CN109422283A - The preparation method of multi-stage artery structure molecular sieve, the molecular sieve of preparation and its purposes - Google Patents
The preparation method of multi-stage artery structure molecular sieve, the molecular sieve of preparation and its purposes Download PDFInfo
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- CN109422283A CN109422283A CN201710784663.0A CN201710784663A CN109422283A CN 109422283 A CN109422283 A CN 109422283A CN 201710784663 A CN201710784663 A CN 201710784663A CN 109422283 A CN109422283 A CN 109422283A
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- molecular sieve
- sapo
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- artery structure
- stage artery
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- 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 184
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 182
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 210000001367 artery Anatomy 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000007547 defect Effects 0.000 claims abstract description 33
- 239000011148 porous material Chemical group 0.000 claims description 45
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005287 template synthesis Methods 0.000 abstract 1
- 239000011799 hole material Substances 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910052753 mercury Inorganic materials 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 241000269350 Anura Species 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 olefin hydrocarbon Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 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 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
-
- 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)
-
- B01J35/633—
-
- B01J35/643—
-
- B01J35/647—
-
- B01J35/651—
-
- B01J35/653—
-
- B01J35/657—
-
- 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
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- 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
-
- 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
-
- 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
Abstract
The problem of the present invention relates to a kind of preparation method of multi-stage artery structure molecular sieve, the molecular sieve of preparation and its purposes, mainly solve to use operating process present in mesoporous template synthesis process cumbersome, at high cost and defect-containing crystal molecular sieve losses.The present invention preferably solves the problems, such as this by using the technical solution that the molecular sieve with crystal defect carries out hydrothermal crystallizing as crystal seed, can be used in the industrial production of multi-stage artery structure molecular sieve.
Description
Technical field
The present invention relates to a kind of preparation method of multi-stage artery structure molecular sieve, the molecular sieve of preparation and its purposes.
Background technique
1984, aperture was invented in the silicoaluminophosphamolecular molecular sieves of 0.4nm or so by U.S. combinating carbide company (UCC)
(abbreviation SAPO molecular sieve).SAPO molecular sieve is by AlO4、SiO4And PO4The crystal network structure that tetrahedron is constituted, it is brilliant intracorporal
Duct is because of Si4+Replace P5+Or Al3+The acidity of generation is replaced with metal and is generated acid.In SAPO Series Molecules sieve,
SAPO-34 molecular sieve because its with good thermal stability and hydrothermal stability, moderate acid, higher specific surface area and
The micropore canals of high-sequential, and be widely used in modern petroleum processing industry.Most noticeable is the molecular sieve application
In methanol-to-olefins (MTO) reaction, the conversion ratio of methanol can be made to reach 100%, the selectivity of ethylene and propylene can be more than
70%, C5 +The content of component is less, and almost without aromatic hydrocarbons generation.But the relatively long and narrow duct of SAPO molecular sieve shows seriously
Shape-selective limitation, on the one hand hinder the contact in activated centre inside raw molecule and its duct, on the other hand can make reactant,
The diffusion of middle transition product and final product and mass transfer are restricted, and easily because carbon deposit causes duct to be blocked, cause to urge
The inactivation of agent limits the performance of its catalytic performance.
In order to overcome the shortcomings of single microcellular structure molecular screen material, many researchers have been prepared in conjunction with multiple hole road advantage
Novel molecular sieve, i.e. hierarchical porous structure molecular sieve.According to cellular structure type, multistage porous molecular sieve can be divided into following two categories:
One kind is micropore-mesoporous-microporous composite molecular sieve that two-phase cocrystallization molecular sieve is formed, and this kind of material is answered by two or more
Close micropore canals composition；Another kind of is mesopore/macropore-mesoporous-microporous composite molecular sieve, and this kind of material has micropore and mesoporous/big simultaneously
Two kinds of hole pore canal system, can greatly improve the diffusion of material, improve the catalytic performance of material, in the reaction for being related to macromolecular
And good catalyzed conversion performance is shown in the reaction for needing quickly to spread.
For this purpose, there has been proposed the preparation sides through hydrothermal synthesis after and mesoporous template is added in gel rubber system
Method.It is template that Choi etc., which is reported using the long chain alkyl ammonium salt of silanization, has provided mesoporous knot through a step hydrothermal synthesis
The AlPO of structure4- n Series Molecules sieve (Choi M, Srivastava R, Ryoo R.Chemical Communications,
2006；(42):4380-4382.)；Then, Danilina and Chen Lu etc. is using a kind of multi-functional long chain silicone as silicon source, respectively
Hydrothermal synthesis provides SAPO-5 (Danilina N, Krumeich F, the van Bokhoven J.Journal of hierarchical porous structure
Of Catalysis, 2010,272 (1): 37-43.) and SAPO-34 molecular sieve (Chen Lu, Wang Runwei, Ding Shuandeng institution of higher education
Journal, 2010；31(9):1693-1696.)；Fan etc. by be added long-chain organic phosphine as mesoporous template, can be in routine
Synthesize SAPO-11 molecular sieve (Fan Y, Xiao H, Shi G, et with abundant meso-hole structure under hydrothermal condition
al.Journal of Catalysis,2012,285(1):251-259.)；Cui etc. is using polyethylene glycol (PEG) as mesoporous mould
Plate agent, synthesizes the SAPO-34 molecular sieve with hierarchical porous structure under hydrothermal conditions, and can by the amount of modulation PEG come
Change mesoporous size (Cui Y, Zhang Q, He J, et al.Particuology, 2013；11(4):468-474.).
