CN106823828B - A kind of synthetic method of molecular screen membrane - Google Patents
A kind of synthetic method of molecular screen membrane Download PDFInfo
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- CN106823828B CN106823828B CN201710094924.6A CN201710094924A CN106823828B CN 106823828 B CN106823828 B CN 106823828B CN 201710094924 A CN201710094924 A CN 201710094924A CN 106823828 B CN106823828 B CN 106823828B
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- molecular screen
- screen membrane
- base substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention discloses a kind of synthetic method of molecular screen membrane, by synthesizing one layer of crystal layer of sigma 1 on carrier, then DD3R crystal layers are synthesized thereon so as to synthesize molecular screen membrane, the molecular screen membrane prepared using this method is not likely to produce other types crystal, the degree of purity of molecular screen membrane crystal is maintained, improves permeance property.
Description
Technical field
The application is related to a kind of synthetic method of film, more particularly to a kind of synthetic method of molecular screen membrane.
Background technology
Organic solvent plays very important effect in modern industry, all available for medicine, chemical industry, material, metallurgy etc.
It is multi-field.In some application scenarios, the purity requirement to organic solvent is harsher, such as requires that organic solvent purity exists
More than 99.99%, and water is one of dopant type common in organic solvent, because it dissolves each other with some organic solvents, therefore it is de-
Water seems particularly significant in product purification.
In existing dehydration of organic solvent technique, infiltration evaporation is a kind of ideal technique, and it has, and energy consumption is low, work
Many advantages, such as skill is simple.And for infiltration evaporation technique, infiltrating and vaporizing membrane is the key factor in infiltration evaporation technique.
And existing infiltrating and vaporizing membrane includes organic film and the class of inoranic membrane two substantially, and molecular screen membrane is common inorganic infiltrating and vaporizing membrane
Type, because the features such as its Stability Analysis of Structures receives many concerns.
According to the difference of crystalline texture, molecular sieve has a different configurations, for example, LTA, MFI, MOR, AFI, FER, FAU,
DDR etc..DDR is the crystallization that main component is made up of silica, and its micropore is formed by the polyhedron containing aerobic 8 yuan of rings, simultaneously
The micropore diameter of the yuan of rings of oxygen 8 is 4.4 × 3.6 angstroms.Because the skeleton structure of its intimate total silicon and suitable pore diameter range, DDR molecules
Sieve membrane ought to turn into a kind of one of huge molecular screen membrane species of application potential.DD3R is a kind of molecule of common DDR configurations
Sieve, has the more synthetic methods on DD3R molecular screen membranes in the prior art, but at present, its industrial applications is less,
The reason for excluding synthetic method complexity, it is mainly due to film and other types crystal is easily produced in crystallization process, special
It is not SGT.The appearance of other types crystal can seriously reduce the performance of film, so as to have impact on its application.
Based on prior art and experience, the appearance of other kinds of crystal is often caused by the later half of molecular screen membrane crystallization
Section, that is to say, that the possibility for occurring stray crystal in the crystallization time of front half section is smaller.But if use the crystalline substance of short time
Change, molecular screen membrane film layer is relatively thin, it is difficult to ensures its permeance property.
The content of the invention
Occurs other types crystal in crystallization process to solve molecular screen membrane, the invention provides a kind of conjunction of molecular screen membrane
Into method.
Technical scheme is as follows：
A kind of synthetic method of molecular screen membrane, it is characterised in that comprise the following steps：
（1）Carrier is soaked in deionized water, dried with standby.Carrier is soaked in deionized water can be effective
The impurity in carrier is removed to influence subsequent film crystallization.
（2）Sigma-1 sieve particles are added in ethanol to prepare crystal seed coating liquid, wherein sigma-1 quality point
Number is 1-10%, and ultrasound, stir process.It is to be placed in water crystal seed liquid to prepare crystal seed coating liquid in the prior art, and this hair
The bright way that discards tradition, according to the inherently characteristic of sigma-1 crystal, creative crystal seed is placed in ethanol prepares crystal seed
Coating liquid, the molecular screen membrane prepared using same sigma-1 crystal, same concentration is as a result found, in selectivity and infiltration
In terms of flux, the film prepared using ethanol as crystal seed coating liquid is far better than use water as retarder thinner.Preferably,
A certain amount of boehmite sol is added in crystal seed coating liquid can lift adhesion of the crystal seed on carrier as adhesive.
