CN1049844C - Process for preparation of molecular sieve membrane on porous silicate material surface - Google Patents
Process for preparation of molecular sieve membrane on porous silicate material surface Download PDFInfo
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- CN1049844C CN1049844C CN 92102902 CN92102902A CN1049844C CN 1049844 C CN1049844 C CN 1049844C CN 92102902 CN92102902 CN 92102902 CN 92102902 A CN92102902 A CN 92102902A CN 1049844 C CN1049844 C CN 1049844C
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- Prior art keywords
- molecular sieve
- porous
- porous silicate
- silicate material
- sieve membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000011247 coating layer Substances 0.000 claims abstract 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005373 porous glass Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000012010 growth Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 2
- 239000005416 organic matter Substances 0.000 claims 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000008707 rearrangement Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012808 vapor phase Substances 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 6
- 239000002345 surface coating layer Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention discloses a preparation method for molecular sieve films on the surfaces of porous silicate materials, and the present invention which belongs to the technical field of inorganic synthesis relates to surface chemistry, physical chemistry and material science. The present invention is characterized in that the thin layer of the molecular sieve film is prepared in a non-aqueous system, namely that the present invention provides a method for preparing the molecular sieve films on the surfaces of the porous silicate materials, and the method comprises that the porous silicate materials and silicate materials with a coating layer are placed in the liquid phase of organic matters, the vapor phase of the organic matters and the vapour atmosphere of water for being heated. The method solves the problems that membrane scientists expect to solve all the time, and achieves the purposes of improving the permeability and the selectivity of film materials.
Description
The present invention is the method at a kind of preparation of molecular sieve membrane on porous silicate material surface, specifically, uses for reference molecular sieve synthetic theory and skill exactly, has the inorganic functional membrane of molecular level sieve aperture, i.e. molecular screen membrane in the manufacturing of porous silicate bill of material surface layer.The invention belongs to inorganic synthetic category, relate to technical fields such as surface chemistry, physical chemistry and Materials science.
Inorganic functional membrane with even molecular level sieve aperture is the insurmountable always problem of membrane science man.For now, functional film material mainly is meant organic high molecular layer, promptly crosslinked that form and have the fixed orifices of statistical distribution and a nethike embrane in tiny molecule gap by linear organic polymer, because these holes are uneven, and the selection that molecule sees through is determined by the uneven hole that effective pore radius minimum in these distributions and molecule gap constitute just, so the transmitance of present mould material and selectivity are difficult to improve.The membrane science man manages to produce the mould material of the uniform pore size of molecular level always, reaches to improve mould material transmitance and basic goal optionally.
The new way that addresses the above problem has been opened up in the imagination and the research of the molecular sieve functional membrane that late nineteen eighties occurs.The salient feature of molecular sieve is that the aperture is even, molecular level sieve aperture with standard, its molecule shape selectivity can rank first in various types of materials, the chemically modified of the molecular sieve of Chu Xianing in recent years, be that isomorphous substitution, surface properties are regulated, the accurate adjusting of molecular sieve bore diameter can manually design the character of molecular sieve in many aspects, can select duct window, pore canal system, vestibule electrostatic field to a certain extent artificially, to affinity of molecule etc., can actively play the purpose of " molecule is selected shape ".Molecular screen membrane can stand nearly 1000 ℃ thermal environment and strong acid, alkali corrosion medium in addition, this be organic high molecular layer can not compare.
Japan scientist in the eighties middle and later periods in hydrothermal system, tentatively attempted the preparation [1] [2] of molecular sieve coherent film, they respectively aluminum oxide substrate and borosilicate glass surface preparation A, ZSM-5 molecular screen membrane, the epoch of having started molecular screen membrane.
