CN111359442B - PTFE composite membrane for MABR and preparation method thereof - Google Patents
PTFE composite membrane for MABR and preparation method thereof Download PDFInfo
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- CN111359442B CN111359442B CN202010179714.9A CN202010179714A CN111359442B CN 111359442 B CN111359442 B CN 111359442B CN 202010179714 A CN202010179714 A CN 202010179714A CN 111359442 B CN111359442 B CN 111359442B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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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
- B01D67/0002—Organic membrane manufacture
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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
- B01D69/06—Flat membranes
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a PTFE composite membrane for MABR, which comprises a hydrophobic hollow fiber porous supporting tube membrane and a hydrophilic polytetrafluoroethylene porous flat sheet membrane wrapping layer arranged on the surface of the hydrophobic hollow fiber porous supporting tube membrane; the contact angle of the hydrophobic hollow fiber porous support tube membrane is larger than 130 degrees; the instant contact angle of the hydrophilic polytetrafluoroethylene porous flat sheet membrane wrapping layer is less than 60 degrees, and can be reduced to 0 degree within 30 seconds, the inner main body of the prepared PTFE composite membrane is of a super-hydrophobic characteristic by wrapping the surface of the hydrophobic microporous membrane and ultrasonically spot-welding the hydrophilic PTFE membrane layer of the thin layer, and the PTFE composite membrane has excellent oxygen mass transfer performance, and the thin layer on the surface of the PTFE composite membrane is of a super-hydrophilic characteristic, and has excellent microbial affinity performance.
Description
Technical Field
The invention belongs to the technical field of membrane bioreactors, and particularly relates to a preparation technology of a polymer membrane material for a membrane aeration membrane bioreactor, in particular to a PTFE composite membrane for MABR and a preparation method thereof.
Background
MABR (membrane aeration membrane bioreactor) is a novel sewage treatment technology developed in recent decades. In recent years, with the increasing maturity of research teams such as professor Li Baoan of Tianjin university and the like on research of MABR engineering application technology, the MABR engineering application technology is popular in water quality purification applications of rivers, landscape lakes and the like.
In the MABR system, the membrane material not only serves as an oxygen supply element, but also serves as a growth carrier for microorganisms, and is the core heart of the system. Research shows that although the hydrophilic microporous membrane has good microbe affinity, the microporous membrane is easy to grow and attach. However, water molecules are very easily adsorbed in the membrane pores, so that oxygen can reach the outer wall of the membrane after preferentially selecting water filled in the membrane pores. Meanwhile, the mass transfer resistance of the hydrophilic membrane to oxygen in water is very large due to the low amount of dissolved oxygen in water. Therefore, the membrane materials used in the conventional MABR system are mainly a hydrophobic microporous membrane, a dense membrane and a microporous membrane covered by a thin dense membrane layer. For example, chinese patent No. (201610972696.3) discloses a PTFE hollow fiber membrane for bubble-free aeration oxygenation and hydrophobicity and a preparation method thereof, wherein the PTFE membrane is a super-hydrophobic microporous membrane. However, due to the hydrophobic property of the surface of the hydrophobic membrane, the affinity of the hydrophobic membrane to microorganisms is often poor, which is not favorable for the stable attachment and growth of microorganisms on the surface of the membrane material. The dense membrane has high gas mass transfer resistance due to its thick thickness, resulting in low gas flux and poor oxygen supply capability to microorganisms in the MABR system. Researchers cover a thin compact membrane on the surface of a hydrophobic microporous membrane to integrate the performances of the hydrophobic microporous membrane and the membrane, for example, chinese patent (201310048862.7) discloses a composite membrane for MABR and a preparation method thereof, in particular to a PVDF membrane material coated with levodopa on the surface, but the problems of insufficient oxygen supply, poor microbial affinity and the like exist all the time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the PTFE composite membrane for the MABR with affinity to surface microorganisms and low oxygen mass transfer resistance.
