CN108636129B - Preparation method of ceramic hollow fiber oxygen permeable membrane - Google Patents
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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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
The invention provides a preparation method of a ceramic hollow fiber oxygen permeable membrane, which comprises the following steps: (1) preparing a metal acetate mixture according to the composition of metal ions in the ceramic oxygen-permeable membrane material, adding citric acid, performing ball milling refining, and calcining to obtain a ceramic oxygen-permeable membrane powder material; (2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), and mixing the powder material with an organic polymer and a solvent to obtain a membrane casting solution; (3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane. The preparation method shortens preparation route and time, and eliminates NOxThe emission pollutes the environment, the energy consumption and the production cost are greatly reduced, and the method is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of ceramic oxygen permeable membranes, and particularly relates to a preparation method of a ceramic hollow fiber oxygen permeable membrane.
Background
The ceramic oxygen permeable membrane is an inorganic membrane made of oxygen ion-electron mixed conduction ceramic material, and oxygen can be transferred from a high oxygen partial pressure side to a low oxygen partial pressure side in the form of oxygen ions at high temperature (> 700 ℃) so as to realize oxygen separation. Compared with the traditional cryogenic rectification or PSA method, the method has the advantages of high oxygen permeation selectivity (up to 100% in theory), high oxygen permeation rate (2-3 orders of magnitude faster than an organic membrane), low oxygen production cost (30-50% lower than the traditional cryogenic rectification or PSA method), simple process and operation (single-stage oxygen production) and the like, is particularly suitable for small-scale oxygen environment, and has very wide market prospect.
Ceramic hollow fiber oxygen permeable membrane with high oxygen permeability and unit bodyThe ceramic oxygen permeable membrane has the advantages of large membrane area, stable structure and the like, is easy to solve engineering problems of membrane strength, high-temperature sealing, connection and the like, is easy to assemble into a ceramic membrane module and an oxygen generation system, and provides important basic conditions for the commercial application of the ceramic oxygen permeable membrane technology. Such ceramic hollow fiber oxygen permeable membranes are mostly prepared by the phase inversion-sintering method (CN 100361730C; X.Tan, Preparation of LSCF ceramic fiber membranes for oxygen production by a phase-inversion/sintering technique, Ind.Eng.chem.Res.,44(2005)61-66), the preparation process generally uses nitrate as raw material, firstly uses spray pyrolysis method or sol-gel method to prepare ceramic oxygen-permeable membrane powder material (Mengxuchxia et al, China non ferrous metals academic report, 16(12):2077-, therefore, in the preparation process, NO matter the spray pyrolysis method or the sol-gel method is used for preparing the ceramic oxygen permeable membrane powder, a nitrate solution needs to be prepared, and then the solution is evaporated to be dry, so that a large amount of energy is consumed, and a large amount of NO is generated.xCausing environmental pollution, which inevitably increases the production and application cost of the hollow fiber ceramic oxygen permeable membrane.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of a ceramic hollow fiber oxygen permeable membrane, which eliminates NOxThe emission pollutes the environment, the energy consumption and the production cost are greatly reduced, and the method is suitable for large-scale production and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a ceramic hollow fiber oxygen permeable membrane, which comprises the following steps:
(1) preparing a metal acetate mixture according to the composition of metal ions in the ceramic oxygen-permeable membrane material, adding citric acid, then ball-milling, and calcining to obtain a ceramic oxygen-permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), and mixing the ceramic oxygen permeable membrane powder material with an organic polymer and a solvent to obtain a membrane casting solution;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
In a preferred embodiment of the present invention, the molar ratio of the metal acetate mixture to citric acid in step (1) is 1 (1-5), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and 1 (2-3) is preferred.
In a preferred embodiment of the present invention, the temperature of the calcination in step (1) is 600 to 1000 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, or 1000 ℃, but is not limited to the recited values, and other values not recited in the above range are also applicable, preferably 700 to 800 ℃.
In a preferred embodiment of the present invention, the calcination time in step (1) is 1 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and preferably 3 to 4 hours.
In the invention, the raw materials after ball milling are dried before calcination.
Preferably, the ball milling time in step (1) and step (2) is 2-8 h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values in the range of the recited values are also applicable, preferably 4-6 h.
