CN115571976A - Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes - Google Patents
Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes Download PDFInfo
- Publication number
- CN115571976A CN115571976A CN202211053345.4A CN202211053345A CN115571976A CN 115571976 A CN115571976 A CN 115571976A CN 202211053345 A CN202211053345 A CN 202211053345A CN 115571976 A CN115571976 A CN 115571976A
- Authority
- CN
- China
- Prior art keywords
- membrane
- hollow fiber
- mabr
- ehbr
- fiber membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 145
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- UEKDBDAWIKHROY-UHFFFAOYSA-L bis(4-bromo-2,6-ditert-butylphenoxy)-methylalumane Chemical compound [Al+2]C.CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-].CC(C)(C)C1=CC(Br)=CC(C(C)(C)C)=C1[O-] UEKDBDAWIKHROY-UHFFFAOYSA-L 0.000 title claims abstract 16
- 239000012510 hollow fiber Substances 0.000 claims abstract description 86
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 238000007493 shaping process Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002074 melt spinning Methods 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 239000004743 Polypropylene Substances 0.000 claims description 57
- 239000000654 additive Substances 0.000 claims description 32
- 230000000996 additive effect Effects 0.000 claims description 22
- 238000004804 winding Methods 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000005067 remediation Methods 0.000 claims 2
- 238000007664 blowing Methods 0.000 claims 1
- 239000012982 microporous membrane Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of sewage treatment, in particular to a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps: s1: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid; s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping; s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 Adding the mixture into the colloidal solution for 10-60 minutes, and washing with deionized water; s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃; s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane. The raw materials of the invention have low priceThe membrane flux is higher, which is beneficial to oxygen transmembrane transmission, so that the membrane can bear higher aeration pressure in the operation process, and the operation efficiency of an MABR system is ensured.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes.
Background
The Membrane Aeration Bioreactor (MABR) has become one of the key technologies in the sewage treatment field, and the MABR Membrane is also called as an EHBR Membrane in some factories and has unique advantages in the aspects of high COD, high ammonia nitrogen and high phosphorus wastewater treatment. Practice shows that the removal capacity of the system for phosphorus and ammonia nitrogen is improved by 20-30% by combining with a contact oxidation biological activated sludge technical treatment technology. Compared with the traditional membrane bioreactor, the MABR system has lower energy consumption and higher operation efficiency. In addition, due to the characteristics of high membrane accumulation degree, small occupied area and the like, the technology is widely applied to the fields of domestic sewage, reclaimed water reuse and the like.
The MABR system is mainly used for strengthening the removal capacity of COD, phosphorus and ammonia nitrogen in an aerobic or facultative ring, and simultaneously reduces the energy consumption of the system. The main principle is based on the discharge capacity of the metabolites of the biological reaction membrane. The microorganisms in the biological membrane utilize oxygen transferred and diffused through the membrane wall of the bioreactor to decompose and remove nutrients and organic matters in the sewage. Simultaneously takes away CO generated by microbial metabolism 2 A gas. Among various bioreactor water treatment technologies, the MABR technology has good quality of treated effluent, but the MABR technology starts relatively late in China, and in order to promote the MABR engineering application, a novel membrane material with low price and excellent performance is required to be searched or the existing membrane material is required to be improved to explore the membrane pollution and pollutant degradation mechanism, so that the rapid development of the MABR in the field of deep denitrification treatment of wastewater is promoted.
Disclosure of Invention
The invention aims to at least solve one of technical problems in the prior art, and provides a preparation method of an MABR (EHBR) membrane for treating sustainable water of rivers and lakes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an MABR (EHBR) membrane for treating sustainable water of rivers and lakes comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloid solution is added for 10 to 60 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polymeric amine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Further, the preparation process of the composite hollow fiber membrane made of the PP material in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the mixture into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Further, the pH of the deionized water is adjusted to be 1.5 by nitric acid in the S1.
