CN114835138B - Aluminum phosphate molecular sieve membrane and preparation method and application thereof - Google Patents
Aluminum phosphate molecular sieve membrane and preparation method and application thereof Download PDFInfo
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- CN114835138B CN114835138B CN202210265639.7A CN202210265639A CN114835138B CN 114835138 B CN114835138 B CN 114835138B CN 202210265639 A CN202210265639 A CN 202210265639A CN 114835138 B CN114835138 B CN 114835138B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 107
- 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 107
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 62
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 37
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 claims description 12
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 6
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 description 26
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000011010 flushing procedure Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229940043279 diisopropylamine Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 alkyl quaternary ammonium salt ion Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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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)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an aluminum phosphate molecular sieve membrane, a preparation method and application thereof. The aluminum phosphate molecular sieve membrane consists of an aluminum substrate and a molecular sieve coating layer; and the molecular sieve coating layer is formed by stacking micron-level rod-shaped or cubic structures. The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps: 1) Mixing ionic liquid, a phosphorus-containing raw material, a mineralizer and organic amine, and aging to obtain a mixed reaction solution; 2) Immersing the aluminum substrate in the mixed reaction liquid, and carrying out crystallization reaction to obtain the aluminum phosphate molecular sieve membrane. The preparation method can simply, controllably and low-cost prepare the aluminum phosphate molecular sieve membrane with complete, continuous, compact and high crystallinity by introducing different types of organic amine in crystallization reaction, and the aluminum phosphate molecular sieve membrane can be applied to corrosion resistant materials.
Description
Technical Field
The invention relates to the technical field of molecular sieve materials, in particular to an aluminum phosphate molecular sieve membrane, a preparation method and application thereof.
Background
The traditional molecular sieve hydrothermal synthesis method utilizes a hydrothermal synthesis technology, and the high autogenous pressure (the vapor pressure at 180 ℃ can reach 10 bar) of a hydrothermal system determines that the production and preparation process of the molecular sieve always accompanies a certain safety risk. In addition, a large amount of acid-base waste liquid generated in the traditional method also brings a certain pressure to environmental protection. The ionic thermal synthesis method is a new molecular sieve synthesis method taking ionic liquid or eutectic mixture as a medium, wherein the ionic liquid or the eutectic mixture is used as a solvent and a template agent for synthesis reaction. Compared with the traditional hydrothermal system or solvent thermal system, the ionic liquid saturated vapor pressure in the ionic thermal system is extremely low, so that the ionic thermal synthesis reaction can be carried out under normal pressure, and the reaction process is safer.
Along with the continuous and intensive research on molecular sieves, the research discovers that if the molecular sieves are prepared into films, the films can have the properties of the film materials and the molecular sieves at the same time, so that the application range of the molecular sieves is widened. The accurate molecular sieving function of the microporous pore canal of the molecular sieve is combined with the characteristics of high efficiency, low energy consumption, continuous production, strong flexibility, strong stability, corrosion resistance, environmental protection and the like when the film material is used as an integral material, so that the loss of the molecular sieve in practical application can be reduced. But the molecular sieve membrane prepared by adopting the ionic liquid has less types, poor controllability of the membrane microstructure and more complex process.
Therefore, there is a need for a method for synthesizing an aluminum phosphate molecular sieve membrane by ion heat, which has the advantages of strong controllability, multiple types, high crystallinity, simple process and low cost.
Disclosure of Invention
The invention aims at providing a preparation method of an aluminum phosphate molecular sieve membrane.
The second object of the present invention is to provide an aluminum phosphate molecular sieve membrane produced by the above-mentioned production method.
It is a further object of the present invention to provide the use of the above aluminum phosphate molecular sieve membrane.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the present invention provides an aluminum phosphate molecular sieve membrane comprising an aluminum substrate and a molecular sieve coating layer, the molecular sieve coating layer being formed by stacking micron-sized rods.
Preferably, the molecular sieve in the molecular sieve coating layer has high crystallinity.
Preferably, the molecular sieve in the molecular sieve coating layer is an AEL type molecular sieve.
Preferably, the aluminum substrate is metallic aluminum or aluminum alloy.
Preferably, the metal substrate is a sheet material, and the thickness of the sheet material is 0.1 mm-0.3 mm.
In a second aspect, the invention provides a method for preparing an aluminum phosphate molecular sieve membrane, comprising the following steps:
1) Mixing ionic liquid, a phosphorus-containing raw material, a mineralizer and organic amine, and aging to obtain a mixed reaction solution;
2) Immersing the metal substrate in the mixed reaction liquid, and carrying out crystallization reaction to obtain the molecular sieve membrane.
Preferably, the organic amine in step 1) is monoamine or diamine.