The object of the present invention is to provide a kind of technical scheme that in non-aqueous system or vapor phase system, prepares serial molecular screen membrane, thereby it is poor to have solved in hydrothermal system preparation molecular screen membrane adhesion strength, being difficult for independent film forming and silica alumina ratio can not be directed, the problem that liquid phase can not recycle finally reaches and improves zeolite membrane material transmitance and basic goal optionally.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention, it is characterized in that the crystal formation process of molecular screen membrane is polycondensation in non-aqueous system, reset, nucleation, growth is synthetic, just place the organism liquid phase to heat the porous silicate material, organic molecule acts on mutually with solid interface, form molecular screen membrane thin layer with even molecular level sieve aperture at porous silicate bill of material surface layer, its organism liquid phase is an organic amine, the liquid phase of alcohol, the porous silicate material is the porous silicate pottery, sintered glass and the porous silicate pottery that has overlay, the sintered glass that has overlay, the mole compositing range of its organism liquid phase medium is:
R
1：(0.05～100)R
2：(0～75)H
2O，
R in the formula
1Be triethylamine, R
2Be template, comprise quadrol, Tri N-Propyl Amine, n-Butyl Amine 99, tetramethyleneimine, piperidines.
The mole of its porous material and overlay thereof consists of:
(0.1～30)Na
2O：(8～3600)SiO
2：Al
2O
3：(0.1～100)R
2，
Its temperature of reaction is 60～350 ℃, and the reaction times is 5～350 hours.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention, it is characterized in that described porous silicate material also can place the steam atmosphere synthesis of molecular sieve film of organism or water, its mole is formed, Heating temperature is identical with the organism liquid phase, and its reaction time range is 12～600 hours.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention, the size that it is characterized in that described porous silicate material aperture is in micron-nanometer scale, and its shape can be various geometrical shapies, comprises plate, pipe, rod.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention is characterized in that described temperature of reaction is preferably in 100～200 ℃, and the reaction times is preferably in 24～72 hours, and the reaction times in vapor phase is preferably in 48～240 hours.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention also has the diversity of molecular screen membrane chemical composition and the characteristic that can carry out chemically modified.To adjust the shape selectivity and the chemical property of molecular screen membrane, the silicon component can part be replaced by phosphorus, germanium, and the aluminium component can partly or entirely be replaced by boron, iron, and coordination cation can partly or entirely be replaced by lithium, potassium, rubidium, cesium ion.To contain F
-, Cl
-And CO
3 -Compound add in the tabulation face overlay, contain compound in the hole and can obviously adjust the shape selectivity energy.
Embodiment:
Example 1: add the porous ceramic plate of 2 * 3.6cm in the mixed solution with 60ml triethylamine (100wt%) and 40ml quadrol (100wt%), its mol ratio is SiO
2/ Al
2O
3=68, Na
2O/SiO
2=0.11, to react 96 hours down at 180 ℃, the careful rinsing of cooling back water is slowly dried down for 85 ℃, and SEM observes the thin film layer that the surface generates 69 μ m, is the ZSM-5 molecular sieve structure through XRD determining.
Example 2: the porous glass tube (SiO that in the mixed solution of 60ml triethylamine (100wt%) and 40ml quadrol (100wt%), puts into diameter 0.5cm
290.9%, B
2O
33.3%, Al
2O
35.77%, Na
2O 0.03%), react the ZSM-5 molecular screen membrane that can obtain 21 μ m in 72 hours down at 100 ℃.
Example 3: put into the porous glass plate of 1.5 * 2cm in the mixed solution of 60ml triethylamine (100wt%) and 40ml quadrol (100wt%), its mol ratio is: SiO
2/ Al
2O
3=18, B
2O
3/ Al
2O
3=1, Na
2O/SiO
2=0.08, reacted 24 hours down at 150 ℃, can obtain the ZSM-35 molecular screen membrane of 10 μ m.
Example 4: surface coating layer consists of SiO in the mixed solution of 60ml triethylamine (100wt%) and 21ml trolamine (100wt%)
2/ Al
2O
3=12, Na
2O/SiO
2=0.21, F
-/ SiO
2The porous ceramics piece of 1 * 2cm of=0.18 reacted 120 hours down at 200 ℃, and solid surface generates the mordenite molecular sieve membrane of 40 μ m.
Example 5: on the support on the mixing solutions top of 30ml triethylamine (100wt%), 40ml tetraethyl ammonium hydroxide (25wt%) (seeing accompanying drawing), putting into surface coating layer is SiO
2/ Al
2O
3=1278, Na
2O/SiO
2=0.01 porous ceramics, reaction is 252 hours in 200 ℃ steam atmosphere, the careful rinsing of cooling back water, 85 ℃ of slowly oven dry down, can obtain thickness is the ZSM-48 molecular screen membrane of 12 μ m.
