CN114028955A - Repairing method for support body for preparing molecular sieve membrane - Google Patents
Repairing method for support body for preparing molecular sieve membrane Download PDFInfo
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- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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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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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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Abstract
The invention relates to a method for repairing a support body used for preparing a molecular sieve membrane, which is particularly applied to the preparation of the molecular sieve membrane after the repair technology of the surface defects of a ceramic support body is based. The introduced molecular sieve raw powder can strengthen the combination effect between the molecular sieve film layer and the support layer while maintaining the surface structure and properties of the original support, and the molecular sieve raw powder can effectively improve the performance of the molecular sieve film when being used for preparing the molecular sieve film.
Description
Technical Field
The invention relates to the field of preparation of ceramic supports, in particular to repair of surface defects of ceramic supports and application of the repaired supports in preparation of molecular sieve membranes.
Background
With the gradual maturity of the application market of the molecular sieve membrane, the demand of the market for the molecular sieve membrane is increasing, and higher requirements are put on the performance, particularly the flux level, of the molecular sieve membrane. Increasing the flux of the membrane can significantly reduce equipment costs. Research shows that the pore diameter of the support has great influence on the membrane flux, and the ceramic supports with the average pore diameters of 1.0um and 2.0um have the water flux which is 1.5 times that of the ceramic supports after the membrane is prepared into a membrane. Therefore, the larger pore size of the support in a certain range is more beneficial to the membrane flux. However, as the pore size of the support increases, the probability of occurrence of macro-porous defects on the surface of the support also increases, which is disadvantageous for the preparation of the molecular sieve membrane.
Disclosure of Invention
The invention provides a method for repairing surface defects of a ceramic support, which introduces molecular sieve raw powder to strengthen the bonding effect between a molecular sieve film layer and a support layer while maintaining the surface structure and properties of an original support, and effectively improves the performance of the molecular sieve film when the molecular sieve raw powder is used for preparing the molecular sieve film.
A repairing method of a support body for preparing a molecular sieve membrane comprises the following steps:
step 1, preparing repair slurry containing ceramic particles and molecular sieve raw powder;
and 2, coating the repair slurry on the surface of the ceramic support body with the surface defects, and sintering after drying.
The average pore diameter of the ceramic support is 2-5um, and the surface of the ceramic support contains macropores with the diameter of more than 10 um.
In the step 1, the solid content of the ceramic particles in the repair slurry is 5-20 wt%, and the weight of the molecular sieve raw powder is 5-15% of the weight of the ceramic particles.
The ceramic particles are the same material as the ceramic support.
The ceramic particles are made of inorganic powder such as alumina, zirconia, titanium oxide, kaolin, Suzhou soil or mullite and the like.
The raw powder of the molecular sieve is the same as the material of the molecular sieve membrane.
The material of the molecular sieve raw material is NaA, NaY, ZSM or T-type molecular sieve.
The preparation method of the repair slurry comprises the following steps: adding ceramic particles and molecular sieve raw powder into water, adding an adhesive and a dispersing agent, and uniformly stirring.
The preparation method of the repair slurry comprises the following steps: adding ceramic particles, a molecular sieve raw material and an oil phase into water, adding an adhesive and a dispersing agent, dispersing uniformly at a high speed, and obtaining a foam phase and a water phase through rotational flow air flotation; regulating the solid contents of the foam phase and the water phase to 5-20 wt%, and respectively adding an adhesive and a dispersing agent; and in step 2, the surface of the ceramic support is coated with a foam phase and a water phase in sequence.
The diameter range of the bubbles formed by high-speed dispersion is 80-120um, the tangential speed of the cyclone in the cyclone air floatation process is 15-25m/s, and the diameter of the cyclone is 0.2-0.5 m.
The dispersant may be polyacrylamide, polyacrylic acid and its sodium salt, hydroxymethyl cellulose, polyvinyl alcohol, etc.
The binder may be at least one of polymethyl methacrylate or polyvinyl butyral.
In the step 2, the sintering temperature is 1200-1400 ℃, and the sintering time is 1-6 h.
The preparation method of the molecular sieve membrane comprises the following steps: coating a molecular sieve seed crystal suspension on the surface of the obtained support, and preparing a molecular sieve membrane by a hydrothermal synthesis method; the solid content of the molecular sieve seed crystal suspension is 3-10%, the hydrothermal synthesis temperature is 100-.
The molecular sieve membrane obtained by the method is used for solvent dehydration.