（3）Crystal seed liquid is coated in carrier outer surface, repeated 1-5 times, drying prepares inoculation carrier.
（4）With amantadine：Silica：Ethylenediamine：Aluminum oxide：Sodium hydroxide：Water mol ratio is 10:60:180： 2:
3:6000 ratio prepares preparation liquid A.In the prior art there has been no the preparation liquid proportioning for preparing sigma-1 films, the present invention is first
Matched after the proportioning dilution for synthesizing sigma-1 crystal in the prior art as preparation liquid, and the proportioning of amantadine is carried out
Reduce, and experiment has been carried out to specific extension rate and has been attempted, so as to create optimal proportioning, the proportioning is relative to preparation
The proportioning of crystal, the dosage of template is reduced, improves economy.
（5）Inoculation carrier is placed in film forming kettle, pours into preparation liquid A to be totally submerged inoculation carrier.
（6）The crystallization at a temperature of 180 DEG C, crystallization time are 12-24h to prepare molecular screen membrane base substrate A.Sigma-1 crystal
The optimum crystallization temperature of layer is 180 DEG C, has carried out multiple trial according to the temperature, and to specific crystallization time, has as a result found,
Crystallization time 12-24h is optimal, preferably 16h-18h, and crystallization time is too short, and film layer is too thin, along with brilliant subsequently than relatively thin DD3R
Body layer, permeance property cannot ensure, and if crystallization time is long, film layer is thicker, along with follow-up DD3R crystal layers, holds
Crack easily is produced in follow-up film layer roasting process, so as to reduce permeance property.
（7）Molecular screen membrane base substrate A deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
It is dried for standby.
（8）With amantadine：Silica：Ethylenediamine：Water mol ratio is 9:100:150:4000 molar ratio system
Film liquid B.
（9）Molecular screen membrane base substrate A is placed in film forming kettle, pours into preparation liquid A to be totally submerged molecular screen membrane base substrate A；
（10）The crystallization at a temperature of 160 DEG C, crystallization time are 8-24h to prepare molecular screen membrane base substrate B.In sigma-1 films
The certain condition of thickness degree, ensure that the thickness of DD3R film layers is most important, through investigation, optimal crystallization time is 8-24h, preferably
8-12h, too short crystallization time easily produce defect, it is impossible to which sigma-1 layers are completely covered for guarantee, lose top layer total silicon
Fine quality, and other types crystal easily is produced on surface, so as to can not guarantee the degree of purity of film layer, reduce oozing for film layer
Permeability energy.
（11）Molecular screen membrane base substrate B deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
Drying.
（12）By the molecular screen membrane base substrate B after drying in high-temperature roasting kiln roasting to remove amantadine so as to prepare point
Sub- sieve membrane.
Preferably, carrier is chip, tubular type or hollow fiber form.
Preferably, the compound method of the preparation liquid A is：Amantadine and ethylenediamine are sequentially added in container, ultrasound
20-30min is handled so that amantadine is completely dissolved, and continues to add sodium metaaluminate, sodium hydroxide in the case where heating ultrasound condition
And water, and continual ultrasonic 30-60min, wherein ultrasonic temperature are 40-60 DEG C.On the basis of traditional sigma-1 Opacity in lens liquid
Processing is optimized.
Preferably, the compound method of the preparation liquid B is：Amantadine and ethylenediamine are sequentially added in container, ultrasound
20-30min is handled so that amantadine is completely dissolved, and continuation adds water, and continual ultrasonic 30- in the case where heating ultrasound condition
60min, wherein ultrasonic temperature are 60 DEG C, and solution is cooled down in frozen water, continue to be ultrasonically treated 30- after adding silica
60min.Traditional synthetic method needs 90 degrees Celsius of high temperature oil bath, and present invention only requires 60 DEG C of common water-bath, simplify
Experiment condition, but add the success rate of film crystallization on the contrary.