Yang etc., for mesoporous template, synthesizes hierarchical porous structure SAPO- with the surfactant of silanization in the case where microwave-assisted
34, the results showed that, the introducing of microwave can not only effectively shorten crystallization time (only small crystallization process need to can be completed at present 2),
And synthesized product specific surface area with higher and mesoporous Kong Rong (Yang S, Kim J, Chae H, et
al.Materials Research Bulletin,2012；47(11):3888-3892.).Although in the synthesis process will pass through
Mesoporous template is introduced into the synthetic system of molecular sieve the SAPO-34 molecular sieve that can be prepared with hierarchical porous structure, but
Suitable template is not only expensive, but also the process for removing template is also difficult to control.
To solve the above-mentioned problems, poplar He Qin etc. is prepared a kind of with hierarchical porous structure using the method for gas phase crystallization
Silicoaluminophosphate SAPO molecular sieve integral material, the material are shown more in MTO reaction compared to conventional SAPO-34 molecular sieve
High catalytic activity (CN102219237A；Yang H,Liu Z,Gao H,et al.Journal of Materials
Chemistry,2010；20(16):3227-3231.).Recently, silicon source, silicon source, phosphorus source and morpholine are uniformly mixed by Jin etc.
And after grinding, directly the solid mixture is directly placed into baking oven, crystallization 8-24 is small at 200 DEG C under solvent-free conditions
When, products therefrom is washed, after dry, roasting, can be obtained SAPO-34 molecular sieve (Jin Y, Sun with meso-hole structure
Q,Qi G,et al.Angewandte Chemie International Edition,2013；125(35):9342-
9345.), which equally shows preferable catalytic performance in MTO reaction.
In conclusion although the preparation of multilevel hole material at present is the hot spot of numerous scientific research personnel's researchs, existing system
The method of standby multi-stage porous SAPO-34 molecular sieve the disadvantages of all there is operating process is cumbersome and higher cost, and remove mesoporous
The structure of molecular sieve can be destroyed while template.In consideration of it, reducing preparation cost, simplify procedures, exploitation is simple and efficient
Multi-stage porous SAPO-34 molecular sieve preparation route have important practical significance.In addition, in SAPO-34 sieve synthesis procedure
The molecular sieve with imperfect crystal occurred is also problematic in that from the viewpoint of economy if given it up, it is highly desirable to
Effectively recycle these discarded molecular sieves.
Summary of the invention
The present invention provides a kind of preparation method of new multi-stage artery structure molecular sieve.
Specifically, the present invention relates to a kind of preparation method of multi-stage artery structure molecular sieve, including using with crystal
The step of molecular sieve of defect carries out hydrothermal crystallizing as crystal seed.
According to an aspect of the present invention, the molecular sieve with crystal defect, pore structure contain macropore and/or Jie
The ratio of hole, macropore and/or the mesoporous total specific surface area of specific surface area Zhan is not less than 10%, preferably 10~30%；Macropore and/or
Mesoporous Kong Rong accounts for the ratio of total pore volume not less than 15%, preferably 15~50%.
According to an aspect of the present invention, in the molecular sieve with crystal defect, the pore-size distribution of macropore in 100~
2000 nanometers, mesoporous pore-size distribution is in 2~50 nanometers.
According to an aspect of the present invention, the molecular sieve surface pattern with crystal defect is coarse, and has large number of orifices
Hole exists.
According to an aspect of the present invention, the molecular sieve with crystal defect is originated from non-crystallized complete in synthesis process
Molecular sieve.
According to an aspect of the present invention, the non-crystallized complete molecular sieve is defined as, and is based on the complete molecule of crystallization
Sieve, relative crystallinity are 50~75%.
According to an aspect of the present invention, the imperfect crystal is originated from and is modified the complete molecular sieve of crystallization after post treatment
The step of.
According to an aspect of the present invention, it includes making the complete molecular sieve of crystallization and modifying agent that the post-processing is modified
The step of；The modifying agent in the group being made of ammonium hydroxide, oxalic acid, citric acid, sodium carbonate and tetraethyl ammonium hydroxide extremely
Few one kind.
According to an aspect of the present invention, the molecular sieve be selected from SAPO-5, SAPO-8, SAPO-11, SAPO-16,
SAPO-17、SAPO-18、SAPO-20、SAPO-31、SAPO-34、SAPO-35、SAPO-36、SAPO-37、SAPO-40、SAPO-
41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, its metalliferous form and its mixture, preferably SAPO-34.
According to an aspect of the present invention, the method includes by the crystal seed, silicon source, phosphorus source, silicon source, template and water
Mixture hydrothermal crystallizing the step of.
According to an aspect of the present invention, in the mixture, source of aluminium, silicon source, phosphorus source, template and water mole
Than for 1:(0.05~2): (0.05~1.5): (1~10): (10~200), preferably 1:(0.1~1.5): (0.2~1.2):
(2~8): (30~150)；The additional amount of crystal seed is 1.5~20 weight %, preferably 3~15 weight % of solid content.
The invention further relates to a kind of multistage pore canal knots prepared according to the preparation method of the multi-stage artery structure molecular sieve
Structure molecular sieve.
According to an aspect of the present invention, the multi-stage artery structure molecular sieve has micropore, mesoporous and macropore simultaneously；Its
In, micropore size is not more than 1 nanometer, and mesoporous pore size is distributed in 5~30 nanometers, and macropore diameter is distributed in 200~1500 nanometers；It is micro-
0.05~0.30 centimetre of Kong Rongwei of hole contribution3/ gram, 0.10~0.40 centimetre of the Kong Rongwei of mesoporous contribution3/ gram, macropore contribution
0.10~0.60 centimetre of Kong Rongwei3/ gram.