Advantageous effects
For the preparation of the molecular sieve membrane, the support with excellent performance can improve the performance and yield of the membrane product. The flux of the molecular sieve membrane can be effectively improved by increasing the average pore diameter of the support, but the larger pore diameter of the support inevitably introduces more macropore defects. The repairing method provided by the invention can effectively repair the macroporous defect on the surface of the support body, and meanwhile, the used repairing slurry is the same as the material of the original support body, so that the surface property of the original support body can be maintained. In addition, the molecular sieve raw powder is added, and the melting point of the molecular sieve raw powder is lower, so that the sintering strength between the repair layer and the original support body can be improved; on the other hand, the sintered molecular sieve still maintains the performance of partial molecular sieve, and the bonding effect between the membrane layer and the support body can be improved during the preparation of the molecular sieve membrane, so that the overall performance and the qualification rate of the membrane are improved. Through will restoreing the thick liquids and carry out whirl air supporting and handle, carry the effect of smuggleing secretly through the foam, carry the granule of small particle diameter to the foam phase by the bubble on the suspension secretly, realized the separation of the restoration granule of big or small particle diameter, when coating the defect department with the small particle earlier, can go deep into to the region of collapsing better, the problem of the accumulation layer bottom "unsettled" that leads to when having avoided the large granule directly to pile up has avoided the sintering in-process because the region that contracts and lead to collapses formation defect once more.
Drawings
FIG. 1, (a) SEM photograph of a support with a defective area; (b) SEM photograph of support with actual repair area
FIG. 2, (a) SEM photograph of a molecular sieve membrane prepared with a defective support in area; (b) SEM photograph of molecular sieve membrane prepared by support body with repaired area
Detailed Description
The method is suitable for ceramic supports with surface macroporous defects, the average pore diameter range of the whole ceramic support is within 2-5um, but macropores with the pore diameter of more than 20um are usually contained, so that the crystal growth effect of a molecular sieve is poor due to the surface defects of the support in the process of preparing the molecular sieve membrane, the defects are transferred to the molecular sieve membrane, and finally the selective separation performance of the molecular sieve membrane cannot meet the requirements.
The method mainly comprises the steps of preparing modified slurry by utilizing the molecular sieve raw powder, and coating the slurry on the surface of the ceramic support body to fill the macroporous defects. The molecular sieve crystals used herein should be in accordance with the type of molecular sieve membrane to be finally prepared, and for example, molecular sieves of NaA, NaY, ZSM, T type, etc. may be used.
In one embodiment of the present invention, the modified slurry is obtained by adding ceramic particle powder and molecular sieve raw powder into a solvent; the ceramic particles used herein may be the same as the material of the support, and for example, inorganic powders such as alumina, zirconia, titania, kaolin, suzhou clay, and mullite; the solids content of the slurry may be 5-20 wt.%, and the molecular sieve feedstock is preferably present in the solids content of 5-15 wt.%; when the proportion is adopted, if the slurry is completely composed of ceramic particles, molecular sieve crystals cannot be dispersed in the filler, so that the molecular sieve crystals cannot grow at defective positions well when the molecular sieve membrane is finally prepared by hydrothermal synthesis, and the problem of poor generation effect of the molecular sieve membrane still exists; however, if the slurry is prepared from the molecular sieve raw powder, the sintering property difference between the molecular sieve raw powder and the ceramic support body can cause that good phase generation can not be formed in the sintering process, thereby influencing the hole repairing effect. After ceramic particle powder and a molecular sieve raw material are added into the modified slurry, a dispersing agent or an adhesive can be added, wherein the dispersing agent can be polyacrylamide, polyacrylic acid and sodium salt thereof, hydroxymethyl cellulose, polyvinyl alcohol and the like; the binder used here may be at least one of polymethyl methacrylate or polyvinyl butyral.
