CN109678170B - Preparation method of SAPO molecular sieve membrane material - Google Patents
Preparation method of SAPO molecular sieve membrane material Download PDFInfo
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- CN109678170B CN109678170B CN201710978805.7A CN201710978805A CN109678170B CN 109678170 B CN109678170 B CN 109678170B CN 201710978805 A CN201710978805 A CN 201710978805A CN 109678170 B CN109678170 B CN 109678170B
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- 239000012528 membrane Substances 0.000 title claims abstract description 92
- 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 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 241000269350 Anura Species 0.000 title claims description 29
- 239000000463 material Substances 0.000 title description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052593 corundum Inorganic materials 0.000 claims description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HHQMYHMTYIPFEG-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P Chemical compound [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P HHQMYHMTYIPFEG-UHFFFAOYSA-M 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 description 14
- 238000007789 sealing Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000034655 secondary growth Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical class CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a silane modified Silicoaluminophosphate (SAPO) molecular sieve membrane, which mainly solves the problem of the insufficient preparation technology of the prior SAPO molecular sieve membrane. The method comprises the steps of carrying out alkali treatment on a silicon source in a coating liquid in advance, coating a crystal seed layer and the coating liquid on a carrier in sequence, and then treating a molecular sieve membrane prepared by gas phase in-situ crystallization by using silane to obtain the SAPO molecular sieve membrane with high selectivity. The technical scheme is simple to operate, and the obtained SAPO molecular sieve membrane has the advantages of good repeatability, good compactness and uniformity, high quality, low preparation cost, contribution to cyclic utilization of the template agent and capability of being used in industrial production of the molecular sieve membrane.
Description
Technical Field
The invention relates to a preparation method of an SAPO molecular sieve membrane.
Background
The membrane separation technology is a new separation, purification and purification technology, and is widely applied to the fields of food, beverage, metallurgy, paper making, textile, pharmacy, automobile, biology, chemical industry and the like. The inorganic membrane can be classified into an inorganic membrane and an organic membrane according to the membrane material, and the inorganic membrane has excellent chemical stability, thermal stability and mechanical strength compared to the organic membrane. The molecular sieve membrane is a representative inorganic membrane, and has a pore channel with a certain shape, a controllable structure, adjustable and uniform pore diameter distribution, and the pore diameter size is close to the molecular size. The molecular sieve membrane has specific pore structure, so that the molecular sieve membrane has selective permeability and shape-selective catalysis, and can be modified by ion exchange. The molecular sieve membrane has attractive application prospects in the fields of membrane separation, membrane catalysis, membrane reactors and the like due to the separation and catalysis at the molecular level, and has become a research hotspot of inorganic membrane materials in recent years.
The molecular sieve membranes can be divided into three major types, namely filling membranes (embedded membranes), self-supporting membranes and supporting membranes, and the supporting molecular sieve membranes have all the characteristics of molecular sieves, so that the supporting molecular sieve membranes become the molecular sieve membranes with the most development potential. The preparation method of the supporting molecular sieve membrane mainly comprises four types, namely a hydrothermal in-situ generation method, a secondary growth method, a microwave synthesis method and a gas phase crystallization method. The secondary growth method is the most common membrane making method, namely, a layer of pre-synthesized nano-scale molecular sieve crystal is attached to a support body to be used as a seed crystal, and then the seed crystal is immersed into a synthetic liquid for continuous crystallization, so that the growth of the inner plane of the molecular sieve seed crystal is promoted, cracks are reduced, and a continuous molecular sieve membrane is formed. The molecular sieve membrane prepared by the gas phase crystallization method is mainly characterized in that a synthetic liquid is coated on a support body or a support body with pre-attached seed crystals by a spin-coating method or a dipping method, and then the molecular sieve membrane is obtained by crystallization by a gas phase transfer method, so that the membrane layer is thicker due to hydrothermal crystallization and resource waste caused by large-scale use of a template agent is avoided.
In the preparation method of the molecular sieve membrane, the silicon source is directly used, the crystal grains are not uniform, the particles are large, and the formed molecular sieve membrane has many defects and is not beneficial to separation of mixed gas; the in-situ generation method and the secondary growth method are that a molecular sieve is nucleated and grows through a hydrothermal system, so that the shape of particles and the density of crystal nuclei on a carrier cannot be controlled, and a film on the carrier is uneven; in-situ generation method does not use seed crystal, so that the molecular sieve membrane has low compactness; the research on the molecular sieve membrane is mainly focused on the silicon-aluminum oxide material, the research on the silicon-phosphorus-aluminum molecular sieve membrane is less, and the research has a great difference from the industrial application requirements in the aspects of membrane preparation technology, preparation cost, separation effect and the like, and needs to be further researched and solved.