According to an aspect of the present invention, the multi-stage artery structure molecular sieve is multi-stage artery structure SAPO-34 molecule
Sieve.
The invention further relates to a kind of multistage pore canal knots prepared according to the preparation method of the multi-stage artery structure molecular sieve
Application of the structure molecular sieve in oxygenatedchemicals olefine reaction.
Beneficial effects of the present invention: the method for the present invention is based on the defects of imperfect crystal position guiding synthesis multistage pore canal knot
Structure molecular sieve, this method have the advantages that the mesoporous template in 1, synthesis process without valuableness, can effectively save cost；
2, operating process is simple, close with the synthesis process of conventional molecular sieve, it is only necessary to which common crystal seed is changed to the defective crystal seed of tool i.e.
It can；3, crystal seed is from a wealth of sources, can be the complete molecular sieve of non-complete crystallization, is also possible to the complete molecular sieve of crystallization.4,
From the viewpoint of economy, the loss of the discarded molecular sieve with crystal defect occurred in synthesis process is effectively limited.
In addition, methanol-to-olefins technology is developed so far, diene yield (ethylene+propylene) has reached 80~83%, in this base
On plinth, if yield improves 0.5 percentage point, for the device of 10,000 tons, economic benefit will be very considerable.And according to this hair
The SAPO-34 molecular sieve with multi-stage artery structure of bright method preparation is used for oxygenatedchemicals system as catalyst activity component
In olefin hydrocarbon, good catalytic performance is shown, diene (ethylene+propylene) yield can be improved 2 percentage points or more, moreover it is possible to
The reaction stability of catalyst is dramatically increased, 10% or more is improved, achieves preferable technical effect.
Detailed description of the invention
Fig. 1 be [embodiment 1], [embodiment 6], [comparative example 1] preparation SAPO-34 molecular sieve-4 A, F, K XRD spectra.
Wherein A and K is the SAPO-34 molecular sieve for containing only micropore, and F is while having micropore, mesoporous and macropore multi-stage porous SAPO-34 point
Son sieve.As seen from the figure, molecular sieve-4 A, F, K all have characteristic diffraction peak possessed by SAPO-34 molecular sieve.
Fig. 2 is the SEM photograph of the SAPO-34 molecular sieve that is conventional, containing only micropore of [embodiment 1] preparation.As seen from the figure,
Conventional molecular sieve is regular cube pattern, and surface compact is smooth.
Fig. 3 is the SEM photograph of the imperfect crystal of [embodiment 2] preparation, and as seen from the figure, plane of crystal has a large amount of hole.
Fig. 4 is the N of the imperfect crystal of [embodiment 2] preparation2Adsorption-desorption isothermal and pore-size distribution.As seen from the figure, N2
Adsorption/desorption isotherms have apparent hysteresis loop in higher-pressure region.
Fig. 5 is the pressure mercury pore-size distribution of the imperfect crystal of [embodiment 2] preparation.As seen from the figure, the macropore hole of the molecular sieve
Diameter concentrates near 1000 rans.
Fig. 6 is while prepared by [embodiment 6] with micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
SEM photograph.As seen from the figure, multi-stage artery structure molecular sieve is cube pattern, and a large amount of holes occurs in surface.
Fig. 7 is while prepared by [embodiment 6] with micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
N2Adsorption-desorption isothermal and pore-size distribution.As seen from the figure, N2Adsorption/desorption isotherms have apparent hysteresis loop in higher-pressure region, are situated between
Hole aperture concentrates near 12 nanometers.
Fig. 8 is while prepared by [embodiment 6] with micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
Press mercury pore-size distribution.As seen from the figure, the macropore diameter of the molecular sieve concentrates near 500 rans.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing, it should be noted however that protection scope of the present invention is simultaneously
By this, this is not limited, and but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain
Justice.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method or step etc., object derived from the prefix cover it is those of commonly used in the art when the application proposes,
But also includes also being of little use at present, will but become art-recognized for suitable for those of similar purpose.
It should be strongly noted that two or more aspects (or embodiment) disclosed in the context of the present specification
Any combination, the technical solution formed therefrom it can belong to a part of this specification original disclosure each other, while
It falls under the scope of the present invention.
The present invention relates to a kind of preparation methods of multi-stage artery structure molecular sieve, including using the molecule with crystal defect
The step of sieve carries out hydrothermal crystallizing as crystal seed.
According to an aspect of the present invention, the molecular sieve with crystal defect, pore structure is in addition to containing micropore, also
Containing macropore and/or mesoporous, the ratio of macropore and/or the mesoporous total specific surface area of specific surface area Zhan is not less than 10%, preferably 10
~30%；Macropore and/or mesoporous Kong Rong account for the ratio of total pore volume not less than 15%, preferably 15~50%.The micropore, hole
Diameter is less than 2 nanometers；The macropore, aperture are greater than 50 nanometers, and preferred distribution is in 100~2000 nanometers；It is described mesoporous,
Pore-size distribution is in 2~50 nanometers.The molecular sieve with crystal defect, plane of crystal pattern is coarse, and has a large amount of holes
In the presence of.
According to an aspect of the present invention, the molecular sieve with crystal defect can be originated from non-crystallized in synthesis process
Complete molecular sieve.The non-crystallized complete molecular sieve, which refers to, has formd molecular sieve but crystal not yet complete crystallization.