Further preferably, the organic amine in step 1) is one or more of 4-ethylaniline, 4-butylaniline, p-toluidine, diisopropylamine and tetraethylammonium bromide.
Preferably, the cation contained in the ionic liquid in the step 1) is one or more of alkyl quaternary ammonium salt ion [ NR ] 4 +, alkyl quaternary phosphine ion [ PR ] 4 +, alkyl substituted imidazole ion [ Rim ] + and alkyl substituted pyridine ion [ Rpy ] +, and the alkyl is alkyl containing 1-16 carbon atoms.
Preferably, the ionic liquid in step 1) contains one or more anions Br-、C1-、I-、BF4 -、PF6 -、PO4 3-、NO3 -、SO4 2-.
Further preferably, the ionic liquid in the step 1) is one of 1-ethyl-3-methyl imidazole bromide and 1-butyl-3-methyl imidazole bromide.
Preferably, the ionic liquid in the step 1) is obtained by heating an ionic liquid raw material to 80-120 ℃.
Preferably, the phosphorus-containing raw material in the step 1) is phosphoric acid and/or phosphate.
Preferably, the mineralizer in step 1) is hydrofluoric acid and/or ammonium fluoride.
Preferably, the water content in the mixed reaction solution in the step 1) is 0 to 8wt%.
Specifically, the water in the mixed reaction solution is self-contained in the used reagent raw materials.
Preferably, the ageing in step 1) is stirring at 80-100 ℃ for 0.5-3 hours.
Preferably, in the step 1), the molar ratio of the F -、PO4 3-, the organic amine and the ionic liquid in the mixed reaction solution is 1: (1-4): (1-6): (20-160).
Further preferably, in the step 1), the molar ratio of the F -、PO4 3-, the organic amine and the ionic liquid in the mixed reaction solution is 1: (2-4): (2-5): (30-40).
Preferably, the metal substrate in the step 2) is metal aluminum or aluminum alloy.
Preferably, the temperature of the crystallization reaction in the step 2) is 110-300 ℃.
Preferably, the crystallization reaction time in the step 2) is 1 to 48 hours.
Preferably, step 2) further comprises the steps of removing, washing and drying the reacted substrate.
Preferably, the washing is to wash the substrate with deionized water until the washed water is neutral.
Preferably, the drying is performed under a nitrogen atmosphere at 80 to 120 ℃.
In a third aspect, the present invention also provides a corrosion resistant material comprising the aluminium phosphate molecular sieve membrane of the first aspect.
The beneficial effects of the invention are as follows: the preparation method of the molecular sieve membrane can prepare the molecular sieve membrane with complete, continuous, compact and high crystallinity simply, controllably and at low cost through crystallization reaction (ion heat) and introduction of different types of organic amine.
(1) The preparation method adopted in the invention is to use ionic liquid as a reaction medium and add different types of organic amine such as 4-ethylaniline, 4-butylaniline, 2-ethylaniline and the like as a co-template agent, synthesize the microporous aluminum phosphate molecular sieve membrane on an aluminum substrate (pure aluminum sheet or aluminum alloy) in situ, and regulate the morphology and the crystal size of the molecular sieve membrane.
(2) According to the invention, the composition of the organic amine and the ionic liquid is selectable, the combination is adjustable, and the micro structure of the molecular sieve membrane can be regulated and controlled by an ion thermal method, so that the molecular sieve membranes with different topological structures can be synthesized by utilizing the organic amine with different sizes, chain lengths and polarities;
(3) The molecular sieve membrane provided by the invention has a substrate containing aluminum and a compact, complete and continuous molecular sieve outer layer, so that the molecular sieve membrane (integral material) has good corrosion resistance.
Drawings
Fig. 1 is an XRD pattern of the aluminophosphate molecular sieve membrane in example 1, example 3, example 6 and example 8.
Fig. 2 is an SEM image of the aluminum phosphate molecular sieve membrane in example 1.
FIG. 3 is a graph showing the results of corrosion resistance test of the aluminum phosphate molecular sieve membrane in example 1.
Fig. 4 is an SEM image of the aluminum phosphate molecular sieve membrane in example 3.
Fig. 5 is an SEM image of the aluminum phosphate molecular sieve membrane in example 6.
