CN115594196B - Modified SAPO-34 molecular sieve, and preparation method and application thereof - Google Patents
Modified SAPO-34 molecular sieve, and preparation method and application thereof Download PDFInfo
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- CN115594196B CN115594196B CN202211329635.7A CN202211329635A CN115594196B CN 115594196 B CN115594196 B CN 115594196B CN 202211329635 A CN202211329635 A CN 202211329635A CN 115594196 B CN115594196 B CN 115594196B
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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 125
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 68
- 238000002425 crystallisation Methods 0.000 claims abstract description 63
- 230000008025 crystallization Effects 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 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 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 2
- 241000269350 Anura Species 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002253 acid Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 al2O3 Chemical compound 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008689 nuclear function Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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]
-
- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a modified SAPO-34 molecular sieve, a preparation method and application thereof, and belongs to the technical field of molecular sieve materials. The method adopts the steps that seed crystals are added into the crystallization liquid, and the molecular sieve is prepared through hydrothermal crystallization under the action of a template agent, so that the crystallinity of the product is improved, and the average particle size of the product is reduced; the molecular sieve acid amount and acid distribution are further controlled through metal modification, and the microsphere catalyst prepared by spraying is applied to the reaction of preparing olefin from an oxygen-containing compound, and has high catalytic activity, high olefin selectivity and good stability under the conditions of high pressure and high airspeed. The preparation method disclosed by the invention is simple to operate, easy to realize industrial production and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of molecular sieve materials, and particularly relates to a modified SAPO-34 molecular sieve, and a preparation method and application thereof.
Background
The low-carbon olefin, especially ethylene and propylene, is the basis of modern chemical industry and plays a strong supporting role in national economy development. Currently, there are two main routes for producing low-carbon olefins such as ethylene and propylene, one is a traditional petrochemical route and the other is a coal chemical route. Along with the gradual shortage of petroleum resources and the endowment characteristics of fossil energy sources rich in coal resources, the way that the coal is clean and efficiently utilized for olefin production is determined. The methanol-to-olefin technology is significant for economic development and national energy strategy as a novel coal chemical technology route.
In 1984, the United states United Carbide Corporation (UCC) developed a silicoaluminophosphate family of SAPO-n molecular sieves (US 4440871). Wherein the SAPO-34 molecular sieve framework is formed by PO4 and AlO 4 And SiO 4 The three-dimensional framework structure formed by interconnecting the tetrahedral phases is provided with an ellipsoidal cage structure and a three-dimensional pore canal structure which are formed by oxygen eight-membered rings. The effective diameter of the molecular sieve orifice is kept between 0.43 and 0.50nm, and the special pore canal structure, proper protonic acidity and better thermal stability and hydrothermal stability lead the SAPO-34 molecular sieve to have good catalytic activity and selectivity in the reaction of preparing olefin from methanol.
In the existing technology for preparing olefin from methanol, a low-pressure low-space velocity process is mostly adopted, and under the condition of low-pressure reaction, the reactor serving as key equipment is large in volume and large in occupied area; under the condition of low space velocity reaction, the processing capacity of the device is low, so that the annual output of the product is limited, and the technical and economic benefits are affected to a certain extent. Therefore, the catalyst has important industrial significance by trying to improve the catalytic performance of the catalyst under the high-pressure high-space-velocity reaction condition, and the existing catalyst for preparing the olefin from the methanol has the defects of quick deactivation, low selectivity of the low-carbon olefin, low hydrothermal stability and the like under the high-pressure high-space-velocity condition.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified SAPO-34 molecular sieve, and a preparation method and application thereof, which are used for solving the technical problems of quick deactivation, low-carbon olefin selectivity, low hydrothermal stability and the like when the existing catalyst is used for preparing olefin from methanol.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a modified SAPO-34 molecular sieve, which comprises the following steps:
s1: mixing an aluminum source, a seed crystal, a phosphorus source and water or crystallization mother liquor to obtain a mixed solution A; mixing a silicon source, a seed crystal, a template agent and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid;
s2: aging the initial gel crystallization liquid in a hydrothermal synthesis kettle, crystallizing to obtain crystallized slurry, and treating the crystallized slurry to obtain the SAPO-34 molecular sieve.
