CN102247768A - Method for preparing NaA molecular sieve membrane by utilizing thermal impregnation seeding method - Google Patents
Method for preparing NaA molecular sieve membrane by utilizing thermal impregnation seeding method Download PDFInfo
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- CN102247768A CN102247768A CN2011101149289A CN201110114928A CN102247768A CN 102247768 A CN102247768 A CN 102247768A CN 2011101149289 A CN2011101149289 A CN 2011101149289A CN 201110114928 A CN201110114928 A CN 201110114928A CN 102247768 A CN102247768 A CN 102247768A
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Abstract
The invention relates to a method for preparing a NaA molecular sieve membrane by utilizing a thermal impregnation seeding method. In a technical scheme, the method comprises the following steps of: mixing raw materials to prepare a NaA molecular sieve membrane synthetic solution according to the mole ratio of Na2O:SiO2:Al2O3:H2O=2:(0.5-4):1:(45-350); then precoating crystal seeds on a porous alpha-Al2O3 vector tube by utilizing the thermal impregnation seeding method; sealing both ends of the porous alpha-Al2O3 vector tube; placing into a stainless steel crystallization kettle; slowly pouring the NaA molecular sieve membrane synthetic solution; crystallizing for 4-8 hours under the condition of 80-110 DEG C, and then taking out the porous alpha-Al2O3 vector tube; washing with water, and airing under the condition of room temperature; finally drying in an oven at 90-110 DEG C for 6-12 hours to obtain a porous alpha-Al2O3 membranous tube; measuring the permeation flux of the single component N2 of the porous alpha-Al2O3 membranous tube under the condition that differential pressure is 0.1 Mpa; if the permeation flux is less than 10<-7> mol.m<-2>.s<-1>.Pa<-1>, judging that the NaA molecular sieve membrane is prepared; and if not, repeating the steps. The NaA molecular sieve membrane prepared with the method has the advantages of compactness, continuity and good separating property.
Description
Technical field
The invention belongs to NaA molecular screen membrane technical field.Be specifically related to a kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane.
Background technology
The preparation of NaA molecular screen membrane and research have been subjected to extensive attention at home and abroad, the research method of at present synthetic NaA molecular screen membrane and other molecular screen membrane focuses mostly on crystal seed method, and the key of the synthetic NaA molecular screen membrane of crystal seed method is how crystal seed is incorporated on the carrier surface equably.Introducing crystal seed is that a kind of effective control molecular sieve is grown, regulated and control into membrane structure, improves film forming speed and improves the method for synthesizing film quality at carrier surface.Introduce crystal seed under certain condition, can provide organic centre for the carrier surface film forming, constantly draw desired substance from synthetic liquid, fully crystallization is grown up, and fills the space between crystal, obtain fine and close molecular screen membrane, it can shorten the induction period of crystal growth, crosses heterogeneous nucleation stage, thereby has relaxed the condition of film forming, make it in the competition of the required active silica-alumina species of contention crystallization, occupy catbird seat, guarantee fully to be grown to serve as closely twin dense film; Introduce crystal seed and also shortened film formation time simultaneously, reduce crystallization temperature, reduced the crystallization number of times, also just reduced carrier soak time in crystallization liquid, alkali lye is reduced the erosion degree of carrier, thereby avoided carrier in synthetic membrane process, to become fragile and the problem that causes mechanical strength to descend.In addition, introduce the effect that crystal seed can also play directed agents, the type of control synthesizing molecular sieve film suppresses stray crystal and generates.Therefore how crystal seed being incorporated into carrier surface equably also is a difficult problem, the method of introducing crystal seed at present has infusion process, electric pulpating method, vacuum method, polishing method and cross-flow filtration method etc., can both play a role to improving film quality, but the film that synthesizes is defectiveness still, separating property is poor, does not reach the effect of complete molecule screening.