In addition, because the surface macroporous defect usually presents a three-dimensional space structure, if the ceramic particle powder and the molecular sieve raw powder can not effectively fill the space, in the subsequent sintering process, the change of ceramic particle shrinkage, collapse and the like can cause the filler to continue to shrink to the vacant part at the lower part, thus still causing the defect of the membrane; in another embodiment of the present invention, ceramic particle powder and molecular sieve raw powder are added into a solvent, kerosene with a weight of 2-5% of that of the solvent is added, the mixture is stirred at a high speed to form foam, and flotation is performed by a cyclone flotation device, wherein after the foam is formed, the foam has an entrainment effect on small-particle-size particles, so that small-particle ceramic particles and molecular sieve powder can be obtained, and the small-particle-size powder is not easy to form a structure with a gap at the bottom when being modified, so that firstly, water is added into a foam phase obtained in the foam flotation to adjust the solid content to 5-20 wt%, then an adhesive and a dispersant are added, the first coating is performed, and the small particles can be deposited at a defect position; and then, regulating the solid content of the lower layer liquid obtained by rotational flow air flotation to 5-20 wt.%, adding an adhesive and a dispersing agent, coating for the second time, forming a large particle layer with better hardness and rigidity on the surface of the small particles, and sintering to form a stable ceramic structure. The solid content is adjusted and controlled mainly by adding water for dilution or centrifugal dehydration. The diameter range of the bubbles formed after high-speed stirring is 80-120um, the tangential speed of the cyclone is 15-25m/s and the diameter of the cyclone is 0.2-0.5m in the cyclone air floatation process.
When the ceramic support body repaired by the method is used for preparing the molecular sieve membrane, the surface of the support body is coated with molecular sieve crystal seeds, and then the molecular sieve membrane is prepared by adopting a hydrothermal synthesis method.
In the patent, separation factors under different repair conditions are investigated by carrying out pervaporation separation on an ethanol/water mixed solution.
Example 1
1) The average pore diameter is 2umAl2O3Cleaning the surface of the ceramic support body, and drying for later use;
2) al having an average particle diameter of 30um2O3Adding the powder into water, uniformly stirring, wherein the solid content in the water is 8%;
3) adding NaA molecular sieve raw powder into the suspension, wherein the adding amount of the NaA molecular sieve raw powder is 5% of the solid matter;
4) adding the binder and the dispersant and continuously dispersing uniformly;
5) coating the suspension on the surface of the ceramic support by adopting a dip-coating method;
6) drying and keeping the temperature at 1400 ℃ for 2h to obtain the repaired support body.
Example 2
1) Cleaning the surface of the ceramic support body with the average pore diameter of 3 mu m, and drying for later use;
2) al having an average particle diameter of 30um2O3Adding the powder into water, uniformly stirring, wherein the solid content in the water is 5%;
3) adding NaA molecular sieve raw powder into the suspension, wherein the adding amount of the NaA molecular sieve raw powder is 10% of the solid matter;
4) adding the binder and the dispersant and continuously dispersing uniformly;
5) coating the suspension on the surface of the ceramic support by adopting a wiping method;
6) drying and preserving heat for 3h at 1300 ℃ to obtain the repaired support body.
Example 3
1) The average pore diameter is 2umAl2O3Cleaning the surface of the ceramic support body, and drying for later use;
2) al having an average particle diameter of 30um2O3Adding the powder into water, uniformly stirring, wherein the solid content in the water is 8%;
3) adding NaA molecular sieve raw powder into the suspension, wherein the adding amount of the NaA molecular sieve raw powder is 5% of the solid matter;
4) adding 3% of kerosene into the suspension, stirring at high speed to form bubbles with the diameter ranging from 80 to 120 microns, performing cyclone air flotation treatment by using a cyclone air flotation device with the diameter of 0.4m, adding water into the foam phase to dilute the foam phase until the solid content is 8.4%, and dehydrating the water phase to the same concentration;
4) respectively adding a binder and a dispersant into the foam phase and the water phase, and continuously and uniformly dispersing;
5) coating the suspension on the surface of a ceramic support by adopting a dip-coating method, coating a foam phase firstly, and then coating a water phase;
6) drying and keeping the temperature at 1400 ℃ for 2h to obtain the repaired support body.
Example 4
The difference from example 2 is that: and carrying out rotational flow air flotation treatment on the repair slurry.
1) Average pore diameter3umAl2O3Cleaning the surface of the ceramic support body, and drying for later use;
2) al having an average particle diameter of 30um2O3Adding the powder into water, uniformly stirring, wherein the solid content in the water is 5%;
3) adding NaA molecular sieve raw powder into the suspension, wherein the adding amount of the NaA molecular sieve raw powder is 10% of the solid matter;
4) adding 3% of kerosene into the suspension, stirring at high speed to form bubbles with the diameter ranging from 80 to 120 microns, performing cyclone air flotation treatment by using a cyclone air flotation device with the diameter of 0.4m, adding water into the foam phase to dilute the foam phase until the solid content is 8.4%, and dehydrating the water phase to the same concentration;
4) respectively adding a binder and a dispersant into the foam phase and the water phase, and continuously and uniformly dispersing;
5) coating the suspension on the surface of a ceramic support by adopting a dip-coating method, coating a foam phase firstly, and then coating a water phase;
6) drying and keeping the temperature at 1400 ℃ for 2h to obtain the repaired support body.
