CN112573532B - Low-silicon aluminum phosphate-based CHA molecular sieve with triclinic system, and preparation method and application thereof - Google Patents
Low-silicon aluminum phosphate-based CHA molecular sieve with triclinic system, and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 66
- 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 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000017 hydrogel Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 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 39
- 229910052676 chabazite Inorganic materials 0.000 description 36
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbon olefin Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
-
- 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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- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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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
- C01P2002/30—Three-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention relates to the technical field of low-silicon CHA molecular sieves, in particular to a low-silicon aluminum phosphate-based CHA molecular sieve with a triclinic system, and a preparation method and application thereof: 1) Preparation of silicon aluminum phosphate xerogel: sequentially adding an aluminum source, phosphoric acid, hydrofluoric acid and a silicon source into deionized water, stirring uniformly in an ice bath, and then dropwise adding Propylene Oxide (PO) to obtain hydrogel; drying the obtained hydrogel to obtain fluorine-containing silicon aluminum phosphate xerogel; 2) Mixing the fluorine-containing silicon aluminum phosphate xerogel obtained in the step 1) with deionized water, adding an organic amine template agent, stirring, and drying to obtain a precursor synthesized by a molecular sieve; 3) And (3) heating and crystallizing the precursor in a closed environment, and washing, drying and roasting after crystallization to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system. The CHA structured silicon aluminum phosphate molecular sieve prepared by the invention belongs to a triclinic system, has the characteristics of low silicon content and low acidity, and has important application value in the reaction of preparing olefin (MTO) from long-service-life methanol.
Description
Technical Field
The invention relates to the technical field of low-silicon CHA molecular sieves, in particular to a low-silicon aluminum phosphate-based CHA molecular sieve with a triclinic system, a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The molecular sieve material has the characteristics of regular pore canal structure, adjustable active site, good hydrothermal stability, high surface area, large pore volume and the like, and has important application in the fields of catalysis, adsorption, separation and the like.
The CHA (International molecular sieves Association designation code) structured silicoaluminophosphate molecular sieves (http:// www.iza-structure.org/databases /) have molecular sieves with unique three-dimensional cross-channel and eight-membered ring channel Chabazite (CHA) cage structures and have excellent catalytic performance in the methanol to light olefin (MTO) process. However, the inventors found that the CHA structure aluminophosphate molecular sieve (SAPO-34) framework prepared by conventional hydrothermal synthesis at present has a relatively high silicon content (Si/Al > 0.15), and that too high a silicon content can lead to rapid deactivation in MTO reaction, requiring frequent regeneration.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention discloses a method for preparing a silicoaluminophosphate molecular sieve with a low silicon CHA (Si/Al < 0.02) structure by adding a proper amount of HF and a xerogel conversion method, wherein the SAPO-34 molecular sieve with a low silicon-aluminum ratio has more weak acid centers, can slow down the conversion of the methylbenzene in the carbon deposit to the polycyclic aromatic hydrocarbon, enhances the carbon deposit resistance of the molecular sieve, and improves the selectivity of the low carbon olefin.
The invention takes fluorine-containing super-concentrated silicon aluminum phosphate gel as a precursor, prepares the low silicon aluminum phosphate molecular sieve with the CHA structure by a dry condensation conversion method, and the prepared molecular sieve belongs to a triclinic system and has the characteristics of low silicon content and low acidity.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a low-silicon aluminum phosphate based CHA molecular sieve having a triclinic system, the method comprising the steps of:
1) Preparing silicon aluminum phosphate xerogel: sequentially adding an aluminum source, phosphoric acid, hydrofluoric acid and a silicon source into deionized water, stirring uniformly in an ice bath, dropwise adding Propylene Oxide (PO), and ultrasonically removing bubbles to obtain hydrogel; drying the obtained hydrogel to obtain fluorine-containing silicon aluminum phosphate xerogel;
2) Mixing the fluorine-containing silicon aluminum phosphate xerogel obtained in the step 1) with a certain amount of deionized water, adding an organic amine template agent, stirring for a certain time, and drying to obtain a precursor synthesized by a molecular sieve;
3) And (3) heating and crystallizing the precursor prepared in the step (2) in a reaction kettle, and washing, drying and roasting after crystallization to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
In a second aspect of the present invention, there is provided a low-silicon aluminum phosphate based CHA molecular sieve having a triclinic system prepared by the method of the first aspect.