Infusion process is to introduce crystal seed at present to use commonplace a kind of method; infusion process is that molecular screen primary powder is made the crystal seed aqueous solution according to a certain ratio; then the crystal seed aqueous solution being put into after with the polytetrafluoroethylene (PTFE) shutoff in the support tube two ends floods; crystal grain in the crystal seed aqueous solution can be diffused into carrier surface and suppressed by vector absorption from solution under the effect of concentration gradient; behind the dipping certain hour; take out support tube, after drying, the roasting, then have one deck seed coating layer to form at carrier surface.Such as (Xiaochun Xu such as Xu Xiaochuns, Weishen Yang, Jie Liu, Liwu Lin.Synthesis of NaA zeolite membranes from clear solution[J] .Microporous and Mesoporous materials, 2001,43:299-311.) with porous α-Al
2O
3Carrier impregnation is in 0.5% the NaA molecular sieve crystal seed aqueous solution to mass fraction, takes out the porous α after will flooding again-Al behind the dipping 30s
2O
3Carrier is dry 24h under 150 ℃ of conditions, has obtained to scribble in advance the porous α of crystal seed-Al
2O
3Carrier is pressed Na then
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 50: 5: 1: 1000, NaOH, aluminium foil, Ludox, deionized water are mixed, and obtain the synthetic liquid of NaA molecular screen membrane, prepared the NaA molecular screen membrane through twice Hydrothermal Synthesis.The n-C of prepared NaA molecular screen membrane
4H
10The permeation flux test shows, utilizes the NaA molecular screen membrane of infusion process preparation to have the diameter defective bigger than NaA molecular sieve bore diameter, and the permeation flux of prepared NaA molecular screen membrane is relatively low; And for example Cheng Zhi woods etc. (Cheng Zhilin, Chao Zisheng, Wan Huilin. the permeability and separation performance [J] of little molecule inorganic gas on the NaA molecular screen membrane. the chemistry circular, 2003,7:488-491) utilize infusion process at porous α-Al
2O
3Seeded on the carrier adopts repeatedly synthetic method, synthesizes comparatively fine and close NaA molecular screen membrane under heating using microwave 15min.But from temperature to H
2/ N
2Desired separated optionally influence, along with the rising of temperature, heat expansion does not match and produces stress and cause rete high temperature to produce splitting scarce, prepared film defective increasing to some extent between rete and the carrier layer; In addition, the NaA molecular screen membrane after repeatedly synthesizing still exists defective or pin hole, and the separation selectivity of film improves not remarkable.
Application hot dipping stain crystal seed method prepares the method for NaA molecular screen membrane and also studies so far report.
Summary of the invention
The present invention is intended to overcome the prior art defective, and purpose provides a kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane, with the NaA molecular screen membrane densification of this method preparation, continuous, separating property is good.
For achieving the above object, the technical solution used in the present invention is:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (0.5～4): 1: (45～350) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.5～1.0h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 0.5～3h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane.
Second step, with porous α-Al
2O
3Support tube is carried out preliminary treatment, again with pretreated porous α-Al
2O
3Support tube two ends teflon seal.
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 3.5～4.5 hours under 170 ℃～180 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 10～30s.
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 530～580 ℃ with the speed of 4～6 ℃/min, under 530～580 ℃ of conditions, calcine 3～5h.
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 4～8h under 80 ℃～110 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 6～12h of 90～110 ℃, obtains porous α-Al
2O
3The film pipe.
The 6th step, be under the 0.1Mpa condition, measure porous α-Al at pressure reduction
2O
3The one pack system N of film pipe
2Permeation flux is if permeation flux is less than 10
-7Molm
-2S
-1Pa
-1, then make the NaA molecular screen membrane; Otherwise, repeated for first to the 5th step.
The preparation method of the described 4A molecular sieve crystal seed aqueous solution is: the 4A molecular screen primary powder joined in the deionized water, and mechanical agitation 10～15min, ultrasonic then concussion 20～30min makes the 4A molecular sieve crystal seed aqueous solution of 0.5～2.0wt.%.
