CN109772176B - Design method of high-flux porous membrane - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
A design method of a high-flux porous membrane. The porous membrane structure is formed by a tubular structure or a lamellar structure, the tubular structure or the lamellar structure is directionally arranged along the transmembrane direction to form a straight channel penetrating through two ends of the porous membrane, the straight channel provides a fluid transmembrane transport path and transmembrane flow resistance, and meanwhile, a flat interface at the atomic level of the tubular structure or the lamellar structure and high porosity provide flow resistance for fluid transport; placing the porous membrane in a solution tank, and ionizing the porous membrane under the action of an aqueous solution to enable the surface of a pore channel to have charges; the ionized nano-channel generates repulsion action on ions carrying the same charge, thereby preventing the ions from entering the pore channel; the extremely narrow interlamellar spacing provides a spatial dimension restriction for hydrated ions larger than the interlamellar spacing dimension, thereby restricting the passage of the hydrated ions, solvent molecules, ions and particles in the aqueous solution, and the solvent molecules, ions and particles in the aqueous solution are transported through the limited spatial distance from one side of the porous membrane to the other side of the porous membrane along the straight through channel under the action of the driving force.
Description
Technical Field
The invention relates to a structural design of a high-flux membrane, in particular to a design method of a high-flux porous membrane, which mainly adopts a transverse structure penetrating through two ends of the membrane and carries out rapid transmembrane transport of fluid between layers.
Background
There is a need for efficient separation in applications ranging from water purification to petroleum refining, chemical production and carbon capture. The membrane structure and the material are the key of the membrane technology, and the key technical breakthrough of the high-performance membrane structure and the material directly influences the popularization of the membrane technology in practical application. This has prompted vigorous search for new high performance separation membranes. The core indicators of membrane performance are selectivity and flux, which are key common problems in many chemical processes. They are closely related to the separation efficiency and the running cost of the membrane. However, selectivity and permeability (flux) are two mutually limiting factors, e.g., increasing the average pore size and porosity of the membrane, etc., often leading to a decrease in selectivity; reducing pore size can improve selectivity but reduce permeability. New materials have been emerging during the last 20 years, but the experimentally observed upper limit of selectivity-permeability has not changed much. This upper limit occurs in almost all membrane materials, including desalination membranes, forward osmosis membranes, porous ultrafiltration membranes, polymer electrolyte membranes for fuel cells, pervaporation membranes, and ion exchange membranes (Ho Bum Park, Jovan Kamcev, Lloyd M.Robeson, Menachem Elimelch, Benny D.Freeman, Maximizing The right stuff: The trade-off between membrane permeability and selectivity, Science,2017,356,1137).
Aiming at the goals of improving selectivity and permeability, the current main research directions comprise surface modification promotion and affinity of transported substances to improve permeability, preparation of a membrane material with very narrow pore size distribution to improve selectivity, construction of a through straight-hole structure or construction of a low-friction material surface to reduce flow resistance, increase of porosity to improve flux, reduction of membrane thickness to reduce flow resistance and the like. The membrane material has excellent transmission performance and certain mechanical strength to adapt to production and installation; has certain chemical and thermal tolerance; meanwhile, the preparation with large area and low cost can be realized to meet the requirement of industrialization. These requirements are difficult to achieve simultaneously in currently available materials (Ho Bum Park, Chul Ho Jung, Young Moo Lee1, Angle J.Hill, Steven J.pas, Stephen T.Mudie, Elizabeth Van Wagner, Benny D.Freeman, David J.Cookson, Polymers with visities tubular for Fast Selective Transport of ll SmallMolecules and Ions. science,2007,318,254).
Disclosure of Invention
The invention aims to provide a design method of a high-flux porous membrane, which mainly adopts a transverse structure penetrating through two ends of the membrane and carries out rapid transmembrane transport of fluid between layers.
The design method of the high-flux porous membrane comprises the following specific steps:
1) the porous membrane structure is formed by a tubular structure or a lamellar structure, the tubular structure or the lamellar structure is directionally arranged along the transmembrane direction to form a straight channel penetrating through two ends of the porous membrane, the straight channel provides a fluid transmembrane transport path and transmembrane flow resistance, and meanwhile, a flat interface at the atomic level of the tubular structure or the lamellar structure and high porosity provide flow resistance for fluid transport;
2) placing the porous membrane in a solution tank, and ionizing the porous membrane under the action of an aqueous solution to enable the surface of a pore channel to have charges;
3) the ionized nano-channel generates repulsion action on ions carrying the same charge, thereby preventing the ions from entering the pore channel; the extremely narrow interlamellar spacing provides a spatial dimension restriction for hydrated ions larger than the interlamellar spacing dimension, thereby restricting their passage, solvent molecules, ions and particulates in the aqueous solution, under the driving force, pass through the through straight channels (or sheets) from one side of the porous membrane to the other, completing the transport of fluid over a limited spatial distance.
