CN111099607A - Silicon-doped aluminophosphates and methods of synthesis thereof - Google Patents
Silicon-doped aluminophosphates and methods of synthesis thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 12
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 239000012452 mother liquor Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- AMNPXXIGUOKIPP-UHFFFAOYSA-N [4-(carbamothioylamino)phenyl]thiourea Chemical compound NC(=S)NC1=CC=C(NC(N)=S)C=C1 AMNPXXIGUOKIPP-UHFFFAOYSA-N 0.000 claims description 17
- 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 17
- 239000000908 ammonium hydroxide Substances 0.000 claims description 17
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- RHQQHZQUAMFINJ-GKWSUJDHSA-N 1-[(3s,5s,8s,9s,10s,11s,13s,14s,17s)-3,11-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-hydroxyethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 RHQQHZQUAMFINJ-GKWSUJDHSA-N 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052908 analcime Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 organic molecules Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- 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
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- 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
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Life Sciences & Earth Sciences (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a novel silicon-doped aluminophosphate and a synthesis method thereof, wherein the aluminophosphate has the following chemical composition in molar ratio on the premise of not calculating moisture: (Si)xAlyPz)O2Wherein 0.001<X is less than or equal to 0.1, y is more than or equal to 0.3, z is more than or equal to 0.3, and X + y + z is 1, the molecular sieve has a unique X-ray diffraction pattern, can be used as an adsorbent, and can also be used as a catalyst or a carrier of the catalyst.
Description
Technical Field
The invention relates to silicon-doped aluminophosphate and a preparation method thereof.
Background
Molecular sieves are a porous crystalline material, and the currently discovered molecular sieves with known structures are more than 230, and molecular sieves with new structures are still emerging. Most molecular sieves have a large internal ratioSurface area and open interior spaces that can serve as sites for reactions to occur and also to accommodate guest molecules such as metals, metal oxides, organic molecules, water molecules, and the like. The molecular sieve has uniform and regular pore channels, and the size of the pore channels is in the same order of magnitude as that of molecules, so that the entrance and exit of the molecules can be selected, and the shape-selective effect is obtained. Because of the above characteristics, molecular sieves are widely used as catalysts, carriers of catalysts, adsorbents, detergents and the like, and are widely applied in the fields of petrochemical industry, environmental protection, adsorption and separation. The framework of molecular sieves is generally composed of coordinating Tetrahedra (TO)4) Connected by common vertices (typically oxygen atoms), and in the case of zeolitic molecular sieves, the tetrahedra in the framework are predominantly SiO4Tetrahedron and AlO4 -The tetrahedra being replaced by other tetrahedra to form a plurality of molecular sieves of various framework structures or of various framework compositions, e.g. AlO4 -The tetrahedron may be GaO4 -Or ZnO4 2-Tetrahedron substitution, thereby reacting with SiO4The tetrahedron together form the framework of the heteroatom molecular sieve, and Ge and Si have similar coordination property, and Ge can also form a tetrahedron coordination structure, and GeO is adopted4And SiO4The linkages of (a) can form a large number of novel germanium-containing molecular sieve structures.
If SiO4Tetrahedral PO4 +The tetrahedra are substituted to form another large class of molecular sieve family, i.e., aluminum phosphate molecular sieves whose framework is AlO4 -And PO4 +The oxygen atoms are linked, so that the whole molecular sieve skeleton is electrically neutral. Of course, like zeolitic molecular sieves, the aluminoxy tetrahedra or the phosphoxy tetrahedra of the aluminophosphate molecular sieve can also be replaced by other tetrahedra, the most common of which are the silicon-oxy tetrahedra and the zinc-oxy tetrahedra, which, due to the introduction of these tetrahedra, give the aluminophosphate type molecular sieve new characteristics. The artificial synthesis of aluminophosphate molecular sieves is studied later than zeolite molecular sieves. In 1971, Flanigen et al report the synthesis of aluminum phosphate Molecular sieves [ Molecular Sieve Zeolites-I, ACS, Washingtom D.C ], under hydrothermal synthesis conditions, mixing oxides of aluminum, silicon and phosphorus to obtain Si-P-Al Molecular sieves having the same crystal structure as analcime, chabazite, Phillips-harmome, L-type Molecular Sieve, A-type Molecular Sieve and B-type Molecular Sieve, wherein the phosphorus content is 5-25% (using P-type Molecular Sieve) and2O5meter), but no structure was found to be distinct from the zeolitic molecular sieve. 1982, U.S. Pat. No. 4310440, which uses organic amine or quaternary ammonium compound as template agent, hydrothermally synthesizes a series of aluminum phosphate molecular sieves, which include: AlPO4-5,AlPO4-8,AlPO4-9,AlPO4-11,AlPO4-12,AlPO4-14,AlPO4-16,AlPO4-17,AlPO4-18,AlPO4-20,AlPO4-21,AlPO4-22,AlPO4-23,AlPO4-25,AlPO4-26,AlPO4-28,AlPO431, the type of organic template is one of the key factors for determining the structure of the aluminophosphate molecular sieve, and so far, organic amine is the most widely used template in the synthesis of the aluminophosphate molecular sieve. Compared with a silicon-aluminum zeolite molecular sieve, the industrial application of the phosphorus-aluminum molecular sieve is rare, and only the SAPO-34 molecular sieve and the SAPO-11 molecular sieve are industrially applied at present. Recently, it is believed that SAPO molecular sieves can be used as part of coupled catalysts in the reaction of preparing olefin from synthesis gas, and the application of SAPO molecular sieves is disclosed in [ Science,2016,351,1065-1068 ] and the potential application of the aluminum phosphate molecular sieves includes their use as adsorbents or good carriers of catalysts.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel silicon-doped aluminophosphate which is not related in the prior art and a synthesis method thereof.