Complete crystallization refers to that molecular sieve complete by crystallization, even if extending crystallization time, size, pattern and the opposite crystallization of molecular sieve crystal
Degree will not change.Compared with the complete molecular sieve of crystallization, non-crystallized complete molecular sieve relative crystallinity be 50~
75%.So the non-crystallized complete molecular sieve is defined as, it is based on the complete molecular sieve of crystallization, relative crystallinity 50
~75%.
According to an aspect of the present invention, the molecular sieve with crystal defect can also originate from completely dividing crystallization
The step that son sieve is modified after post treatment.The modified post-processing includes the step for making crystallization complete molecular sieve and modifying agent
Suddenly.The modifying agent in the group being made of ammonium hydroxide, oxalic acid, citric acid, sodium carbonate and tetrapropylammonium hydroxide at least one
Kind.The step of modifying agent is contacted with the complete molecular sieve of crystallization can carry out according to mode known in the art, such as make to contain
The aqueous solution of modifying agent is contacted with the complete molecular sieve of crystallization.Generally, the concentration of modifying agent in aqueous solution is rubbed for 0.05~0.5
You/liter, the mass ratio of aqueous solution and the complete molecular sieve butt of crystallization containing modifying agent is (25~70): 1.Contact Temperature is 50
~90 DEG C, the time is 6~24 hours.
According to an aspect of the present invention, it is selected from as the molecular sieve with crystal defect of crystal seed with crystal defect
SAPO-5、SAPO-8、SAPO-11、SAPO-16、SAPO-17、SAPO-18、SAPO-20、SAPO-31、SAPO-34、SAPO-
35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, its is metalliferous
Form and its mixture, preferably with the SAPO-34 molecular sieve of crystal defect.Correspondingly, the multi-stage artery structure molecular sieve
SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO- selected from multi-stage artery structure
31、SAPO-34、SAPO-35、SAPO-36、SAPO-37、SAPO-40、SAPO-41、SAPO-42、SAPO-44、SAPO-47、
SAPO-56, its metalliferous form and its mixture, preferably the SAPO-34 molecular sieve of multi-stage artery structure.
According to an aspect of the present invention, point of multi-stage artery structure is synthesized using the molecular sieve with crystal defect as crystal seed
Son sieve, is included the steps that the mixture hydrothermal crystallizing of the crystal seed, silicon source, phosphorus source, silicon source, template and water.With crystal
The molecular sieve of defect can be non-removed template method, be also possible to be fired the molecular sieve after removed template method；Preferably,
Used defect crystal seed is removed template method.In the mixture, source of aluminium, silicon source, phosphorus source, template and water rub
You are than being 1:(0.05~2): (0.05~1.5): (1~10): (10~200), preferably 1:(0.1~1.5): (0.2~
1.2): (2~8): (30~150)；The additional amount of crystal seed is 1.5~20 weight %, preferably 3~15 weight % of solid content.
Silicon source is selected from least one of the group being made of ethyl orthosilicate, white carbon black or silica solution, and phosphorus source is selected from by phosphoric acid, phosphoric acid
At least one of the group of salt or phosphorous acid composition, silicon source are selected from the group of aluminium isopropoxide, boehmite or aluminium oxide composition
At least one of.Template in the group being made of tetraethyl oxyammonia, triethylamine, diethylamine or morpholine at least one
Kind.Hydrothermal crystallizing temperature is 150~250 DEG C, preferably 170~210 DEG C.The hydrothermal crystallizing time be 3~50 hours, preferably 10~35
Hour.The method also includes the step of by the product washings of hydrothermal crystallizing, drying, roasting, these can be according to this field
Known mode is operated.
The invention further relates to a kind of multistage pore canal knots prepared according to the preparation method of the multi-stage artery structure molecular sieve
Structure molecular sieve.
According to an aspect of the present invention, the multi-stage artery structure molecular sieve has micropore, mesoporous and macropore simultaneously；Its
In, micropore size is not more than 1 nanometer, and mesoporous pore size is distributed in 5~30 nanometers, and macropore diameter is distributed in 200~1500 nanometers；It is micro-
0.05~0.30 centimetre of Kong Rongwei of hole contribution3/ gram, 0.10~0.40 centimetre of the Kong Rongwei of mesoporous contribution3/ gram, macropore contribution
0.10~0.60 centimetre of Kong Rongwei3/ gram.The multi-stage artery structure molecular sieve is selected from SAPO-5, SAPO- of multi-stage artery structure
8、SAPO-11、SAPO-16、SAPO-17、SAPO-18、SAPO-20、SAPO-31、SAPO-34、SAPO-35、SAPO-36、
SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, its metalliferous form and its mixed
Close object, preferably the SAPO-34 molecular sieve of multi-stage artery structure.
The invention further relates to a kind of multistage pore canal knots prepared according to the preparation method of the multi-stage artery structure molecular sieve
Application of the structure molecular sieve in oxygenatedchemicals olefine reaction.
The oxygenatedchemicals is selected from by methanol, ethyl alcohol, normal propyl alcohol, isopropanol, C4-20Alcohol, ethyl methyl ether, dimethyl ether, diethyl
At least one of ether, diisopropyl ether, formaldehyde, dimethyl carbonate, group of Ketene dimethyl composition, preferably methanol or dimethyl ether.It is described
Alkene includes ethylene, propylene or combinations thereof.
For be at the temperature of light olefin by oxygenate conversion can be in very wide range, this is depended on,
It is at least partially dependent on, catalyst, the knot of regenerated catalyst portion and reactor assembly and reactor in catalyst mixture
Structure.Although these methods are not limited by temperature, if the temperature by this method control at 200~700 DEG C, desired
It is 250~600 DEG C of temperature, it is most desirable to which 300~500 DEG C of temperature then can achieve best result.Lower temperature
Lower reaction speed is normally resulted in, and the formation speed of desired Light olefin products can significantly slow down.But work as temperature
When degree is higher than 700 DEG C, this method will not generate the Light olefin products of optimised quantity, and form coke and light saturation on a catalyst
The speed of object then becomes too fast.