In step 1), the straight channel can adopt the shortest fluid transmembrane transport path; the direction of the fluid transmission in the pore canal or between layers is consistent with the transmembrane direction, the direction of the channel and the transmembrane direction are less than 90 degrees, the channel does not need to completely penetrate through two ends of the porous membrane, and a plurality of channels can be connected in front and back to form a transmembrane transmission channel; the lamellar structure can adopt a two-dimensional lamellar structure; the tubular structure can adopt a one-dimensional tubular structure, the one-dimensional tubular structure forms a porous membrane, fluid is transmitted inside the pipeline or between the pipelines, the fluid is transmitted in one dimension in a two-dimensional limited space in three dimensions of the space, the two-dimensional lamellar structure forms the porous membrane, the fluid is transmitted or flows between lamellae, and the fluid is transmitted in the one-dimensional limited space; the straight channel penetrating through the two ends of the porous membrane can be composed of a one-dimensional tubular structure or a two-dimensional lamellar structure to form the straight channel penetrating through the two ends of the porous membrane, the diameter of the one-dimensional tubular structure can be 0.1 nm-10 mu m, and the length of the one-dimensional tubular structure can be 1 nm-10 mm; the sheet diameter of the two-dimensional lamellar structure can be 10 nm-1 mm, and the interlayer spacing can be 0.1 nm-10 mu m; the thickness of the straight channel penetrating through the two ends of the porous membrane can be 5 nm-10 mm; the one-dimensional tubular structure includes but is not limited to carbon nanotubes, boron nitride tubes, carbon fibers, and the like; the two-dimensional lamellar structure includes but is not limited to graphene, graphene oxide, molybdenum disulfide, black phosphorus, boron nitride, silicon alkene, germanium alkene and the like. The preparation method of the one-dimensional tubular structure and the two-dimensional lamellar structure comprises but is not limited to one of physical stripping, electrostatic self-assembly, lamellar stacking, chemical self-assembly, interface and multiphase self-assembly, spin coating, vacuum filtration, inkjet and spray method, sol-gel method, gas phase-solution-solid phase method, sonication method, solvothermal method, template method, chemical vapor deposition method and the like; the ion selection mode of the transmembrane inner wall with the charged straight channel structure comprises anion selectivity and cation selectivity, and the selectivity comprises multiple components such as ions, molecules, particles and the like.
In the step 3), the charges carried by the inner surface of the nanochannel can be the charges carried by the material surface itself, or the charges formed after chemical modification or irradiation treatment; the charge carried may be positive or negative.
The high-flux porous membrane may have a porosity of 20% to 90%.
The invention utilizes a two-dimensional material sheet layer or a one-dimensional pipeline to prepare the nano porous membrane which is directionally arranged along the transmembrane direction by the two-dimensional sheet layer or the one-dimensional pipeline. The nano structure has uniform interlayer spacing and abundant surface charges, so that high ion selectivity is provided, meanwhile, a flat interface at a two-dimensional lamellar atomic level, a through straight pore channel and high porosity provide extremely low flow resistance for fluid transportation, and the limitation of permeability-selectivity in the existing material is expected to be broken through, wherein the selectivity is derived from the steric hindrance and the physical size effect of the pore diameter or the interlayer spacing, the surface charge effect, the chemical interaction and the like.
The invention provides a high-flux porous membrane structure, which consists of a tubular structure or a lamellar structure, forms a straight channel penetrating through two ends of a membrane and provides extremely low transmembrane flow resistance; these straight channels have a very narrow pore size or interlamellar spacing distribution, providing high selectivity of the porous membrane; the porous membrane also has a very high porosity providing high flux. The high-flux porous membrane structure can be widely applied to a forward osmosis process, a reverse osmosis process, a pervaporation process and an electrodialysis process, and can also be applied to systems such as filtration, separation, detection, salt difference energy conversion, battery diaphragms, proton exchange membranes, electrodialysis, membrane absorption, membrane extraction, membrane distillation, membrane reactors and the like of gas, liquid and solid; the high-throughput nature of which is of great significance in the above-mentioned field.
Drawings
FIG. 1 is a schematic diagram of a nanoporous membrane with two-dimensional sheets oriented along the transmembrane direction.