S3: and heating the SAPO-34 molecular sieve, performing molecular activation treatment, cooling to obtain the treated SAPO-34 molecular sieve, gasifying the metal salt aqueous solution, and contacting the gasified metal salt aqueous solution with a hydrothermal synthesis kettle of the treated SAPO-34 molecular sieve to obtain the modified SAPO-34 molecular sieve.
Further, in S1, the seed crystal is a SAPO molecular sieve or an AlPO4 molecular sieve; the granularity of the seed crystal is 50 nm-12 mu m.
Further, in S1, the seed crystal is one or more of SAPO-5, SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-44, alPO4-5 and AlPO 4-11; the granularity of the seed crystal is 1-8 mu m.
Further, in S1, the aluminum source is one or more of boehmite, pseudo-boehmite, alumina sol, alumina, aluminum hydroxide, soluble aluminum salt and aluminum isopropoxide; the phosphorus source is one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide; the silicon source is one or more of silica sol, tetraethoxysilane, active silicon dioxide, white carbon black and kaolin; the template agent is one or more of diethylamine, triethylamine, morpholine, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, di-n-propylamine and diisopropylamine.
Further, in S1, the mass ratio of the seed crystal in the mixed solution a to the seed crystal in the mixed solution B is (1:7) - (4:1); the dry basis weight percentage of the seed crystal in the initial gel crystallization liquid is 0.1-5%.
Further, in S1, in the initial gel crystallization liquid, the molar ratio of SiO2, al2O3, P2O5, template agent and water is (0.05-1.2): 1: (0.8-2): (0.5-10): (30-90).
Further, in S2, the initial gel crystallization liquid is put into a hydrothermal synthesis kettle for aging treatment and crystallization treatment; the technological parameters of the aging treatment and the crystallization treatment are as follows: aging at room temperature-150 ℃ for 0-24 h, and crystallizing at 170-220 ℃ for 8-48 h; the treatment of the slurry after crystallization comprises cooling, washing, drying and roasting.
Further, in S3, heating the SAPO-34 molecular sieve to 300-600 ℃ under the protection of inert gas, stabilizing for 0.5-3 h to perform molecular activation treatment, and then cooling to 120-240 ℃ to obtain the treated SAPO-34 molecular sieve; the metal salt aqueous solution is inorganic metal salt aqueous solution or organic metal salt aqueous solution; the contact time is 0.5-3 h.
The invention also discloses a modified SAPO-34 molecular sieve prepared by the preparation method.
The invention also discloses application of the modified SAPO-34 molecular sieve, wherein the modified SAPO-34 molecular sieve is used as a catalyst in the reaction of preparing olefin from oxygen-containing compounds.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a modified SAPO-34 molecular sieve, which adopts a two-stage crystallization method, and has the advantages of more crystal nucleus formation and slower growth speed during the low-temperature stage of aging treatment, thereby being beneficial to the perfect growth of crystal nuclei; the crystal nucleus is grown rapidly in the high temperature section of crystallization treatment, and finally the molecular sieve crystal with higher crystallinity and smaller grain diameter is obtained compared with the one-step crystallization method. In addition, the seed crystal auxiliary crystallization method is adopted, and more substances with similar crystal nucleus function are provided from the beginning by adding the seed crystal, so that the molecular sieve crystal with smaller particle size can be obtained, and the crystallization time can be shortened. The special pore structure, proper protonic acidity and the like are key to the SAPO-34 molecular sieve to show good catalytic activity and selectivity in the reaction of preparing olefin from methanol. The acidity of the molecular sieve has an important impact on the MTO reaction. According to the method, the gasified metal salt aqueous solution is contacted with the SAPO-34 molecular sieve, the introduction of metal ions can cause the change of the acidity of the molecular sieve, and the acid center strength can form a medium-strength acid center after being modulated, so that the method is beneficial to the generation of low-carbon olefin; and secondly, the aperture is reduced by introducing metal ions, so that the diffusion of macromolecules is limited, the diffusion rate of small molecules is improved, and the selectivity of the low-carbon olefin is improved. The method adopts the steps that seed crystals are added into the crystallization liquid, and the molecular sieve is prepared through hydrothermal crystallization under the action of a template agent, so that the crystallinity of the product is improved; the preparation method is simple to operate, easy to realize industrialized production and has wide application prospect.