Fig. 6 is an SEM image of the aluminum phosphate molecular sieve membrane in example 8.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) Adding 30.5g of 1-ethyl-3-methyl imidazole bromide into a 100mL beaker, heating to 120 ℃ to melt to obtain an ionic liquid;
2) Uniformly dropwise adding 0.2g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 1.72g of 85wt% phosphoric acid, and finally adding 1.8g of 4-ethylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 4-ethyl aniline: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 2
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) Adding 30.5g of 1-ethyl-3-methyl imidazole bromide into a 100mL beaker, heating to 100 ℃ to melt to obtain an ionic liquid;
2) Uniformly dropwise adding 0.2g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 1.72g of 85wt% phosphoric acid, and finally adding 1.07g of 4-ethylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 4-ethyl aniline: the molar ratio of the ionic liquid is 1:4:2.4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 6 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 3
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) Adding 20g of 1-ethyl-3-methyl imidazole bromide into a 100mL beaker, heating to 100 ℃ to melt to obtain an ionic liquid;
2) Uniformly dropwise adding 0.14g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 1.15g of 85wt% phosphoric acid, and finally adding 1.49g of 4-butylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 4-butylaniline: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 4
A method for preparing a molecular sieve membrane, comprising the steps of:
1) 15.3g of 1-ethyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 1.12g of 4-butylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 4-butylaniline: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 6 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 5
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 17.5g of 1-butyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 1.12g of 4-butylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 4-butylaniline: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 6 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 6
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 15.3g of 1-ethyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 0.90g of 2-ethylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 2-ethyl aniline: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 180 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 7
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 17.5g of 1-butyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 1.12g of 2-ethylaniline to keep the ionic liquid at 90 ℃ and stirring for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: 2-ethyl aniline: the molar ratio of the ionic liquid is 1:4:5:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 8
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 15.3g of 1-ethyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 0.81g of p-toluidine, so that the ionic liquid is kept at 90 ℃ and stirred for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: para-toluidine: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 9
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 17.5g of 1-butyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 1.08g of p-toluidine, so that the ionic liquid is kept at 90 ℃ and stirred for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: para-toluidine: the molar ratio of the ionic liquid is 1:4:5:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 10
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) Adding 30.5g of 1-ethyl-3-methyl imidazole bromide into a 100mL beaker, heating to 120 ℃ to melt to obtain an ionic liquid;
2) Uniformly dropwise adding 0.2g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 1.72g of 85wt% phosphoric acid, and finally adding 1.51g of diisopropylamine, so that the ionic liquid is kept at 90 ℃ and stirred for more than 30min to obtain an ionic reaction liquid, wherein F -：PO4 3-: diisopropylamine: the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Example 11
The preparation method of the aluminum phosphate molecular sieve membrane comprises the following steps:
1) 15.3g of 1-ethyl-3-methyl imidazole bromide is added into a 100mL beaker, and the temperature is raised to 100 ℃ to melt, so as to obtain an ionic liquid;
2) Uniformly dropwise adding 0.1g of 40wt% hydrofluoric acid into the ionic liquid, dropwise adding 0.86g of 85wt% phosphoric acid, and finally adding 0.426g of 4-ethylaniline and 0.42g of tetraethylammonium bromide, wherein the molar ratio of the 4-ethylaniline to the tetraethylammonium bromide is 3:1, keeping the ionic liquid at 90 ℃ and stirring for more than 30 minutes to obtain an ionic reaction liquid, wherein F -：PO4 3-: organic amine (sum of 4-ethylaniline and tetraethylammonium bromide): the molar ratio of the ionic liquid is 1:4:4:40, a step of performing a;
3) Transferring the ion reaction liquid and the rectangular flaky aluminum substrate into a reaction kettle, ensuring that the aluminum substrate is completely immersed in the ion reaction liquid, heating the reaction kettle to 190 ℃, keeping the temperature for 8 hours, cooling the reaction kettle to room temperature, stably taking out the reacted aluminum substrate, flushing with deionized water, and drying under the conditions of nitrogen atmosphere and 80 ℃ to obtain the aluminum phosphate molecular sieve membrane.
Characterization and performance testing
1) XRD (X-Ray Diffraction) spectra of the aluminum phosphate molecular sieve films in example 1, example 3, example 6 and example 8 are shown in FIG. 1.
As can be seen from fig. 1: the aluminum phosphate molecular sieve membranes in examples 1, 3,6 and 8 are pure phases and contain no mixed crystals; the molecular sieve crystals constituting the molecular sieve membrane have an AEL structure confirmed by the international zeolite association, have a one-dimensional ten-membered ring straight pore structure, and have an X-ray diffraction pattern having at least the following diffraction peaks (characteristic peaks):
The characteristic peak has 2 theta (unit: °) of ：8.03±0.2;9.40±0.2;13.12±0.2;15.63±0.2;16.20±0.2;18.95±0.2;20.37±0.2;20.93±0.2;22.10±0.2;22.43±0.222.70±0.2;23.17±0.2;24.70±0.2;26.54±0.2.
2) SEM (Scanning Electronic Microscopy, scanning electron microscope) images of the aluminum phosphate molecular sieve membrane in example 1 are shown in fig. 2. SEM images of the aluminum phosphate molecular sieve membrane in example 3 are shown in fig. 4. SEM image of the aluminum phosphate molecular sieve membrane in example 6 is shown in fig. 5. SEM image of the aluminum phosphate molecular sieve membrane in example 8 is shown in fig. 6.