FIG. 2 is a schematic diagram of a nanoporous membrane with two-dimensional sheets arranged perpendicular to the transmembrane direction.
Fig. 3 is a cross-sectional SEM photograph of the graphene oxide membrane high-flux porous membrane in examples 2 and 3.
FIG. 4 is a schematic diagram of a salt difference energy conversion apparatus.
Fig. 5 is an output power diagram in embodiment 1.
Fig. 6 is a schematic view of the suction filtration apparatus.
Fig. 7 is a schematic view of an ion trapping device.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The embodiment of the high-flux porous membrane design method provided by the invention comprises the following specific steps:
1) the porous membrane structure is formed by a tubular structure or a lamellar structure, the tubular structure or the lamellar structure is directionally arranged along the transmembrane direction to form a straight channel penetrating through two ends of the porous membrane, the straight channel provides a fluid transmembrane transport path and transmembrane flow resistance, and meanwhile, a flat interface at the atomic level of the tubular structure or the lamellar structure and high porosity provide flow resistance for fluid transport; the straight channel can adopt the shortest fluid transmembrane transport path; the direction of the fluid transmission in the pore canal or between layers is consistent with the transmembrane direction, the direction of the channel and the transmembrane direction are less than 90 degrees, the channel does not need to completely penetrate through two ends of the porous membrane, and a plurality of channels can be connected in front and back to form a transmembrane transmission channel; the lamellar structure adopts a two-dimensional lamellar structure; the tubular structure adopts a one-dimensional tubular structure, the one-dimensional tubular structure forms a porous membrane, fluid is transmitted inside the pipeline or between the pipelines, the fluid is transmitted in one dimension in a two-dimensional limited space in three dimensions of the space, the porous membrane is formed by a two-dimensional lamellar structure, the fluid is transmitted or flows between lamellae, and the fluid is transmitted in the one-dimensional limited space; the straight channel penetrating through the two ends of the porous membrane is composed of a one-dimensional tubular structure or a two-dimensional lamellar structure to form the straight channel penetrating through the two ends of the porous membrane, the diameter of the one-dimensional tubular structure is 0.1 nm-10 mu m, and the length of the one-dimensional tubular structure is 1 nm-10 mm; the sheet diameter of the two-dimensional lamellar structure is 10 nm-1 mm, and the interlayer spacing is 0.1 nm-10 mu m; the thickness of the straight channel penetrating through the two ends of the porous membrane is 5 nm-10 mm; the one-dimensional tubular structure includes but is not limited to carbon nanotubes, boron nitride tubes, carbon fibers, and the like; the two-dimensional lamellar structure includes but is not limited to graphene, graphene oxide, molybdenum disulfide, black phosphorus, boron nitride, silicon alkene, germanium alkene and the like. The preparation method of the one-dimensional tubular structure and the two-dimensional lamellar structure comprises but is not limited to one of physical stripping, electrostatic self-assembly, lamellar stacking, chemical self-assembly, interface and multiphase self-assembly, spin coating, vacuum filtration, inkjet and spray method, sol-gel method, gas phase-solution-solid phase method, sonication method, solvothermal method, template method, chemical vapor deposition method and the like; the ion selection mode of the transmembrane inner wall with the charged straight channel structure comprises anion selectivity and cation selectivity, and the selectivity comprises multiple components such as ions, molecules, particles and the like.
2) Placing the porous membrane in a solution tank, and ionizing the porous membrane under the action of an aqueous solution to enable the surface of a pore channel to have charges;
3) the ionized nano-channel generates repulsion action on ions carrying the same charge, thereby preventing the ions from entering the pore channel; the extremely narrow interlamellar spacing provides a spatial dimension restriction for hydrated ions larger than the interlamellar spacing dimension, thereby restricting their passage, solvent molecules, ions and particulates in the aqueous solution, under the driving force, pass through the through straight channels (or sheets) from one side of the porous membrane to the other, completing the transport of fluid over a limited spatial distance. The charges carried by the inner surface of the nano channel can be the charges carried by the surface of the material, and can also be the charges formed after chemical modification or irradiation treatment; the charge carried may be positive or negative.
The high-flux porous membrane may have a porosity of 20% to 90%.