Described with porous α-Al
2O
3Support tube is carried out preliminary treatment and is referred to: earlier with porous α-Al
2O
3The outer surface of support tube successively uses 600
#With 800
#Sand papering is smooth, the porous α after will polishing again-Al
2O
3Support tube successively is immersed in 0.5～1mol/L hydrochloric acid and the 0.5～1mol/L sodium hydroxide solution, and soak time is 20～28h, ultrasonic concussion 20～30min after taking out, be washed to neutrality, dry under the room temperature condition, under 140～160 ℃ of conditions, dry then, stand-by.
Because adopt technique scheme, the present invention utilizes porous α-Al
2O
3Carrier makes moisture from porous α-Al through long high temperature drying
2O
3Spin off porous α after treatment-Al in the micropore of support tube fully
2O
3Support tube is equivalent to a vacuum body, as porous α-Al
2O
3When support tube contacted with the finely dispersed crystal seed aqueous solution, solution entered into rapidly porous α-Al
2O
3In the support tube micropore, under the drive of water, seed particles " is taken out " to micropore surface, and is subjected to powerful attraction and is attached to securely porous α-Al
2O
3The support tube surface, seed particles is at porous α-Al
2O
3The support tube surface is built up and is constantly thickened, with porous α-Al
2O
3The duct on support tube surface is blocked, and makes seed particles build up and constantly thicken on its surface, at porous α-Al
2O
3The synthetic NaA molecular screen membrane densification in support tube surface, continuously, separating property is good.
The present invention utilizes the NaA molecular screen membrane of hot dipping stain crystal seed method preparation, the N that has
2Permeation flux is 0.299 * 10
-8(molm
-2S
-1Pa
-1), the NaA molecular screen membrane densification of preparation, continuously is described; The NaA molecular screen membrane of preparation is carried out the ethanol dehydration separating experiment under 70 ℃ of conditions, the ethanol dehydration separation factor that obtains is 15600, illustrates that the NaA molecular screen membrane separating property of preparation is good.
Therefore, the prepared NaA molecular screen membrane of the present invention has densification, continuous, the good characteristics of separating property.
The specific embodiment
The present invention will be further described below in conjunction with the specific embodiment, is not the restriction to its protection domain.
For avoiding repetition, first " preparation method of the 4A molecular sieve crystal seed aqueous solution " and " the porous α-Al that this specific embodiment is related
2O
3Support tube is carried out preliminary treatment " unified being described below, repeat no more among the embodiment:
The preparation method of the 4A molecular sieve crystal seed aqueous solution is: the 4A molecular screen primary powder joined in the deionized water, and mechanical agitation 10～15min, ultrasonic then concussion 20～30min makes the 4A molecular sieve crystal seed aqueous solution of 0.5～2.0wt.%;
Porous α-Al
2O
3Support tube is carried out preliminary treatment: earlier with porous α-Al
2O
3The outer surface of support tube successively uses 600
#With 800
#Sand papering is smooth, the porous α after will polishing again-Al
2O
3Support tube successively is immersed in 0.5～1mol/L hydrochloric acid and the 0.5～1mol/L sodium hydroxide solution, and soak time is 20～28h, ultrasonic concussion 20～30min after taking out, be washed to neutrality, dry under the room temperature condition, under 140～160 ℃ of conditions, dry then, stand-by.
Embodiment 1
A kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane.Its preparation process is as follows:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (0.5～1): 1: (45～100) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.5～0.8h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 0.5～1h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane.
Second step, with porous α-Al
2O
3Support tube is carried out preliminary treatment, again with pretreated porous α-Al
2O
3Support tube two ends teflon seal.
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 3.5～4.0 hours under 170 ℃～175 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 10～20s.
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 530～540 ℃ with the speed of 4～5 ℃/min, under 530～540 ℃ of conditions, calcine 3～4h.
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 4～5h under 80 ℃～90 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 6～8h of 90～95 ℃, obtains porous α-Al
2O
3The film pipe.
The 6th step, be under the 0.1Mpa condition, measure porous α-Al at pressure reduction
2O
3The one pack system N of film pipe
2Permeation flux is if permeation flux is less than 10
-7Molm
-2S
-1Pa
-1, then make the NaA molecular screen membrane; Otherwise, repeated for first to the 5th step.