Preferably, described to be roasted to stage roasting, actual conditions is：The frequency that heated up during -300 DEG C of room temperature is 2 DEG C/
The frequency that heated up when min, 300-600 DEG C is 1 DEG C/min, is 0.5 DEG C/min at 600-700 DEG C, 2-4h, 700- are maintained at 700 DEG C
The frequency that cools at 300 DEG C is 1 DEG C/min, and 300- room temperatures are 2 DEG C/min.It is that the film is difficult to greatly that crack, which easily occurs, in such DDR film
One of the reason for sizable application.But based on to DD3R and sigma-1 research find, sigma-1 do film forming layer relative to
Do not allow to be also easy to produce defect for DD3R, and due to sigma-1 and DD3R hot coefficient similar, therefore, loaded on sigma-1 layers
DD3R, also reduce the probability that DD3R produces defect.On this basis, at utmost to ensure that defect produces probability, but it is right
Innovated in the baking modes of film, and propose stage baking modes, fall below defect generation probability minimum.
The molecular screen membrane prepared by the above method, it has sigma-1 crystal layers and DD3R crystal layers, wherein sigma-
The thickness of 1 crystal layer is 1-1.3 μm, and the thickness of silica alumina ratio 20-40, DD3R crystal layer is 0.5-0.8 μm, and silica alumina ratio is at least
10000.And in terms of permeance property, at being 60 DEG C in feeding temperature, ethanol mass concentration is 50% material in ethanol/water system
In liquid, the molecular screen membrane separation factor prepared using the present invention is more than 1000, and flux is more than 3kg/m3.h。
The present invention compares compared with the prior art, has advantages below：
1. the present invention has synthesized one layer of sigma-1 crystal layer between traditional DD3R films and carrier, due to sigma-1
The presence of crystal layer, DD3R films only need shorter crystallization time, therefore its film layer other types crystal is less, and due to
Sigma-1 films easily keep the clarity of crystal, therefore whole molecular screen membrane crystal clarity is higher.And due to sigma-1 and
DD3R apertures are similar, and and can ensures the permeance property of film layer.
2. in molecular screen membrane prepared by the present invention, because sigma-1 crystal layers are between DD3R crystal layers and carrier,
Sigma-1 crystal layers will not contact with solvent in crystallization process, maintain the good characteristic of the intimate total silicon of film surface.
Embodiment
Embodiment 1
（1）By homemade Alpha-alumina (d50=0.80 μm) chip carrier is placed in baking oven after soaking 6h in deionized water
Drying is with standby at 60 DEG C.
（2）By sigma-1 sieve particles（About 800nm）Add in ethanol to prepare crystal seed coating liquid, wherein sigma-1
Mass fraction be 2%, and add a certain amount of adhesive boehmite sol, magnetic agitation processing 10min after ultrasonic 5min.
（3）Crystal seed layer is coated on carrier first with spin-coating method 1 time, continue with leaching Tu method and crystal seed 2 is coated on carrier
Secondary, at 60 DEG C prepared by drying to be inoculated with carrier.
（4）10g amantadines and ethylenediamine are sequentially added in container, are ultrasonically treated 20min so that amantadine is complete
Dissolving, and continue to add sodium metaaluminate 1g, sodium hydroxide 1g and water 500g successively under 60 DEG C of heating ultrasound conditions, and persistently surpass
Sound 30min, Ludox 79.2g is finally added dropwise to prepare preparation liquid A.
（5）Inoculation carrier is placed in chip film film forming kettle, crystal seed layer down, pours into preparation liquid A to be totally submerged inoculation
Carrier.
（6）The crystallization at a temperature of 180 DEG C, crystallization time are 16h to prepare molecular screen membrane base substrate A.
（7）Molecular screen membrane base substrate A deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
It is dried for standby.