The invention also discloses the modified SAPO-34 molecular sieve prepared by the method, and the molecular sieve is prepared by adding seed crystals into crystallization liquid and performing hydrothermal crystallization under the action of a template agent, so that the obtained modified SAPO-34 molecular sieve has high catalytic activity, high olefin selectivity and good stability, and has a wide application prospect.
The invention also discloses the application of the modified SAPO-34 molecular sieve as a catalyst in the reaction of preparing olefin from methanol, and the related experimental results show that the modified molecular sieve prepared by the method is prepared into a fluidized bed catalyst, and is applied to the reaction of preparing low-carbon olefin from methanol, wherein the reaction temperature is 450-500 ℃, the reaction pressure is 0.15-0.4 MPaG, and the space velocity is 5-10 h -1 Under the high pressure and high space velocity reaction condition, the total diene selectivity of ethylene and propylene can exceed 87 percent, the total low-carbon olefin selectivity of ethylene, propylene and butylene can be close to 94 percent, and the catalytic effect is obvious.
Drawings
FIG. 1 is an XRD pattern of a modified SAPO-34 molecular sieve prepared according to various examples of the invention, and a molecular sieve of a comparative example.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
Research shows that the small-grain molecular sieve carrier can raise the specific activity of molecular sieve, shorten the diffusion path of reactant and product molecule, reduce diffusion limit, prolong the service life of catalyst and raise the carbon deposit deactivation resistance of catalyst. However, the existing method for reducing the crystal size of the SAPO-34 molecular sieve product by adopting seed crystal auxiliary crystallization has definite limit on the seed crystal size, and nano-scale particles are required. The reaction of preparing olefin from methanol belongs to the solid acid catalytic reaction, the strength and the number of acid centers in a molecular sieve framework directly influence the selectivity of low-carbon olefin, and the proper acid quantity and acid distribution are beneficial to the generation of low-carbon olefin. The introduction of metal ions causes changes in molecular sieve acidity and pore size. The small pore opening can limit the diffusion of macromolecules, is favorable for the improvement of the selectivity of small-molecule low-carbon olefin, can form an acid center with medium strength after the strength of the acid center is modulated, and is also favorable for the generation of low-carbon olefin.
The method adopts the steps that seed crystals are added into the crystallization liquid, and the molecular sieve is prepared through hydrothermal crystallization under the action of a template agent, so that the crystallinity of the product is improved; the molecular sieve acid amount and acid distribution are further controlled through metal modification, and the microsphere catalyst prepared by spraying is applied to the reaction of preparing olefin from an oxygen-containing compound, and has high catalytic activity, high olefin selectivity and good stability under the conditions of high pressure and high airspeed.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means molar ratios, unless otherwise specified.
Example 1
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing pseudo-boehmite (aluminum source), SAPO-5 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; mixing template agent composed of silica sol (silicon source), SAPO-5 (seed crystal), morpholine and tetraethylammonium hydroxide with water to obtainMixing the solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, the mole ratio of morpholine to tetraethylammonium hydroxide in the template agent is 10:1, in the initial gel crystallization liquid obtained, the mole ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.3:1:0.8:3.4:55, the mass ratio of the seed crystal to the crystallization liquid dry basis is 0.1%, and the adding ratio of the seed crystal for the previous and the subsequent two times is 2:1, a step of;
s2: placing the obtained initial gel crystallization liquid into a hydrothermal synthesis kettle, firstly aging at 150 ℃ for 12 hours, then crystallizing at 200 ℃ for 20 hours, and then cooling, washing, drying and roasting to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 400 ℃ under the protection of inert gas, stabilizing for 2 hours to perform molecular activation treatment, and then cooling to 150 ℃; and (3) gasifying the calcium nitrate aqueous solution, and then, contacting the gasified calcium nitrate aqueous solution with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 1h to obtain the modified SAPO-34 molecular sieve, wherein the content of Ca metal ions in the modified SAPO-34 molecular sieve is 2.45%.