Embodiment 2
A kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane.Its preparation process is as follows:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (1～2): 1: (100～200) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.7～1.0h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 1.0～1.5h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane.
Second step, with embodiment 1.
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 4.0～4.5 hours under 175 ℃～180 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 20～30s.
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 540～550 ℃ with the speed of 5～6 ℃/min, under 540～550 ℃ of conditions, calcine 4～5h.
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 5～6h under 90 ℃～100 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 7～9h of 95～100 ℃, obtains porous α-Al
2O
3The film pipe.
The 6th the step, with embodiment 1.
Embodiment 3
A kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane.Its preparation process is as follows:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (2～3): 1: (200～300) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.7～1.0h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 1.5～2.0h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane.
Second step, with embodiment 1.
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 4.0～4.5 hours under 170 ℃～175 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 20～30s.
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 550～565 ℃ with the speed of 4～5 ℃/min, under 550～565 ℃ of conditions, calcine 4～5h.
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 6～7h under 100 ℃～110 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 8～10h of 100～105 ℃, obtains porous α-Al
2O
3The film pipe.
The 6th the step, with embodiment 1.
Embodiment 4
A kind of method of utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane.Its preparation process is as follows:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (3～4): 1: (300～350) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.5～0.8h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 2.0～3.0h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane.
Second step, with embodiment 1.
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 3.5～4.0 hours under 175 ℃～180 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 10～20s.
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 565～580 ℃ with the speed of 5～6 ℃/min, under 565～580 ℃ of conditions, calcine 3～4h.
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 7～8h under 105 ℃～110 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 10～12h of 105～110 ℃, obtains porous α-Al
2O
3The film pipe.
The 6th the step, with embodiment 1.
This specific embodiment is utilized porous α-Al
2O
3Support tube makes moisture from porous α-Al through long high temperature drying
2O
3Spin off porous α after treatment-Al in the micropore of support tube fully
2O
3Support tube is equivalent to a vacuum body, as porous α-Al
2O
3When support tube contacted with the finely dispersed crystal seed aqueous solution, solution entered into rapidly porous α-Al
2O
3In the support tube micropore, under the drive of water, seed particles " is taken out " to micropore surface, and is subjected to powerful attraction and is attached to securely porous α-Al
2O
3The support tube surface, seed particles is at porous α-Al
2O
3The support tube surface is built up and is constantly thickened, with porous α-Al
2O
3The duct on support tube surface is blocked, and makes seed particles build up and constantly thicken on its surface, at porous α-Al
2O
3The synthetic NaA molecular screen membrane densification in support tube surface, continuously, separating property is good.
This specific embodiment is utilized the NaA molecular screen membrane of hot dipping stain crystal seed method preparation, the N that has
2Permeation flux is 0.299 * 10
-8(molm
-2S
-1Pa
-1), the NaA molecular screen membrane densification of preparation, continuously is described; The NaA molecular screen membrane of preparation is carried out the ethanol dehydration separating experiment under 70 ℃ of conditions, the ethanol dehydration separation factor that obtains is 15600, illustrates that the NaA molecular screen membrane separating property of preparation is good.
Therefore, the prepared NaA molecular screen membrane of this specific embodiment has densification, continuous, the good characteristics of separating property.