Further, the drying temperature in the S5 is 70-100 ℃.
Further, the adding amount of the additive in the step one is 0.2-1%.
Further, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive to the mixture is 2.
Further, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Further, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Further, the MABR (EHBR) film prepared by the present invention is a microporous film.
In summary, the present application has the following beneficial effects:
1. the MABR membrane structure is in a hollow fiber shape, so that the MABR biological membrane can be in full contact with pollutants in sewage, and the flow rate of the sewage can also provide shearing force around the biological membrane to control the growth of the biological membrane;
2. the MABR film can provide oxygen required by life activities for microorganisms in the film and is also a carrier for the growth of the microorganisms;
3. TiO of the invention 2 Deposited on the surface of the MABR film, the hydrophilicity of the film is increased, and the film is suitable for the attachment growth of microorganisms;
3. the surface of the membrane is rough, so that the surface area for attaching dirt is increased, and the attachment and growth of microorganisms are facilitated;
5. the additive is added to improve the brittleness of the hollow fiber membrane, and reduce the bending of the hollow fiber protofilament during the extrusion process;
6. the raw materials of the invention have low price and high membrane flux, which is beneficial to oxygen transmembrane transmission, so that the membrane can bear high aeration pressure in the operation process, and the operation efficiency of an MABR system is ensured.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a scanning electron micrograph of an MABR (EHBR) film of example 4 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
The invention provides a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloidal solution is put for 10 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Preferably, the preparation process of the composite hollow fiber membrane made of the PP material in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Preferably, the nitric acid in S1 adjusts the pH of the deionized water to be 1.5.
Preferably, the drying temperature in the S5 is 70-100 ℃.
Preferably, the additive is added in an amount of 0.5% in the first step.
Preferably, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive is 2.
Preferably, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Preferably, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Preferably, the MABR (EHBR) film produced by the present invention is a microporous film.
Example 2
The invention provides a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloidal solution is put for 30 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Preferably, the preparation process of the composite hollow fiber membrane made of the PP material in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Preferably, the nitric acid in S1 adjusts the pH of the deionized water to be 1.5.
Preferably, the drying temperature in the S5 is 70-100 ℃.
Preferably, the additive is added in an amount of 1% in the first step.
Preferably, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive is 2.
Preferably, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Preferably, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Preferably, the MABR (EHBR) film produced by the present invention is a microporous film.
Example 3
The invention provides a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloid solution is put for 20 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polymeric amine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Preferably, the preparation process of the composite hollow fiber membrane made of PP in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Preferably, the pH of the deionized water is adjusted to be 1.5 by the nitric acid in the S1.
Preferably, the drying temperature in the S5 is 70-100 ℃.
Preferably, the additive is added in the first step in an amount of 0.5%.
Preferably, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive is 2.
Preferably, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Preferably, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Preferably, the MABR (EHBR) film produced by the present invention is a microporous film.
Example 4
The invention provides a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloid solution is put for 40 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Preferably, the preparation process of the composite hollow fiber membrane made of the PP material in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Preferably, the pH of the deionized water is adjusted to be 1.5 by the nitric acid in the S1.
Preferably, the drying temperature in the S5 is 70-100 ℃.
Preferably, the additive is added in an amount of 0.5% in the first step.
Preferably, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive is 2.
Preferably, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Preferably, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Preferably, the MABR (EHBR) film produced by the present invention is a microporous film.
Example 5
The invention provides a preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes, which comprises the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1: dissolving titanium tetraisopropoxide in ethanol, dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloid solution is added for 10 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the membrane in a diisocyanate-based hexane solution, and crosslinking the membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked membrane, and rolling to obtain the MABR (EHBR) membrane.
Preferably, the preparation process of the composite hollow fiber membrane made of PP in S2 includes:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blast drying oven at 50 ℃ for constant-temperature drying for 12h;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
Preferably, the pH of the deionized water is adjusted to be 1.5 by the nitric acid in the S1.