In a preferred embodiment of the present invention, the ceramic oxygen permeable membrane powder after ball milling and sieving in step (2) has an average particle size of 0.1 to 10 μm, such as 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, but is not limited to the values listed above, and other values not listed within this range are also applicable, preferably 0.5 to 3 μm.
As a preferred embodiment of the present invention, the organic polymer in step (2) comprises any one or a combination of at least two of polysulfone, polyethersulfone, polyetherimide, polyvinyl alcohol or polyvinyl butyral, and the combination is exemplified by, but not limited to: combinations of polysulfone and polyethersulfone, polyethersulfone and polyetherimide, polyetherimide and polyvinyl alcohol, polyvinyl alcohol and polyvinyl butyral, polyvinyl butyral and polysulfone or polysulfone, polyethersulfone and polyetherimide, and the like.
As a preferred embodiment of the present invention, the solvent in step (2) comprises any one or a combination of at least two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide, and the combination is typically but not limited to: a combination of N-methylpyrrolidone and N, N-dimethylformamide, a combination of N, N-dimethylformamide and N, N-dimethylacetamide, a combination of N, N-dimethylacetamide and dimethyl sulfoxide, a combination of dimethyl sulfoxide and N-methylpyrrolidone, a combination of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, or the like.
As a preferable technical scheme of the invention, the composition of the casting solution in the step (2) comprises, by mass, 60-75% of ceramic oxygen permeable membrane powder, 3-7% of an organic polymer and 20-30% of a solvent.
The mass fraction of the ceramic oxygen permeable membrane powder may be 60%, 62%, 65%, 68%, 70%, 72%, 75%, etc., the mass fraction of the organic polymer may be 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, etc., and the mass fraction of the solvent may be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc., but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) preparing a metal acetate mixture according to the composition of metal ions in the ceramic oxygen permeable membrane material, adding a ligand, and then ball-milling for 2-8 h, wherein the molar ratio of the metal acetate mixture to citric acid is 1 (1-5), and calcining at 600-1000 ℃ to obtain a ceramic oxygen permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (2), mixing the refined and screened ceramic oxygen permeable membrane powder with an average particle size of 0.1-10 mu m, and mixing the refined and screened ceramic oxygen permeable membrane powder with an organic polymer and a solvent to obtain a membrane casting solution, wherein the membrane casting solution comprises, by mass, 60-75% of the ceramic oxygen permeable membrane powder, 3-7% of the organic polymer and 20-30% of the solvent;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
The phase inversion-sintering method in step (3) of the present invention is a prior art and is disclosed in patent CN 1676198A: a ceramic hollow fiber membrane reactor for oxygen generation by air separation and a preparation method and application thereof; CN 101200374A: a preparation method of a ceramic hollow fiber membrane with a composite structure; CN 101279205A: a ceramic hollow fiber oxygen permeable membrane with a catalyst loaded on the surface and a preparation method thereof; CN 101302121A, a surface nano-coating modified ceramic oxygen-permeable membrane and a preparation method thereof, and CN 102895886A: a hollow fiber ceramic oxygen permeable membrane with a double-composite asymmetric structure and a preparation method thereof. Therefore, the present invention does not describe the specific operation of the method.
The invention develops a new method of ceramic hollow fiber oxygen permeable membrane using acetate as initial raw material on the basis of the above patent, the method only uses ball-milling solid complexing reaction, avoids the process of evaporating liquid to form sol-gel by long-time heating of traditional liquid phase reaction, greatly shortens reaction time, reduces energy consumption, and simultaneously, because nitrate is not used, NO is avoided in the process of calciningxAnd (5) discharging.
Compared with the prior art, the invention at least has the following beneficial effects:
the invention provides a preparation method of a ceramic hollow fiber oxygen permeable membrane, which simplifies the preparation process of the ceramic hollow fiber oxygen permeable membrane and eliminates NOxThe emission pollutes the environment, the energy consumption and the production cost are greatly reduced, and the method is suitable for large-scale production and application. Meanwhile, the oxygen permeability of the ceramic hollow fiber oxygen permeable membrane can reach 2.14mL/cm at the temperature of 900 DEG C2·min。
Drawings
FIG. 1 shows the preparation of example 1La of (2)0.6Sr0.4CoO3-δXRD patterns of the ceramic powder and the hollow fiber membrane;
FIG. 2 shows La prepared in example 10.6Sr0.4CoO3-δGraph of oxygen permeation quantity and temperature of hollow fiber membrane.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
In order to better illustrate the present invention and facilitate understanding of the technical solutions of the present invention, the present invention is further described below by examples, but the embodiments of the present invention are not limited thereto and should not be construed as limiting the scope of the present invention.