Example 6: with diameter is that the porous ceramic plate surface coating layer of 2cm consists of 3.0Na
2O: 3.0SiO
2: Al
2O
3: 320H
2The thin layer of O is put into water vapour atmosphere after the oven dry down for 85 ℃, and 120 ℃ were reacted 36 hours, is the X type molecular screen membrane of 56 μ m through SEM and XRD detection.
Example 7: under example 6 described conditions, the chemical constitution of surface coating layer is adjusted into 2.0Na
2O: 2.1SiO
2: Al
2O
3: 320H
2O result can obtain the A type molecular sieve film of 88 μ m.
Example 8: under example 6 described conditions, the chemical constitution of surface coating layer is adjusted into (SiO
2+ P
2O
5)/Al
2O
3=5.6, SiO
2/ P
2O
5=6, Na
2O/SiO
2=0.9, H
2O/Na
2O=100 reacted 60 hours down at 144 ℃, obtained the y-type zeolite membrane of 69 μ m.
The method of preparation of molecular sieve membrane on porous silicate material surface of the present invention, it is poor to have solved in hydrothermal system preparation molecular screen membrane adhesion strength, be difficult for independent film forming problem, liquid phase can recycle simultaneously, not only reduced cost, but also reduced and pollute, see from product performance and can accomplish directed design silica alumina ratio, be convenient to carry out chemically modified and this property of given purpose simultaneously.Molecular screen membrane thin layer and porous substrate substrate form compound parting material, can be used for reverse osmosis, ultrafiltration etc. and separate purposes, also can be used for energy transformation and catalytic process, this method has solved the membrane science man and has looked forward to the problem that solves always, has reached raising mould material transmitance and purpose optionally.
Documents:
[1] day clear 59-213615 of disclosure special permission communique
[2] day clear 63-291809 of disclosure special permission communique
Description of drawings:
1, silicate material
2, sample table
3, liquid phase
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102902 CN1049844C (en) | 1992-04-20 | 1992-04-20 | Process for preparation of molecular sieve membrane on porous silicate material surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102902 CN1049844C (en) | 1992-04-20 | 1992-04-20 | Process for preparation of molecular sieve membrane on porous silicate material surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077658A CN1077658A (en) | 1993-10-27 |
| CN1049844C true CN1049844C (en) | 2000-03-01 |
Family
ID=4939916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92102902 Expired - Fee Related CN1049844C (en) | 1992-04-20 | 1992-04-20 | Process for preparation of molecular sieve membrane on porous silicate material surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049844C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9600082D0 (en) * | 1996-01-04 | 1996-03-06 | Exxon Chemical Patents Inc | Molecular sieves and processes for their manufacture |
| CN1061900C (en) * | 1996-06-05 | 2001-02-14 | 中国石油化工总公司 | SAPO-34/ceramic composite separation film and preparation thereof |
| CN1061903C (en) * | 1996-06-05 | 2001-02-14 | 中国石油化工总公司 | SAPO-34/metal or ceramic catalyzing composite material and preparation thereof |
| CN100341783C (en) * | 2005-04-07 | 2007-10-10 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve membrane on porous ceramic carrier by utilizing hydrothermal synthesis |
| CN101279208B (en) * | 2008-05-20 | 2010-06-09 | 吉林大学 | Method for preparing Y type molecular sieve film |
| CN103449474B (en) * | 2012-06-01 | 2014-12-31 | 中国石油化工股份有限公司 | Phosphorus-containing ZSM-5 molecular sieve membrane and preparation method thereof |
| CN107303506B (en) * | 2016-04-21 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of paraffin hydrocarbon selects the preprocess method of type isomerization catalyst |
| CN114471184B (en) * | 2021-12-20 | 2023-07-07 | 南京工业大学 | A cationic-modified molecular sieve membrane, its preparation method and its use in dehydration of high-boiling-point organic solvents |
-
1992
- 1992-04-20 CN CN 92102902 patent/CN1049844C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1077658A (en) | 1993-10-27 |
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