Light olefin will be formed in very wide pressure limit, although not necessarily generating by optimised quantity, the press packet
It includes but is not limited to, pressure is 0.1kPa~5MPa, and desired pressure is 5kPa~1MPa, and highly desirable pressure is 20kPa
~500kPa.Pressure except above-mentioned pressure limit can also be used and be not excluded in the scope of the present invention.It is lower and compared with
High pressure can apply detrimental effect to selectivity, conversion ratio, coking yield and/or reaction rate；But it still can generate light
Alkene, therefore, these pressure limits are considered as a part of the invention.
Weight space velocity WHSV for oxygenate conversion reaction, it is desirable to sufficiently high to maintain catalyst in reaction condition
Being in down and in the structure and design of reactor can fluidized state.Generally, WHSV is l~5000hr-1, it is desirable to 2
~3000hr-1, more desirably 5~1500hr-1。
In the conversion process of oxygenatedchemicals to alkene, carbonaceous sediment is accumulated for promoting the catalyst of conversion reaction
On.In certain situation, the accumulation of these carbonaceous sediments will lead to the catalytic capability of oxygen compound feedstock to light olefins
Decline.In this case, catalyst loses amount of activated.When catalyst no longer can be by oxygenate conversion at olefin product
When, catalyst is considered losing activity completely.As a nonessential step in oxygenatedchemicals into olefin reaction
Suddenly, partial catalyst is taken out from reactor, and from least part in the partial catalyst taken out in reactor
It is regenerated in regenerating unit.Pass through regeneration, it means that carbonaceous sediment is at least partly to be removed from catalyst.Again
Catalyst after life can be then returned in reactor through cooling or without cooling.It is as desired, for regenerated
The produced quantity of partial catalyst is account for the catalytic amount come out in reactor 0.1~99%.It more desirably is that the produced quantity is
0.2~50% is accounted for, is to account for 0.5~5% highly desirablely.
Catalyst can regenerate in any method of interval, continuous, semicontinuous or combinations thereof.Continuous catalyst regeneration
It is desired method.Desirably, catalyst is reproduced the water that carbon deposition quantity accounts for 0.01~15 weight % of catalytic amount
It is flat.Catalyst regeneration temperature should be at 250~750 DEG C, it is desirable at 500~700 DEG C.
In the method for the present invention, XRD data are measured using German Brooker AXS D8Advance type X-ray diffractometer, are used for
Characterize the calculating of the crystal structure and relative crystallinity of molecular sieve；N2Adsorption-desorption data are inhaled by U.S. Mike ASAP-2020
Attached instrument measures, for measuring specific surface area, the Kong Rong, mesoporous and micropore pore-size distribution of molecular sieve；Mercury pressuring data and aperture point
Cloth is measured by the full-automatic mercury injection apparatus of Thermo, and the macropore diameter for characterizing molecular sieve is distributed；SEM picture is by Dutch FEI
Quanta200F field emission scanning electron microscope obtains, for characterizing the pattern of molecular sieve.
Below by specific embodiment, the invention will be further elaborated.
[embodiment 1]
Preparation contains only the SAPO-34 molecular sieve of micropore.
With silica solution (30 weight %SiO2), boehmite (70 weight %Al2O3) and phosphoric acid (85 weight %H3PO4)
Respectively silicon, aluminium and phosphorus source, triethylamine NEt3For template, according to SiO2: Al2O3: P2O5: NEt3: H2O=1.0:1.0:0.6:
The molar ratio of 3:50 is mixed, mixture in 200 DEG C crystallization 48 hours.After crystallization, cooling, mistake is carried out to crystallization product
Filter, washing, 120 DEG C of drying 6 hours are denoted as A to get to routine, the SAPO-34 molecular sieve that contains only micropore.
The XRD spectra of A is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieve to be had
Some characteristic diffraction peaks, 2 θ are 9.5o、15.9o、20.5o、26oWith 31oThere is diffraction maximum, illustrates that synthesized product is pure
SAPO-34 molecular sieve, relative crystallinity are defined as 100%.
The SEM photograph of A is regular cube pattern as shown in Fig. 2, surface is very smooth, 3-5 μm of Product size.
The Micropore volume of A is 0.28cm3/ g, micropore size are distributed in 0.3~0.5nm.
According to SEM photograph, N2Physical absorption as a result, can prove that prepared is general microporous molecular sieve.
[embodiment 2]
Prepare the SAPO-34 molecular sieve seed with crystal defect.
Raw material is taken from the SAPO-34 molecular sieve-4 A that is conventional, containing only micropore according to [embodiment 1] preparation.
It weighs 30g molecular sieve-4 A and places it in the citric acid solution of 0.05M, wherein the dosage of citric acid solution is
0.9L obtains product B after stirring 10 hours at 75 DEG C after filtration, washing and drying.
The XRD spectra of B is similar with A, relative crystallinity 85%.
As shown in figure 3, apparent hole configurations occurs in the surface of molecular sieve, molecular sieve crystal has largely the SEM photograph of B
Defect.
The micropore size of B is distributed in 0.3~0.5nm, no apparent mesoporous pore size distribution, and macropore diameter is distributed in 800~
1200 nanometers.