Example 1
This example provides La0.6Sr0.4CoO3-δA method of making a (LSC) ceramic hollow fiber membrane, the method comprising the steps of:
(1) according to La0.6Sr0.4CoO3-δIn the preparation method, 1.9624g of lanthanum acetate, 8.2284g of strontium acetate and 24.908g of cobalt acetate are weighed according to the molar ratio of La to Sr to Co of 0.6:0.4:1 to prepare a metal acetate mixture, 57.642g of citric acid is added to the mixture, ball milling is carried out for 8 hours, the molar ratio of the metal acetate mixture to the citric acid is 1:3, and the mixture is calcined at 800 ℃ to obtain the ceramic oxygen permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), wherein the average particle size of the ceramic oxygen permeable membrane powder after ball-milling and screening is 0.5-3 mu m, and weighing and mixing the ceramic oxygen permeable membrane powder with polysulfone and NMP in a mass percentage ratio of 70% to 5% to 25% to obtain a casting membrane solution;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
The specific operation of phase inversion-sintering is as follows: and placing the casting solution into a charging tank, standing, carrying out vacuum degassing on the casting solution for 1h by using a vacuum pump, then extruding the casting solution into a normal-temperature water bath by using deionized water as an internal solidification solution through a hollow fiber spinning die, soaking the spun hollow fibers in the solidification solution for 24h, taking out, straightening and drying to obtain the hollow fiber membrane precursor. And (3) putting the hollow fiber membrane precursor into a suspension furnace, and sintering at 1400 ℃ for 4h to obtain the compact ceramic hollow fiber oxygen permeable membrane.
The XRD crystal phase structures of the prepared compact ceramic hollow fiber oxygen permeable membrane are measured, and as shown in figure 1, the LSC ceramic powder and the ceramic hollow fiber membrane have the same perovskite structure.
Determination of oxygen transmission rate of LSC hollow fiber membranes: introducing helium as purge gas into the tube of the hollow fiber membrane, allowing air to flow outside the membrane, measuring flow rate and composition of permeated gas by soap bubble flowmeter and gas chromatography respectively, and measuring oxygen permeation flux of LSCF hollow fiber membrane with temperature by FIG. 2, wherein the oxygen permeation flux obtained at 900 deg.C is 2.14mL/cm2·min。
Example 2
This example provides La0.6Sr0.4Co0.2Fe0.8O3-δA method of making a (LSCF) ceramic hollow fiber membrane, the method comprising the steps of:
(1) according to La0.6Sr0.4Co0.2Fe0.8O3-δIn the preparation method, lanthanum acetate (18.9624g), strontium acetate (8.2284g), cobalt acetate (4.9816g) and iron acetate (18.628g) are weighed according to the molar ratio of La to Sr to Co to Fe of 0.6:0.4:0.2:0.8 to prepare a metal acetate mixture, citric acid (19.214g) is added to the metal acetate mixture, the mixture is subjected to ball milling for 8 hours, the molar ratio of the metal acetate mixture to the citric acid is 1:1, and the mixture is calcined at 600 ℃ to obtain a ceramic oxygen-permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), wherein the average particle size of the ceramic oxygen permeable membrane powder after ball-milling and screening is 0.4-2.8 mu m, and weighing and mixing the ceramic oxygen permeable membrane powder, polyetherimide and DMAC in a mass percentage ratio of 65% to 6% to 29% to obtain a casting solution;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
The specific operation of phase inversion-sintering is as follows: and placing the casting solution into a charging tank, standing, carrying out vacuum degassing on the casting solution for 1h by using a vacuum pump, then extruding the casting solution into a normal-temperature water bath by using deionized water as an internal solidification solution through a hollow fiber spinning die, soaking the spun hollow fibers in the solidification solution for 24h, taking out, straightening and drying to obtain the hollow fiber membrane precursor. And putting the hollow fiber membrane precursor into a suspension burning furnace, and sintering at 1350 ℃ for 4h to obtain the compact ceramic hollow fiber oxygen permeable membrane.