Preferably, the drying temperature in the S5 is 70-100 ℃.
Preferably, the additive is added in the first step in an amount of 0.2%.
Preferably, the additive is a mixture of naphthenic oil and aromatic hydrocarbon, and the mass ratio of the additive is 2.
Preferably, the winding speed of the hollow fiber membrane yarn in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
Preferably, the present invention provides an MABR (EHBR) film prepared by the above preparation method, wherein the MABR (EHBR) film has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
Preferably, the MABR (EHBR) film produced by the present invention is a microporous film.
The above examples 1 to 5 were subjected to the performance test, and the results thereof were as follows:
the invention controls the composite hollow fiber membrane made of PP material to be soaked in TiO 2 Control of the length of time in colloidal solution 2 The adhesion content of the hollow fiber precursor and the addition amount of the additive are changed to control the conditions that the hollow fiber precursor is not easy to bend and the like in the extrusion process, and the roughness of the finished product MABR (EHBR) film can be effectively changed; from the results of the examples, the composite hollow fiber membrane made of PP material was soaked in TiO 2 The nano-particle content is increased due to the long time in the colloidal solution, the pores formed by stretching the hollow fiber protofilament are increased, the gas flux is increased, and meanwhile, the composite hollow fiber membrane made of PP (polypropylene) is soaked in TiO 2 Length of time in colloidal solution due to TiO 2 Is a hydrophilic substance, so that the contact angle of the MABR (EHBR) film is reduced, proving that TiO 2 The nano particles are successfully added into a PP composite hollow fiber membrane, additives such as naphthenic oil, aromatic hydrocarbon mixture and the like are added at the same time, the surface of the membrane is smoother when more additives are added, the contact angle is larger, but the influence on the gas flux is small, and TiO 2 After the nanoparticles and the additives are added, the roughness of the MABR (EHBR) film is greatly improved, and as can be seen from figure 2 in the attached figure of the specification, the surface of the MABR (EHBR) film prepared in example 4 has more TiO 2 And the nano particles increase the surface roughness of the film, and the grain direction grows along the stretching direction, so that the permeability of the film is enhanced because the nano particles cause more surface holes on the stretched grains.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of an MABR (EHBR) membrane for treating sustainable water in rivers and lakes is characterized by comprising the following steps:
S1：TiO 2 preparing a colloidal solution: according to the volume ratio of 1:10 dissolving titanium tetraisopropoxide in ethanol, then dropwise adding the solution into 1L of deionized water, stirring, and adjusting the pH value of the deionized water by using nitric acid;
s2: preparing a PP composite hollow fiber membrane by adopting melt spinning and stretching and shaping;
s3: immersing a PP composite hollow fiber membrane into the TiO prepared by S1 2 The colloid solution is added for 10 to 60 minutes and washed by deionized water;
s4: soaking the washed PP composite hollow fiber membrane in a polyamine solution, then soaking the PP composite hollow fiber membrane in a diisocyanate-based hexane solution, and crosslinking the PP composite hollow fiber membrane in a heat treatment at 110 ℃;
s5: and (3) carrying out heat drying treatment on the crosslinked PP composite hollow fiber membrane, and rolling to obtain the MABR (EHBR) membrane.
2. The method for preparing a MABR (EHBR) membrane for river and lake sustainable water treatment according to claim 1, wherein the preparation process of the PP composite hollow fiber membrane in S2 comprises:
the method comprises the following steps: adding PP (polypropylene) raw materials into a hopper, placing the hopper into a double-screw high-speed mixer, stirring, and adding additives while stirring;
step two: cutting the mixed raw material obtained in the step one into particles by using an electric granulator, and collecting the particles for later use;
step three: placing the obtained granules in a constant-temperature air-blowing drying box at 50 ℃ for constant-temperature drying for 12 hours;
step four: the dried granules are melted and extruded to form hollow fiber protofilaments after passing through a single-screw spinning machine;
step five: cooling and solidifying the hollow fiber membrane wires through a cold water bath, and winding the cooled and formed hollow fiber membrane wires on a winding device;
step six: and stretching and shaping the hollow fiber membrane filaments to obtain the PP composite hollow fiber membrane.