The high-flux porous membranes in the following examples all have high ion selectivity. The porous membrane is placed in a specific solution tank (the type of the solution tank is determined according to specific embodiments), and under the action of the aqueous solution, the porous membrane is ionized to charge the surfaces of the channels. According to the coulomb effect, the ionized nanochannel can generate repulsion action on ions carrying the same charge so as to prevent the ions from entering the pore channel; very narrow interlamellar spacings can provide a spatial dimension restriction for hydrated ions larger than the interlamellar spacing dimension, thereby restricting their passage. Solvent molecules, ions and particles in the solution can reach the other side of the membrane from one side of the membrane along a through straight channel (or a sheet layer) under the action of driving force, and the transportation speed of the fluid is greatly improved only by a distance in a limited space. Referring to a schematic diagram of the nanoporous film in which the two-dimensional sheets are arranged in a direction across the membrane in fig. 1 and a schematic diagram of the nanoporous film in which the two-dimensional sheets are arranged perpendicular to the direction across the membrane in fig. 2, it can be seen that the structure in fig. 1 is more beneficial to fluid transportation.
Specific examples are given below.
Example 1 salt differential-to-Electrical energy conversion
Preparing a molybdenum disulfide high-flux selective membrane: preparing molybdenum disulfide dispersion liquid with uniform sheet diameter by using an ultrasonic cell crusher, and forming a required two-dimensional layered film on a cellulose film or a nuclear pore film by adopting a method of vacuum suction filtration of the molybdenum disulfide dispersion liquid. Due to negative charges carried by the molybdenum disulfide sheet layer, in the deposition process, the molybdenum disulfide sheet layer is self-assembled into a porous membrane material with the interlayer spacing of 0.8-1.1 nm under the action of electrostatic repulsion. And further performing high-temperature heat treatment to obtain the nuclear pore membrane-molybdenum disulfide composite material. And then embedding the sample with epoxy resin, processing the embedded single molybdenum disulfide nano porous material into a proper size by a slicing method, assembling the sample into a large-area sample, and finally grinding and thinning the surface of the membrane to obtain the sample with the required area and thickness.
As shown in fig. 4, the molybdenum disulfide high-flux membrane was encapsulated in a solution tank, seawater (500mm nacl solution) was added to the left solution tank, and river water (10mm nacl solution) was added to the right solution tank; driven by the ion concentration gradient, the net diffusion of ions across the membrane results in a net current and electromotive force, and can output electrical energy to an external circuit.
According to formula Pout＝I2.And R, calculating the output power of the system. Wherein P isoutFor the output power of the system, I is the current in the system, and R is the load resistance in the external circuit.
When the concentration of the solution tank is kept unchanged, the maximum output power of the system can be obtained by adjusting the magnitude of the load resistance in the external circuit, and the result is shown in fig. 5. Wherein the thickness of the molybdenum disulfide mixed film is 250 μm, and the effective film area is 1mm multiplied by 6 μm.
Example 2 desalination of sea Water
Preparing a graphene oxide high-flux selective membrane: and uniformly coating the suspension of the graphene oxide on a cellulose membrane by using a spin coating method, and performing heat treatment to obtain the porous membrane structure of the graphene oxide. A transmission electron micrograph of the cross section of the prepared graphene oxide film is shown in fig. 3. Then embedding the sample by organic glass, processing the embedded single nano porous material into a proper size by a slicing method, assembling the sample into a large-area sample, and finally grinding and thinning the surface to prepare the sample with the required area and thickness; the exposed end of the thinned graphene oxide high-flux film presents a lamellar structure in fig. 3.
As shown in fig. 6, the graphene oxide porous membrane is packaged into a suction filtration tank, NaCl solutions of different salinity are added into the inlet chamber of the tank, and vacuum pumping is performed at the suction filtration port. Under the action of the external atmospheric pressure, water molecules pass through the graphene oxide film to the other side of the film, and Na+And Cl-Plasma ions are blocked outside the membrane due to the space-limiting effect of the graphene oxide layer spacing.In the test process, the effective area of the graphene oxide film is 4cm2. When the concentration of NaCl was 0.8 wt%, 3.5 wt%, 4 wt% and 10 wt%, respectively, the retention rates corresponded to 99.3%, 98%, 97.5% and 96%, respectively.
Example 3 sieving of different ions
As shown in fig. 7, a high-throughput graphene oxide film was placed between two solution tanks, and a transmission electron micrograph of the cross section of the graphene oxide film is shown in fig. 3. The left solution tank was filled with 30mM NaCl and MgCl2The mixed solution was filled with pure water in the right solution tank. The effective area of the graphene oxide film is 1mm2. A voltage of 0.01V across the membrane was applied to the graphene oxide membrane by a voltage source, while a pressure differential of 1 atmosphere was applied across the membrane. After 2 hours, Mg could be measured in the right solution tank2+Is 1mM and Na+The concentration of (2) is 0.01mM, which shows that the graphene oxide film can realize screening of different ions under the assistance of an electric field.