Determination of oxygen transmission rate of LSCF hollow fiber membranes: introducing helium as purge gas into the hollow fiber membrane tube, allowing air to flow outside the membrane, measuring flow rate and composition of permeated gas by soap bubble flowmeter and gas chromatography, and obtaining oxygen permeation of 1.14mL/cm at 900 deg.C2·min。
Example 3
The present embodiment provides: la0.6Ba0.4FeO3-δA method for preparing a (LBF) ceramic hollow fiber membrane, said method comprising the steps of:
(1) according to La0.6Ba0.4FeO3-δIn the ceramic oxygen permeable membrane, 18.9624g of lanthanum acetate, 10.9372g of barium acetate and 24.6g of iron acetate are weighed according to the molar ratio of La to Ba to Fe of 0.6 to 0.4 to 1 to prepare a metal acetate mixture, 38.428g of citric acid is added to the mixture, the mixture is ball-milled for 6 hours, the molar ratio of the metal acetate mixture to the citric acid is 1 to 2, and the mixture is calcined at 900 ℃ to obtain a ceramic oxygen permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), wherein the average particle size of the ceramic oxygen permeable membrane powder after ball-milling and screening is 0.4-6 mu m, and weighing and mixing the ceramic oxygen permeable membrane powder, polyether sulfone and DMF according to the mass percentage of 65% to 7% to 28% to obtain a casting membrane solution;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
The specific operation of phase inversion-sintering is as follows: and placing the casting solution into a charging tank, standing, carrying out vacuum degassing on the casting solution for 1h by using a vacuum pump, then extruding the casting solution into a normal-temperature water bath by using deionized water as an internal solidification solution through a hollow fiber spinning die, soaking the spun hollow fibers in the solidification solution for 24h, taking out, straightening and drying to obtain the hollow fiber membrane precursor. And (3) putting the hollow fiber membrane precursor into a suspension furnace, and sintering at 1300 ℃ for 4h to obtain the compact ceramic hollow fiber oxygen permeable membrane.
Determination of the oxygen transmission rate of LBF hollow fiber membranes: helium is used as purge gas to be introduced into the tube of the hollow fiber membrane, air flows through the outside of the membrane, and the flow rate and composition of the permeation gas are respectively measured by a soap bubble flow meter and a gas chromatograph. Oxygen transmission of 2.6mL/cm at 950 deg.C2·min。
Example 4
This example provides La0.6Ca0.4FeO3-δA method of making a (LCF) ceramic hollow fiber membrane, the method comprising the steps of:
(1) according to La0.6Ca0.4FeO3-δIn the preparation method, 18.9624g of lanthanum acetate, (7.0472g) of calcium acetate and 23.285g of iron acetate are weighed according to the molar ratio of La to Ca to Fe of 0.6 to 0.4 to 1 to prepare a metal acetate mixture, 23.285g of citric acid is added to the mixture, ball milling is carried out for 8 hours, the molar ratio of the metal acetate mixture to the citric acid is 1 to 5, and the mixture is calcined at 700 ℃ to obtain a ceramic oxygen permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), wherein the average particle size of the ceramic oxygen permeable membrane powder after ball-milling and screening is 1-8 mu m, and weighing the ceramic oxygen permeable membrane powder, polyether sulfone and NMP to mix the ceramic oxygen permeable membrane powder, polyether sulfone and NMP according to the mass percentage of 75% to 3% to 22% to obtain a casting membrane solution;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
The specific operation of phase inversion-sintering is as follows: and placing the casting solution into a charging tank, standing, carrying out vacuum degassing on the casting solution for 1h by using a vacuum pump, then extruding the casting solution into a normal-temperature water bath by using deionized water as an internal solidification solution through a hollow fiber spinning die, soaking the spun hollow fibers in the solidification solution for 24h, taking out, straightening and drying to obtain the hollow fiber membrane precursor. And putting the hollow fiber membrane precursor into a suspension burning furnace, and sintering at 1350 ℃ for 4h to obtain the compact ceramic hollow fiber oxygen permeable membrane.