In order to overcome the above defects, a preparation method of a high-quality, simple and environment-friendly synthetic silicon-phosphorus-aluminum molecular sieve membrane is particularly needed.
Disclosure of Invention
The invention aims to solve the technical problem of insufficient preparation technology of the prior SAPO molecular sieve membrane. The invention provides a novel modification method of an SAPO molecular sieve membrane, and the material has good thickness, compactness and repeatability.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a preparation method of an SAPO molecular sieve membrane comprises the following steps:
a) respectively soaking the carrier in acid and alkali, cleaning to neutrality, drying, and roasting for later use;
b) coating the seed crystal on the treated carrier;
c) phosphorus source, aluminum source,Uniformly mixing the silicon source subjected to alkali treatment with water to obtain silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P according to theory2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O3＝0.05～2.80；
d) Coating the silicon-phosphorus-aluminum oxide solution on the carrier obtained in the step b), drying, placing the carrier on the upper part of a reaction kettle, adding a mixture of organic amine and water into the bottom of the reaction kettle, wherein the ratio of the organic amine/water is 0.001-2, and carrying out gas phase crystallization;
(e) and after the reaction is finished, cooling the reaction kettle, washing the sample with water, and drying to obtain the SAPO type molecular sieve membrane.
f) Soaking the SAPO type molecular sieve membrane obtained in the step e) in a silane solution, and roasting to obtain the silane modified SAPO type molecular sieve membrane.
In the above steps, the phosphorus source, the aluminum source, the alkali-treated silicon source and water are mixed uniformly at-20 ℃ to 100 ℃, preferably, the aluminum source is mixed in the water, the phosphorus source is added while stirring, the mixture is stirred vigorously for 3 to 4 hours to be hydrolyzed completely to obtain a white milk-like uniform solution, then the alkali-treated silicon source is added, and the mixture is stirred to obtain the silicon-phosphorus-aluminum oxide sol. So as to improve the compactness of the molecular sieve membrane.
In the above technical scheme, the alkali for treating the carrier is at least one selected from sodium hydroxide, potassium hydroxide, ammonia water, tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, triethylamine or ethylenediamine; the acid is at least one selected from hydrochloric acid, nitric acid or sulfuric acid.
The concentration of the acid-base soaking is 0.1-2%, and the soaking time is 0.5-48 h; preferably, the concentration of the acid-base soaking is 0.2-1.5%, and the treatment time is 1-24 hours.
The seed crystal is coated by at least one of coating and pulling, preferably pulling for several times.
The silicon source is at least one selected from silica sol, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and silica sol; the aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride or aluminum sulfate; the phosphorus source is at least one selected from phosphoric acid, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium hydrogen phosphate.
The weight ratio of the silicon-phosphorus-aluminum mixture is selected from: h2O/Al2O3＝3.00～13.00；SiO2/Al2O3＝0.07～0.80；P2O5/Al2O30.06-2.30 percent; (ii) a 0.003-1 of organic amine/water.
The organic amine template agent is at least one of tetraethyl ammonium hydroxide, triethylamine or ethylenediamine.
The silane is selected from one of methoxysilanes such as dimethoxysilane, diethoxysilane and the like.
The crystallization temperature is 150 ℃ and 220 ℃, and the crystallization time is 0.1-5 days; preferably, the crystallization time is 0.2 to 4 days.
The carrier is alumina.
The alkali treatment is specifically realized by placing a silicon source in an alkaline solution for heating and refluxing; preferably, the alkali is sodium hydroxide or ammonia water, and the treatment time is 1-12 hours.