Claims (6)
1. A design method of a high-flux porous membrane is characterized by comprising the following specific steps:
1) the laminated structure is directionally arranged along the transmembrane direction to form straight channels penetrating through two ends of the porous membrane, the straight channels provide a fluid transmembrane transport path and transmembrane flow resistance, and meanwhile, the atomic level flat interface and high porosity of the laminated structure provide flow resistance for fluid transport; the straight channel adopts a shortest fluid transmembrane transport path, the direction of the fluid transmission in the pore channel or between layers is consistent with the transmembrane direction, and the direction of the straight channel and the transmembrane direction are less than 90 degrees; the straight channels penetrate through two ends of the porous membrane, and a plurality of straight channels are connected in front and back to form a transmembrane transport channel;
the lamellar structure adopts a two-dimensional lamellar structure; the porous membrane is formed by a two-dimensional lamellar structure, and fluid is transported between lamellae; the straight channel penetrating through two ends of the porous membrane consists of a two-dimensional lamellar structure;
2) placing the porous membrane in a solution tank, and ionizing the porous membrane under the action of an aqueous solution to enable the surface of a pore channel to have charges;
3) the nano-channel with the charged surface generates repulsion action on ions carrying the same charge, so that the ions are prevented from entering the pore channel; the extremely narrow interlamellar spacing provides a spatial dimension restriction for hydrated ions larger than the interlamellar spacing dimension, thereby restricting their passage; solvent molecules, ions and particles in the aqueous solution are transported by a distance in a limited space from one side of the porous membrane to the other side along the through straight channel under the action of the driving force.
2. The method for designing the high-throughput porous membrane according to claim 1, wherein in the step 1), the sheet diameter of the two-dimensional sheet structure is 10nm to 1mm, and the layer spacing is 0.1nm to 10 μm.
3. The method for designing a high throughput porous membrane according to claim 1, wherein in step 1), the thickness of the through channel penetrating both ends of the porous membrane is 5nm to 10 mm.
4. The method for designing the high-throughput porous membrane according to claim 1, wherein in step 1), the two-dimensional lamellar structure is selected from one of graphene, graphene oxide, molybdenum disulfide, black phosphorus, boron nitride, silicon alkene or germanium alkene.
5. The method of claim 1, wherein in step 1), the two-dimensional lamellar structure is prepared by one of physical exfoliation, electrostatic self-assembly, lamellar stacking, chemical self-assembly, interfacial and multiphase self-assembly, spin coating, vacuum filtration, inkjet and spray methods, sol-gel methods, gas-solution-solid phase methods, sonication, solvothermal methods, templating methods, and chemical vapor deposition methods; the ion selection mode of the transmembrane inner wall with the charged straight channel structure comprises anion selectivity and cation selectivity, and the selectivity comprises various components such as ions, molecules and particles.
6. The method for designing the high-throughput porous membrane according to claim 1, wherein in the step 3), the charges carried by the inner surface of the nanochannel are charges carried by the material surface itself or charges formed after chemical modification or irradiation treatment; the charge carried is either positive or negative.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910221565.5A CN109772176B (en) | 2019-03-22 | 2019-03-22 | Design method of high-flux porous membrane |
| PCT/CN2020/080374 WO2020192575A1 (en) | 2019-03-22 | 2020-03-20 | Porous membrane, and preparation method therefor and use method thereof |
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| CN104607069A (en) * | 2015-01-27 | 2015-05-13 | 清华大学 | Compound desalination membrane as well as preparation method and application thereof |
| KR20160076182A (en) * | 2014-12-22 | 2016-06-30 | 인하대학교 산학협력단 | Method of manufacturing for graphene/carbon nanotube composite membrane |
| CN106390748A (en) * | 2016-09-28 | 2017-02-15 | 天津工业大学 | Preparation method of high-throughput and multilayer sandwich type composite nano-filtration membrane |
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| KR20160076182A (en) * | 2014-12-22 | 2016-06-30 | 인하대학교 산학협력단 | Method of manufacturing for graphene/carbon nanotube composite membrane |
| CN104607069A (en) * | 2015-01-27 | 2015-05-13 | 清华大学 | Compound desalination membrane as well as preparation method and application thereof |
| CN106390748A (en) * | 2016-09-28 | 2017-02-15 | 天津工业大学 | Preparation method of high-throughput and multilayer sandwich type composite nano-filtration membrane |
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