CN117815928A - Preparation method of tubular pervaporation membrane, tubular pervaporation membrane and application of tubular pervaporation membrane - Google Patents
Preparation method of tubular pervaporation membrane, tubular pervaporation membrane and application of tubular pervaporation membrane Download PDFInfo
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- CN117815928A CN117815928A CN202211184205.0A CN202211184205A CN117815928A CN 117815928 A CN117815928 A CN 117815928A CN 202211184205 A CN202211184205 A CN 202211184205A CN 117815928 A CN117815928 A CN 117815928A
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- tubular
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- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 238000005373 pervaporation Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- -1 polydimethylsiloxane Polymers 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 3
- 102000008186 Collagen Human genes 0.000 claims description 3
- 108010035532 Collagen Proteins 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920001436 collagen Polymers 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 11
- 238000005470 impregnation Methods 0.000 abstract description 7
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 54
- 239000000243 solution Substances 0.000 description 33
- 238000000926 separation method Methods 0.000 description 9
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
The invention discloses a preparation method of a tubular pervaporation membrane, which adopts an impregnation method or an interfacial polymerization method to generate a thin film selective layer on the inner side of a general tubular membrane so as to upgrade the tubular pervaporation membrane. The tubular pervaporation membrane of the present invention is useful in filtration devices or systems for separating clean water from contaminated aqueous mixed liquids.
Description
Technical Field
The invention relates to a preparation method of a tubular pervaporation membrane, the tubular pervaporation membrane, and also relates to application of the pervaporation membrane prepared by the method, a thin film selection layer is prepared based on a common tubular membrane, and the thin film selection layer is upgraded into the tubular pervaporation membrane and is applied to filtering equipment or a system to separate and obtain a clean water source.
Background
The known membrane separation technology is applied to industrial procedures such as wastewater treatment, sea water desalination treatment, drinking water preparation, separation and purification of organic matters contained in foods and water, drug release, gas and/or liquid purification, concentration and fractionation of a liquid mixture, preparation of ultrapure water required by the electronic industry and the like, and has wide application range, rapidness and high efficiency economic benefit. However, the conventional tubular membrane is difficult to handle the separation of constant boiling substances and near boiling substances.
In recent decades, the method is poured into a Pervaporation method (Pervaporation), and has the characteristics of high separation degree, simple operation, no pollution, low energy consumption and the like. For example, university of pharmacological science and technology of Jianan proposes a method for preparing an ion exchange membrane with pervaporation separation efficiency and forming an asymmetric membrane thereof, which is applied to a pervaporation separation process of aqueous organic mixed solution such as ethanol-water solution and organic acid-water, and the patent rights of Taiwan No. I368630 are obtained.
Disclosure of Invention
In view of the above, a main object of the present invention is to provide a method for producing a tubular pervaporation membrane, wherein a thin film selective layer is formed inside a general tubular membrane by impregnation or interfacial polymerization, and the tubular membrane is upgraded to the tubular pervaporation membrane.
It is another object of the present invention to provide a tubular pervaporation membrane prepared by the preparation method.
It is a further object of the present invention to provide the use of the tubular pervaporation membrane in a filtration device or system to separate and obtain clean water from a contaminated aqueous mixed liquor.
To achieve the above object, the present invention provides a method for preparing the same, comprising: preparing a tubular film which is composed of at least two layers of structures with an outer layer surrounding a base film layer; distributing the solution on the inner side of the base film layer; and drying the solution to form a hydrophilic and compact film selective layer and attaching the film selective layer to the inner side of the base film layer, so that the tubular film is a tubular pervaporation film.
In the impregnation method, according to a preferred embodiment of the preparation method of the present invention, the solution is a polymer solution prepared from at least one selected from polyvinyl alcohol (PVA), cellulose Acetate (CA), polydimethylsiloxane (PDMS), carboxymethyl cellulose (CMC), collagen, chitosan (Chitosan), and chitin.
In terms of impregnation, according to a further preferred embodiment of the production method according to the present invention, the tubular membrane receives a polymer solution distributed inside the base membrane layer, dried with a heating device into a hydrophilic and dense film selection layer, and attached inside the base membrane layer.
In terms of impregnation, according to still further preferred embodiments of the preparation method of the present invention, the polymer solution flows into the inner side of the base film layer to be uniformly distributed, the tubular film is rotated for a period of time to distribute the polymer solution on the inner side of the base film layer, the tubular film is laid flat, and the excess polymer solution is poured out.
In view of the interfacial polymerization method, according to a preferred embodiment of the preparation method of the present invention, the solution is selected from the group consisting of a monomer having an amine functional group and pure water formulated at a concentration ofThe tubular film is soaked in the aqueous amine solution and taken out, so that the acyl chloride solution and the aqueous amine solution on the inner side of the base film layer are polymerized to form a hydrophilic and compact film selective layer, and the tubular film is dried by heating equipment, so that the film selective layer is attached on the inner side of the base film layer.