The Kong Rongwei 0.23cm of micropore contribution3/ g, the Kong Rongwei 0.20cm of big-mesoporous contribution3/g.Therefore, big-mesoporous
The ratio that Kong Rong accounts for total pore volume is 47%.
Greatly-mesoporous specific surface area Zhan total specific surface area ratio is 25%.
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, be with crystal defect prepared by provable
Multi-stage artery structure molecular sieve.
[embodiment 3]
Prepare the SAPO-34 molecular sieve seed with crystal defect.
Preparation method is with [embodiment 2], and only raw material used is industrial general microporous SAPO-34 molecular sieve,
Products C is obtained after filtration, washing and drying.
The XRD spectra of C is similar with A, relative crystallinity 82%.
The SEM photograph of C is similar with Fig. 3, and apparent hole configurations occurs in the surface of molecular sieve, and molecular sieve crystal has largely
Defect.
The micropore size of C is distributed in 0.3~0.5nm, and mesoporous pore size distribution concentrates on 20 nanometers, and macropore diameter is distributed in
750~1150 nanometers.
The Kong Rongwei 0.25cm of micropore contribution3/ g, the Kong Rongwei 0.22cm of big-mesoporous contribution3/g.Therefore, big-mesoporous
The ratio that Kong Rong accounts for total pore volume is 47%.
Greatly-mesoporous specific surface area Zhan total specific surface area ratio is 25%.
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, be with crystal defect prepared by provable
Multi-stage artery structure molecular sieve.
[embodiment 4]
Prepare the SAPO-34 molecular sieve seed with crystal defect.
Raw material is taken from the SAPO-34 molecular sieve-4 A that is conventional, containing only micropore according to [embodiment 1] preparation.
Preparation method is with [embodiment 2], and only solution used is oxalic acid solution, concentration 0.03M, reaction temperature and when
Between be respectively 80 DEG C and 15 hours, obtain product D after filtration, washing and drying.
The XRD spectra of D is similar with the A in Fig. 1, relative crystallinity 80%.
The SEM photograph of D is similar with Fig. 3, and apparent hole configurations occurs in the surface of molecular sieve, and molecular sieve crystal has largely
Defect.
The micropore size of D is distributed in 0.3~0.5nm, no apparent mesoporous pore size distribution, and macropore diameter is distributed in 750~
1150 nanometers.
The Kong Rongwei 0.22cm of micropore contribution3/ g, the Kong Rongwei 0.18cm of big-mesoporous contribution3/g.Therefore, big-mesoporous
The ratio that Kong Rong accounts for total pore volume is 45%.
Greatly-mesoporous specific surface area Zhan total specific surface area ratio is 20%.
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, be with crystal defect prepared by provable
Multi-stage artery structure molecular sieve.
[embodiment 5]
Prepare the SAPO-34 molecular sieve seed with crystal defect.
Raw material is taken from the SAPO-34 molecular sieve-4 A that is conventional, containing only micropore according to [embodiment 1] preparation.
Preparation method is with [embodiment 2], and only solution used is tetraethyl ammonium hydroxide solution, concentration 0.10M, instead
Answering temperature and time is respectively 70 DEG C and 8 hours, obtains product E after filtration, washing and drying.
The XRD spectra of E is similar with the A in Fig. 1, relative crystallinity 85%.
The SEM photograph of E is similar with Fig. 3, and apparent hole configurations occurs in the surface of molecular sieve, and molecular sieve crystal has largely
Defect.
The micropore size of E is distributed in 0.3~0.5nm, no apparent mesoporous pore size distribution, and macropore diameter is distributed in 500~
800 nanometers.
The Kong Rongwei 0.28cm of micropore contribution3/ g, the Kong Rongwei 0.25cm of big-mesoporous contribution3/g.Therefore, big-mesoporous
The ratio that Kong Rong accounts for total pore volume is 47%.
Greatly-mesoporous specific surface area Zhan total specific surface area ratio is 25%.
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, be with crystal defect prepared by provable
Multi-stage artery structure molecular sieve.
[embodiment 6]
Preparation is simultaneously containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
With silica solution (30 weight %SiO2), boehmite (70 weight %Al2O3) and phosphoric acid (85 weight %H3PO4)
Respectively silicon, aluminium and phosphorus source, triethylamine NEt3It is template with tetraethyl ammonium hydroxide TEAOH, according to SiO2: Al2O3: P2O5:
NEt3: TEAOH:H2The molar ratio of O=1.0:1.0:0.6:2.0:1.0:50 is mixed, and is eventually adding by [embodiment 2] method
The imperfect crystal B of preparation, the additional amount of crystal are the 10% of solid content, and after crystal is added, mixture is in 200 DEG C of crystallization.Crystallization
After, to crystallization product carry out it is cooling, be filtered, washed, 120 DEG C drying 6 hours, and roast at 550 DEG C 5 hours to get
To containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve, being denoted as F simultaneously.
The XRD spectra of F is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieve to be had
Some characteristic diffraction peaks illustrate that synthesized product is pure SAPO-34 molecular sieve.
The SEM photograph of F is as shown in fig. 6, the crystal of molecular sieve is cube, but molecular sieve surface occurs more significantly
Hole configurations.
F micropore size is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 10~20nm, and macropore diameter is distributed in 300~
500 nanometers；The Kong Rongwei 0.21cm of micropore contribution3/ g, the Kong Rongwei 0.13cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.12cm3/g。
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, suffice to show that prepared is simultaneously containing micro-
Hole, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve.
[embodiment 7]
Preparation is simultaneously containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
With [embodiment 6], only imperfect crystal used is to take off after being fired by crystal C prepared by [embodiment 3] method
Template agent removing, products therefrom are denoted as G.