Example 5
The difference from example 3 is that: in step 5), the aqueous phase is coated first, and then the foam phase is coated.
1) The average pore diameter is 3umAl2O3Cleaning the surface of the ceramic support body, and drying for later use;
2) al having an average particle diameter of 30um2O3Adding the powder into water, uniformly stirring, wherein the solid content in the water is 5%;
3) adding NaA molecular sieve raw powder into the suspension, wherein the adding amount of the NaA molecular sieve raw powder is 10% of the solid matter;
4) adding 3% of kerosene into the suspension, stirring at high speed to form bubbles with the diameter ranging from 80 to 120 microns, performing cyclone air flotation treatment by using a cyclone air flotation device with the diameter of 0.4m, adding water into the foam phase to dilute the foam phase until the solid content is 8.4%, and dehydrating the water phase to the same concentration;
4) respectively adding a binder and a dispersant into the foam phase and the water phase, and continuously and uniformly dispersing;
5) coating the suspension on the surface of a ceramic support by adopting a dip-coating method, coating a water phase, and then coating a foam phase;
6) drying and keeping the temperature at 1400 ℃ for 2h to obtain the repaired support body.
Comparative example 1
The average pore diameter of the unrepaired pores in example 1, 2umAl2O3A ceramic support.
Comparative example 2
The difference from example 1 is that: adding only Al into the repair slurry2O3The powder material, but not adding NaA molecular sieve raw powder, the total solid content is still 8.4%.
Comparative example 3
The difference from example 1 is that: only NaA molecular sieve raw powder is added into the repair slurry, and Al is not added2O3Powder, total solids content was still 8.4%.
The support bodies prepared in the above examples and comparative examples were subjected to NaA molecular sieve membrane preparation, in which a NaA molecular sieve seed crystal suspension (solid content 3-10%) was first prepared, coated on the surface of the support body, and then placed in a synthetic fluid for hydrothermal synthesis, the ratio of the synthetic fluid was controlled at a12O3:SiO2:Na2O:H2O is 1:3:4:105, the hydrothermal synthesis temperature is 130 ℃, and the time is 3.5 h. And tested for an ethanol/water separation process at an operating temperature of 70 c, the separation system being a 10 wt.% ethanol/water solution. After 2h of run, the fluxes and separation factors were as follows:
as can be seen from the above table, the method of the present invention can realize surface modification of the ceramic support body with surface defects, and prepare a qualified molecular sieve membrane applied to the solvent dehydration process; by comparing example 1 with comparative example 1, the separation factor of the dehydration process was increased from 120 to 9530 after the defects of the support were eliminated; as can be seen from the comparison between example 1 and comparative examples 1-2, if only the slurry of alumina is used for surface coating, a modification layer with molecular sieve seeds cannot be generated at the defect, so that the seed growth effect in this region during hydrothermal synthesis is not good, and the selective separation of the finally obtained molecular sieve membrane is still low; if only the molecular sieve seed crystal is used for coating, the molecular sieve seed crystal cannot be effectively subjected to phase formation and shrinkage with the surface ceramic of the support body during sintering, so that the existence of hole defects is still caused, and the repair effect is poor; it can be seen from the comparison between the embodiment 1 and the embodiment 3 that when the slurry is subjected to the cyclone air flotation treatment, particles with small particle size can be firstly accumulated at the defect, the condition that large particles are suspended due to direct coating is avoided, the structural collapse after sintering is avoided, and the selectivity of the molecular sieve membrane is improved, and the comparison between the embodiment 3 and the embodiment 5 shows that if the aqueous phase is directly coated in advance, the condition that the large particles are accumulated in the defect in a suspended manner cannot be avoided, the modification structure is poor, and the separability of the molecular sieve membrane is still poor after sintering.
Claims (10)
1. A method for repairing a support used for preparing a molecular sieve membrane is characterized by comprising the following steps:
step 1, preparing repair slurry containing ceramic particles and molecular sieve raw powder;
and 2, coating the repair slurry on the surface of the ceramic support body with the surface defects, and sintering after drying.