In order to solve the technical problem, the invention provides silicon-doped aluminophosphate, and the molecular sieve has the following chemical composition in molar ratio on the premise of not calculating moisture: (Si)xAlyPz)O2Wherein 0.001<x is 0.1 or less, y is 0.3 or more, z is 0.3 or more, and x + y + z is 1, more preferably (Si)xAlyPz)O2Wherein 0.001<x is less than or equal to 0.1, y is more than or equal to 0.4, z is more than or equal to 0.4, and x + y + z is 1. The molecular sieve comprises an X-ray diffraction pattern as shown in the following table:
wherein the relative intensity is calculated based on the area of the diffraction peak.
The preparation of the silicon-doped aluminophosphate comprises the following steps:
a) silicon source, aluminum source, phosphorus source, organic matter R and water are mixed according to (0.01-0.10) SiO2:Al2O3:(2.0～3.6)P2O5:
(3.1～6.0)R:(50～500)H2Mixing the O in proportion to obtain a synthetic mother solution;
b) putting the synthetic mother liquor into a closed reaction container for crystallization;
obtaining a precursor of silicon-doped aluminophosphate; and roasting the precursor of the silicon-doped aluminophosphate to obtain the silicon-doped aluminophosphate.
In the above technical scheme, wherein R is N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide, the chemical structural formula can be represented as:
in the technical scheme, the synthetic mother liquor is placed in a closed reaction container for crystallization, the crystallization temperature is 150-200 ℃, and the crystallization time is 24-160 hours. In the technical scheme, the precursor of the silicon-doped aluminophosphate is roasted according to a conventional roasting method, for example, roasting treatment is carried out at 500-750 ℃ in an air atmosphere, so that the silicon-doped aluminophosphate can be obtained.
In the technical scheme, the silicon source, the aluminum source, the phosphorus source, the organic matter R and the water are (0.01-0.09) SiO2:Al2O3:(2.0～3.6)P2O5:(3.6～4.8)R:(100～300)H2And mixing the components in proportion of O uniformly.
The preparation method of the silicon-doped aluminophosphate comprises the steps that a silicon source is at least one of silica sol, white carbon black or tetraethyl orthosilicate, an aluminum source is at least one of pseudo-boehmite, aluminum isopropoxide, aluminum sol and alumina, and a phosphorus source is one or more of phosphoric acid, phosphorous acid or phosphorus pentoxide.
The invention also provides a composition comprising the silicon-doped aluminophosphate or the silicon-doped aluminophosphate synthesized according to the method, and a binder.
The invention also provides the application of the silicon-doped aluminophosphate synthesized by the method or the composition as an adsorbent or a catalyst.
The invention provides silicon-doped aluminophosphate, which is directionally obtained by simultaneously controlling the feed ratio of reaction raw materials under the combined action of a silicon source, an aluminum source, a phosphorus source and an organic matter R.
Drawings
FIG. 1 is an XRD pattern of the silicon doped aluminophosphate obtained in example 1.
The invention is further illustrated by the following examples, which do not limit the scope of the invention.