The XRD spectra of G is similar with the F in Fig. 1.
The SEM photograph of G is similar with Fig. 6, and molecular sieve surface has more apparent hole configurations.
G micropore size is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 10~20nm, and macropore diameter is distributed in 300~
500 nanometers；The Kong Rongwei 0.20cm of micropore contribution3/ g, the Kong Rongwei 0.15cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.13cm3/g。
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, suffice to show that prepared is simultaneously containing micro-
Hole, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve.
[embodiment 8]
Preparation is simultaneously containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
With [embodiment 6], only imperfect crystal used is the crystal D prepared by [embodiment 4] method, products therefrom note
For H.
The XRD spectra of H is similar with the F in Fig. 1.
The SEM photograph of H is similar with Fig. 6, and molecular sieve surface has more apparent hole configurations.
H micropore size is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 8~18nm, and macropore diameter is distributed in 200~
600 nanometers；The Kong Rongwei 0.21cm of micropore contribution3/ g, the Kong Rongwei 0.12cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.15cm3/g。
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, suffice to show that prepared is simultaneously containing micro-
Hole, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve.
[embodiment 9]
Preparation is simultaneously containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
With [embodiment 6], only imperfect crystal used is the crystal E prepared by [embodiment 5] method, products therefrom note
For I.
The XRD spectra of I is similar with the F in Fig. 1.
The SEM photograph of I is similar with Fig. 6, and molecular sieve surface has more apparent hole configurations.
I micropore size is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 15~25nm, and macropore diameter is distributed in 250~
600 nanometers；The Kong Rongwei 0.15cm of micropore contribution3/ g, the Kong Rongwei 0.18cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.12cm3/g。
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, suffice to show that prepared is simultaneously containing micro-
Hole, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve.
[embodiment 10]
Preparation is simultaneously containing micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve
With [embodiment 6], only imperfect crystal used is the molecular sieve of non-complete crystallization.Imperfect crystal preparation method is such as
Under: with silica solution (30 weight %SiO2), boehmite (70 weight %Al2O3) and phosphoric acid (85 weight %H3PO4) respectively
For silicon, aluminium and phosphorus source, triethylamine NEt3For template, according to SiO2: Al2O3: P2O5: NEt3: H2O=1.0:1.0:0.6:3:50
Molar ratio mixed, mixture is in 200 DEG C of crystallization 10h.After crystallization, crystallization product cool down, filter, is washed
It washs, dry and roasts, obtain the imperfect crystal for Zeolite synthesis, relative crystallinity 60%.
The micropore size of gained imperfect crystal is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 10~35nm, macropore hole
Diameter is distributed in 300~800nm.The Kong Rongwei 0.18cm of micropore contribution3/ g, the Kong Rongwei 0.10cm of big-mesoporous contribution3/g.Cause
This, the ratio that big-mesoporous Kong Rong accounts for total pore volume is 36%.Greatly-mesoporous specific surface area Zhan total specific surface area ratio is
15%.
The synthesis of molecular sieve is prepared according to the method for [embodiment 6], products obtained therefrom J.
The XRD spectra of J is similar with the F in Fig. 1.
The SEM photograph of J is similar with Fig. 6, and molecular sieve surface has more apparent hole configurations.
J micropore size is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 15~30nm, and macropore diameter is distributed in 200~
600 nanometers；The Kong Rongwei 0.22cm of micropore contribution3/ g, the Kong Rongwei 0.15cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.10cm3/g。
According to SEM photograph, N2Physical absorption and pressure mercury characterization are as a result, suffice to show that prepared is simultaneously containing micro-
Hole, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve.
[embodiment 11-15]
By [embodiment 6-10] resulting SAPO-34 molecular sieve tabletting, the catalyst for methanol to olefins reaction is made.
Using fixed-bed catalytic reactor, reactor is stainless steel tube, investigates process conditions used are as follows: loaded catalyst
2.0g, reaction temperature are 460 DEG C, weight space velocity 3h-1, pressure 0.1MPa, evaluation result is as shown in table 1.It can be seen that containing simultaneously
There are micropore, mesoporous and macropore multistage pore canal SAPO-34 molecular sieve for diene yield can be significantly improved, and urge in MTO reaction
Agent has preferable stability.
[comparative example 1]
By [embodiment 1] resulting SAPO-34 molecular sieve-4 A tabletting, the catalyst for methanol to olefins reaction is made.It adopts
With fixed-bed catalytic reactor, reactor is stainless steel tube, investigates process conditions used are as follows: loaded catalyst 2.0g,
Reaction temperature is 460 DEG C, weight space velocity 3h-1, pressure 0.1MPa, evaluation result is as shown in table 1.
Table 1
Claims (16)
1. a kind of preparation method of multi-stage artery structure molecular sieve, including using have the molecular sieve of crystal defect as crystal seed into
The step of row hydrothermal crystallizing.
2. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that described to be lacked with crystal
Sunken molecular sieve, pore structure contain macropore and/or mesoporous, the ratio of macropore and/or the mesoporous total specific surface area of specific surface area Zhan
Not less than 10%, preferably 10~30%；Macropore and/or mesoporous Kong Rong account for the ratio of total pore volume not less than 15%, preferably 15~
50%.
3. the preparation method of multi-stage artery structure molecular sieve according to claim 2, which is characterized in that described to be lacked with crystal
In sunken molecular sieve, the pore-size distribution of macropore is in 100~2000 nanometers, and mesoporous pore-size distribution is in 2~50 nanometers.
4. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that described to be lacked with crystal
Sunken molecular sieve surface pattern is coarse, and with the presence of a large amount of holes.
5. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that described to be lacked with crystal
Sunken molecular sieve is originated from non-crystallized complete molecular sieve in synthesis process.
6. the preparation method of multi-stage artery structure molecular sieve according to claim 5, which is characterized in that described non-crystallized complete
Molecular sieve be defined as, be based on the complete molecular sieve of crystallization, relative crystallinity be 50~75%.
7. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that described to be lacked with crystal
Sunken molecular sieve is originated from the step for being modified the complete molecular sieve of crystallization after post treatment.
8. the preparation method of multi-stage artery structure molecular sieve according to claim 7, which is characterized in that the post-processing is modified
Include the steps that making the complete molecular sieve of crystallization and modifying agent；The modifying agent is selected from by ammonium hydroxide, oxalic acid, citric acid, carbon
At least one of the group of sour sodium and tetraethyl ammonium hydroxide composition.
9. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that the molecular sieve is selected from
SAPO-5、SAPO-8、SAPO-11、SAPO-16、SAPO-17、SAPO-18、SAPO-20、SAPO-31、SAPO-34、SAPO-
35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, its is metalliferous
Form and its mixture.
10. the preparation method of multi-stage artery structure molecular sieve according to claim 9, which is characterized in that the molecule screening
From SAPO-34.
11. the preparation method of multi-stage artery structure molecular sieve according to claim 1, which is characterized in that the method includes
The step of by the mixture hydrothermal crystallizing of the crystal seed, silicon source, phosphorus source, silicon source, template and water.
12. the preparation method of multi-stage artery structure molecular sieve according to claim 11, which is characterized in that the mixture
In, source of aluminium, silicon source, phosphorus source, the molar ratio of template and water are 1:(0.05~2): (0.05~1.5): (1~10): (10
~200), preferably 1:(0.1~1.5): (0.2~1.2): (2~8): (30~150)；The additional amount of crystal seed is solid content
1.5~20 weight %, preferably 3~15 weight %.
13. multi-stage artery structure prepared by the preparation method of any multi-stage artery structure molecular sieve of claim 1~12 point
Son sieve.
14. the 3 multi-stage artery structure molecular sieve according to claim 1, which is characterized in that the multi-stage artery structure molecular sieve
There is micropore, mesoporous and macropore simultaneously；Wherein, micropore size is not more than 1 nanometer, and mesoporous pore size is distributed in 5~30 nanometers, macropore
Pore-size distribution is in 200~1500 nanometers；0.05~0.30 centimetre of Kong Rongwei of micropore contribution3/ gram, the Kong Rongwei of mesoporous contribution
0.10~0.40 centimetre3/ gram, 0.10~0.60 centimetre of Kong Rongwei of macropore contribution3/ gram.
15. the 3 multi-stage artery structure molecular sieve according to claim 1, which is characterized in that the multi-stage artery structure molecular sieve
For multi-stage artery structure SAPO-34 molecular sieve.
16. multi-stage artery structure prepared by the preparation method of any multi-stage artery structure molecular sieve of claim 1~12 point
Application of the son sieve in oxygenatedchemicals olefine reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209406A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of CHA/AEI composite molecular sieve, composite molecular sieve and application thereof |
| CN112619697A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555024A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Synthesis method of SAPO-34 molecular sieve |
| US20100087610A1 (en) * | 2008-10-06 | 2010-04-08 | Vaughn Stephen N | Method Of Preparing And Using A Molecular Sieve |
| CN101850986A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Method for modifying titanium-silicalite |
| CN102336412A (en) * | 2011-06-24 | 2012-02-01 | 神华集团有限责任公司 | SAPO-34 molecular sieve preparation method |
| US20120316312A1 (en) * | 2008-07-25 | 2012-12-13 | Mertens Machteld M | Synthesis of Chabazite-Containing Molecular Sieves and Their Use in the Conversion of Oxygenates to Olefins |
| CN104229829A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain SAPO-34 molecular sieve |
| CN104525250A (en) * | 2015-01-09 | 2015-04-22 | 中国科学院上海高等研究院 | SAPO-34 molecular sieve based catalyst of hierarchical pore structure and preparation and application thereof |
-
2017
- 2017-09-04 CN CN201710784663.0A patent/CN109422283B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120316312A1 (en) * | 2008-07-25 | 2012-12-13 | Mertens Machteld M | Synthesis of Chabazite-Containing Molecular Sieves and Their Use in the Conversion of Oxygenates to Olefins |
| US20100087610A1 (en) * | 2008-10-06 | 2010-04-08 | Vaughn Stephen N | Method Of Preparing And Using A Molecular Sieve |
| CN101850986A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | Method for modifying titanium-silicalite |
| CN101555024A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Synthesis method of SAPO-34 molecular sieve |
| CN102336412A (en) * | 2011-06-24 | 2012-02-01 | 神华集团有限责任公司 | SAPO-34 molecular sieve preparation method |
| CN104229829A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain SAPO-34 molecular sieve |
| CN104525250A (en) * | 2015-01-09 | 2015-04-22 | 中国科学院上海高等研究院 | SAPO-34 molecular sieve based catalyst of hierarchical pore structure and preparation and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209406A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of CHA/AEI composite molecular sieve, composite molecular sieve and application thereof |
| CN112209406B (en) * | 2019-07-12 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of CHA/AEI composite molecular sieve, composite molecular sieve and application thereof |
| CN112619697A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
| CN112619697B (en) * | 2019-09-24 | 2023-08-04 | 中国石油化工股份有限公司 | Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve |
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