The invention provides a PTFE composite membrane for MABR, which comprises a hydrophobic hollow fiber porous supporting tube membrane and a hydrophilic polytetrafluoroethylene porous flat sheet membrane wrapping layer arranged on the surface of the hydrophobic hollow fiber porous supporting tube membrane; the contact angle of the hydrophobic hollow fiber porous support tube membrane is larger than 130 degrees; the instantaneous contact angle of the hydrophilic polytetrafluoroethylene porous flat membrane wrapping layer is less than 60 degrees, and the instantaneous contact angle can be reduced to 0 degree within 30 seconds.
The aperture of the hydrophobic hollow fiber porous supporting tube membrane is 0.5-5 microns, the thickness of the tube wall is 0.1-1 mm, and the tensile strength is not less than 6MPa. The material includes but is not limited to PP, PE, PVDF, PTFE and other hydrophobic polymer materials.
The pore diameter of the hydrophilic polytetrafluoroethylene porous flat membrane is 0.1-0.5 micron, and the thickness of the membrane layer is 5-30 micron.
The invention also provides a preparation method of the PTFE composite membrane for MABR, which comprises the following steps:
1) Carrying out hydrophilization modification on the polytetrafluoroethylene flat microporous membrane;
2) Slitting the hydrophilic modified polytetrafluoroethylene flat microporous membrane to obtain a strip-shaped hydrophilic polytetrafluoroethylene porous flat membrane with the width of 5-20 mm;
3) And wrapping the strip-shaped hydrophilic polytetrafluoroethylene porous flat sheet membrane on the outer surface of the hydrophobic hollow fiber porous support tube membrane, and performing low-temperature ultrasonic spot welding to obtain the PTFE composite membrane for MABR.
Compared with the prior art, the invention has the following advantages:
according to the invention, the PTFE membrane layer which is wrapped on the surface of the high-strength polymer hydrophobic microporous membrane and is hydrophilic is subjected to ultrasonic spot welding, so that the prepared PTFE composite membrane has an inner main body with super-hydrophobic characteristic and excellent oxygen mass transfer performance, and the surface thin layer with super-hydrophilic characteristic and excellent microbial affinity performance. The hollow fiber microporous membrane with the super-hydrophobic characteristic prepared from the hydrophobic high polymer material is used as a main oxygen transmission medium, oxygen can reach the outer wall of the membrane only by diffusing through the membrane pores, the mass transfer resistance of the oxygen depends on the size of the membrane pores and the aeration pressure, and in practical engineering application, the quantitative supply of the oxygen of an MABR system can be realized by regulating and controlling the air supply pressure or flow according to requirements. Meanwhile, the invention wraps and ultrasonically spot-welds the super-hydrophilic PTFE thin layer membrane on the outer wall of the hydrophobic hollow fiber microporous membrane, thereby effectively overcoming the problem of poor microbial affinity on the surface of the super-hydrophobic microporous membrane. The hydrophilic PTFE film layer has excellent microbial affinity and is beneficial to the adhesion and growth of microbes on the surface of the film. Meanwhile, the larger PTFE membrane pore structure can provide an attachment growth space for microorganisms, so that a gradient transition structure is formed between the biofilm layer and the PTFE membrane. Compared with a compact membrane, in the operation process of the MABR system, along with the growth of microorganisms and the formation of the microbial membrane, the thin PTFE membrane layer is finally integrated with the microbial membrane layer (the microorganisms grow and attach in the microporous structure of the PTFE membrane), so that the influence on the oxygen mass transfer resistance is very small. The PTFE material has stable physical and chemical properties, is basically not degraded and aged by microorganisms in the processes of forming a microbial film and operating an MABR system, and has long-term stability. The strength of the hydrophobic hollow fiber porous support tube membrane selected by the technology of the invention is more than 6MPa, and the PTFE wrap membrane has excellent flexibility, so that the prepared PTFE composite membrane has good mechanical properties. In conclusion, the PTFE composite membrane for the MABR prepared by the invention has high bubble point pressure and oxygen flux, good mechanical property and surface microbial affinity, and is very suitable for the application of an MABR system.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a PTFE composite film for MABR obtained in example 1.