As can be seen from fig. 2, 4, 5 and 6: the molecular sieve membranes prepared in the examples 1, 3, 6 and 8 have compact, complete and continuous surfaces, which shows that the organic amine of 4-ethylaniline, 4-butylaniline, 2-ethylaniline and p-toluidine can generate a layer of compact molecular sieve membrane on the surface of an aluminum substrate through an ion thermal synthesis method, thereby being beneficial to isolating the corrosion of the outside on metal aluminum and improving the corrosion resistance; among them, the surfaces of the molecular sieve films in example 1, example 6 and example 8 were observed as a micrometer-sized, ordered, cauliflower-like structure composed of rod-like structures; microspheres consisting of rod-like structures on the micrometer scale were observed on the surface of the molecular sieve membrane in example 3.
Meanwhile, the order of the crystal size of the molecular sieve membrane from large to small is as follows: example 1 > example 3> example 6. The length of the rod-shaped unit structure of the molecular sieve membrane in example 1 is about 100 μm to 400 μm, the length of the rod-shaped unit structure of the molecular sieve membrane in example 3 is about 20 μm to 200 μm, and the length of the rod-shaped unit structure of the molecular sieve membrane in example 6 is about 50 μm to 100 μm.
3) Sample tested: the aluminum phosphate molecular sieve membrane and pure aluminum substrate of example 1.
Method and conditions for corrosion resistance testing of materials: preparing a 3.5% NaCl solution as an etching solution, pouring the etching solution into an etching tank, wherein a working electrode is a bare aluminum substrate or an aluminum sheet coated with a molecular sieve membrane prepared by the scheme, a counter electrode is a Pt sheet, and a reference electrode is (Ag/AgCl)/KCl (3.5M). Before corrosion testing, the molecular sieve is stabilized in the corrosive liquid for 30min, and then Tafel polarization curve scanning is carried out, wherein the scanning range is 0V to-1.6V, and the scanning speed is 5mV/s. The results of the corrosion resistance test of the material are shown in fig. 3.
As can be seen from fig. 3: the molecular sieve membrane of example 1 has better corrosion resistance than a pure aluminum substrate.
The organic amine species and aluminum phosphate molecular sieve membrane types and microscopic morphology parameters selected in examples 1-12 are shown in table 1.
TABLE 1 summary of Performance parameters of organic amine species and aluminum phosphate molecular sieves selected for use in examples 1-12
As can be seen from table 1: organic amine raw materials of 4-ethylaniline, 4-butylaniline, 2-ethylaniline, p-toluidine and diisopropylamine are selected, and the preparation method of the embodiment 1-9 is adopted to obtain the aluminum phosphate molecular sieve with the AEL structure. Organic amine of 4-ethylaniline, 4-butylaniline and p-toluidine is selected to prepare molecular sieve membranes with different rod-shaped units to form a cauliflower-shaped AEL structure through crystallization reaction; the molecular sieve membrane with compact spherical AEL structure composed of rod units can be prepared by selecting 2-ethylaniline or 4-ethylaniline and tetraethylammonium bromide.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (2)
1. The preparation method of the aluminum phosphate molecular sieve membrane is characterized by comprising the following steps of:
1) Mixing ionic liquid, a phosphorus-containing raw material, a mineralizer and organic amine, and aging to obtain a mixed reaction solution;
2) Immersing an aluminum substrate in the mixed reaction liquid, and carrying out crystallization reaction to obtain an aluminum phosphate molecular sieve membrane;
the organic amine in the step 1) is one or more of 4-ethylaniline, 4-butylaniline, p-toluidine and tetraethylammonium bromide;
The aluminum phosphate molecular sieve membrane consists of an aluminum substrate and a molecular sieve coating layer; the molecular sieve coating layer is formed by stacking micron-level rod-shaped structures; the molecular sieve in the molecular sieve coating layer is AEL type molecular sieve; the aluminum substrate is metal aluminum or aluminum alloy;
The ionic liquid in the step 1) is one of 1-ethyl-3-methyl imidazole bromide and 1-butyl-3-methyl imidazole bromide; the phosphorus-containing raw material in the step 1) is phosphoric acid and/or phosphate; the mineralizer in the step 1) is hydrofluoric acid and/or ammonium fluoride;
The molar ratio of F -、PO4 3-, organic amine and ionic liquid in the mixed reaction liquid in the step 1) is 1: (2-4): (2-5): (30-40).
2. The method of manufacture of claim 1, wherein: the temperature of the crystallization reaction in the step 2) is 110-300 ℃; and 2) the time of the crystallization reaction is 1-48 h.
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