CN104724723A - Synthesis method of aluminum phosphate molecular sieve membrane - Google Patents
Synthesis method of aluminum phosphate molecular sieve membrane Download PDFInfo
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- CN104724723A CN104724723A CN201310714944.0A CN201310714944A CN104724723A CN 104724723 A CN104724723 A CN 104724723A CN 201310714944 A CN201310714944 A CN 201310714944A CN 104724723 A CN104724723 A CN 104724723A
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- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- 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 61
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title abstract 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 81
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000004411 aluminium Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 35
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 15
- 230000035515 penetration Effects 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 61
- 239000013078 crystal Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 22
- 229910000838 Al alloy Inorganic materials 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 10
- 230000002421 anti-septic effect Effects 0.000 description 9
- 230000012010 growth Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000034655 secondary growth Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- -1 amine ion Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 239000000126 substance 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
-
- 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
- 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
Landscapes
- 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 discloses a synthesis method of an aluminum phosphate molecular sieve membrane. The synthesis method comprises the following steps that a precursor solution is stirred at a temperature of 80-100 DEG C for 1-10h to obtain a synthesis liquid, a metal substrate is vertically put into the synthesis liquid and undergoes a synthesis reaction at a temperature of 130-220 DEG C for 0.5-48h, and the product is taken out, is cooled to a room temperature, is washed by distilled water until a pH value is 7 and is dried by an oven so that the aluminum phosphate molecular sieve membrane is obtained. The synthesis method is simple and fast. The aluminum phosphate molecular sieve membrane has good compactness, and molecular sieve tunnels are high orientedly paved on the surface of the substrate and prevent penetration of a corrosion liquid to the substrate from membrane gaps or tunnels so that corrosion resistance is improved. The molecular sieve has high synthesis repeatability and is suitable for industrial popularization.
Description
Technical field
The invention belongs to synthesis and the Application Areas of molecular screen membrane, in particular, provide a kind of synthetic method of aluminophosphate molecular sieve membrane.
Background technology
Molecular screen membrane is a brand-new and full of challenges research direction as anticorrosion coating material in molecular sieve research field.This has benefited from several large feature of molecular screen material itself: (1) most of molecular screen material is nontoxic, and some of them are used to food and medicine; (2) excellent thermostability and chemical stability; (3) template used in sieve synthesis procedure, such as amine ion, can be fixed on as corrosion inhibitor in the pore passage structure of molecular sieve, improves the antiseptic property of molecular screen membrane further.The distinctive nontoxicity of molecular sieve and high chemistry and thermostability make it have the possibility of Chromium coating replacing high toxicity conventional at present, high carcinogenic as eco-friendly metallic coating.Investigators have synthesized MFI molecular sieve coating and SAPO-11 molecular sieve coating on aluminium alloy, stainless steel and carbon steel, all demonstrate good corrosion resistance, and this series of activities opens the new direction of molecular screen membrane investigation and application.
As a desirable molecular screen membrane corrosion protection coating, except the compactness of film itself and orientation, the orientation in the duct of the molecular sieve crystal in film is also vital.The duct being parallel to substrate can prevent corrosive fluid from directly entering from duct and contact substrate and produce corrosion, and the molecular screen membrane of this orientation and duct have barrier effect (impermeablebarrier) for much corrosive gas or liquid.That is, the preparation of fine and close, that duct orientation is controlled molecular screen membrane is applied to high-performance corrosion protection coating to it or long-term antiseptic property is vital.But, the densification of current bibliographical information, the molecular screen membrane of high orientation be nearly all in film duct perpendicular to substrate carrier, the molecular screen membrane of this orientation and duct thereof are conducive to diffusion and the circulation of molecule, obviously be very favourable to it as separatory membrane or membrane reactor, but then there is limitation for as corrosion protection coating.The traditional hydrothermal synthesis method of the employing such as Yan has prepared fine and close high silicon MFI molecular screen membrane in different metal base, although this coating shows good antiseptic property, the orientation of the high silicon MFI molecular sieve of preparation is not very desirable.The method of the hot microwave-assisted of the employing ion such as Cai has prepared the SAPO-11 molecular screen membrane of height c-axle orientation on aluminium alloy, shows good antiseptic property.But duct is perpendicular to aluminum alloy substrate in SAPO-11 molecular screen membrane, in film, this orientation in duct is obviously disadvantageous for its rot-resistant permanent stability.In addition, M.Tsapatsis etc. find when studying the antiseptic property of MCM-22/Silica hybridized film, for this mould material, and its anti-corrosion function being more conducive to this film along the little boring ratio of six annulus of c-axle orientation along 12 annulus macropores of a-axle orientation.This orientation antiseptic property to film also further demonstrating crystal duct in the molecular screen membrane as corrosion protection coating is very important.
