CN109264740A - A kind of preparation method and application of nanometer of SAPO-34 molecular sieve - Google Patents
A kind of preparation method and application of nanometer of SAPO-34 molecular sieve Download PDFInfo
- Publication number
- CN109264740A CN109264740A CN201811154321.1A CN201811154321A CN109264740A CN 109264740 A CN109264740 A CN 109264740A CN 201811154321 A CN201811154321 A CN 201811154321A CN 109264740 A CN109264740 A CN 109264740A
- Authority
- CN
- China
- Prior art keywords
- solution
- sapo
- nanometer
- molecular sieve
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- 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 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 8
- 239000010935 stainless steel Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- -1 aluminum alkoxide Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 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 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- SNEFVJQHWBOIMY-UHFFFAOYSA-M hexadecyl(trimethoxy)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](OC)(OC)OC SNEFVJQHWBOIMY-UHFFFAOYSA-M 0.000 claims 1
- 230000001629 suppression Effects 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The preparation method and application of a kind of nanometer of SAPO-34 molecular sieve, is related to catalyst.Nanometer SAPO-34 molecular sieve is with a thickness of 10~100nm, and average grain diameter is the nanometer sheet of 300nm~1 μm.Silicon source is added to the water, stirs, is configured to solution 1；Silicon source is added in solution 1, stirring is configured to solution 2；Template is added in solution 2, stirring is configured to solution 3；Inhibitor is added in solution 3, stirring is configured to solution 4；Phosphorus source is added in solution 4, stirring is configured to solution 5；Solution 5 is placed in water-bath, heating stirring obtains gel；Gained gel is added to the water, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, heats, reaction kettle is cooled to room temperature, is washed, dry, roasting obtains a nanometer SAPO-34 molecular sieve.The nanometer SAPO-34 molecular sieve is applied in the reaction for preparing light olefins from methanol, i.e. MTO reaction.
Description
Technical field
The present invention relates to catalyst, more particularly, to a kind of nanometer of SAPO-34 molecular sieve and the preparation method and application thereof.
Background technique
SAPO-34 molecular sieve is a kind of micro-pore zeolite molecular sieve with CHA topological structure, since it has suitable acid
The advantages that intensity, good hydrothermal stability, shows good catalytic performance in methanol-to-olefins (MTO) reaction.So
And the SAPO-34 molecule sieve size of conventional method preparation is larger, is all cube or cuboid, granularity is usually in 1~5 μ
M causes the utilization rate of its active sites lower, and its micropore canals is long and narrow, and it is short etc. to will lead to MTO reaction easy in inactivation, single pass life
Problem.Studies have shown that reducing SAPO-34 zeolite crystal size, the resistance to mass tranfer in reaction, intensified response process can reduce
In diffusion, so as to achieve the effect that reduce carbon distribution, extend catalyst life.
Currently, researchers mainly use mixed templates method, Microwave-assisted firing method, SAPO-34 crystal seed method, ultrasound point
The methods of arching pushing synthesizes a nanometer SAPO-34.Such as, Shima Masoumi etc. (Applied Catalysis A General,
2015,493:103-111) synthesized using mixed templates (diethylamine, triethylamine, tetraethyl ammonium hydroxide, morpholine)
SAPO-34 size is 0.64~3.25 μm.Hendrik van Heyden etc. (Chemistry of Materials,
2008,20 (9): 2956-2963) according to micro-wave oven hydro-thermal process molecular sieve, the SAPO-34 size synthesized is 100nm
Cube, they have found compared with traditional hydrothermal synthesis, and micro-wave oven hydro-thermal process energy utilization rate is high, the nanometer synthesized
SAPO-34 has the characteristics that rapidly and uniformly nucleation rate, regular appearance.(the Chemical Communications such as Chen
2017,53 (100): 13328) using the method for addition crystal seed SAPO-34 come synthesis of molecular sieve, the SAPO-34 size that synthesizes
Size is 100-600nm.(2012,19 (3): Ultrasonics Sonochemistry 554) utilizes ultrasound to S.Askari etc.
Method synthesizes nanometer SAPO-34, and obtained SAPO-34 is the spherical shape of 100~600nm size, they have found to synthesize using ultrasonic method
Molecular sieve has the characteristics that simple and effective, molecular sieve size is adjustable.