Claims (3)
1. one kind is utilized hot dipping to steep the method that crystal seed method prepares the NaA molecular screen membrane, it is characterized in that its preparation process is:
The first step, press Na
2O: SiO
2: Al
2O
3: H
2The mol ratio of O is 2: (0.5～4): 1: (45～350) meter joins sodium aluminate and NaOH in the deionized water earlier mechanical agitation 0.5～1.0h; Under the mechanical agitation condition, slowly add again Ludox, continue mechanical agitation 0.5～3h behind the adding Ludox, make the synthetic liquid of NaA molecular screen membrane;
Second step, with porous α-Al
2O
3 yearsThe body pipe carries out preliminary treatment, again with pretreated porous α-Al
2O
3Support tube two ends teflon seal;
The 3rd step, the porous α after will sealing-Al
2O
3Support tube was dried 3.5～4.5 hours under 170 ℃～180 ℃ conditions, was impregnated into immediately after the taking-up in the 4A molecular sieve crystal seed aqueous solution, and dip time is 10～30s;
The 4th step, the porous α after will flooding-Al
2O
3After taking out, support tube repeated for the 3rd step; Porous α after will flooding again-Al
2O
3Dry at ambient temperature after support tube is taken out, insert in the Muffle furnace, be warming up to 530～580 ℃ with the speed of 4～6 ℃/min, under 530～580 ℃ of conditions, calcine 3～5h;
The 5th step, the first porous α after will calcining-Al
2O
3Support tube two ends teflon seal vertically is placed in the stainless steel crystallizing kettle, slowly pours the porous α of the synthetic liquid of NaA molecular screen membrane to the calcining-Al into
2O
3Support tube submergence, again crystallization 4～8h under 80 ℃～110 ℃ conditions; Then with the porous α after the crystallization-Al
2O
3Support tube is taken out, and is washed to neutrality, dries under the room temperature condition, places at last baking oven 6～12h of 90～110 ℃, obtains porous α-Al
2O
3The film pipe;
The 6th step, be under the 0.1Mpa condition, measure porous α-Al at pressure reduction
2O
3The one pack system N of film pipe
2Permeation flux is if permeation flux is less than 10
-7Molm
-2S
-1Pa
-1, then make the NaA molecular screen membrane; Otherwise, repeated for first to the 5th step.
2. the method for utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane according to claim 1, the preparation method who it is characterized in that the described 4A molecular sieve crystal seed aqueous solution is: the 4A molecular screen primary powder is joined in the deionized water, mechanical agitation 10～15min, ultrasonic then concussion 20～30min makes the 4A molecular sieve crystal seed aqueous solution of 0.5～2.0wt.%.
3. the method for utilizing hot dipping stain crystal seed method to prepare the NaA molecular screen membrane according to claim 1 is characterized in that described with porous α-Al
2O
3Support tube is carried out preliminary treatment and is referred to: earlier with porous α-Al
2O
3The outer surface of support tube successively uses 600
#With 800
#Sand papering is smooth, the porous α after will polishing again-Al
2O
3Support tube successively is immersed in 0.5～1mol/L hydrochloric acid and the 0.5～1mol/L sodium hydroxide solution, and soak time is 20～28h, ultrasonic concussion 20～30min after taking out, be washed to neutrality, dry under the room temperature condition, under 140～160 ℃ of conditions, dry then, stand-by.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192858A (en) * | 2014-08-12 | 2014-12-10 | 大连理工大学 | Method for preparing zeolite membrane by introducing crystal seeds with hot impregnation method |
| CN106830195A (en) * | 2017-02-23 | 2017-06-13 | 大连理工大学 | A kind of method that use NaA zeolite membranes carry out pervaporation desalination |
| CN108854584A (en) * | 2018-06-12 | 2018-11-23 | 山东理工大学 | The method of ring focusing single mold microwave synthesis NaA molecular sieve membrane |
| CN112933986A (en) * | 2021-02-02 | 2021-06-11 | 黄山学院 | Method for synthesizing molecular sieve membrane with high water permeability |
| CN114225718A (en) * | 2021-12-24 | 2022-03-25 | 中国科学院上海硅酸盐研究所 | NaA molecular sieve membrane on surface of porous silicon nitride ceramic and preparation method thereof |
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| 周志辉: "NaA分子筛膜及分子筛/炭复合膜的制备与应用", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, 15 May 2009 (2009-05-15), pages 020 - 66 * |
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| CN106830195A (en) * | 2017-02-23 | 2017-06-13 | 大连理工大学 | A kind of method that use NaA zeolite membranes carry out pervaporation desalination |
| CN108854584A (en) * | 2018-06-12 | 2018-11-23 | 山东理工大学 | The method of ring focusing single mold microwave synthesis NaA molecular sieve membrane |
| CN112933986A (en) * | 2021-02-02 | 2021-06-11 | 黄山学院 | Method for synthesizing molecular sieve membrane with high water permeability |
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