Example 2
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing aluminum isopropoxide (aluminum source), SAPO-11 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; ethyl orthosilicate (silicon source), SAPO-11 (seed), triethylamine: mixing a template agent consisting of diethylamine with water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, triethylamine in the template agent: the molar ratio of diethylamine is 4:1, in the initial gel crystallization liquid obtained, the mole ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.8:1:1:8:70, the mass ratio of the seed crystal to the crystallization liquid dry basis is 2%, and the adding ratio of the seed crystal for the two times before and after is 4:1, a step of;
s2: the obtained initial gel crystallization liquid is put into a hydrothermal synthesis kettle, aged for 16 hours at 100 ℃, crystallized for 48 hours at 170 ℃, cooled, washed, dried and roasted to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 300 ℃ under the protection of inert gas, stabilizing for 3 hours to perform molecular activation treatment, and then cooling to 120 ℃; and gasifying the mixed aqueous solution of magnesium nitrate and manganese nitrate, and then contacting the gasified mixed aqueous solution with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 3 hours to obtain the modified SAPO-34 molecular sieve, wherein the content of Mg metal ions in the modified SAPO-34 molecular sieve is 2.45%, and the content of Mn metal ions is 2.96%.
Example 3
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing aluminum sol (aluminum source), alPO4-5 (seed crystal) and phosphorus pentoxide (phosphorus source) with water at room temperature to obtain a mixed solution A; mixing active silicon dioxide (silicon source), alPO4-5 (seed crystal), di-n-propylamine (template agent) and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; in the initial gel crystallization liquid obtained, the mole ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.05:1:1.5:10:30, the mass ratio of the seed crystal to the crystallization liquid dry basis is 4%, and the adding ratio of the seed crystal for the two previous and subsequent times is 1:7, preparing a base material;
s2: placing the obtained initial gel crystallization liquid into a hydrothermal synthesis kettle, crystallizing at 220 ℃ for 8 hours, and then cooling, washing, drying and roasting to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 550 ℃ under the protection of inert gas, stabilizing for 2 hours to perform molecular activation treatment, and then cooling to 200 ℃; and gasifying the aqueous solution of zinc acetate, and then contacting the gasified aqueous solution of zinc acetate with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 0.5h to obtain the modified SAPO-34 molecular sieve, wherein the content of Zn metal ions in the modified SAPO-34 molecular sieve is 1.12%.
Example 4
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing boehmite (aluminum source), alPO4-11 (seed crystal) and phosphorous acid (phosphorus source) with water at room temperature to obtain a mixed solution A; mixing template agent composed of tetraethoxysilane (silicon source), alPO4-11 (seed crystal), diisopropylamine and tetraethylammonium chloride with water to obtain mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, the mol ratio of diisopropylamine and tetraethylammonium chloride in the template agent is 1:2, in the initial gel crystallization liquid obtained, the mole ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=1.2:1:2:0.5:50, the mass ratio of the seed crystal to the crystallization liquid dry basis is 1%, and the adding ratio of the seed crystal for the two times is 1:1, a step of;
s2: the obtained initial gel crystallization liquid is put into a hydrothermal synthesis kettle, aged for 24 hours at 120 ℃, crystallized for 30 hours at 180 ℃, cooled, washed, dried and roasted to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 600 ℃ under the protection of inert gas, stabilizing for 0.5h for molecular activation treatment, and then cooling to 160 ℃; and gasifying the mixed aqueous solution of strontium chloride and nickel nitrate, and then contacting the gasified mixed aqueous solution with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 1.5 hours to obtain the modified SAPO-34 molecular sieve, wherein the content of Sr metal ions in the modified SAPO-34 molecular sieve is 1.18%, and the content of Ni metal ions is 2.43%.