In view of the interfacial polymerization process, a further preferred embodiment of the preparation process according to the invention is characterized in that the acid chloride solution is selected from the group consisting of monomers containing acid chloride functional groups formulated with an alkane solutionThe material of the film selection layer is organic high molecular polymer containing Polyamide (PA for short) by concentration solution.
Thus, the invention generates a film selection layer on the inner side of a general tubular film by an impregnation method or an interfacial polymerization method, and completes the preparation flow of upgrading the tubular film into a tubular pervaporation film.
The invention also provides the tubular pervaporation membrane prepared by the method.
At the application level, the invention proposes the use of a tubular pervaporation membrane prepared by the method described above in a filtration device or system for aqueous mixed liquids.
According to a preferred embodiment of the use according to the invention, in particular, the membrane selection layer separates the filter device or system into a liquid phase chamber and a gas phase chamber. The water-containing mixed liquid passes through the liquid phase chamber, and liquid water molecules are adsorbed on the surface of the hydrophilic film selection layer. The low pressure evaporates into gaseous water molecules which can penetrate the membrane selective layer and diffuse to the other side. And desorbing water molecules on the other side of the film selection layer, and condensing the water molecules into water in a gas phase chamber.
Thus, the present invention applies a tubular pervaporation membrane to a filtration device or system to separate and obtain clean water from a contaminated aqueous mixed liquor.
Drawings
FIG. 1Figure 4 shows a first set of procedures for preparing tubular pervaporation membranes according to the present invention.
FIG. 5FIG. 7 shows a second set of procedures for preparing tubular pervaporation membranes according to the present invention.
Figure 8 shows a schematic of a tubular pervaporation membrane application.
Fig. 9 shows a partially enlarged use state of the pervaporation membrane.
Reference numerals illustrate:
a tubular membrane 10; an outer layer 11; an intermediate layer 12; a base film layer 13; a polymer solution 14; film selection layers 15, 23; arrow 16; a heating device 17; a heat source 18; a container 20; an aqueous amine solution 21; acid chloride solution 22; a width 24; a raw water tank 30; a filter pump 31; a filter 32; a heat pump 33; a first heat exchanger 34; a first circulation pump 35; a second heat exchanger 36; a second circulation pump 37; a vacuum pump 38; a liquid phase chamber 40; water molecules 41, 44; dirt 42; a gas phase chamber 43.
Detailed Description
For purposes of clarity, understanding, and appreciation of the various aspects, features and advantages of the invention, one or more presently preferred embodiments will be described in connection with the accompanying drawings.
Next, embodiments of the present invention are described with reference to the drawings. In the drawings, the same or similar structures or elements are denoted by the same reference numerals. It is contemplated that the described embodiments are merely exemplary of some, but not all embodiments of the present invention. Other embodiments, or configurations that may be altered or varied as desired, can be derived based on the examples described and are within the scope of the invention.
In the following description, directional terms such as "up", "down", "left", "right", "front", "rear", "inner", "outer" and "side" refer only to the directions of the drawings. The use of directional terms is provided for better, more clear description and understanding of the present invention and does not explicitly indicate or imply that the devices or components in question must be in a particular orientation, configuration or operation and should not be construed as limiting the technical content of the present invention.
In the following description, "mounted," "connected," or "connected" or "disposed on …" are to be construed broadly, such as fixedly connected, detachably connected, integrally connected, mechanically connected, directly connected, indirectly connected, or connected within two components, unless otherwise specified and clear. It will be understood by those skilled in the art that the foregoing terms are used in a generic or empirical manner in connection with the various embodiments of the invention, or even the specific meaning of the invention.
In the following description, unless otherwise indicated, the term "plurality" means two or more.
As in figure 1The first set of flow paths for the preparation process of the present invention, shown in fig. 4, upgrades the general tubular membrane 10 to a tubular pervaporation membrane.
In general, the preparation method of the invention comprises the following steps: firstly, preparing a tubular membrane 10, wherein an outer layer 11 wraps an intermediate layer 12, and the intermediate layer 12 surrounds a base membrane layer 13 to form a three-layer structure; distributing the solution inside the base film layer 13; the solution dries to a thin film selective layer 15 and adheres to the inside of the base film layer 13, making the tubular film 10 a tubular pervaporation film.
Wherein the outer layer 11 is a non-woven fabric, a non-woven fabric or a woven fabric made of at least one organic polymer selected from polypropylene (PP), polyethylene terephthalate (PET), nylon (Nylon) and polylactic acid (PLA), and is used as a first supporting layer of the tubular membrane 10.