The above method has been achieved with significant achievement, but still has certain difficulty, for example Microwave-assisted firing method synthesizes
Technical requirements are high, and cost is big；The molecule sieve size that mixed templates method, SAPO-34 crystal seed method and ultrasonic dispersion synthesize compared with
Greatly, unevenly the features such as, can not achieve industrialization.This application provides the synthetic method of a kind of nanometer of SAPO-34 molecular sieve,
Inhibitor is added, and passes through the ratio of modulation template and inhibitor, is synthesized with a thickness of nanoscale lamella pattern molecular sieve,
Reactivity worth is improved, the service life of catalyst is substantially extended.And preparation process is simple, at low cost, yield is higher, is suitble to big rule
Mould industrial production.
Summary of the invention
The first object of the present invention, which is to provide, can reach reduction carbon distribution, enhance a kind of nanometer of SAPO-34 of service life effect
Molecular sieve.
The second object of the present invention is to provide the preparation method of a kind of nanometer of SAPO-34 molecular sieve.
The third object of the present invention is to provide the application of a kind of nanometer of SAPO-34 molecular sieve.
The nanometer SAPO-34 molecular sieve is with a thickness of 10~100nm, and average grain diameter is the nanometer sheet of 300nm~1 μm.
The preparation method of the nanometer SAPO-34 molecular sieve the following steps are included:
1) silicon source is added to the water, stirs, is configured to solution 1；
In step 1), source of aluminium can be selected from boehmite, aluminium isopropoxide, sodium aluminate, activated alumina, alkoxy
At least one of aluminium etc.；The concentration of volume percent of the solution 1 can be 3%~10%, time of the stirring can for 1~
10h。
2) silicon source is added in solution 1, stirring is configured to solution 2；
In step 2), the silicon source can be selected from silica solution, ethyl orthosilicate, sodium metasilicate, fumed silica, activity two
At least one of silica etc.；The molar ratio of the silicon source and silicon source can be 0.06~0.6, and the time of the stirring can be 1
~10h.
3) template is added in solution 2, stirring is configured to solution 3；
In step 3), the template can be selected from tetraethylammonium bromide, dimethyl stearyl [3- (trimethoxy silicon
Base) propyl] ammonium chloride (TPOAC), dimethyl hexadecyl base [3- (trimethoxy silicon substrate) propyl] ammonium chloride (TPHAC), 16
Alkyl trimethoxy ammonium bromide (CTAB), diethylamine (DEA), triethylamine (TEA), morpholine (MOR), tetraethyl ammonium hydroxide
At least one of (TEAOH) etc.；The molar ratio of the template and silicon source can be 0.05~4.0, and the time of the stirring is 1
~5h.
4) inhibitor is added in solution 3, stirring is configured to solution 4；
In step 4), the inhibitor can be selected from polyethylene glycol (PEG), dodecyl polyoxyethylene ether (Brij-35),
At least one of methylenum careuleum (MB) etc.；The molar ratio of the inhibitor and silicon source can be 0.02~0.6, the time of the stirring
It can be 1~3h.
5) phosphorus source is added in solution 4, stirring is configured to solution 5；
In step 5), phosphorus source can be selected from least one in phosphoric acid, phosphate, phosphite, tributyl phosphate etc.
Kind；The molar ratio of phosphorus source and silicon source can be 0.05~2.0, and the time of the stirring can be 10~36h.
6) solution 5 is placed in water-bath, heating stirring obtains gel；
In step 6), the temperature of the heating can be 60~100 DEG C, and the time of the stirring can be 0.5~5h.
7) gel obtained by step 6) is added to the water, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, adds
Reaction kettle is cooled to room temperature by heat, is washed, dry, and roasting obtains a nanometer SAPO-34 molecular sieve.
In step 7), the mass ratio of the water and gel can be (10~20) ︰ 1；The condition of the heating can be in baking oven
In in 170~220 DEG C of 6~96h of heating；The condition of the drying can in a vacuum drying oven dry 6 at 80~120 DEG C~
12h；The roasting can be roasted in Muffle furnace, wherein maturing temperature can be 400~600 DEG C, and the rate of roasting can be 2~3
DEG C/min, the time of roasting can be 2~8h.