Example 5
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing pseudo-alumina (aluminum source), SAPO-18 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; mixing a template agent consisting of white carbon black (silicon source), SAPO-18 (seed crystal), triethylamine and tetraethyl ammonium bromide with water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, the mol ratio of triethylamine and tetraethylammonium bromide in the template agentIs 3:1, in the initial gel crystallization liquid obtained, the mole ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.4:1:0.95:6:90, the mass ratio of the seed crystal to the crystallization liquid dry basis is 3%, and the adding ratio of the seed crystal for the two times is 1:3, a step of;
s2: the obtained initial gel crystallization liquid is put into a hydrothermal synthesis kettle, aged for 24 hours at room temperature, crystallized for 16 hours at 210 ℃, and subjected to cooling treatment, washing treatment, drying treatment and roasting treatment to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 450 ℃ under the protection of inert gas, stabilizing for 3 hours to perform molecular activation treatment, and then cooling to 240 ℃; and gasifying the mixed aqueous solution of cobalt acetate and nickel acetate, and then contacting the gasified mixed aqueous solution with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 2 hours to obtain the modified SAPO-34 molecular sieve, wherein the content of Co metal ions in the modified SAPO-34 molecular sieve is 0.27%, and the content of Ni metal ions is 0.30%.
Example 6
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing aluminum hydroxide (aluminum source), SAPO-34 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; mixing kaolin (silicon source), SAPO-34 (seed crystal), tetraethylammonium hydroxide (template agent) and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, in the obtained initial gel crystallization liquid, the mol ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.6:1:1.3:1.6:45, the mass ratio of the seed crystal to the crystallization liquid dry basis is 5%, and the adding ratio of the seed crystal for the previous and the subsequent two times is 3:1, a step of;
s2: placing the obtained initial gel crystallization liquid into a hydrothermal synthesis kettle, firstly aging at 80 ℃ for 12 hours, then crystallizing at 175 ℃ for 36 hours, and then cooling, washing, drying and roasting to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 300 ℃ under the protection of inert gas, stabilizing for 2.5h to perform molecular activation treatment, and then cooling to 210 ℃; and gasifying the aqueous solution of ferric chloride, and then contacting the gasified aqueous solution of ferric chloride with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 2 hours to obtain the modified SAPO-34 molecular sieve, wherein the content of Fe metal ions in the modified SAPO-34 molecular sieve is 0.2%.
Example 7
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing aluminum isopropoxide (aluminum source), SAPO-44 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; mixing silica sol (silicon source), SAPO-44 (seed crystal), triethylamine (template agent) and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein, in the obtained initial gel crystallization liquid, the mol ratio of each oxide is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.2:1:1:3.2:60, the mass ratio of the seed crystal to the crystallization liquid dry basis is 3%, and the adding ratio of the seed crystal for the two times is 1:5;
s2: placing the obtained initial gel crystallization liquid into a hydrothermal synthesis kettle, firstly aging at 140 ℃ for 8 hours, then crystallizing at 220 ℃ for 24 hours, and then cooling, washing, drying and roasting to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 500 ℃ under the protection of inert gas, stabilizing for 1h to perform molecular activation treatment, and then cooling to 180 ℃; and gasifying the aqueous solution of nickel nitrate, and then contacting the gasified aqueous solution of nickel nitrate with the treated SAPO-34 molecular sieve in a hydrothermal synthesis kettle for 3 hours to obtain the modified SAPO-34 molecular sieve, wherein the nickel metal ion content in the modified SAPO-34 molecular sieve is 0.84%.