According to the method, the silicon source is subjected to alkali treatment, and is decomposed into uniform silicon dioxide small particles, so that the generated silicon-phosphorus-aluminum molecular sieve membrane is good in compactness and few in defects. The secondary growth method and the gas phase crystallization method are organically combined, the obtained silicon-phosphorus-aluminum molecular sieve membrane has good continuity, the thickness of the silicon-phosphorus-aluminum molecular sieve membrane is easy to control, and the silicon-phosphorus-aluminum molecular sieve membrane is compact and has good repeatability. The silicon-phosphorus-aluminum molecular sieve membrane is obtained through gas phase crystallization, the thickness of the silicon-phosphorus-aluminum molecular sieve membrane can be further regulated and controlled by regulating the crystallization times, and the compactness of the molecular sieve membrane with modified silane can be further improved. The invention has simple preparation process, easy control, high crystallinity, high quality of silicon-phosphorus-aluminum molecular sieve membrane and CO treatment2And CH4The mixed gas is separated, and then the mixed gas is separated,high selectivity and good technical effect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the SAPO molecular sieve membrane obtained in [ example 1 ].
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
12.3g of aluminum isopropoxide was mixed in ionized water, 11.97g of phosphoric acid was added while stirring, and strong stirring was carried out for 3-4 hours to completely hydrolyze and obtain a white milky homogeneous solution. Then 6g of silica sol which had been treated by refluxing in an alkali solution was added thereto, and the mixture was stirred at room temperature for 3 hours. Sealing two ends of a pretreated carrier tube pre-coated with seed crystals, vertically placing the carrier tube into the mixed solution, pulling the carrier tube for several times, drying the carrier tube at room temperature, placing the carrier tube on the upper part of a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of 3g of template tetraethylammonium hydroxide and 10g of water into the bottom of the reaction kettle, sealing the reaction kettle, and standing and crystallizing the mixture for 48 hours under the self pressure. And (3) taking out the carrier after crystallization is finished, repeatedly washing the carrier for several times by using deionized water until the value of the solution is neutral, then immersing the SAPO-34 molecular sieve membrane obtained after drying and roasting into dimethoxysilane, taking out the SAPO-34 molecular sieve membrane after 2 hours, and drying and roasting the SAPO-34 molecular sieve membrane to obtain the silane modified SAPO molecular sieve membrane. SEM is shown in figure 1.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7
[ examples 2 to 14 ]
SAPO molecular sieve membranes were prepared according to the procedures and conditions of example 1, except that the raw material (table 1) ratios, the types of templates, the crystallization temperature, and other parameters were changed, as shown in table 1. Characterization of the synthesized product indicated that the result had a crystal structure similar to that of [ example 1 ]. In the invention, the organic amine/water ratio is 0.001-2, and the individual data in the table are not in the range, please check.
TABLE 1
Comparative example 1 silane-free modified molecular sieve membrane
12.3g of aluminum isopropoxide was mixed in ionized water, 11.97g of phosphoric acid was added while stirring, and strong stirring was carried out for 3-4 hours to completely hydrolyze and obtain a white milky homogeneous solution. Then 6g of silica sol which had been treated by refluxing in an alkali solution was added thereto, and the mixture was stirred at room temperature for 3 hours. Sealing two ends of a pretreated carrier tube pre-coated with seed crystals, vertically placing the carrier tube into the mixed solution, pulling the carrier tube for several times, drying the carrier tube at room temperature, placing the carrier tube on the upper part of a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of 3g of template tetraethylammonium hydroxide and 10g of water into the bottom of the reaction kettle, sealing the reaction kettle, and standing and crystallizing the mixture for 48 hours under the self pressure. And after crystallization, taking out the carrier, repeatedly washing the carrier for several times by using deionized water until the value of the solution is neutral, and then drying and roasting the washed carrier to obtain the SAPO molecular sieve membrane. XRD results show that the obtained product is a silane-free modified SAPO molecular sieve membrane.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7
Comparative example 2 preparation of molecular sieve membrane by Secondary crystallization
12.3g of aluminum isopropoxide, 11.97g of phosphoric acid, 6g of silica sol and 60g of template agent R1 are weighed and mixed, and stirred for 3 hours to form mixed liquid A. Sealing two ends of the carrier tube coated with the seed crystal, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining body, pouring the mixed solution A into the reaction kettle, and standing and crystallizing for 24 hours under the self pressure after sealing. And (3) taking out the carrier after crystallization is finished, repeatedly washing the carrier for several times by using deionized water until the value of the solution is neutral, and drying and roasting the washed solution to obtain the SAPO-34 molecular sieve membrane prepared by the traditional method. The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7；R1/Al2O3＝10