The nanometer SAPO-34 molecular sieve can answer in the reaction for preparing light olefins from methanol (ethylene, propylene, butylene)
With i.e. MTO reaction.The step of application, is as follows:
Nanometer SAPO-34 molecular sieve is fitted into fixed bed high pressure microreactor, MTO reaction, reaction condition are carried out are as follows:
Methanol is carried by nitrogen, and methanol quality air speed is 2.0~4.0h-1, nitrogen volume space velocity is 5000~8000h-1, reaction temperature
It is 400~450 DEG C, the reaction time is 10h or more.
The nanometer SAPO-34 molecular sieve can characterize it by the method for X-ray diffraction (XRD), scanning electron microscope (SEM)
Crystal structure, pattern size.
Compared with prior art, the beneficial effect of nanometer SAPO-34 molecular sieve provided by the invention is mainly reflected in following
Aspect:
(1) catalyst provided by the invention has excellent catalytic performance in MTO reaction, so that C2-4Olefine selective
Up to 85% or more.
(2) by changing different templates agent, the conditions such as inhibitor, can effectively the partial size to SAPO-34 molecular sieve into
Row regulation, changes its thickness between 300nm~1 μm in 10~100nm, average grain diameter.
(3) the nanometer SAPO-34 molecule sieve size produced is smaller, improves conversion ratio and selectivity in reaction, greatly
Width extends the service life of catalyst.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1~6 and comparative example 1 are related to the XRD spectra of catalyst.
Fig. 2 is 1 scanning electron microscope (SEM) photograph of the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment, the system for provided a kind of nanometer of SAPO-34 molecular sieve that present invention be described in more detail
Preparation Method and catalytic applications.
Embodiment 1
It weighs 3.4g boehmite to be added in 39.6g deionized water, stirs 2h at room temperature, form solution 1；It weighs
The silica solution of 0.6g is added in solution 1, stirs 2h at room temperature, forms solution 2；The tetraethyl ammonium hydroxide for weighing 21.2g adds
Enter into solution 2, stir 2h, forms solution 3；It weighs 0.39g polyethylene glycol to be added in solution 3, stirs 2h, form solution 4；
It weighs 4.62g phosphoric acid to be added in solution 4, stirs 36h at room temperature, form solution 5；Solution 5 is put into water-bath, 90 DEG C
Lower stirring 4h forms gel；The deionized water of 40g is added in gel, then its whole is transferred to polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene liner, heated for 24 hours at 180 DEG C；Reaction kettle is cooled to room temperature, mother liquor centrifugation is taken out, by it
Then centrifuge washing puts it into dry 8h under 100 DEG C of baking oven to neutrality；By gained sample as in dry air, with 3
DEG C/heating rate of min rises to 600 DEG C of roasting 8h, the solid sample after roasting is formed, sieving obtains 30~60 purposes
Grain, as molecular sieve are labeled as SAPO-34-1.Scanning electron microscope (SEM) photo is as shown in Fig. 2, SEM photograph shows that product is to receive
Rice sheet.
The catalysis reaction carries out in fixed bed high pressure microreactor, which is characterized in that it is low to be mainly used for methanol system
Carbene hydrocarbon reaction, steps are as follows: weighing 1.0g molecular sieve and is fitted into fixed bed high pressure microreactor, carries out MTO reaction.Reaction
Condition are as follows: methanol is carried by nitrogen, and methanol quality air speed is 2.0~4.0h-1, nitrogen volume space velocity is 5000~8000h-1, instead
Answering temperature is 400~450 DEG C, and the reaction time is 10h or more.Specific reactivity worth is listed in Table 1 below.