Example 8
The preparation method of the modified SAPO-34 molecular sieve comprises the following steps:
s1: mixing pseudo-boehmite (aluminum source), SAPO-35 (seed crystal), phosphoric acid (phosphorus source) and water at room temperature to obtain a mixed solution A; silica sol (silicon source), SAPO-35 (seed crystal), triethylamine and diethylamine are formedMixing the template agent and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid; wherein the mol ratio of triethylamine to diethylamine is 7:1, and the mol ratio of each oxide in the obtained initial gel crystallization liquid is SiO 2 :Al 2 O 3 :P 2 O 5 :R:H 2 O=0.25:1:1.1:4.5:40, the mass ratio of the seed crystal to the crystallization liquid dry basis is 2.5%, and the adding ratio of the seed crystal for the previous and the subsequent two times is 2:1;
s2: placing the obtained initial gel crystallization liquid into a hydrothermal synthesis kettle, firstly aging at 150 ℃ for 10 hours, then crystallizing at 200 ℃ for 28 hours, and then cooling, washing, drying and roasting to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve to 600 ℃ under the protection of inert gas, stabilizing for 1h to perform molecular activation treatment, and then cooling to 120 ℃; and gasifying the aqueous solution of zinc nitrate, and then contacting the gasified aqueous solution with the treated SAPO-34 molecular sieve for 2.5 hours to obtain the modified SAPO-34 molecular sieve, wherein the Zn metal ion content in the modified SAPO-34 molecular sieve is 0.69%.
The seed crystals used in the above examples, SAPO-5, SAPO-11, alPO4-5, alPO4-11, SAPO-34, were purchased from a new materials Co., ltd; SAPO-35, SAPO-18, SAPO-34, and SAPO-44 molecular sieves are available from a company.
In the embodiment, firstly, mixing an aluminum source, a seed crystal, water or crystallization mother liquor, and then adding a phosphorus source to form a mixed solution; mixing a silicon source, a seed crystal, a template agent and water to form another mixed solution; mixing, crystallizing, cooling, centrifuging, drying and roasting the two mixed liquids to obtain the SAPO-34 molecular sieve. The template, raw materials, raw material ratios (molar ratios), mass ratios of seed crystals and crystallization liquid dry basis, crystallization temperatures and times required for preparing SAPO-34 are shown in Table 1 below.
Table 1 statistics of parameters for the preparation of SAPO-34 molecular sieves from examples 1 to 8
The SAPO-34 molecular sieves prepared in the examples 1 to 8 are respectively filled into a fixed bed or a tubular furnace reactor, nitrogen is introduced for activation, then the temperature is reduced, and the gasified metal salt solution is contacted with the molecular sieves to finish modification. Mixing and pulping the modified molecular sieve, a binder and a matrix material, spray forming and roasting to obtain the microsphere catalyst for the reaction of preparing olefin from methanol. The activation conditions, modified salt solutions, modification conditions, modified molecular sieve metal content, etc. for preparing the modified SAPO-34 are listed in table 2.
TABLE 2 parameter statistics for preparing modified SAPO-34 molecular sieves from examples 1-8
Application examples
The modified SAPO-34 molecular sieves prepared in examples 2 to 6, and the purchased molecular sieves of comparative examples 1 and 2 were each weighed 5g of sample and charged into a fixed fluidized bed microreactor, and methanol-to-olefin reaction evaluation was performed. Methanol is pumped into the gasification reactor by a plunger pump, gasified and then enters the fixed fluidized bed reactor. The reaction temperature was 465℃and the reaction pressure was 0.2MPaG, methanol (80 wt%) weight space velocity was 6h -1 . The obtained product was analyzed by gas chromatography on line, and the analysis data results are shown in Table 3.
As can be seen from Table 3, the overall selectivity (highest (ethylene+propylene) selectivity at 99.5% methanol conversion) of ethylene and propylene of the catalyst containing SAPO-34 active components prepared by the method of the invention is improved to different degrees, and the catalyst has high diene selectivity and low olefin selectivity under high pressure and high space velocity reaction conditions.
TABLE 3 results of methanol-to-olefins reaction at high pressure and high space velocity for samples
The modified SAPO-34 molecular sieves prepared in examples 2 to 6 were respectively weighed 5g of the samples and put into a fixed fluidized bed microreactor for evaluation of methanol-to-olefin reaction, and the obtained online detection results are shown in Table 4. It can be seen from Table 4 that under the high pressure and high space velocity reaction conditions, the diene selectivity and the low carbon olefin selectivity are both high.