The material of the intermediate layer 12 is selected in the same range as the outer layer 11, and is used as a second support layer for the tubular film 10.
In addition, the base film layer 13 adopts at least one organic high polymer selected from polyvinylidene fluoride (PVDF), polyphenylene oxide sulfone (PES), polyarylsulfone (PSU), polyacrylonitrile (PAN), acetate Fiber (PTFE), polytetrafluoroethylene (Nylon) and polyvinyl chloride (PVC), and an asymmetric pore structure is realized according to a wet phase conversion method or an electrostatic spinning technology.
The solution is selected from polymer solution 14 prepared from at least one of polyvinyl alcohol (PVA), cellulose Acetate (CA), polydimethylsiloxane (PDMS), carboxymethyl cellulose (CMC), collagen, chitosan (Chitosan) and chitin. The polymer solution 14 is flowed into the tubular film 10 and distributed inside the base film layer 13. Then, the tubular film 10 is left to standExcess polymer solution 14 is poured (see FIG. 2). To be distributed uniformly, the tubular film 10 is rotated approximately +_ in the direction of arrow 16 (see FIG. 3)>The polymer solution 14 is uniformly distributed inside the base film layer 13. Then, the tubular film 10 is put into the heating device 17 to +.>Is about +.f. of the tubular membrane 10 is dried by the heat source 18 of (a)>To dryness, the polymer solution 14 attached to the inner side of the base film layer 13 is made into a hydrophilic and dense film selective layer 15, whereby the tubular film 10 is upgraded to a tubular pervaporation film.
As shown in FIG. 5A second set of procedures for the preparation of the present invention is shown in fig. 7, which enables the upgrading of a typical tubular membrane 10 to a tubular pervaporation membrane.
The preparation method comprises the following steps: firstly, preparing a tubular membrane 10, wherein an outer layer 11 surrounds a base membrane layer 13 to form a two-layer structure; distributing the solution inside the base film layer 13; the solution dries to a thin film selective layer 23 and adheres to the inside of the base film layer 13, making the tubular film 10 a tubular pervaporation film.
Wherein the solution is prepared from monomer containing amine functional group and pure water with concentration of Is used for containing the required amine water solution 21 by a container 20 for soaking the tubular membrane 10> And then taking out. Preparing the monomer containing acyl chloride functional group and alkane solution into the concentration +.>Is introduced into the inner side of the base film layer 13 and polymerized with the aqueous amine solution 21>And then within the heating device 17 at aboutIs dried by the heat source 18->To dry, get hydrophilic and compactThe membrane selection layer 23 of (2) also enables the tubular membrane 10 to be upgraded to a tubular pervaporation membrane. The material of the thin film selection layer 23 is an organic polymer containing Polyamide (PA for short).
Either the impregnation method or the interfacial polymerization method, a thin film selective layer 15 or 23 is formed on the inner side of a general tubular membrane 10, and the tubular pervaporation membrane upgrading operation is completed.
The film selective layer 15 or 23 formed on the inner side of the general tubular film 10 is the tubular pervaporation film obtained by the preparation method according to the present invention. The thin film selective layer 15 or 23 in the tubular pervaporation membrane may be used alone as a pervaporation membrane.
In fig. 8 and 9, the tubular pervaporation membrane is applied to a filtration device (or system) to separate and obtain clean water from an aqueous mixed liquor. Wherein the filtration apparatus (or system) utilizes a set of lines to connect a raw water tank 30, a filtration pump 31 and a filter 32 together to form a filtration (or separation) circuit for recycling. The filtration apparatus (or system) uses other lines to combine a heat pump 33, a first heat exchanger 34, a first circulation pump 35, a second heat exchanger 36, a second circulation pump 37, and a vacuum pump 38 into a heat exchange circuit for use in a cycle.
After the energization, the heat pump 33 converts the electric energy into the heat energy of the fluid, exchanges heat with the above-mentioned filtration (or separation) circuit by the first heat exchanger 34 to cool, returns to the heat pump 33 via the first circulation pump 35 to warm, and then is transferred to the first heat exchanger 34. The vacuum pump 38 draws gas from the filter 32, depressurizing the filter 32. The fluid in the second heat exchanger 36 absorbs the air temperature of the filter 32, exchanges heat with the heat pump 33 to reduce the temperature, returns to the second heat exchanger 36 via the second circulation pump 37, and absorbs the air temperature of the filter 32 again.
From a separation point of view, the aqueous mixed liquid in the raw water tank 30 is heated by receiving the heat energy of the first heat exchanger 34 in the path of the filter pump 31 to the filter 32 and back to the raw water tank 30. The tubular pervaporation membrane produced in the above manner is used in a filter 32 to separate (filter) the aqueous mixed liquid.