In a third aspect of the present invention there is provided the use of a low silicon aluminum phosphate based CHA molecular sieve having a triclinic system as described in the second aspect in the preparation of olefins from Methanol (MTO).
The specific embodiment of the invention has the following beneficial effects:
the prepared CHA molecular sieve belongs to a triclinic system, and has the characteristics of low silicon (Si/Al is less than 0.02), high crystallinity, small crystal grains and the like, so that the catalytic activity of the CHA molecular sieve is effectively improved;
simple operation steps, low cost, environmental protection and easy industrial application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an XRD spectrum of a low silicon CHA structure silicoaluminophosphate molecular sieve prepared in example 1 of the present invention;
FIG. 2 shows the nitrogen physisorption and desorption isotherms and BJH mesoporous distribution of the low silicon CHA structured silicoaluminophosphate molecular sieve prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of a low silicon CHA structured silicoaluminophosphate molecular sieve prepared according to example 1 of the present invention.
FIG. 4 is a graph showing the catalytic performance of a low silicon CHA structured silicoaluminophosphate molecular sieve prepared in example 1 of the present invention and a high silicon CHA molecular sieve prepared in comparative example 1 in a methanol-to-olefins (MTO) reaction.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In a first aspect of the present invention, there is provided a method for preparing a low-silicon aluminum phosphate based CHA molecular sieve having a triclinic system, the silicoaluminophosphate gel being a precursor, the low-silicon silicoaluminophosphate molecular sieve having the CHA structure being prepared by a dry coacervation conversion method, comprising the steps of:
1) Preparation of silicon aluminum phosphate xerogel: sequentially adding an aluminum source, phosphoric acid, hydrofluoric acid and a silicon source into deionized water, stirring uniformly in an ice bath, dropwise adding Propylene Oxide (PO), and ultrasonically removing bubbles to obtain hydrogel; drying the obtained hydrogel to obtain fluorine-containing silicon aluminum phosphate xerogel;
2) Mixing the fluorine-containing silicon aluminum phosphate xerogel obtained in the step 1) with a certain amount of deionized water, adding an organic amine template agent, stirring for a certain time, and drying to obtain a precursor synthesized by a molecular sieve;
3) And (3) heating and crystallizing the precursor prepared in the step (2) in a reaction kettle, and washing, drying and roasting after crystallization to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
In a specific embodiment, al in the mesohydrogel of step 1) 2 O 3 ：P 2 O 5 ：SiO 2 ：HF：PO：H 2 The molar ratio of O is 1:0.2 to 5.0:0.001 to 2.0:0.02 to 2.0:2.0 to 10.0:5.0 to 100;
al in the fluorine-containing silicoaluminophosphate xerogel of the step 1) 2 O 3 ：P 2 O 5 ：SiO 2 ：HF：SiO 2 ：H 2 The molar ratio of O is 1:0.2 to 5.0:0.001 to 2.0:0.02 to 2.0:1.0 to 5.0;
the drying temperature in the step 1) is 60-120 ℃ and the drying time is 2-12 h;
in a specific embodiment, the stirring time in the step 2) is 1-24h, stirring is carried out at room temperature, and the drying temperature is 40-120 ℃;
in a specific embodiment, the crystallization temperature in step 3) is 120-200 ℃ and the crystallization time is 0.5-48 h;
the drying temperature is as follows: the drying time is 2 to 12 hours at the room temperature to 120 ℃; roasting for 2-12 h at 400-600 ℃ under the air condition;
preferably, the aluminium source is selected from aluminium chloride, pseudo-boehmite and aluminium isopropoxide.
Preferably, the silicon source is selected from the group consisting of white carbon black, water glass, silica sol and tetraethyl silicate.
Preferably, the phosphoric acid concentration is 70 to 99wt%, more preferably 85wt%.