（8）10g amantadines and 66.96g ethylenediamines are sequentially added in container, are ultrasonically treated 20min so that adamantane
Amine is completely dissolved, and continues to add water 535g under 60 DEG C of heating ultrasound conditions, and continual ultrasonic 30min, and solution is placed in into ice
Cooled down in aqueous mixtures, and add Ludox 148g in the cooling condition.Ultrasonic 30min is heated again obtains casting solution B.
（9）Molecular screen membrane base substrate B is placed in film forming kettle, pours into preparation liquid B to be totally submerged molecular screen membrane base substrate A.
（10）The crystallization at a temperature of 160 DEG C, crystallization time are 12h to prepare molecular screen membrane base substrate B.
（11）Molecular screen membrane base substrate B deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
Drying.
（12）By the molecular screen membrane base substrate B after drying in high-temperature roasting kiln roasting to remove amantadine so as to prepare point
Sub- sieve membrane.
Embodiment 2
（1）By homemade Alpha-alumina tubular media (d50=1.2 μm) in deionized water soak 8h after be placed in baking oven
Drying is with standby at 60 DEG C.
（2）By sigma-1 sieve particles（About 800nm）Add in ethanol to prepare crystal seed coating liquid, wherein sigma-1
Mass fraction be 2%, and add a certain amount of adhesive boehmite sol, magnetic agitation processing 10min after ultrasonic 5min.
（3）Crystal seed is coated on carrier using dip-coating 2 times, every time lasting 5s, at 60 DEG C drying prepare inoculation carrier.
（4）10g amantadines and ethylenediamine are sequentially added in container, are ultrasonically treated 20min so that amantadine is complete
Dissolving, and continue to add sodium metaaluminate 1g, sodium hydroxide 1g and water 500g successively under 60 DEG C of heating ultrasound conditions, and persistently surpass
Sound 30min, Ludox 79.2g is finally added dropwise to prepare casting solution A.
（5）Inoculation carrier is placed in tubular membrane film forming kettle, pours into preparation liquid A to be totally submerged inoculation carrier.
（6）The crystallization at a temperature of 180 DEG C, crystallization time are 12h to prepare molecular screen membrane base substrate A;
（7）Molecular screen membrane base substrate A deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
It is dried for standby；
（8）10g amantadines and ethylenediamine are sequentially added in container, are ultrasonically treated 20min so that amantadine is complete
Dissolving, and continue to add water 500g under 60 DEG C of heating ultrasound conditions, and continual ultrasonic 30min, solution is placed in frozen water and mixed
Cooled down in thing, and add Ludox in the cooling condition.Ultrasonic 30min is heated again obtains casting solution B.
（9）Molecular screen membrane base substrate A is placed in film forming kettle, pours into preparation liquid B to be totally submerged molecular screen membrane base substrate A；
（10）The crystallization at a temperature of 160 DEG C, crystallization time are 12h to prepare molecular screen membrane base substrate B;
（11）Molecular screen membrane base substrate B deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and
Drying.
（12）By the molecular screen membrane base substrate B after drying in high-temperature roasting kiln roasting to remove amantadine so as to prepare point
Sub- sieve membrane.
By molecular screen membrane prepared by embodiment 1,2 in the case where feeding temperature is 60 DEG C, ethanol mass concentration in ethanol/water system
To carry out infiltration evaporation experiment in 50% feed liquid, molecular screen membrane separation factor prepared by embodiment 1 is 5000, flux 3kg/
m3.h, and embodiment 2 prepare molecular screen membrane separation factor be 3500, flux 4.53kg/m3.h。
Highly preferred embodiment of the present invention is the foregoing is only, is not intended to limit the invention.It is all the present invention principle and
Any modification, equivalent substitution and improvements done within spirit etc., should be included within the scope of the present invention.