FIG. 2 is a scanning electron micrograph of the surface of the PTFE composite film for MABR obtained in example 1.
FIG. 3 is a scanning electron micrograph of the surface of the PTFE composite film for MABR obtained in example 1 after 9 days of biofilm formation.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Hereinafter, a PTFE composite membrane for MABR and a method for manufacturing the same according to the present invention will be described in detail with reference to specific examples.
Example 1
Selecting a PTFE flat membrane with the thickness of 10 microns and the average pore diameter of 0.2 micron, and sequentially carrying out hydrophilic modification on (hydroxyethyl methacrylate and hydroxymethyl acrylamide) prepolymerization solution to obtain a hydrophilic PTFE flat membrane; the test result shows that the initial instantaneous water drop contact angle of the PTFE flat sheet membrane is 55 degrees, and the initial instantaneous water drop contact angle can be reduced to 0 degree within 20 seconds.
Cutting the hydrophilic modified PTFE plate microporous membrane to obtain a strip-shaped PTFE plate microporous membrane with the width of 10 mm;
and (3) selecting a polytetrafluoroethylene hollow fiber tube membrane with the outer diameter of 3mm, the tube wall of 0.5 mm, the average pore diameter of 1 micron, the tensile breaking force of 90N and the water drop contact angle of 145 degrees, wrapping the banded PTFE flat sheet membrane obtained in the step (2) on the surface of the polytetrafluoroethylene hollow fiber tube membrane at an angle of 45 degrees, and continuously welding the banded PTFE flat sheet membrane at room temperature through two ultrasonic welding joints which are distributed in a 90-degree staggered manner to obtain the PTFE composite membrane for MABR.
As shown in fig. 1, the obtained PTFE composite membrane for MABR had a two-layer composite structure in which a very thin hydrophilic PTFE flat sheet membrane was coated on the outer layer of a relatively thick hydrophobic PTFE hollow fiber tubular membrane. As shown in figure 2, the surface of the obtained composite membrane well keeps the specific bidirectional stretching structural hole of the PTFE flat sheet membrane.
And carrying out performance test on the obtained PTFE composite membrane. The result shows that the tensile breaking force of the PTFE composite membrane is more than 90 newtons, and the bubble point pressure is more than 0.6MPa. The contact angle of the water drop on the outer surface of the film is 55 degrees, the contact angle of the water drop on the inner surface of the film can be reduced to 0 degree within 20 seconds, the contact angle of the water drop on the inner surface of the film is 145 degrees, and the water drop is not wetted. After the activated sludge is cultured, aeration and biofilm formation are carried out by an MABR system, and a layer of microbial film with uniform thickness can be successfully attached and grown on the surface of the film after 9 days. And (3) drying the PTFE composite membrane attached with the growing microbial membrane, observing under a microscope, and forming an obvious biofilm formation layer on the surface of the composite membrane as shown in figure 3. As can be seen from comparison of FIG. 2, after the microbial biofilm grows, a good microbial film layer is formed on the surface of the composite film.
Example 2
Selecting a PTFE flat membrane with the thickness of 20 microns and the average pore diameter of 0.1 micron, and carrying out hydrophilic modification through (N-vinyl pyrrolidone and vinyl triethoxysilane) prepolymerization solution to obtain a hydrophilic PTFE flat membrane; the test result shows that the initial instantaneous water drop contact angle of the PTFE flat sheet membrane is 35 degrees, and can be reduced to 0 degree within 10 seconds.