Preferably, the hydrofluoric acid concentration is 30 to 70wt%, and more preferably 40wt%.
Preferably, the organic amine is one or more of N-methylimidazole, morpholine, N-dimethyl-diisopropylethylamine, diethylamine, triethylamine and tetraethylammonium chloride. .
In a second aspect of the present invention, there is provided a low-silicon aluminum phosphate based CHA molecular sieve having a triclinic system prepared by the method of the first aspect.
In a third aspect of the present invention there is provided the use of a low silicon aluminum phosphate based CHA molecular sieve having a triclinic system as described in the second aspect in the preparation of olefins from Methanol (MTO).
The invention is further illustrated and described below with reference to examples.
Example 1
Adding 4.08g of crystalline aluminum chloride, 1.25g of phosphoric acid with the mass concentration of 85%, 0.16g of hydrofluoric acid with the mass concentration of 40% and 0.02g of white carbon black into 18.0g of deionized water in sequence, stirring uniformly in an ice bath, dropwise adding 6.0mL of Propylene Oxide (PO), and removing bubbles by ultrasound to prepare hydrogel; drying the obtained hydrogel for 4 hours at 100 ℃ to obtain silicon aluminum phosphate xerogel; uniformly mixing the xerogel with 18.0g of deionized water and 1.0g of diethylamine, stirring at room temperature for 4 hours, and drying at 100 ℃ to obtain a molecular sieve precursor; and (3) placing the precursor in a reaction kettle, crystallizing at 200 ℃ for 24 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 120 ℃ oven for drying for 6 hours, and then roasting for 10 hours in an air atmosphere at 500 ℃ to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 2
2.56g of crystalline aluminum chloride, 1.05g of phosphoric acid with the mass concentration of 85%, 0.16g of hydrofluoric acid with the mass concentration of 40% and 0.04g of white carbon black are sequentially added into 18.0g of deionized water, 5.0mL of Propylene Oxide (PO) is added dropwise after stirring uniformly in an ice bath, and bubbles are removed by ultrasound, so that hydrogel is prepared. Drying the obtained hydrogel for 4 hours at 100 ℃ to obtain silicon aluminum phosphate xerogel; uniformly mixing the xerogel with 18.0g of deionized water and 1.0g of triethylamine, stirring for 4 hours at room temperature, and drying at 100 ℃ to obtain a molecular sieve precursor. And (3) placing the precursor in a reaction kettle, crystallizing at 180 ℃ for 24 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 120 ℃ oven for drying for 6 hours, and then roasting for 10 hours in an air atmosphere at 500 ℃ to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 3
Adding 4.28g of crystalline aluminum chloride, 1.25g of phosphoric acid with the mass concentration of 85%, 0.16g of hydrofluoric acid with the mass concentration of 40% and 0.06g of tetraethoxysilane into 18.0g of deionized water in sequence, stirring uniformly in an ice bath, dropwise adding 6.0mL of Propylene Oxide (PO), and removing bubbles by ultrasound to prepare hydrogel; and drying the obtained hydrogel for 4 hours at 100 ℃ to obtain the silicon aluminum phosphate xerogel. Uniformly mixing the xerogel with 18.0g of deionized water and 1.0g of morpholine, stirring at room temperature for 6 hours, and drying at 100 ℃ to obtain a molecular sieve precursor; and (3) placing the precursor into a reaction kettle, crystallizing at 190 ℃ for 10 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid into a 120 ℃ oven for drying for 6 hours, and then roasting at 520 ℃ in air atmosphere for 10 hours to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 4
4.08g of crystalline aluminum chloride, 1.25g of phosphoric acid with the mass concentration of 85%, 0.16g of hydrofluoric acid with the mass concentration of 40% and 0.06g of tetraethoxysilane are sequentially added into 18.0g of deionized water, 8.0mL of Propylene Oxide (PO) is added dropwise after stirring uniformly in an ice bath, and bubbles are removed by ultrasound, so that hydrogel is prepared. And drying the obtained hydrogel for 4 hours at 100 ℃ to obtain the silicon aluminum phosphate xerogel. The xerogel is uniformly mixed with 18.0g of deionized water and 1.0g of 1-methylimidazole, stirred for 4 hours at room temperature, and then dried at 100 ℃ to obtain a molecular sieve precursor. And (3) placing the precursor in a reaction kettle, crystallizing at 200 ℃ for 10 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 100 ℃ oven for drying for 6 hours, and then roasting for 8 hours in an air atmosphere at 500 ℃ to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 5