The membrane selection layer 15 separates the filter 32 into a liquid phase chamber 40 and a gas phase chamber 43. The aqueous mixed liquor passes through the liquid phase chamber 40 and the film selective layer 15 intercepts large particulate contaminants 42. Based on the condition that the partial pressure of vapor is less than the saturated vapor pressure, the liquid water molecules 41 adsorb the surface of the thin film selection layer 15 and vaporize into smaller volume water molecules 44. The gaseous water molecules 44 permeate into one surface of the film selection layer 15 in a concentration gradient # △ C) Is a driving force, and spreads to the other surface along the width 24 direction. The water molecules 44 desorbed from the thin film selective layer 15 enter the gas phase chamber 43, are condensed from the gas phase into water by heat exchange in the second heat exchanger 36, and flow to the other place by the vacuum pump 38.
Thus, the present invention applies a tubular pervaporation membrane to a filtration device or system to separate and obtain clean water from a contaminated aqueous mixed liquor.
Those skilled in the art will understand and appreciate that changes can be made to the above-described embodiments without departing from the broad inventive concept thereof. Therefore, the present invention is not limited to the specific embodiments disclosed in the specification, but is intended to cover and protect the literal content defined in the claims, for the purpose of modifying the spirit and scope of the present invention.
Claims (9)
1. A method for preparing a tubular pervaporation membrane, characterized in that: comprising the following steps:
preparing a tubular film which is composed of at least two layers of structures with an outer layer surrounding a base film layer;
distributing the solution on the inner side of the base film layer; and
the solution dries to a hydrophilic and dense film selective layer and adheres to the inner side of the base film layer, making the tubular film a tubular pervaporation film.
2. The method for preparing a tubular pervaporation membrane according to claim 1, wherein the solution is a polymer solution prepared from at least one selected from the group consisting of polyvinyl alcohol, acetate fiber, polydimethylsiloxane, carboxymethyl cellulose, collagen, chitosan and chitin.
3. The method of preparing a tubular pervaporation membrane according to claim 2, wherein the tubular membrane receives a polymer solution, the polymer solution is distributed on the inner side of the base membrane layer, and the tubular membrane is dried by a heating device, so that the polymer solution becomes a film selective layer and is attached on the inner side of the base membrane layer.
4. A method of preparing a tubular pervaporation membrane according to claim 3, wherein the polymer solution flows into the inner side of the base membrane layer, the tubular membrane is rotated for a period of time to distribute the polymer solution on the inner side of the base membrane layer, the tubular membrane is laid flat and the excess polymer solution is poured out.
5. The method for preparing a tubular pervaporation membrane according to claim 1, wherein the solution is selected from the group consisting of monomers containing amine functional groups and pure water in a concentration ofThe tubular film is soaked in the aqueous amine solution and taken out, so that the acyl chloride solution and the aqueous amine solution on the inner side of the base film layer are polymerized to form a film selection layer, and the tubular film is dried by heating equipment, so that the film selection layer is attached on the inner side of the base film layer.
6. The method of preparing a tubular pervaporation membrane according to claim 5, wherein said acid chloride solution is selected from the group consisting of monomers containing acid chloride functional groups and alkane solutionsA solution of a concentration.
7. A tubular pervaporation membrane prepared according to the preparation method of any of claims 1 to 6.
8. Use of a tubular pervaporation membrane according to claim 7, characterized in that the tubular pervaporation membrane produced according to the method according to any of claims 1 to 6 is used in a filtration device or system for aqueous mixed liquids.
9. Use of a tubular pervaporation membrane according to claim 8, wherein the membrane selective layer separates the filtration device or system into a liquid phase chamber and a gas phase chamber, wherein the aqueous mixed liquid passes through the liquid phase chamber, liquid water molecules are adsorbed on the surface of the hydrophilic membrane selective layer, low pressure vaporised into gaseous water molecules which permeate the membrane selective layer and diffuse to the other side, desorb from the membrane selective layer into the gas phase chamber and condense into water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211184205.0A CN117815928A (en) | 2022-09-27 | 2022-09-27 | Preparation method of tubular pervaporation membrane, tubular pervaporation membrane and application of tubular pervaporation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211184205.0A CN117815928A (en) | 2022-09-27 | 2022-09-27 | Preparation method of tubular pervaporation membrane, tubular pervaporation membrane and application of tubular pervaporation membrane |
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| Publication Number | Publication Date |
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| CN117815928A true CN117815928A (en) | 2024-04-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202211184205.0A Pending CN117815928A (en) | 2022-09-27 | 2022-09-27 | Preparation method of tubular pervaporation membrane, tubular pervaporation membrane and application of tubular pervaporation membrane |
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| Country | Link |
|---|---|
| CN (1) | CN117815928A (en) |
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- 2022-09-27 CN CN202211184205.0A patent/CN117815928A/en active Pending
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