Embodiment 2
It weighs 3.4g boehmite to be added in 39.6g deionized water, stirs 2h at room temperature, form solution 1；It weighs
The silica solution of 0.6g is added in solution 1, stirs 2h at room temperature, forms solution 2；The tetraethyl ammonium hydroxide for weighing 21.2g adds
Enter into solution 2, stir 2h, forms solution 3；It weighs 1.32g polyethylene glycol to be added in solution 3, stirs 2h, form solution 4；
It weighs 4.62g phosphoric acid to be added in solution 4, stirs 36h at room temperature, form solution 5；Solution 5 is put into water-bath, 90 DEG C
Lower stirring 4h forms gel；The deionized water of 40g is added in gel, then its whole is transferred to polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene liner, heated for 24 hours at 180 DEG C；Reaction kettle is cooled to room temperature, mother liquor centrifugation is taken out, by it
Then centrifuge washing puts it into dry 8h under 100 DEG C of baking oven to neutrality；By gained sample as in dry air, with 3
DEG C/heating rate of min rises to 600 DEG C of roasting 8h, the solid sample after roasting is formed, sieving obtains 30~60 purposes
Grain, as molecular sieve are labeled as SAPO-34-2.Catalysis reaction is carried out in fixed bed high pressure microreactor, reaction condition and
For product analysis with embodiment 1, reactivity worth is shown in Table 1.
Embodiment 3
It weighs 3.4g boehmite to be added in 39.6g deionized water, stirs 2h at room temperature, form solution 1；It weighs
The silica solution of 0.6g is added in solution 1, stirs 2h at room temperature, forms solution 2；The tetraethyl ammonium hydroxide for weighing 21.2g adds
Enter into solution 2, stir 2h, forms solution 3；It weighs 1.98g polyethylene glycol to be added in solution 3, stirs 2h, form solution 4；
It weighs 4.62g phosphoric acid to be added in solution 4, stirs 36h at room temperature, form solution 5；Solution 5 is put into water-bath, 90 DEG C
Lower stirring 4h forms gel；The deionized water of 40g is added in gel, then its whole is transferred to polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene liner, heated for 24 hours at 180 DEG C；Reaction kettle is cooled to room temperature, mother liquor centrifugation is taken out, by it
Then centrifuge washing puts it into dry 8h under 100 DEG C of baking oven to neutrality；By gained sample as in dry air, with 3
DEG C/heating rate of min rises to 600 DEG C of roasting 8h, the solid sample after roasting is formed, sieving obtains 30~60 purposes
Grain, as molecular sieve are labeled as SAPO-34-3.Catalysis reaction is carried out in fixed bed high pressure microreactor, reaction condition and
For product analysis with embodiment 1, reactivity worth is shown in Table 1.
Embodiment 4
It weighs 3.4g boehmite to be added in 39.6g deionized water, stirs 2h at room temperature, form solution 1；It weighs
The silica solution of 0.6g is added in solution 1, stirs 2h at room temperature, forms solution 2；The tetraethyl ammonium hydroxide for weighing 21.2g adds
Enter into solution 2, stir 2h, forms solution 3；It weighs 3.96g polyethylene glycol to be added in solution 3, stirs 2h, form solution 4；
It weighs 4.62g phosphoric acid to be added in solution 4, stirs 36h at room temperature, form solution 5；Solution 5 is put into water-bath, 90 DEG C
Lower stirring 4h forms gel；The deionized water of 40g is added in gel, then its whole is transferred to polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene liner, heated for 24 hours at 180 DEG C；Reaction kettle is cooled to room temperature, mother liquor centrifugation is taken out, by it
Then centrifuge washing puts it into dry 8h under 100 DEG C of baking oven to neutrality；By gained sample as in dry air, with 3
DEG C/heating rate of min rises to 600 DEG C of roasting 8h, the solid sample after roasting is formed, sieving obtains 30~60 purposes
Grain, as molecular sieve are labeled as SAPO-34-4.Catalysis reaction is carried out in fixed bed high pressure microreactor, reaction condition and
For product analysis with embodiment 1, reactivity worth is shown in Table 1.
Embodiment 5
Step in the present embodiment with it is identical in embodiment 2, unlike: template by 21.2g tetraethyl
Ammonium hydroxide changes into the triethylamine of 9.51g, is labeled as SAPO-34-5.Catalysis reaction is in fixed bed high pressure microreactor
It carries out, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Embodiment 6
Step in the present embodiment with it is identical in embodiment 2, unlike: silicon source by 3.4g boehmite
It is changed to the aluminium isopropoxide of 5.2g, is labeled as SAPO-34-6.Catalysis reaction carries out in fixed bed high pressure microreactor, reacts
With embodiment 1, reactivity worth is shown in Table 1 for condition and product analysis.