Measurement ofOxygen permeation rate of LCF hollow fiber membranes: helium is used as purge gas to be introduced into the tube of the hollow fiber membrane, air flows through the outside of the membrane, and the flow rate and composition of the permeation gas are respectively measured by a soap bubble flow meter and a gas chromatograph. Oxygen permeation of 1.7mL/cm was obtained at 900 deg.C2·min。
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. A preparation method of a ceramic hollow fiber oxygen permeable membrane is characterized by comprising the following steps:
(1) preparing a metal acetate mixture according to the composition of metal ions in the ceramic oxygen-permeable membrane material, adding citric acid, then ball-milling, and calcining to obtain a ceramic oxygen-permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), and mixing the ceramic oxygen permeable membrane powder material with an organic polymer and a solvent to obtain a membrane casting solution;
(3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare a ceramic oxygen permeable membrane;
the molar ratio of the metal acetate mixture to the citric acid in the step (1) is 1 (1-5);
the metal acetate mixture is any one of a mixture of strontium acetate, lanthanum acetate and cobalt acetate, a mixture of strontium acetate, lanthanum acetate, iron acetate and cobalt acetate, a mixture of lanthanum acetate, barium acetate and iron acetate and a mixture of lanthanum acetate, calcium acetate and iron acetate.
2. The preparation method of claim 1, wherein the molar ratio of the metal acetate mixture to the citric acid in the step (1) is 1 (2-3).
3. The method according to claim 1, wherein the calcination in step (1) is carried out at a temperature of 600 to 1000 ℃.
4. The method according to claim 3, wherein the calcining temperature in step (1) is 700 to 800 ℃.
5. The preparation method of claim 1, wherein the calcination time in step (1) is 1-5 h.
6. The preparation method of claim 5, wherein the calcination time in step (1) is 3-4 h.
7. The preparation method of claim 1, wherein the ball milling time in the steps (1) and (2) is 2-8 h.
8. The preparation method of claim 7, wherein the ball milling time in the steps (1) and (2) is 4-6 h.
9. The preparation method of claim 1, wherein the average particle size of the ceramic oxygen permeable membrane powder subjected to ball milling and screening in the step (2) is 0.1-10 μm.
10. The preparation method of claim 9, wherein the average particle size of the ceramic oxygen permeable membrane powder subjected to ball milling and screening in the step (2) is 0.5-3 μm.
11. The method according to claim 1, wherein the organic polymer in step (2) comprises any one of polysulfone, polyethersulfone, polyetherimide, polyvinyl alcohol or polyvinyl butyral or a combination of at least two of them.
12. The method according to claim 1, wherein the solvent in the step (2) comprises any one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide, or a combination of at least two thereof.
13. The preparation method of the composite oxygen-permeable membrane as claimed in claim 1, wherein the composition of the membrane casting solution in the step (2) comprises, by mass, 60-75% of ceramic oxygen-permeable membrane powder, 3-7% of organic polymer and 20-30% of solvent.
14. The method for preparing according to any one of claims 1 to 13, characterized in that it comprises the following steps:
(1) preparing a metal acetate mixture according to the composition of metal ions in the ceramic oxygen permeable membrane material, adding a ligand, and then ball-milling for 4-6 hours, wherein the molar ratio of the metal acetate mixture to citric acid is 1 (2-3), and calcining at 700-800 ℃ to obtain a ceramic oxygen permeable membrane powder material;
(2) ball-milling and screening the ceramic oxygen permeable membrane powder material obtained in the step (1), wherein the average particle size of the ceramic oxygen permeable membrane powder after ball-milling and screening is 0.5-3 mu m, and mixing the ceramic oxygen permeable membrane powder with an organic polymer and a solvent to obtain a membrane casting solution, wherein the membrane casting solution comprises, by mass, 60-75% of the ceramic oxygen permeable membrane powder, 3-7% of the organic polymer and 20-30% of the solvent;
(3) and (3) carrying out phase transformation-sintering on the casting solution obtained in the step (2) to prepare the ceramic oxygen permeable membrane.
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| CN102775134A (en) * | 2012-07-25 | 2012-11-14 | 华南理工大学 | Anti-CO2 mixed conductor oxygen permeable membrane, preparation method and application thereof |
| WO2017062663A1 (en) * | 2015-10-07 | 2017-04-13 | University Of Maryland, College Park | Systems, methods, and devices for direct conversion of methane |
| CN105709594B (en) * | 2016-01-21 | 2018-10-02 | 昆明理工大学 | CO in a kind of power-plant flue gas2The method of recycling |
| KR101893458B1 (en) * | 2016-10-10 | 2018-10-04 | 해성디에스 주식회사 | Graphene membrane and method for manufacturing the same |
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