3.06g of crystalline aluminum chloride, 1.15g of phosphoric acid with the mass concentration of 85%, 0.24g of hydrofluoric acid with the mass concentration of 40% and 0.05g of tetraethoxysilane are sequentially added into 18.0g of deionized water, 6.0mL of Propylene Oxide (PO) is added dropwise after stirring uniformly in an ice bath, and bubbles are removed by ultrasound, so that hydrogel is prepared. And drying the obtained hydrogel for 4 hours at 100 ℃ to obtain the silicon aluminum phosphate xerogel. Uniformly mixing the xerogel with 18.0g of deionized water and 1.5g of morpholine, stirring at room temperature for 4 hours, and drying at 100 ℃ to obtain a molecular sieve precursor. And (3) placing the precursor in a reaction kettle, crystallizing at 180 ℃ for 10 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 120 ℃ oven for drying for 12 hours, and then roasting in an air atmosphere at 550 ℃ for 10 hours to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 6
3.68g of crystalline aluminum chloride, 0.98g of phosphoric acid with the mass concentration of 85%, 0.19g of hydrofluoric acid with the mass concentration of 40% and 0.10g of white carbon black are sequentially added into 18.0g of deionized water, 7.0mL of Propylene Oxide (PO) is added dropwise after stirring uniformly in an ice bath, and bubbles are removed by ultrasound, so that the hydrogel is prepared. And drying the obtained hydrogel for 6 hours at 100 ℃ to obtain the silicon aluminum phosphate xerogel. Uniformly mixing the xerogel with 18.0g of deionized water and 1.8g of diethylamine, stirring for 4 hours at room temperature, and then drying at 100 ℃ to obtain a molecular sieve precursor. And (3) placing the precursor in a reaction kettle, crystallizing at 180 ℃ for 15 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 120 ℃ oven for drying for 6 hours, and then roasting in 500 ℃ air atmosphere for 10 hours to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Example 7
2.98g of crystalline aluminum chloride, 1.20g of phosphoric acid with the mass concentration of 85%, 0.30g of hydrofluoric acid with the mass concentration of 40% and 0.08g of tetraethoxysilane are sequentially added into 20.0g of deionized water, 7.0mL of Propylene Oxide (PO) is added dropwise after stirring uniformly in an ice bath, and bubbles are removed by ultrasound, so that hydrogel is prepared. And drying the obtained hydrogel for 4 hours at 100 ℃ to obtain the silicon aluminum phosphate xerogel. Uniformly mixing the xerogel with 20.0g of deionized water and 1.0g of diethylamine, stirring for 4 hours at room temperature, and then drying at 100 ℃ to obtain a molecular sieve precursor. And (3) placing the precursor in a reaction kettle, crystallizing at 190 ℃ for 8 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid in a 120 ℃ oven for drying for 6 hours, and then roasting in an air atmosphere at 520 ℃ for 12 hours to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system.
Comparative example 1
Preparing a high-silicon CHA molecular sieve by a traditional hydrothermal method:
2.80g of pseudo-boehmite is dissolved in 20.0g of deionized water and stirred for 2 hours, then 4.50g of phosphoric acid and 0.72g of tetraethoxysilane are respectively added under the stirring state, the stirring is continued for 2 hours, then 5.10g of morpholine is added, and the stirring is carried out for 24 hours at room temperature to obtain the molecular sieve precursor. And (3) placing the precursor into a reaction kettle, crystallizing at 200 ℃ for 24 hours, taking out, cooling the reaction kettle, washing the product with deionized water for 3 times, placing the final white solid into a 120 ℃ oven for drying for 6 hours, and roasting in an air atmosphere at 520 ℃ for 12 hours to obtain the high-silicon CHA molecular sieve.
Experimental example
The low-silicon CHA molecular sieve prepared in example 1 and the high-silicon CHA molecular sieve prepared in comparative example 1 are used as catalysts to catalyze the reaction of Methanol To Olefins (MTO), and the specific steps are as follows: the baked low-silicon CHA molecular sieve is used as a catalyst, methanol is used as a raw material, and the catalyst is placed in a 10mL fixed bed reactor at 400-480 ℃ and normal pressure for 1-5h -1 Under these reaction conditions, the reaction results are shown in FIG. 4.
As can be seen from fig. 4, the low-silicon CHA molecular sieve prepared in example 1 of the present invention shows a longer lifetime and higher ethylene and propylene yields in the MTO reaction than the high-silicon CHA molecular sieve prepared by conventional hydrothermal synthesis, which illustrates the advantages of the low-silicon CHA molecular sieve.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for preparing a low silicon aluminum phosphate based CHA molecular sieve having a triclinic system, comprising the steps of:
1) Preparation of silicon aluminum phosphate xerogel: sequentially adding an aluminum source and phosphorus into deionized waterAcid, hydrofluoric acid and a silicon source, stirring uniformly in an ice bath, dropwise adding Propylene Oxide (PO), and ultrasonically removing bubbles to prepare hydrogel; drying the obtained hydrogel to obtain fluorine-containing silicon aluminum phosphate xerogel; in the hydrogel of step 1), al 2 O 3 ：P 2 O 5 ：SiO 2 ：HF：PO：H 2 The molar ratio of O is 1:0.2 to 5.0:0.001 to 2.0:0.02 to 2.0:2.0 to 10.0:5.0 to 100;
2) Mixing the fluorine-containing silicon aluminum phosphate xerogel obtained in the step 1) with deionized water, adding an organic amine template agent, stirring, and drying to obtain a precursor synthesized by a molecular sieve;
3) Heating and crystallizing the precursor prepared in the step 2) in a reaction kettle, and washing, drying and roasting after crystallization to obtain the low-silicon aluminum phosphate group CHA molecular sieve with a triclinic system;
the crystallization temperature in the step 3) is 120-200 ℃ and the crystallization time is 0.5-48 h;
wherein Si/Al in the low-silicon aluminum phosphate-based CHA molecular sieve is less than 0.02;
the concentration of the phosphoric acid is 70-99 wt% and the concentration of the hydrofluoric acid is 30-70 wt%.
2. The method of claim 1, wherein the fluorine-containing silicoaluminophosphate xerogel of step 1) contains Al 2 O 3 ：P 2 O 5 ：SiO 2 ：HF：H 2 The molar ratio of O is 1:0.2 to 5.0:0.001 to 2.0:0.02 to 2.0:1.0 to 5.0.
3. The process according to claim 1, wherein the drying temperature in step 1) is 60 to 120℃and the drying time is 2 to 12 hours.
4. The process according to claim 1, wherein the stirring time in step 2) is 1 to 24 hours, stirring is performed at room temperature, and the drying temperature is 40 to 120 ℃.
5. The method of claim 1, wherein the drying temperature in step 3) is: the drying time is 2 to 12 hours at the room temperature to 120 ℃; roasting is carried out for 2-12 h at 400-600 ℃ under the air condition.
6. The method of claim 1, wherein,
the aluminum source is selected from aluminum chloride, pseudo-boehmite, and aluminum isopropoxide;
alternatively, the silicon source is selected from the group consisting of white carbon black, water glass, silica sol, and tetraethyl silicate;
or the organic amine is one or more of N-methylimidazole, morpholine, N-dimethyl-diisopropylethylamine, diethylamine, triethylamine and tetraethylammonium chloride.
7. The method of claim 1, wherein,
the phosphoric acid concentration is 85wt%;
the hydrofluoric acid concentration was 40wt%.
8. A low silicon aluminum phosphate CHA molecular sieve having a triclinic system prepared by the method of any one of claims 1-7.
9. Use of the low silicon aluminum phosphate CHA molecular sieve with triclinic system of claim 8 in Methanol To Olefins (MTO).
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