3. The method for preparing a membrane MABR (EHBR) for treating river and lake sustainable water according to claim 1, wherein the pH of the deionized water is adjusted to 1.5 by nitric acid in S1.
4. The preparation method of a membrane for river and lake sustainable water remediation MABR (EHBR) according to claim 1, wherein the drying temperature in S5 is 70-100 ℃.
5. The method for preparing an MABR (EHBR) membrane for river and lake sustainable water treatment according to claim 2, wherein the additive is added in an amount of 0.2% -1% in the first step.
6. The method for preparing a MABR (EHBR) membrane for treating river and lake sustainable water, according to claim 5, wherein the additive is a mixture of naphthenic oil and aromatic hydrocarbons, and the mass ratio of the naphthenic oil to the aromatic hydrocarbons is 2.
7. The method for preparing an MABR (EHBR) membrane for river and lake sustainable water treatment according to claim 2, wherein the winding speed of the hollow fiber membrane filaments in the fifth step is 300-500m/min, and the cooling temperature is 30 ℃.
8. The method for preparing a membrane for river and lake sustainable water remediation MABR (EHBR) according to any one of claims 1 to 7, wherein the MABR (EHBR) has an inner diameter of 20 to 800 μm and a wall thickness of 50 to 300 μm.
9. The method for preparing a membrane for river and lake sustainable water treatment MABR (EHBR) according to claim 8, wherein the MABR (EHBR) membrane is a microporous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211053345.4A CN115571976A (en) | 2022-08-31 | 2022-08-31 | Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211053345.4A CN115571976A (en) | 2022-08-31 | 2022-08-31 | Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115571976A true CN115571976A (en) | 2023-01-06 |
Family
ID=84579451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211053345.4A Pending CN115571976A (en) | 2022-08-31 | 2022-08-31 | Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115571976A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657449A (en) * | 2013-12-17 | 2014-03-26 | 大连天承科技有限公司 | Novel hydrophilic hollow fiber membrane preparation method |
| CN103768958A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrophilic polypropylene hollow fiber micro-porous membrane and making method thereof |
| CN103861467A (en) * | 2013-12-28 | 2014-06-18 | 太平洋水处理工程有限公司 | Low-temperature hydrothermal method for preparing strong hydrophilic anti-pollution composite membrane and application of membrane |
| CN105854638A (en) * | 2016-04-14 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Permanently hydrophilic PTFE hollow fiber membrane and preparation method thereof |
| CN110180403A (en) * | 2019-04-30 | 2019-08-30 | 浙江汉青环境科技有限公司 | A kind of fiber tube enhancement type doughnut composite biological film and preparation method and application |
| CN110548412A (en) * | 2019-09-18 | 2019-12-10 | 山东华象环保科技有限公司 | Hydrophilic polypropylene hollow fiber membrane and preparation method thereof |
| WO2021232649A1 (en) * | 2020-05-18 | 2021-11-25 | 浙江长兴求是膜技术有限公司 | Preparation method for high-performance mabr hollow fiber composite membrane |
| CN113731194A (en) * | 2021-09-16 | 2021-12-03 | 佛山市澳欣膜科技有限公司 | MABR hollow fiber composite membrane and preparation method and application thereof |
-
2022
- 2022-08-31 CN CN202211053345.4A patent/CN115571976A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103768958A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrophilic polypropylene hollow fiber micro-porous membrane and making method thereof |
| CN103657449A (en) * | 2013-12-17 | 2014-03-26 | 大连天承科技有限公司 | Novel hydrophilic hollow fiber membrane preparation method |
| CN103861467A (en) * | 2013-12-28 | 2014-06-18 | 太平洋水处理工程有限公司 | Low-temperature hydrothermal method for preparing strong hydrophilic anti-pollution composite membrane and application of membrane |