2. The method for repairing a support used for preparing a molecular sieve membrane according to claim 1, wherein the ceramic support has an average pore diameter in the range of 2-5um, and contains macropores with a surface size of 10um or more;
in the step 1, the solid content of the ceramic particles in the repair slurry is 5-20 wt%, and the weight of the molecular sieve raw powder is 5-15% of the weight of the ceramic particles.
3. The method for repairing a support used for preparing a molecular sieve membrane according to claim 1, wherein the ceramic particles are the same material as the ceramic support; the ceramic particles are made of inorganic powder such as alumina, zirconia, titanium oxide, kaolin, Suzhou soil or mullite and the like.
4. The method for repairing a support used in the production of a molecular sieve membrane according to claim 1, wherein the molecular sieve raw powder is the same material as the molecular sieve membrane.
5. The method for repairing a support used in the preparation of a molecular sieve membrane according to claim 1, wherein the material of the molecular sieve raw material is NaA, NaY, ZSM or T-type molecular sieve.
6. The method for repairing a support used for preparing a molecular sieve membrane according to claim 1, wherein the method for preparing the repair slurry comprises the following steps: adding ceramic particles and molecular sieve raw powder into water, adding an adhesive and a dispersing agent, and uniformly stirring.
7. The method for repairing a support used for preparing a molecular sieve membrane according to claim 1, wherein the method for preparing the repair slurry comprises the following steps: adding ceramic particles, a molecular sieve raw material and an oil phase into water, adding an adhesive and a dispersing agent, dispersing uniformly at a high speed, and obtaining a foam phase and a water phase through rotational flow air flotation; regulating the solid contents of the foam phase and the water phase to 5-20 wt%, and respectively adding an adhesive and a dispersing agent; and in step 2, sequentially coating the surface of the ceramic support with a foam phase and a water phase;
the diameter range of the bubbles formed by high-speed dispersion is 80-120um, the tangential speed of the cyclone in the cyclone air floatation process is 15-25m/s, and the diameter of the cyclone is 0.2-0.5 m.
8. The method for repairing a support used for preparing a molecular sieve membrane according to claim 1, wherein the dispersant is selected from polyacrylamide, polyacrylic acid and its sodium salt, hydroxymethyl cellulose, polyvinyl alcohol, etc.; the adhesive can be at least one of polymethyl methacrylate or polyvinyl butyral; in the step 2, the sintering temperature is 1200-1400 ℃, and the sintering time is 1-6 h.
9. A preparation method of a molecular sieve membrane comprises the following steps: preparing a molecular sieve membrane by hydrothermal synthesis after coating a molecular sieve seed suspension on the surface of the support obtained in claim 1; the solid content of the molecular sieve seed crystal suspension is 3-10%, the hydrothermal synthesis temperature is 100-.
10. Use of the molecular sieve membrane obtained by the preparation method of claim 9 in solvent dehydration.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152843A1 (en) * | 2010-12-17 | 2012-06-21 | General Electric Company | Ceramic membranes |
| CN106478079A (en) * | 2016-10-18 | 2017-03-08 | 山东硅元新型材料有限责任公司 | The method that asymmetric micropore ceramics inner surface prepares NaA molecular screen membrane |
| CN108126533A (en) * | 2017-12-13 | 2018-06-08 | 浙江大学 | A kind of method added molecular sieve sintering and prepare porous ceramic support and Vacuum-assisted method molecular screen membrane |
| CN109665810A (en) * | 2019-02-13 | 2019-04-23 | 安徽峰可达科技股份有限公司 | A kind of molecular screen membrane supporter and preparation method thereof and molecular screen membrane |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152843A1 (en) * | 2010-12-17 | 2012-06-21 | General Electric Company | Ceramic membranes |
| CN103249474A (en) * | 2010-12-17 | 2013-08-14 | 通用电气公司 | Alumina ceramic membranes |
| CN106478079A (en) * | 2016-10-18 | 2017-03-08 | 山东硅元新型材料有限责任公司 | The method that asymmetric micropore ceramics inner surface prepares NaA molecular screen membrane |
| CN108126533A (en) * | 2017-12-13 | 2018-06-08 | 浙江大学 | A kind of method added molecular sieve sintering and prepare porous ceramic support and Vacuum-assisted method molecular screen membrane |
| CN109665810A (en) * | 2019-02-13 | 2019-04-23 | 安徽峰可达科技股份有限公司 | A kind of molecular screen membrane supporter and preparation method thereof and molecular screen membrane |
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