Table 4 sample results of methanol-to-olefins reaction under different conditions
FIG. 1 shows XRD patterns of modified SAPO-34 molecular sieves prepared in examples 2 to 6, and commercially available molecular sieves of comparative examples 1 and 2, and it can be seen from the figure that the crystalline phases of examples and comparative examples are CHA structures.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. The preparation method of the modified SAPO-34 molecular sieve is characterized by comprising the following steps of:
s1: mixing an aluminum source, a seed crystal, a phosphorus source and water or crystallization mother liquor to obtain a mixed solution A; mixing a silicon source, a seed crystal, a template agent and water to obtain a mixed solution B; mixing the mixed solution A and the mixed solution B, and reacting to obtain initial gel crystallization liquid;
in the S1, the mass ratio of the seed crystal in the mixed solution A to the seed crystal in the mixed solution B is (1:7) - (4:1); the dry basis weight percentage of the seed crystal in the initial gel crystallization liquid is 0.1% -5%;
s2: aging the initial gel crystallization liquid, crystallizing to obtain crystallized slurry, and treating the crystallized slurry to obtain the SAPO-34 molecular sieve;
s3: heating the SAPO-34 molecular sieve, performing molecular activation treatment, cooling to obtain a treated SAPO-34 molecular sieve, gasifying the metal salt aqueous solution, and contacting the gasified metal salt aqueous solution with the treated SAPO-34 molecular sieve to obtain a modified SAPO-34 molecular sieve;
s3, heating the SAPO-34 molecular sieve to 300-600 ℃ under the protection of inert gas, stabilizing for 0.5-3 h to perform molecular activation treatment, and then cooling to 120-240 ℃ to obtain the treated SAPO-34 molecular sieve; the metal salt aqueous solution is inorganic metal salt aqueous solution or organic metal salt aqueous solution; the contact time is 0.5-3 h.
2. The method for preparing a modified SAPO-34 molecular sieve as defined in claim 1, wherein in S1, the seed crystal is a SAPO molecular sieve or an AlPO4 molecular sieve; the granularity of the seed crystal is 50 nm-12 mu m.
3. The method for preparing a modified SAPO-34 molecular sieve as defined in claim 2, wherein in S1, the seed crystal is one or more of SAPO-5, SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-44, alPO4-5 and AlPO 4-11; the granularity of the seed crystal is 1-8 mu m.
4. The method of claim 1, wherein in S1, the aluminum source is one or more of boehmite, pseudo-boehmite, alumina sol, alumina, aluminum hydroxide, soluble aluminum salt and aluminum isopropoxide; the phosphorus source is one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide; the silicon source is one or more of silica sol, tetraethoxysilane, active silicon dioxide, white carbon black and kaolin; the template agent is one or more of diethylamine, triethylamine, morpholine, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, di-n-propylamine and diisopropylamine.
5. The method of claim 1, wherein in S1, the initial gel crystallization liquid comprises SiO 2 、Al 2 O 3 、P 2 O 5 The molar ratio of the template agent to the water is (0.05-1.2): 1: (0.8-2): (0.5-10): (30-90).
6. The method for preparing a modified SAPO-34 molecular sieve as defined in claim 1, wherein in S2, the initial gel crystallization liquid is put into a hydrothermal synthesis kettle for aging treatment and crystallization treatment; the technological parameters of the aging treatment and the crystallization treatment are as follows: aging at room temperature to 150 ℃ for 8-24 hours, and crystallizing at 170-220 ℃ for 8-48 hours; the treatment of the slurry after crystallization comprises cooling, washing, drying and roasting.
7. A modified SAPO-34 molecular sieve, characterized in that it is prepared by a method for preparing a modified SAPO-34 molecular sieve according to any one of claims 1 to 6.
8. The use of the modified SAPO-34 molecular sieve as claimed in claim 7, as a catalyst in an oxygenate to olefins reaction.
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