As the molecular screen membrane of corrosion protection coating, normally molecular sieve is grown on claimed metallic carrier or substrate.Modal molecular screen membrane synthetic method has two kinds: one is in-situ synthesis, only metallic carrier need be put into reaction soln, through hydro-thermal, solvent thermal or ion thermal synthesis.Although this Measures compare is simple, there is very large challenge in this method in the orientation, compactness etc. of controlling diaphragm.Another kind of conventional synthetic method is crystal seed secondary growth method, and being usually first deposited on carrier by molecular sieve nanosized seeds, is then the diauxic growth of crystal seed.The method is separately carried out at nucleation and crystal growth, thus more effectively can control the thickness of crystallographic dimension, orientation and film.The formation of molecular screen membrane comprises coring and increment two committed steps of crystal grain, and the crucial part that crystal seed secondary growth method successfully can prepare alignment films is just by the nucleation and growth process of crystal grain separately.And in position in ion thermal synthesis process, how Reasonable Regulation And Control nucleus nucleation rate on the metallic substrate and coverage, thus further the orientation in regulatory molecule sieve membrane and duct thereof for simply, there is very large challenge for original position molecular screen membrane synthesis fast.When crystal seed secondary growth method prepares orientation molecular screen membrane, investigators find: when crystal seed is when the coverage (or grain density) of substrate surface is very high, the limited space of substrate surface inhibits the interior growth (in-plane growth) of crystal seed, thus impels crystal seed to obtain most long axis normal in the molecular screen membrane of substrate surface along its most major axis outgrowth (out-of-plane growth); Along with crystal seed coverage reduces, outgrowth and the interior growth of crystal seed coexist, and cause the generation of the mixed and disorderly molecular screen membrane of No yield point; When the coverage of crystal seed is extremely low, according to maximum energy criterion, enough spaces make crystal seed trend towards lying low in substrate surface growth along its most major axis, thus obtain the molecular screen membrane being laid in substrate surface.
The present invention makes full use of ionic liquid steam and to force down and self not only as solvent but also can be used as the unique advantage of template, by containing the outer aluminium of aluminium substrate and H in synthesis liquid
+the Al that reaction generates
3+as aluminium source.The Al that this mode produces
3+concentration be considerably less with quantity compared with additional aluminium source, the nucleus quantity generated and surface coverage are also low-down, thus can be all laid in the densification of substrate containing aluminium substrate Surface Creation film and duct, orientation is conducive to the aluminophosphate molecular sieve membrane of anticorrosion application.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of aluminophosphate molecular sieve membrane, the molecular screen membrane that the method synthesizes has good antiseptic property, and synthesis has high duplication.
The invention provides a kind of synthetic method of aluminophosphate molecular sieve membrane, the method key step is as follows: stirred under 80 ~ 100 DEG C of conditions by precursor solution and prepare synthesis liquid in 1 ~ 10 hour; Metal base is vertically put into synthesis liquid, synthesis liquid is synthesized 0.5 ~ 48 hour at 130 DEG C ~ 220 DEG C temperature; Take out and be cooled to room temperature after synthesis, being washed with distilled water to neutrality, drying, obtain aluminophosphate molecular sieve membrane.Wherein, the mol ratio of described precursor solution composition is a IL:b PO
4 3-: c F
-, a=25 ~ 40, b=2 ~ 10, c=0.5 ~ 10; The metal that described metal base is pure Al sheet, aluminiferous metals, surface are coated with aluminium, surface are coated with the one in the alloy slice of aluminium.
The synthetic method of aluminophosphate molecular sieve membrane provided by the invention, described PO
4 3-for phosphorus source, phosphorus source is the one in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate.Described F-is fluorine source, and fluorine source is hydrofluoric acid or Neutral ammonium fluoride.Described IL is halogenated imidazole base ionic liquid.
The aluminophosphate molecular sieve membrane of the present invention's synthesis can be laid in substrate surface, make film and duct all be parallel to substrate, prevent corrosive fluid from entering corrosion substrate from duct, show outstanding antiseptic property, and using method provided by the invention to synthesize, the repeatability of synthesis is quite high.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of aluminophosphate molecular sieve membrane;
Fig. 2 is the X-ray diffractogram of embodiment 1 synthesizing molecular sieve film;
Fig. 3 is the scanning electron microscope diagram on embodiment 1 synthesizing molecular sieve film surface;
Fig. 4 is the scanning electron microscope diagram on embodiment 2-in-1 one-tenth molecular screen membrane surface;
Fig. 5 is the X-ray diffractogram of embodiment 4 synthesizing molecular sieve film;
Fig. 6 is the scanning electron microscope diagram of embodiment 4 synthesizing molecular sieve film;
Fig. 7 is the DC polarization curve of the 2-in-1 one-tenth molecular screen membrane of embodiment in 0.1MNaCl solution;
Fig. 8 is comparative example 1 synthesizing molecular sieve film scanning electron microscope diagram.
Embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
The preparation of embodiment 1 aluminophosphate molecular sieve membrane
Synthesizing molecular sieve film substrate used is fine aluminium sheet, and purity is 99.99%, and long is 37mm, and wide is 18mm.Substrate uses ultrasonic washing in front acetone, then dries up for subsequent use with high-pressure air.
The synthesis liquid of synthesizing molecular sieve film is prepared as follows:
By 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.
Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane obtained is AEL structure (as shown in Figure 2) through X-ray diffraction levies in kind.Can see that from electron scanning micrograph the compactness of membrane is very high, present petal-shaped, and film itself and crystal duct orientation thereof are all laid in substrate surface (shown in Fig. 3).
The preparation of embodiment 2 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, just change the Heating temperature of synthesis liquid: by 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 150 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular sieve obtained is AEL structure through X-ray diffraction levies in kind, but the compactness of film is poor.
The preparation of embodiment 3 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, just change the Heating temperature of synthesis liquid: by 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 220 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular sieve obtained is AEL structure through X-ray diffraction levies in kind, but the compactness of film is poor.
The preparation of embodiment 4 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, the composition content just changing synthesis liquid is as follows: by 0.51 gram of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.It is AEL structure that the molecular sieve XRD that Al sheet grows confirms, electron scanning micrograph finds, the compactness of film is higher, but its orientation is except containing being laid in except the crystal of substrate surface, there is the molecular sieve that some orientations are mixed and disorderly.
The preparation of embodiment 5 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, the composition content just changing synthesis liquid was as follows: by 1.72 grams of phosphoric acid (85%) with join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.It is AEL structure that the molecular sieve XRD that Al sheet grows confirms, electron scanning micrograph finds, the compactness of film is higher, but its orientation is poor, there is the molecular sieve that a large amount of orientation is mixed and disorderly.
The preparation of embodiment 6 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, the synthesising reacting time just changing synthesis liquid is as follows: by 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.The aluminum alloy sheet processed vertically is positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 1 hour at such a temperature; Aluminum alloy sheet after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.It is AEL structure that the molecular sieve XRD that Al sheet grows confirms, electron scanning micrograph finds, the compactness of film is poor.
The preparation of embodiment 7 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, the synthesising reacting time just changing synthesis liquid is as follows: by 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.The aluminum alloy sheet processed vertically is positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 20 hours at such a temperature; Aluminum alloy sheet after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.It is AEL structure that the molecular sieve XRD that Al sheet grows confirms, electron scanning micrograph finds, the compactness of film is higher, and the orientation of film is film itself and crystal duct is substantially laid in substrate surface along c-axle, but obviously has the dissolution phenomena of molecular sieve to occur.
The preparation of embodiment 8 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, be adopted substrate be flaky aluminum alloy A A2204-T3, long is 37mm, and wide is 18mm.Basement membrane polishes flat with spun yarn paper before using, and ultrasonic washing in acetone, then high-pressure air dries up for subsequent use.By 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.The aluminum alloy sheet processed vertically is positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 4 hours at such a temperature; Aluminum alloy sheet after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.Fig. 4 is electron scanning micrograph, can see that the compactness of membrane is very high, and film itself and crystal duct orientation thereof are all laid in substrate surface.
The preparation of embodiment 9 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, be adopted substrate be that on Porous Stainless Steel, vacuum is coated with the thick fine aluminium of one deck 2 μm, basal diameter is 19.5mm, and thick is 1mm.The supersound washing in acetone of the stainless steel-based end, then dries up with high-pressure air.Aluminium paste vacuum and steam is plated to by vacuum plating unit at stainless steel-based the end.By 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Stainless steel substrates surface being coated with aluminium is vertically positioned in tetrafluoroethylene synthesis reactor, pours among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C by synthesis liquid, and keeps heating 4 hours at such a temperature; Stainless steel substrates after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The pattern of the molecular screen membrane of synthesis gained is similar to fine aluminium sheet.This example illustrates and adopts the method can grow aluminophosphate molecular sieve membrane easily in other metal base.
The preparation of embodiment 10 aluminophosphate molecular sieve membrane
By the operation that embodiment 1 is identical, just ionic liquid replaces with 1-butyl-3-methyl-imidazoles bromine.By 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-butyl-3-methyl-imidazoles bromide anion liquid, 90 DEG C of heated and stirred 1 hour.Fine aluminium sheet is vertically positioned in tetrafluoroethylene synthesis reactor, synthesis liquid is poured among synthesis reactor, is wrapped with heating jacket by outside synthesis reactor, electrically heated to 190 DEG C, and keep heating 4 hours at such a temperature; Aluminium flake after synthesis is through deionized water wash, and high-pressure air dries up, and then 60 DEG C of oven for drying are spent the night.The molecular screen membrane obtained is AFI type molecular screen membrane (as shown in Figure 5) through X-ray diffraction levies in kind.Can see that from electron scanning micrograph the compactness of membrane is very high, present thin petal-shaped, and film itself and crystal duct orientation thereof are all laid in substrate surface (shown in Fig. 6).