Detailed Description
[ example 1 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the above synthetic mother liquor in a sealed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate, wherein the XRD pattern is shown in figure 1, and the obtained silicon-doped aluminophosphate has a composition (excluding water content) (Si content)0.01Al0.5P0.49)O2。
[ example 2]
Weighing 16.5 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:3.6R:142H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.01Al0.5P0.49)O2。
[ example 3 ]
Weighing 24.8 g of 16.31% by mass of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R), adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:5.4R:213H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.01Al0.5P0.49)O2。
[ example 4 ]
27.5 g of 16.31% by weight of N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution are weighed, 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol are added while stirring, then 0.68ml of 85% phosphoric acid solution is slowly dropped, and the synthesis mother liquor with the following molar ratio composition can be obtained after uniform stirring:
0.05SiO2:1.0Al2O3:2.4P2O5:6.0R:237H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.009Al0.5P0.491)O2。
[ example 5 ]
Weighing 22 g of 16.31% by mass of an N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.558ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.09SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.CThe crystallization time is 84 hours, and the crystallized product is washed and dried to obtain silicon-doped aluminophosphate, and the composition of the obtained silicon-doped aluminophosphate (excluding water content) (Si)0.015Al0.5P0.485)O2。
[ example 6 ]
Weighing 22 g of 16.31% by mass of an N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide solution (hereinafter abbreviated as R), adding 0.43 g of aluminum isopropoxide and 0.434ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.07SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.013Al0.5P0.487)O2。
[ example 7 ]
Weighing 22 g of 16.31% by mass of an N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.186ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the above synthetic mother liquor in a sealed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate(excluding water content) (Si)0.009Al0.5P0.491)O2。
[ example 8 ]
Weighing 22 g of 16.31% by mass of an N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.124ml of 2% silica sol while stirring, slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.02SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.008Al0.5P0.492)O2。
[ example 9 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.062ml of 2% silica sol while stirring, slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.01SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.003Al0.5P0.487)O2。
[ example 10 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 120 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.01Al0.5P0.49)O2。
[ example 11 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 185 deg.C for 84 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.01Al0.5P0.49)O2。
[ example 12 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 195 deg.C for 72 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.011Al0.5P0.489)O2。
[ example 13 ]
Weighing 22 g of 16.31% by mass of an N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.558ml of 2% silica sol while stirring, then slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain a synthetic mother liquor with the following molar ratio:
0.09SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 195 deg.C for 72 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.013Al0.5P0.487)O2。
[ example 14 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.062ml of 2% silica sol while stirring, slowly dropwise adding 0.68ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.01SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 160 deg.C for 120 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.002Al0.5P0.498)O2。
[ example 14 ]
Weighing 22 g of 16.31 mass percent N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide (hereinafter abbreviated as R) solution, adding 0.43 g of aluminum isopropoxide and 0.31ml of 2% silica sol while stirring, then slowly dropwise adding 1.02ml of 85% phosphoric acid solution, and uniformly stirring to obtain the synthetic mother liquor with the following molar ratio:
0.05SiO2:1.0Al2O3:3.6P2O5:4.8R:190H2O
crystallizing the synthetic mother liquor in a closed reaction container at 175 deg.C for 120 hr, washing and drying the crystallized product to obtain silicon-doped aluminophosphate (Si-doped aluminophosphate) with composition (excluding water content) (Si)0.01Al0.5P0.49)O2。
Claims (11)
1. A silicon-doped aluminophosphate, the molecular sieve having a chemical composition, without calculating moisture, in the following molar ratios: (Si)xAlyPz)O2Wherein 0.001<X is less than or equal to 0.1, y is more than or equal to 0.3, z is more than or equal to 0.3, and X + y + z is 1, wherein the molecular sieve comprises an X-ray diffraction pattern shown in the following table:
2. the silicon-doped aluminophosphate according to claim 1, characterised in that it has a chemical composition, without calculation of moisture, in the following molar ratios: (Si)xAlyPz)O2Wherein 0.001<x is less than or equal to 0.1, y is more than or equal to 0.4, z is more than or equal to 0.4, and x + y + z is 1.
3. The preparation method of the silicon-doped aluminophosphate comprises the following steps:
a) silicon source, aluminum source, phosphorus source, organic matter R and water are mixed according to (0.01-0.10) SiO2:Al2O3:(2.0～3.6)P2O5:(3.1～6.0)R:(50～500)H2Mixing the O in proportion to obtain a synthetic mother solution;
b) crystallizing the synthetic mother liquor;
optionally calcining to obtain the silicon-doped phosphoaluminate.
4. The method according to claim 3, wherein the silicon source, the aluminum source, the phosphorus source, the organic substance R and the water are mixed in a ratio of (0.01 to 0.09) SiO2:Al2O3:(2.0～3.6)P2O5:(3.6～4.8)R:(100～300)H2And uniformly mixing the O in proportion to obtain the synthetic mother liquor.
5. The process of claim 3, wherein the organic compound R is N, N' - [1, 4-phenylenebis (methylene) ] bis (1, 4-diazacyclo [2,2,2] octane) ammonium hydroxide.
6. The method of claim 3, wherein the crystallization temperature is 150-200 ℃ and the crystallization time is 24-160 hours.
7. The method of claim 3, wherein the aluminum source comprises at least one of pseudoboehmite, aluminum isopropoxide, aluminum sol, aluminum hydroxide and aluminum oxide.
8. A method as claimed in claim 3 wherein the source of phosphorus is selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide.
9. The method of claim 3, wherein the silicon source comprises one of silica sol, silica white, and tetraethyl orthosilicate.
10. A composition comprising a silicon doped aluminophosphate according to any of claims 1 to 2 or synthesized according to any of claims 3 to 9, and a binder.
11. Use of a silicon doped aluminophosphate synthesized by the method of any one of claims 3 to 9 or the composition of claim 10 as an adsorbent or catalyst.
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