| CN105854638A (en) * | 2016-04-14 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Permanently hydrophilic PTFE hollow fiber membrane and preparation method thereof |
| CN110180403A (en) * | 2019-04-30 | 2019-08-30 | 浙江汉青环境科技有限公司 | A kind of fiber tube enhancement type doughnut composite biological film and preparation method and application |
| CN110548412A (en) * | 2019-09-18 | 2019-12-10 | 山东华象环保科技有限公司 | Hydrophilic polypropylene hollow fiber membrane and preparation method thereof |
| WO2021232649A1 (en) * | 2020-05-18 | 2021-11-25 | 浙江长兴求是膜技术有限公司 | Preparation method for high-performance mabr hollow fiber composite membrane |
| CN113731194A (en) * | 2021-09-16 | 2021-12-03 | 佛山市澳欣膜科技有限公司 | MABR hollow fiber composite membrane and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金关泰: "高分子化学的理论和应用进展", 31 March 1995, 中国石化出版社, pages: 340 - 341 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101205526B (en) | Method for rapidly culturing anaerobic ammonium oxidation bacteria by up-flow type anaerobic sludge bed reactor | |
| CN102660813B (en) | Biological activated carbon fibe, ecological carbon fiber composite comprising same and preparation method thereof | |
| CN102491498B (en) | Ecological carbon-fiber composite, preparation method thereof and sewage treatment reactor containing ecological carbon-fiber composite | |
| CN111410315B (en) | Ecological treatment device for sewage treatment | |
| JP2002524224A (en) | Wastewater treatment method for removal of organic matter and nitrogen | |
| CN111470714B (en) | Environment-friendly recycling method for aquaculture wastewater | |
| CN113060830B (en) | Method for accelerating aerobic sludge granulation by using tourmaline as crystal nucleus | |
| CN102489156A (en) | Bio-carbon-fiber flat membrane component and sewage treatment reactor | |
| CN111410301A (en) | Method for culturing hydrogen autotrophic denitrification granular sludge | |
| CN115571976A (en) | Preparation method of MABR (EHBR) membrane for treating sustainable water of rivers and lakes | |
| CN109231433A (en) | A kind of sewage treatment biomembrane composite carrier and preparation method | |
| CN111484120A (en) | Suspended filler ball for treating sewage by biomembrane method and preparation method thereof | |
| CN110981079A (en) | Sewage treatment process applying microbial carrier | |
| CN113651489B (en) | Kitchen waste sewage treatment system | |
| KR101389560B1 (en) | Treatment method of waste water using metallic hollow fiber having porosity and Device thereof | |
| CN110282739A (en) | A method of processing low ratio of carbon to ammonium spread source sanitary sewage | |
| CN105064006A (en) | Modified sawdust-pumice micropowder-doped polylactic acid-polypropylene biological film composite fiber carrier material and preparation method thereof | |
| CN211141646U (en) | Anaerobic-aerobic integrated treatment device for tobacco sheet wastewater produced by papermaking method | |
| CN113072170B (en) | Biological rotating disc material and preparation method thereof | |
| CN115159669B (en) | Aerobic suspension carrier and preparation method thereof | |
| AU2021104804A4 (en) | Process for efficiently treating refinery wastewater based on microalgae membrane bioreactor (mmbr) | |
| Almusawy et al. | Mitigation of membrane fouling in waste water treatment plants by using MBBR & sponge membrane bioreactor (sponge-MBR) | |
| CN115521564B (en) | PVA composite porous material and application | |
| CN117682663A (en) | Biochar suspension carrier with synchronous short-cut nitrification and denitrification functions and preparation method thereof | |
| Salim et al. | Treatment of wastewater using woven and non woven coir geotextiles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |