CN110342538A - A kind of synthetic method and its application of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve - Google Patents
A kind of synthetic method and its application of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve Download PDFInfo
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- CN110342538A CN110342538A CN201910525358.9A CN201910525358A CN110342538A CN 110342538 A CN110342538 A CN 110342538A CN 201910525358 A CN201910525358 A CN 201910525358A CN 110342538 A CN110342538 A CN 110342538A
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- molecular sieve
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- silicoaluminophosphate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 85
- 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 85
- 239000013078 crystal Substances 0.000 title claims abstract description 73
- 238000010189 synthetic method Methods 0.000 title claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 44
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 16
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 229940043279 diisopropylamine Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000002791 soaking Methods 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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 22
- 239000000499 gel Substances 0.000 description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- -1 Ethylene, propylene Chemical group 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZTRPYTHOEREHEN-UHFFFAOYSA-N piperazine pyridine Chemical compound N1CCNCC1.N1=CC=CC=C1.N1=CC=CC=C1 ZTRPYTHOEREHEN-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 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
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the synthetic methods and its application of a kind of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve.Raw material silicon source, phosphorus source, silicon source, organic amine and deionized water are added to the container mixing first, obtain homogeneous gel；It places it in crystallizing kettle, heating carries out pre- Crystallizing treatment, is down to room temperature after processing；Then crystal seed is added to be mixed, continues heat temperature raising and carries out crystallization；Products therefrom centrifuge separation, washing and drying, obtain product little crystal grain silicoaluminophosphate SAPO-34 molecular sieve after crystallization.Using the fine grain SAPO-34 molecular sieve of the method for the present invention preparation after high-temperature roasting removes organic amine template, the catalyst of oxygenate conversion alkene may be used as, as catalyst in use, its catalytic performance is excellent.
Description
One, technical field:
The present invention relates to a kind of synthetic methods of molecular sieve, more particularly to a kind of little crystal grain silicoaluminophosphate SAPO-34 points
The synthetic method of son sieve.
Two, background technique:
Ethylene, propylene are important basic chemical industry raw material, are mainly obtained by petroleum path.At present in the world absolutely mostly
Several ethylene comes from steam cracking technology, and propylene is then mainly with the by-product of the joint product of steam cracking production ethylene and catalytic cracking
Two kinds of forms of product obtain.But it is increasingly depleted with petroleum resources, the technology of exploitation Non oil-based route production ethylene, propylene is aobvious
It must be even more important.It is mature via the technology of synthesis gas production methanol from coal or natural gas.Therefore, development is with coal/day
Right gas is raw material, is a practicable technology path via preparing low carbon olefin hydrocarbon with methanol.
Molecular sieve is the porous material with regular framework structure, in the structure there are many channel of uniform pore diameter and greatly
Hole can only allow the molecule less than its aperture to pass through.The methanol to olefins reaction occurred over a molecular sieve is typical shape-selective
Catalytic process.Different kinds of molecules sieve is used equally for catalysis methanol olefine reaction.It is anti-that ZSM-5 molecular sieve has been reported for this earliest
It answers, it has the characteristics that react service life length, but the selectivity of low-carbon alkene is relatively low, and has the macromolecular complex such as aromatic hydrocarbons in product
Matter.Pore zeolite is demonstrated by higher selectivity of light olefin in methanol to olefins reaction, but inactivates quickly.American Association carbon
Compound company discloses the synthetic method of silicoaluminophosphate Series Molecules sieve in patent US4440871.So far, with SAPO-
34 molecular sieves are that the small pore molecular sieve of representative shows good catalytic performance in methanol to olefins reaction, wherein SAPO-34
It is best.
Currently, the template for synthesizing the use of SAPO-34 molecular sieve has tetraethyl ammonium hydroxide, morpholine, triethylamine, piperazine
Pyridine etc., the pattern and physicochemical properties different from of the molecular sieve of different templates agent synthesis, with the property of specific template and
Synthesis condition is related.In order to promote performance of the SAPO-34 in methanol to olefins reaction, researcher attempts synthesis Jie's micropore
SAPO-34 molecular sieve or nanometer SAPO-34 molecular sieve extend the catalytic life of molecular sieve to reduce the limitation of diffusion mass transfer.It is logical
Often the method for preparation Jie's micropore composite zeolite is that surfactant is added into synthetic system.In addition, Wei Fei etc. is with triethylamine
Template, kaolin are sial raw material, the SAPO-34 molecular sieve (CN101176851) of hydrothermal synthesis nanoscale twins aggregation,
Show the extended methanol to olefins reaction service life.CN1596221 discloses a kind of using ethyl orthosilicate as silicon source acquisition granule
Spend the method for SAPO-34 molecular sieve.WO 00/06493, which is disclosed, a kind of obtains the side of small crystal grain molecular sieve by stirring or rolling
Method.CN1596222 discloses the method using organic alkali solution pretreatment silicon source synthesizing small-grain SAPO molecular sieve.
CN101056708 discloses a kind of method of synthesized silicon-aluminum phosphate molecular sieve, and this method is by phosphorus source and a kind of crystallization director
After mixing, adds silicon source and silicon source carries out crystallization.CN101284673 is disclosed is added crystal seed reduction in synthesis Primogel
The method of SAPO-34 Size of Zeolite.
Although having more document and patent to study the synthesis of SAPO-34 molecular sieve, about SAPO-34
The synthesis of molecular sieve and catalytic performance still have the space of promotion.
Three, summary of the invention:
The technical problem to be solved by the present invention is according to the current condition of SAPO-34 Zeolite synthesis method, the present invention is mentioned
A kind of synthetic method for little crystal grain silicoaluminophosphate SAPO-34 molecular sieve with smaller particle size and more excellent catalytic performance and its
Using.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
The present invention provides a kind of synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, and the synthetic method includes
Following steps:
A, raw material silicon source, phosphorus source, silicon source, organic amine and deionized water are added to the container first and are stirred mixing, mixed
Homogeneous gel is obtained after even；
Mol ratio between source of aluminium, phosphorus source, silicon source, organic amine and deionized water be 1.0:0.7~2.5:0.1~
0.8:1.5~5.0:10~100；
B, the obtained homogeneous gel of step a is placed in crystallizing kettle, is warming up to 160~210 DEG C and carries out pre- Crystallizing treatment, in advance
The time of Crystallizing treatment is 0.5~4h；Its product is down to room temperature after pre- Crystallizing treatment；
C, then SAPO-34 molecular sieve is added in the pre- crystallization liquid that step b is obtained as crystal seed and is mixed, after mixing
Hydrogel warms to crystallization, crystallization time is carried out under the conditions of 180~220 DEG C be 4~30h；
The SAPO-34 molecular sieve is the 0.2~3% of homogeneous gel gross mass as the additive amount of crystal seed；
D, products therefrom after crystallization is centrifuged, washing and drying, obtains product little crystal grain silicoaluminophosphate
SAPO-34 molecular sieve.
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, silicon source described in step a is thin to intend
At least one of diaspore, aluminium isopropoxide, aluminium oxide and aluminium hydroxide；Phosphorus source is in phosphoric acid, phosphate and phosphorous acid
At least one；The silicon source is at least one of silica solution, White Carbon black and ethyl orthosilicate；The organic amine is tetraethyl
At least one of ammonium hydroxide, morpholine, triethylamine, di-n-propylamine, diethylamine, n-butylamine, diisopropylamine and piperidines.
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, the phosphate is hexa metaphosphoric acid
Potassium, ammonium dihydrogen phosphate or potassium dihydrogen phosphate.
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, in step b pre- Crystallizing treatment when
Between be 1~3h.
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, crystallization time described in step c is
12~for 24 hours.
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, as crystal seed in step c
SAPO-34 molecule sieve size < 500nm (size < 500nm in any dimension direction).
According to the synthetic method of above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, to products therefrom described in step d
Using deionized water as detergent when being washed；Drying temperature is 120 DEG C when the drying, and drying time is 4~12h.
Additionally, it is provided a kind of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve prepared according to the method described above is with low-carbon alcohols
Or dimethyl ether is that raw material prepares the application in low-carbon alkene method as catalyst.
According to above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve prepared using low-carbon alcohols or dimethyl ether as raw material it is low
As the application of catalyst in carbon olefin method, the little crystal grain silicoaluminophosphate SAPO-34 molecular sieve passes through before being used as catalyst
High-temperature roasting removes template.
According to above-mentioned little crystal grain silicoaluminophosphate SAPO-34 molecular sieve prepared using low-carbon alcohols or dimethyl ether as raw material it is low
As the application of catalyst, the detailed process of the high-temperature roasting in carbon olefin method are as follows:
The little crystal grain silicoaluminophosphate SAPO-34 molecular sieve of above-mentioned preparation is carried out using rotary kiln or box-type high-temperature furnace
High-temperature roasting is kept the temperature when temperature reaches 400~600 DEG C in high-temperature calcination process, and soaking time is 4~8h, after roasting
It is cooled to room temperature, gained little crystal grain silicoaluminophosphate SAPO-34 molecular sieve is low as preparing using low-carbon alcohols or dimethyl ether as raw material
Catalyst in carbon olefin method is applied.
The raw material " organic amine " used in technical solution of the present invention is as synthesizing small-grain silicoaluminophosphate SAPO-34 molecule
The template of sieve.
Positive beneficial effect of the invention:
1, organic amine template is removed through high-temperature roasting using fine grain SAPO-34 molecular sieve prepared by the method for the present invention
Afterwards, the catalyst that may be used as oxygenate conversion alkene, as catalyst in use, its catalytic performance is excellent.
2, synthetic method of the present invention reduces crystal seed at the beginning of crystallization by introducing crystal seed into the gel after pre- Crystallizing treatment
The excessive dissolution that phase may occur achievees the purpose that maximize performance crystal seed effect, help to obtain the molecular sieve of smaller particle size
Product and higher product yield.Meanwhile prepared SAPO-34 molecular sieve shows excellent methanol to olefins reaction
Can, the reaction service life extends, and diene selective is high.
Four, specific embodiment:
Specific embodiment is set forth below, and the invention will be further described, but the present invention is not by these following embodiments
Limitation.
Embodiment 1:
The preparation method for the SAPO-34 molecular sieve seed that the present invention uses:
The preparation method is implemented according to method disclosed in embodiment 2 in patent CN1596222, then in preparation method
The raw material used is changed: tetraethyl ammonium hydroxide being used to synthesize nanometer SAPO-34 molecular sieve for template；Final gel rubs
Your proportion is 1Al2O3:1P2O5:0.3SiO2:2.0TEAOH:52H2O, used raw material be alkaline silica sol (30% weight),
TEAOH aqueous solution (35% weight), boehmite (65% weight), phosphoric acid (85% weight) and deionized water；Finally closed
CHA crystal phase is shown as at the XRD spectra of molecular sieve SAPO-34 product.Granularity is measured using Malvern laser particle analyzer, and 50% point
The small 200nm of meso-position radius of son sieve crystal, 10% is greater than 350nm.
Embodiment 2:
The synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve of the present invention, the detailed step of the synthetic method are as follows:
A, with 10g boehmite (70% weight), 15.82g phosphoric acid (85% weight), 4.5g alkaline silica sol (30%
Weight), 5.15g morpholine (99.5% weight), 13.86g triethylamine (99.5% weight) and 37g deionized water be raw material, first
Phosphoric acid is mixed with deionized water, boehmite is then added and stirs 30 minutes, continuously adds alkaline silica sol and stirs evenly,
It is subsequently added into triethylamine and morpholine, closed stirring 30 minutes is uniformly mixed so as to obtain homogeneous gel；
B, the obtained homogeneous gel of step a is transferred in Autoclaves for synthesis sealing (Autoclaves for synthesis is one in crystallizing kettle
Kind), it is warming up to 180 DEG C and carries out pre- Crystallizing treatment, the time of pre- Crystallizing treatment is 2h；Room is cooled to after pre- Crystallizing treatment
Temperature；
C, the pre- crystalline substance that step b is cooled to room temperature is added as crystal seed in SAPO-34 molecular sieve 0.86g prepared by embodiment 1
Change and mixed in liquid, is sealed after mixing, crystallization, crystallization time 20h are carried out under the conditions of being warming up to 180 DEG C；
D, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product little crystal grain silicoaluminophosphate SAPO-34 molecular screen primary powder is obtained after drying
17g。
The XRD of SAPO-34 zeolite product synthesized by the present embodiment shows that its crystal phase is CHA, and crystallinity is good；Sample
Granularity measured using Malvern laser particle analyzer, the meso-position radius of 50% molecular sieve crystal is less than 800nm, and 10% is greater than 1.1 μm.
Comparative example 1:
A kind of synthetic method of silicoaluminophosphate SAPO-34 molecular sieve, the detailed step of the synthetic method are as follows:
A, with 10g boehmite (70% weight), 15.82g phosphoric acid (85% weight), 4.5g alkaline silica sol (30%
Weight), 5.15g morpholine (99.5% weight), 13.86g triethylamine (99.5% weight) and 37g deionized water be raw material, first
Phosphoric acid is mixed with deionized water, boehmite is then added and stirs 30 minutes, continuously adds alkaline silica sol and stirs evenly,
It is subsequently added into the SAPO-34 molecular sieve 0.86g of the preparation of embodiment 1, and triethylamine and morpholine is added, closed stirring 30 minutes mixes
It is even to obtain homogeneous gel；
B, the gel that step a is obtained is transferred in Autoclaves for synthesis be warming up to 180 DEG C under the conditions of carry out crystallization, crystallization time
For 22h, room temperature is chilled to after crystallization；
C, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product silicoaluminophosphate SAPO-34 molecular screen primary powder 14.6g is obtained after drying.
The XRD of zeolite product synthesized by the comparative example 1 shows that its crystal phase is CHA, and crystallinity is good.Sample
Granularity is measured using Malvern laser particle analyzer, and for the meso-position radius of 50% molecular sieve crystal less than 1.1 μm, 10% is greater than 1.4 μm.
Comparative example 2:
A kind of synthetic method of silicoaluminophosphate SAPO-34 molecular sieve, the detailed step of the synthetic method are as follows:
A, with 10g boehmite (70% weight), 15.82g phosphoric acid (85% weight), 4.5g alkaline silica sol (30%
Weight), 5.15g morpholine (99.5% weight), 13.86g triethylamine (99.5% weight) and 37g deionized water be raw material, first
Phosphoric acid is mixed with deionized water, boehmite is then added and stirs 30 minutes, continuously adds alkaline silica sol and stirs evenly,
It is subsequently added into triethylamine and morpholine, closed stirring 30 minutes is uniformly mixed so as to obtain homogeneous gel；
B, the gel that step a is obtained is transferred in Autoclaves for synthesis be warming up to 180 DEG C under the conditions of carry out crystallization, crystallization time
For 22h, room temperature is chilled to after crystallization；
C, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product silicoaluminophosphate SAPO-34 molecular screen primary powder 14.3g is obtained after drying.
The XRD of zeolite product synthesized by the comparative example shows that its crystal phase is CHA, and crystallinity is good.The grain of sample
Degree is measured using Malvern laser particle analyzer, and for the meso-position radius of 50% molecular sieve crystal less than 4.5 μm, 10% is greater than 5.8 μm.
Embodiment 3:
The synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve of the present invention, the detailed step of the synthetic method are as follows:
A, with 10.8g aluminium hydroxide (65% weight), 12.65g phosphoric acid (85% weight), 4.4g ethyl orthosilicate, 5.15g
Morpholine (99.5% weight), 13.86g diisopropylamine (99.5% weight) and 20g deionized water be raw material, first by phosphoric acid with go
Then ionized water mixing is added aluminium hydroxide and stirs 30 minutes, continuously adds ethyl orthosilicate and stir evenly, it is different to be subsequently added into two
Propylamine and morpholine, closed stirring 30 minutes, are uniformly mixed so as to obtain homogeneous gel；
B, the obtained homogeneous gel of step a is transferred in Autoclaves for synthesis and is sealed, be warming up to 160 DEG C and carry out at pre- crystallization
Reason, the time of pre- Crystallizing treatment are 4h；Room temperature is cooled to after pre- Crystallizing treatment；
C, after mixing SAPO-34 molecular sieve 1.4g prepared by embodiment 1 with 5g water as crystal seed, it is cooling to squeeze into step b
It is mixed into the pre- crystallization liquid of room temperature, is sealed after mixing, crystallization, crystallization time 8h are carried out under the conditions of being warming up to 220 DEG C；
D, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product little crystal grain silicoaluminophosphate SAPO-34 molecular screen primary powder is obtained after drying
17.2g。
The XRD of zeolite product synthesized by the embodiment of the present invention shows that its crystal phase is CHA, and crystallinity is good.The grain of sample
Degree is measured using Malvern laser particle analyzer, and the meso-position radius of 50% molecular sieve crystal is less than 700nm, and 10% is greater than 950nm.
Comparative example 3:
A kind of synthetic method of silicoaluminophosphate SAPO-34 molecular sieve, the detailed step of the synthetic method are as follows:
A, the comparative example is with 10.8g aluminium hydroxide (65% weight), 12.65g phosphoric acid (85% weight), the positive silicon of 4.4g
Acetoacetic ester, 5.15g morpholine (99.5% weight), 13.86g diisopropylamine (99.5% weight) and 20g deionized water are raw material, first
Phosphoric acid is mixed with deionized water first, aluminium hydroxide is then added and stirs 30 minutes, continuously adds ethyl orthosilicate and stirs evenly,
It is subsequently added into the SAPO-34 molecular sieve 1.4g of the preparation of embodiment 1, and diisopropylamine and morpholine is added, closed stirring 30 minutes mixes
It is even to obtain homogeneous gel；
B, the obtained homogeneous gel of step a is transferred in Autoclaves for synthesis and is sealed, be warming up to 160 DEG C of crystallization 4h；Then
Crystallization, crystallization time 8h are carried out under the conditions of being continuously heating to 220 DEG C；
C, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product little crystal grain silicoaluminophosphate SAPO-34 molecular screen primary powder is obtained after drying
14.1g。
The XRD of zeolite product synthesized by the comparative example shows that its crystal phase is CHA, and crystallinity is good.The grain of sample
Degree is measured using Malvern laser particle analyzer, and for the meso-position radius of 50% molecular sieve crystal less than 1.1 μm, 10% is greater than 1.3 μm.
Embodiment 4:
The synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve of the present invention, the detailed step of the synthetic method are as follows:
A, with 7.2g r- aluminium oxide (99% weight), 18.82g phosphoric acid (85% weight), 1.2g White Carbon black (99% weight
Amount), 12g diethylamine (99.5% weight) and 65g deionized water be raw material, phosphoric acid is mixed with deionized water first, then plus
Enter r- aluminium oxide to stir 30 minutes, continuously add White Carbon black and stir evenly, be subsequently added into diethylamine, closed stirring 30 minutes mixes
It is even to obtain homogeneous gel；
B, the obtained homogeneous gel of step a is transferred in Autoclaves for synthesis and is sealed, be warming up to 210 DEG C and carry out at pre- crystallization
Reason, the time of pre- Crystallizing treatment are 1.5h；Room temperature is cooled to after pre- Crystallizing treatment；
C, the pre- crystalline substance that step b is cooled to room temperature is added as crystal seed in SAPO-34 molecular sieve 0.35g prepared by embodiment 1
Change and mixed in liquid, is sealed after mixing, crystallization, crystallization time 10h are carried out under the conditions of being warming up to 200 DEG C；
D, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product little crystal grain silicoaluminophosphate SAPO-34 molecular screen primary powder is obtained after drying
14.5g。
The XRD of zeolite product synthesized by the embodiment of the present invention shows that its crystal phase is CHA, and crystallinity is good.The grain of sample
Degree is measured using Malvern laser particle analyzer, and the meso-position radius of 50% molecular sieve crystal is less than 900nm, and 10% is greater than 1.2 μm.
Comparative example 4:
A kind of synthetic method of silicoaluminophosphate SAPO-34 molecular sieve, the detailed step of the synthetic method are as follows:
A, the embodiment is with 7.2g r- aluminium oxide (99% weight), 18.82g phosphoric acid (85% weight), 1.2g White Carbon black
(99% weight), 12g diethylamine (99.5% weight) and 65g deionized water are raw material, first mix phosphoric acid with deionized water,
Then r- aluminium oxide is added to stir 30 minutes, continuously adds White Carbon black and stirs evenly, be subsequently added into the SAPO- of the preparation of embodiment 1
34 molecular sieve 0.35g, continuously add diethylamine, and closed stirring 30 minutes is uniformly mixed so as to obtain homogeneous gel；
B, the obtained homogeneous gel of step a is transferred in Autoclaves for synthesis and is sealed, be warming up to 210 DEG C of crystallization 1.5h；Drop
Temperature is to 200 DEG C of crystallization 10h；
C, products therefrom after crystallization is centrifuged, washing and drying is (using deionized water when washing, when drying
Drying temperature is 120 DEG C, drying time 10h), product little crystal grain silicoaluminophosphate SAPO-34 molecular screen primary powder is obtained after drying
11.3g。
The XRD of zeolite product synthesized by the comparative example shows that its crystal phase is CHA, and crystallinity is good.The grain of sample
Degree is measured using Malvern laser particle analyzer, and for the meso-position radius of 50% molecular sieve crystal less than 1.5 μm, 10% is greater than 2.1 μm.
Embodiment 5:
Methanol to olefins reaction is carried out to the SAPO-34 molecular sieve that the various embodiments described above synthesize using fixed bed reactors
It can test.
The molecular sieve that any of the above-described embodiment is synthesized first respectively in 600 DEG C of roasting 5h, remove template therein at
Point.Then the molecular sieve tabletting after roasting is sieved, 0.5 gram of 20-40 molecules of interest sieve is taken to be packed into quartz tube reactor；Logical nitrogen
It is warming up to 500 DEG C to activate 1 hour, then cools to 450 DEG C of reaction temperature, reaction pressure is normal pressure, and methanol is entrained by nitrogen
Material, the mass space velocity of methanol are 2.5h-1；With gas chromatographic analysis product.Reaction result is shown in Table 1.
Through experimental test it is found that 2-4 of embodiment of the present invention sample is compared with corresponding comparative example 2-4 sample, this hair
The molecular sieve of bright synthesis shows significantly longer catalytic life and high ethylene, propylene selectivity.
The reaction of methanol conversion result on 1 SAPO-34 of table
*: the reaction service life is defined as the time that methanol conversion is 100%.
Claims (10)
1. a kind of synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, which is characterized in that the synthetic method include with
Lower step:
A, raw material silicon source, phosphorus source, silicon source, organic amine and deionized water are added to the container first and are stirred mixing, after mixing
Obtain homogeneous gel；
Mol ratio between source of aluminium, phosphorus source, silicon source, organic amine and deionized water is 1.0:0.7~2.5:0.1~0.8:
1.5~5.0:10~100；
B, the obtained homogeneous gel of step a is placed in crystallizing kettle, is warming up to 160~210 DEG C and carries out pre- Crystallizing treatment, pre- crystallization
The time of processing is 0.5~4h；Its product is down to room temperature after pre- Crystallizing treatment；
C, then SAPO-34 molecular sieve is added in the pre- crystallization liquid that step b is obtained as crystal seed and is mixed, it is mixed solidifying
Glue carries out crystallization under the conditions of being warming up to 180~220 DEG C, crystallization time is 4~30h；
The SAPO-34 molecular sieve is the 0.2~3% of homogeneous gel gross mass as the additive amount of crystal seed；
D, products therefrom after crystallization is centrifuged, washing and drying, obtains product little crystal grain silicoaluminophosphate SAPO-34
Molecular sieve.
2. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 1, it is characterised in that: step
Silicon source described in rapid a is at least one of boehmite, aluminium isopropoxide, aluminium oxide and aluminium hydroxide；Phosphorus source is phosphorus
At least one of acid, phosphate and phosphorous acid；The silicon source is at least one in silica solution, White Carbon black and ethyl orthosilicate
Kind；The organic amine is tetraethyl ammonium hydroxide, morpholine, triethylamine, di-n-propylamine, diethylamine, n-butylamine, diisopropylamine and piperazine
At least one of pyridine.
3. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 2, it is characterised in that: institute
Stating phosphate is hexa metaphosphoric acid potassium, ammonium dihydrogen phosphate or potassium dihydrogen phosphate.
4. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 1, it is characterised in that: step
The time of pre- Crystallizing treatment is 1~3h in rapid b.
5. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 1, it is characterised in that: step
Crystallization time described in rapid c is 12~for 24 hours.
6. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 1, it is characterised in that: step
SAPO-34 molecule sieve size < 500nm in rapid c as crystal seed.
7. the synthetic method of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 1, it is characterised in that: step
Using deionized water as detergent when being washed described in rapid d to products therefrom；Drying temperature is 120 when the drying
DEG C, drying time is 4~12h.
8. a kind of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to the preparation of claim 1 the method with low-carbon alcohols or
Person's dimethyl ether is that raw material prepares the application in low-carbon alkene method as catalyst.
9. little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 8 is being original with low-carbon alcohols or dimethyl ether
Material prepares the application in low-carbon alkene method as catalyst, it is characterised in that: the little crystal grain silicoaluminophosphate SAPO-34 molecule
Sieve removes template through high-temperature roasting before being used as catalyst.
10. little crystal grain silicoaluminophosphate SAPO-34 molecular sieve according to claim 9 is being original with low-carbon alcohols or dimethyl ether
Material prepares the application in low-carbon alkene method as catalyst, which is characterized in that the detailed process of the high-temperature roasting are as follows:
Little crystal grain silicoaluminophosphate SAPO-34 molecular sieve prepared by claim 1 using rotary kiln or box-type high-temperature furnace into
Row high-temperature roasting is kept the temperature when temperature reaches 400~600 DEG C in high-temperature calcination process, and soaking time is 4~8h, roasting
After be cooled to room temperature, it is raw material preparation that gained little crystal grain silicoaluminophosphate SAPO-34 molecular sieve, which is used as using low-carbon alcohols or dimethyl ether,
Catalyst in low-carbon alkene method is applied.
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| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
| CN113753915A (en) * | 2020-06-01 | 2021-12-07 | 中国石油化工股份有限公司 | Preparation method of small-crystal-grain SAPO-34 molecular sieve, prepared molecular sieve and application |
| CN113955767A (en) * | 2021-12-02 | 2022-01-21 | 郑州大学 | Method for synthesizing nano SAPO-34 molecular sieve with assistance of heterogeneous crystal seeds |
| CN114031092A (en) * | 2021-12-16 | 2022-02-11 | 中节能万润股份有限公司 | Preparation method of SAPO-20 molecular sieve |
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| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
| CN113955767A (en) * | 2021-12-02 | 2022-01-21 | 郑州大学 | Method for synthesizing nano SAPO-34 molecular sieve with assistance of heterogeneous crystal seeds |
| CN113955767B (en) * | 2021-12-02 | 2023-08-04 | 郑州大学 | Method for synthesizing nano SAPO-34 molecular sieve with assistance of heterogeneous seed crystal |
| CN114031092A (en) * | 2021-12-16 | 2022-02-11 | 中节能万润股份有限公司 | Preparation method of SAPO-20 molecular sieve |
| CN114031092B (en) * | 2021-12-16 | 2023-03-24 | 中节能万润股份有限公司 | Preparation method of SAPO-20 molecular sieve |
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