add double screw extruder,
220 DEG C of extruder spout temperature, is gradually heating to 280 DEG C of extrusion temperature, and melting mixing under conditions of 100rpm is squeezed round
Go out in die head and extrude, collected after water cooling, comminutor granulation.
By ETFE/ calcium carbonate blended particles twin-roll machine press molds, 250 DEG C, 100 microns of press mold thickness are adjusted the temperature to.Film
After piece smooth even, temperature is reduced into 170 DEG C can remove diaphragm.
By patterning to required size, calcium carbonate is extracted with concentrated hydrochloric acid, until the dry caudacoria sheet weight of washing is constant.
It is 30% to porosity, 1 micron of aperture, thickness is 104 microns of ETFE microporous barriers.
Embodiment 2
By 60wt% ETFE (weight average molecular weight 2.5 × 106), 40wt% calcium carbonate（5000 mesh）Add double screw extruder,
220 DEG C of extruder spout temperature, is gradually heating to 280 DEG C of extrusion temperature, and melting mixing under conditions of 100rpm is squeezed round
Go out in die head and extrude, collected after water cooling, comminutor granulation.
By ETFE/ calcium carbonate blended particles twin-roll machine press molds, 260 DEG C are adjusted the temperature to, press mold thickness sets 50 microns.
After diaphragm smooth even, temperature is reduced into 170 DEG C can remove diaphragm.
By patterning to required size, calcium carbonate is extracted with concentrated hydrochloric acid, until the dry caudacoria sheet weight of washing is constant.
It is 40% to porosity, 2.5 microns of aperture, thickness is 55 microns of ETFE microporous barriers.
Embodiment 3
By 65wt% ETFE (weight average molecular weight 2.5 × 106), 35wt% calcium carbonate（10000 mesh）Double screw extruder is added, is squeezed
Go out 220 DEG C of machine spout temperature, be gradually heating to 280 DEG C of extrusion temperature, melting mixing under conditions of 80rpm, in round extrusion
Extrude, collected after water cooling in die head, comminutor granulation.
By ETFE/ calcium carbonate blended particles twin-roll machine press molds, 260 DEG C are adjusted the temperature to, the setting 100 of press mold thickness is micro-
Rice.After diaphragm smooth even, temperature is reduced into 170 DEG C can remove diaphragm.
By patterning to required size, calcium carbonate is extracted with concentrated hydrochloric acid, until the dry caudacoria sheet weight of washing is constant.
It is 35% to porosity, 1.5 microns of aperture, thickness is 100 microns of ETFE microporous barriers.
Claims (7)
1. a kind of ethylene-tetrafluoroethylene copolymerized macromolecule（ETFE）Microporous barrier, it is characterized in that high temperature resistant, resistance to organic matter, antipollution,
Acid and alkali-resistance, can be complicated for water quality treatment, intractable oil field reinjection water etc..
2. ethylene-tetrafluoroethylene copolymerized macromolecule（ETFE）The preparation method of microporous barrier, specifically includes following steps：
（1）By ETFE resins and calcium carbonate CaCO3Powder is blended in extruder, and extruder high temperature extrudes continuous fiber, will
The fiber arrived cuts off granulation using comminutor；
（2）By step（1）Obtained blending pellet high temperature press mold；
（3）By step（2）Obtained film removes CaCO by concentrated hydrochloric acid extraction process3；
（4）By step（3）Obtained film washing drying.
3. preparation method according to claim 2, the step（1）In ETFE resins weight average molecular weight 2 × 105
~3 × 106Between ten thousand, the content of ETFE resins is 50~95wt%；Calcium carbonate content is 5~50wt%.
4. preparation method according to claim 2, the step（1）In calcium carbonate particle size range be 0.01 ~ 3 μm.
5. preparation method according to claim 2, the step（1）In extruder in blending temperature be 200 ~ 280 DEG C.
6. preparation method according to claim 2, the step（2）In high temperature press mold temperature be 170 ~ 250 DEG C.
7. preparation method according to claim 2, obtained ethylene-tetrafluoroethylene copolymerized macromolecule (ETFE) microporous barrier
Aperture be 0.1~10 μm, film thickness be 40 ~ 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710350124.6A CN106975367A (en) | 2017-05-18 | 2017-05-18 | Ethylene tetrafluoroethylene copolymerized macromolecule microporous barrier and preparation method thereof |
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| CN201710350124.6A CN106975367A (en) | 2017-05-18 | 2017-05-18 | Ethylene tetrafluoroethylene copolymerized macromolecule microporous barrier and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110103353A (en) * | 2019-05-10 | 2019-08-09 | 张福军 | A kind of preparation method of polytetrafluoroethylene (PTFE) composite sand filtering pipe |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735474A (en) * | 2009-12-23 | 2010-06-16 | 中国石油天然气股份有限公司 | Hydrophilic polyethene microporous membrane and preparation method thereof |
| CN103464009A (en) * | 2013-10-11 | 2013-12-25 | 苏州汇龙膜技术发展有限公司 | Ethylene-tetrafluoroethylene (ETFE) copolymer porous membrane and preparation method thereof |
| CN104119660A (en) * | 2014-06-25 | 2014-10-29 | 内蒙古农业大学 | Method for preparing modified polycarbonate sub-lactone material |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
-
2017
- 2017-05-18 CN CN201710350124.6A patent/CN106975367A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735474A (en) * | 2009-12-23 | 2010-06-16 | 中国石油天然气股份有限公司 | Hydrophilic polyethene microporous membrane and preparation method thereof |
| CN103464009A (en) * | 2013-10-11 | 2013-12-25 | 苏州汇龙膜技术发展有限公司 | Ethylene-tetrafluoroethylene (ETFE) copolymer porous membrane and preparation method thereof |
| CN104119660A (en) * | 2014-06-25 | 2014-10-29 | 内蒙古农业大学 | Method for preparing modified polycarbonate sub-lactone material |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110103353A (en) * | 2019-05-10 | 2019-08-09 | 张福军 | A kind of preparation method of polytetrafluoroethylene (PTFE) composite sand filtering pipe |
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