Step (2), cutting the hydrophilic modified PTFE flat microporous membrane to obtain a strip PTFE flat microporous membrane with the width of 20 mm;
and (3) selecting a polypropylene hollow fiber tubular membrane with the outer diameter of 4mm, the tubular wall of 1 mm, the average pore diameter of 2.5 microns, the tensile strength of 10 MPa and the water drop contact angle of 130 degrees, wrapping the banded PTFE flat sheet membrane obtained in the step (2) on the surface of the tubular membrane in a 30-degree angle manner, and continuously welding the banded PTFE flat sheet membrane at room temperature through two ultrasonic welding joints which are distributed in a 180-degree staggered manner to obtain the PTFE composite membrane for MABR.
And carrying out performance test on the obtained PTFE composite membrane. The result shows that the tensile strength of the PTFE composite membrane is more than 10 MPa, and the bubble point pressure is more than 0.8MPa. The contact angle of the water drop on the outer surface of the film is 35 degrees, the contact angle of the water drop on the inner surface of the film can be reduced to 0 degree within 10 seconds, the contact angle of the water drop on the inner surface of the film is 135 degrees, and the water drop is not wetted. After the activated sludge is cultured, aeration and biofilm formation are carried out by an MABR system, and a layer of microbial film with uniform thickness can be successfully attached and grown on the surface of the film after 7 days.
Example 3
Selecting a PTFE flat sheet membrane with the thickness of 5 microns and the average pore diameter of 0.3 micron, and carrying out hydrophilic modification by using (acrylic acid and vinyl trimethoxy silane) prepolymerization solution to obtain a hydrophilic PTFE flat sheet membrane; the test result shows that the initial instantaneous water drop contact angle of the PTFE flat sheet membrane is 60 degrees, and can be reduced to 0 degree within 30 seconds.
Step (2), cutting the hydrophilic modified PTFE flat microporous membrane to obtain a strip-shaped PTFE flat microporous membrane with the width of 30 mm;
and (3) selecting a polyethylene hollow fiber tube membrane with the outer diameter of 2mm, the tube wall of 0.1 mm, the average pore diameter of 0.5 micron, the tensile strength of 7MPa and the water drop contact angle of 130 degrees, wrapping the banded PTFE flat sheet membrane obtained in the step (2) on the surface of the polyethylene hollow fiber tube membrane in an angle of 55 degrees, and continuously welding the banded PTFE flat sheet membrane at room temperature through two ultrasonic welding joints distributed at an interval of 10cm to obtain the PTFE composite membrane for MABR.
And carrying out performance test on the obtained PTFE composite membrane. The result shows that the tensile strength of the PTFE composite membrane is more than 7MPa, and the bubble point pressure is more than 0.9MPa. The contact angle of the water drop on the outer surface of the film is 60 degrees, the contact angle of the water drop on the inner surface of the film can be reduced to 0 degree within 30 seconds, the contact angle of the water drop on the inner surface of the film is 130 degrees, and the water drop is not wetted. After the activated sludge is cultured, aeration and biofilm formation are carried out by an MABR system, and a layer of microbial film with uniform thickness can be successfully attached and grown on the surface of the film after 12 days.
Example 4
Selecting a PTFE flat membrane with the thickness of 30 microns and the average pore diameter of 0.5 micron, and carrying out hydrophilic modification on a (vinyl alcohol and vinyl trimethoxy silane) prepolymerization solution to obtain a hydrophilic PTFE flat membrane; the test result shows that the initial instantaneous water drop contact angle of the PTFE flat sheet membrane is 45 degrees, and can be reduced to 0 degree within 25 seconds.
Step (2), cutting the hydrophilic modified PTFE flat microporous membrane to obtain a strip PTFE flat microporous membrane with the width of 5 mm;
and (3) selecting a thermotropic phase polyvinylidene fluoride hollow fiber tube membrane with the outer diameter of 2.5mm, the tube wall of 0.5 mm, the average pore diameter of 2 microns, the tensile strength of 6.1 MPa and the water drop contact angle of 140 degrees, wrapping the banded PTFE flat sheet membrane obtained in the step (2) on the surface of the thermotropic phase polyvinylidene fluoride hollow fiber tube membrane in a 45-degree angle manner, and continuously welding the banded PTFE flat sheet membrane at room temperature through two ultrasonic welding joints in 90-degree staggered distribution to obtain the PTFE composite membrane for MABR.