The exposed aluminium alloy of embodiment 11 and be coated with aluminophosphate molecular sieve membrane aluminum alloy substrate corrosion test
Corrosive fluid is the 0.1M NaCl aqueous solution.Poured into by corrosive fluid in corrosion pond, working electrode is molecular sieve diaphragm prepared by exposed aluminium alloy or embodiment 1, and be Pt sheet to electrode, reference electrode is (Ag.AgCl)/KCl (3.5M).Before test corrosion, molecular sieve stablizes 30min in corrosive fluid, then carries out the scanning of DC polarization curve, sweep limit-0.5V ~ 0.5V, sweep velocity 10mV/min.Result as shown in Figure 7.Display molecular screen membrane has good antiseptic property.
The interpolation of comparative example 1 aluminum isopropylate
By the operation that embodiment 1 is identical, just in stock liquid, with the addition of organoaluminum source---aluminum isopropylate.Synthesis liquid is formulated as follows: by 1.72 grams of phosphoric acid (85%) and 0.2 gram of HF(40%) join in 30.57 grams of 1-ethyl-3-methyl-imidazoles bromide anion liquid, then add 1.03 grams of aluminum isopropylates, 90 DEG C of heated and stirred 5 hours.The molecular screen membrane obtained as shown in Figure 8.Can see that from electron scanning micrograph the compactness of membrane is fine, but orientation is very poor, molecular sieve crystal is without any orientation.It can thus be appreciated that body is middle Al mutually
3+existence accelerate the generation of nucleus, improve the coverage of nucleus at substrate surface, thus cause the poor orientation of the molecular screen membrane generated.
Comparative example 2
Document (R.Cai, M.W.Sun, Z.W.Chen, R.Munoz, C.O ' neill, D.E.Beving, Y.S.Yan, Angew.Chem.Int.Ed.2008,47,525) reports SAPO-11 molecular screen membrane prepared by ion thermal synthesis method.Reduced the speed of growth of crystal by the interpolation of Si, make the final SAPO-11 obtained have the c-axle orientation of height, namely in film crystal duct perpendicular to substrate surface.DC polarization curve in 0.1MNaCl corrosive fluid demonstrates, no matter from the OCV angle of film, or from corrosion electric current density angle, all not as crystal duct prepared in the present invention is parallel to the aluminophosphate molecular sieve membrane of substrate surface.
Claims (4)
1. a synthetic method for aluminophosphate molecular sieve membrane, is characterized in that: the method key step is as follows: stirred under 80 ~ 100 DEG C of conditions by precursor solution and prepare synthesis liquid in 1 ~ 10 hour; Metal base is vertically put into synthesis liquid, synthesis liquid is synthesized 0.5 ~ 48 hour at 130 DEG C ~ 220 DEG C temperature; Take out and be cooled to room temperature after synthesis, being washed with distilled water to neutrality, drying, obtain aluminophosphate molecular sieve membrane;
Wherein, the mol ratio of described precursor solution composition is a IL:b PO
4 3-: c F
-, a=25 ~ 40, b=2 ~ 10, c=0.5 ~ 10;
The metal that described metal base is pure Al sheet, aluminiferous metals, surface are coated with aluminium, surface are coated with the one in the alloy slice of aluminium.
2. according to the synthetic method of aluminophosphate molecular sieve membrane described in claim 1, it is characterized in that: described PO
4 3-for phosphorus source, phosphorus source is the one in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate.
3. according to the synthetic method of aluminophosphate molecular sieve membrane described in claim 1, it is characterized in that: described F-is fluorine source, fluorine source is hydrofluoric acid or Neutral ammonium fluoride.
4. according to the synthetic method of aluminophosphate molecular sieve membrane described in claim 1, it is characterized in that: described IL is halogenated imidazole base ionic liquid.
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| CN105239089A (en) * | 2015-10-20 | 2016-01-13 | 华东师范大学 | Ag-ZSM-5 molecular sieve modified electrode and preparation method thereof |
| CN114835138A (en) * | 2022-03-17 | 2022-08-02 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105239089A (en) * | 2015-10-20 | 2016-01-13 | 华东师范大学 | Ag-ZSM-5 molecular sieve modified electrode and preparation method thereof |
| CN114835138A (en) * | 2022-03-17 | 2022-08-02 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
| CN114835138B (en) * | 2022-03-17 | 2024-04-19 | 中山大学 | Aluminum phosphate molecular sieve membrane and preparation method and application thereof |
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