Claims (5)
1. a kind of synthetic method of molecular screen membrane, it is characterised in that comprise the following steps：
（1）Carrier is soaked in deionized water, dried with standby；
（2）Sigma-1 sieve particles are added in ethanol to prepare crystal seed coating liquid, wherein sigma-1 mass fraction is
1-10%, and ultrasound, stir process；
（3）Crystal seed liquid is coated in carrier outer surface, repeated 1-5 times, drying prepares inoculation carrier；
（4）With amantadine：Silica：Ethylenediamine：Aluminum oxide：Sodium hydroxide：Water mol ratio is 10:60:180：2: 3:
6000 ratio prepares preparation liquid A；
（5）Inoculation carrier is placed in film forming kettle, pours into preparation liquid A to be totally submerged inoculation carrier；
（6）The crystallization at a temperature of 180 DEG C, crystallization time are 12-36h to prepare molecular screen membrane base substrate A;
（7）Molecular screen membrane base substrate A deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and dry
It is standby；
（8）With amantadine：Silica：Ethylenediamine：Water mol ratio is 9:100:150:4000 molar ratio preparation liquid
B；
（9）Molecular screen membrane base substrate A is placed in film forming kettle, pours into preparation liquid B to be totally submerged molecular screen membrane base substrate A；
（10）The crystallization at a temperature of 160 DEG C, crystallization time are 8-24h to prepare molecular screen membrane base substrate B;
（11）Molecular screen membrane base substrate B deionized water rinsings after crystallization is terminated, surface p H is dipped to close to neutrality, and dry
It is dry；
（12）By the molecular screen membrane base substrate B after drying in high-temperature roasting kiln roasting to remove amantadine so as to prepare molecular sieve
Film；Wherein the thickness of sigma-1 crystal layers is 1-1.3 μm.
2. synthetic method according to claim 1, it is characterised in that described carrier is chip, tubular type or doughnut
Formula.
3. synthetic method according to claim 1, it is characterised in that the compound method of the preparation liquid A is：By adamantane
Amine and ethylenediamine are sequentially added in container, are ultrasonically treated 20-30min so that amantadine is completely dissolved, and is continued super in heating
Sodium metaaluminate, sodium hydroxide and water are added under the conditions of sound, and continual ultrasonic 30-60min, wherein ultrasonic temperature are 40-60 DEG C.
4. synthetic method according to claim 1, it is characterised in that the compound method of the preparation liquid B is：By adamantane
Amine and ethylenediamine are sequentially added in container, are ultrasonically treated 20-30min so that amantadine is completely dissolved, and is continued super in heating
Under the conditions of sound plus water, and continual ultrasonic 30-60min, wherein ultrasonic temperature are 60 DEG C, and solution is cooled down in frozen water and adds two
Continue to be ultrasonically treated 30-60min after silica.
5. synthetic method according to claim 1, it is characterised in that；Described is roasted to stage roasting, actual conditions
It is：Heating frequency be 2 DEG C/min during -300 DEG C of room temperature, and the frequency that heats up at 300-600 DEG C is 1 DEG C/min, is heated up at 600-700 DEG C
Frequency is 0.5 DEG C/min, maintains 2-4h at 700 DEG C, and cooling frequency be 1 DEG C/min at 700-300 DEG C, and cooling is frequently during 300- room temperatures
Rate is 2 DEG C/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6533855B1 (en) * | 2001-02-13 | 2003-03-18 | Novellus Systems, Inc. | Dispersions of silicalite and zeolite nanoparticles in nonpolar solvents |
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Method for preparing NaA molecular sieve membrane through induction of nanocrystal seeds |
| CN105016354A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院上海高等研究院 | Method for preparing submicron all-silicon DD3R molecular sieve |
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2017
- 2017-02-22 CN CN201710094924.6A patent/CN106823828B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6533855B1 (en) * | 2001-02-13 | 2003-03-18 | Novellus Systems, Inc. | Dispersions of silicalite and zeolite nanoparticles in nonpolar solvents |
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Method for preparing NaA molecular sieve membrane through induction of nanocrystal seeds |
| CN105016354A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院上海高等研究院 | Method for preparing submicron all-silicon DD3R molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 基于Sigma-1晶种诱导DD3R分子筛及DD3R分子筛膜的制备与表征;郑方圆;《万方学位论文》;20131231;第5-6、16、29、41-43、46-47页 * |
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