[ COMPARATIVE EXAMPLE 3 ] preparation of molecular Sieve Membrane from silicon Source without alkali treatment
12.3g of aluminum isopropoxide was mixed in ionized water, 11.97g of phosphoric acid was added while stirring, and strong stirring was carried out for 3-4 hours to completely hydrolyze and obtain a white milky homogeneous solution. Then 6g of silica sol was added and stirred at room temperature for 3 h. Sealing two ends of a pretreated carrier tube pre-coated with seed crystals, vertically placing the carrier tube into the mixed solution, pulling the carrier tube for several times, drying the carrier tube at room temperature, placing the carrier tube on the upper part of a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding a mixed solution of 3g of template tetraethylammonium hydroxide and 10g of water into the bottom of the reaction kettle, sealing the reaction kettle, and standing and crystallizing the mixture for 48 hours under the self pressure. And after crystallization, taking out the carrier, repeatedly washing the carrier for several times by using deionized water until the value of the solution is neutral, and then drying and roasting the washed carrier to obtain the SAPO molecular sieve membrane. XRD results show that the obtained product is a gas phase crystallized SAPO molecular sieve membrane.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7
CO was carried out on the molecular sieve membrane (A) prepared in example 1, the non-silane-modified molecular sieve membrane (B) prepared in comparative example 1, the molecular sieve membrane (C) prepared in comparative example 2 by secondary crystallization, and the molecular sieve membrane (D) prepared in comparative example 3 by alkali-free treatment of silicon source2And CH4The mixed gas was separated, and the results are shown below.
| Sample (I) | CO2Permeability x10-7(molm-2pa-1s-1) | Selective CO2/CH4 |
| A | 1.8 | 91 |
| B | 1.9 | 83 |
| C | 1.1 | 45 |
| D | 1.3 | 57 |
Claims (10)
1. A preparation method of an SAPO molecular sieve membrane comprises the following steps:
a) respectively soaking the carrier in acid and alkali, cleaning to neutrality, drying, and roasting for later use;
b) coating the seed crystal on the treated carrier;
c) uniformly mixing a phosphorus source, an aluminum source, an alkali-treated silicon source and water to obtain silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P theoretically2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O3＝0.05～2.80；
d) Coating the silicon-phosphorus-aluminum oxide solution on the carrier obtained in the step b), drying the carrier, placing the dried carrier on the upper part of a reaction kettle, and adding a mixture of organic amine and water into the bottom of the reaction kettle, wherein the weight ratio of the organic amine to the water is as follows: organic amine/water is 0.001-2, and gas phase crystallization is carried out;
(e) after the gas phase crystallization is finished, cooling the reaction kettle, washing the sample with water, and drying to obtain the SAPO type molecular sieve membrane;
f) soaking the SAPO type molecular sieve membrane obtained in the step e) in a silane solution, and roasting to obtain the silane modified SAPO type molecular sieve membrane.
2. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the alkali for treating the carrier in step a) is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, tetraethyl amine hydroxide, tetraethyl ammonium bromide, triethylamine, and ethylenediamine; the acid is at least one selected from hydrochloric acid, nitric acid or sulfuric acid.
3. The method for preparing the SAPO molecular sieve membrane of claim 1, wherein the concentration of the acid-base soaking in step a) is 0.1-2%, and the treatment time is 0.5-48 hours.
4. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the seed crystal is coated in step b) by at least one of coating or lifting.
5. The method for preparing SAPO molecular sieve membrane of claim 1, wherein in step c) the silicon source is selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, or silica sol; the aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride or aluminum sulfate; the phosphorus source is at least one selected from phosphoric acid, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium hydrogen phosphate.
6. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the weight ratio of the mixture in step c) is: h2O/Al2O3＝3.00～13.00；SiO2/Al2O3＝0.07～0.80；P2O5/Al2O30.06-2.30 percent; 0.003-1 of organic amine/water.
7. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the organic amine in step d) is at least one member selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, and ethylenediamine.
8. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the silane in step f) is selected from the group consisting of dimethoxysilane and diethoxysilane.
9. The method for preparing SAPO molecular sieve membrane of claim 1, wherein the crystallization temperature in step d) is 150 ℃ to 220 ℃ and the crystallization time is 0.1 to 5 days.
10. The preparation method of the SAPO molecular sieve membrane of claim 1, wherein the alkali treatment is realized by placing a silicon source in an alkaline solution and heating and refluxing.
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