And carrying out performance test on the obtained PTFE composite membrane. The result shows that the tensile strength of the PTFE composite membrane is more than 6MPa, and the bubble point pressure is more than 0.7MPa. The contact angle of the water drop on the outer surface of the film is 45 degrees, the contact angle of the water drop on the inner surface of the film can be reduced to 0 degree within 25 seconds, the contact angle of the water drop on the inner surface of the film is 140 degrees, and the water drop is not wetted. After the activated sludge is cultured, aeration and biofilm formation are carried out by an MABR system, and a layer of microbial film with uniform thickness can be successfully attached and grown on the surface of the film after 10 days.
In the above examples, the hydrophilization modification techniques of the PTFE flat membrane are all the various polymer microporous membrane hydrophilization modification techniques commonly used at present, and are intended to obtain a PTFE flat membrane with excellent hydrophilicity, which is used for preparing the hydrophilic outer surface layer of the PTFE composite membrane for MABR of this patent, but not the technique claimed in the claims of this patent.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (1)
1. A PTFE composite membrane for MABR is characterized by comprising a hydrophobic hollow fiber porous supporting tube membrane and a hydrophilic polytetrafluoroethylene porous flat sheet membrane wrapping layer arranged on the surface of the hydrophobic hollow fiber porous supporting tube membrane; the contact angle of the hydrophobic hollow fiber porous support tube membrane is larger than 130 degrees; the instantaneous contact angle of the hydrophilic polytetrafluoroethylene porous flat membrane wrapping layer is less than 60 degrees and is reduced to 0 degree within 30 seconds,
the preparation method of the PTFE composite membrane for MABR comprises the following steps:
1) Carrying out hydrophilization modification on the polytetrafluoroethylene flat microporous membrane;
2) Cutting the hydrophilic modified polytetrafluoroethylene flat microporous membrane to obtain a strip-shaped hydrophilic polytetrafluoroethylene porous flat membrane with the width of 5-20 mm;
3) Wrapping the strip-shaped hydrophilic polytetrafluoroethylene porous flat sheet membrane on the outer surface of the hydrophobic hollow fiber porous support tube membrane, and performing ultrasonic spot welding at room temperature to obtain a PTFE composite membrane for MABR;
the pore diameter of the hydrophobic hollow fiber porous supporting tube membrane is 0.5-5 micrometers, the thickness of the tube wall is 0.1-1 millimeter, the tensile strength is not less than 6MPa, the pore diameter of the hydrophilic polytetrafluoroethylene porous flat sheet membrane is 0.3-0.5 micrometers, and the thickness of the membrane layer is 5-30 micrometers.
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| CN112007519B (en) * | 2020-08-17 | 2023-05-02 | 杭州科百特科技有限公司 | Oxygenation membrane, preparation method thereof and oxygenation assembly |
| CN112295419A (en) * | 2020-10-20 | 2021-02-02 | 淄博蓝景膜环保科技有限公司 | Preparation method of selective permeability MABR composite membrane |
| CN114225719B (en) * | 2021-12-17 | 2024-01-23 | 天津工业大学 | Nano alumina modified hot stretching polyolefin film and preparation method thereof |
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| CN103182254B (en) * | 2013-02-06 | 2015-08-12 | 天津大学 | A kind of composite film for MABR and preparation method |
| CN103949165B (en) * | 2014-03-27 | 2016-04-13 | 浙江净源膜科技股份有限公司 | The preparation method of the heterogeneous hollow-fibre membrane of a kind of polytetrafluoroethylene (PTFE) |
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