Comparative example 1
It weighs 3.4g boehmite to be added in 39.6g deionized water, stirs 2h at room temperature, form solution 1；It weighs
The silica solution of 0.6g is added in solution 1, stirs 2h at room temperature, forms solution 2；The tetraethyl ammonium hydroxide for weighing 21.2g adds
Enter into solution 2, stir 2h, forms solution 3；It weighs 4.62g phosphoric acid to be added in solution 3, stirs 36h at room temperature, formed molten
Liquid 4；Solution 4 is put into water-bath, 4h is stirred at 90 DEG C, forms gel；The deionized water of 40g is added in gel,
Then its whole is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is heated for 24 hours at 180 DEG C；It will reaction
Kettle is cooled to room temperature, and takes out mother liquor centrifugation, then its centrifuge washing to neutrality is put it into dry under 100 DEG C of baking oven
8h；By gained sample as in dry air, 600 DEG C of roasting 8h are risen to the heating rate of 3 DEG C/min, by the solid after roasting
Sample formation, sieving obtain the particle of 30~60 mesh, as molecular sieve, are labeled as SAPO-34-7.Catalysis reaction is in the fixed height of bed
It is carried out in pressure microreactor, with embodiment 1, reactivity worth is shown in Table 1 for reaction condition and product analysis.
Table 1
Fig. 1 provides the embodiment of the present invention 1~6 and comparative example 1 is related to the XRD spectra of catalyst.
Claims (10)
1. a kind of nanometer of SAPO-34 molecular sieve, it is characterised in that with a thickness of 10~100nm, average grain diameter is 300nm~1 μm
Nanometer sheet.
2. the preparation method of as described in claim 1 nanometer of SAPO-34 molecular sieve, it is characterised in that the following steps are included:
1) silicon source is added to the water, stirs, is configured to solution 1；
2) silicon source is added in solution 1, stirring is configured to solution 2；
3) template is added in solution 2, stirring is configured to solution 3；
4) inhibitor is added in solution 3, stirring is configured to solution 4；
5) phosphorus source is added in solution 4, stirring is configured to solution 5；
6) solution 5 is placed in water-bath, heating stirring obtains gel；
7) gel obtained by step 6) is added to the water, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, heated, it will
Reaction kettle is cooled to room temperature, and is washed, dry, and roasting obtains a nanometer SAPO-34 molecular sieve.
3. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 1), the aluminium
Source is selected from least one of boehmite, aluminium isopropoxide, sodium aluminate, activated alumina, aluminum alkoxide；The solution 1
Concentration of volume percent is 3%~10%, and the time of the stirring is 1~10h.
4. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 2), the silicon
Source is selected from least one of silica solution, ethyl orthosilicate, sodium metasilicate, fumed silica, active silica；The silicon source
Molar ratio with silicon source is 0.06~0.6, and the time of the stirring is 1~10h.
5. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 3), the mould
Plate agent is selected from tetraethylammonium bromide, dimethyl stearyl [3- (trimethoxy silicon substrate) propyl] ammonium chloride, dimethyl hexadecyl
Base [3- (trimethoxy silicon substrate) propyl] ammonium chloride, hexadecyl trimethoxy ammonium bromide, diethylamine, triethylamine, morpholine, tetrem
At least one of base ammonium hydroxide；The molar ratio of the template and silicon source is 0.05~4.0, and the time of the stirring is 1
~5h.
6. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 4), the suppression
Preparation is selected from least one of polyethylene glycol, dodecyl polyoxyethylene ether, methylenum careuleum；Mole of the inhibitor and silicon source
Than being 0.02~0.6, the time of the stirring is 1~3h.
7. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 5), the phosphorus
Source is selected from least one of phosphoric acid, phosphate, phosphite, tributyl phosphate；The molar ratio of phosphorus source and silicon source is
0.05~2.0, the time of the stirring is 10~36h.
8. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that described to add in step 6)
The temperature of heat is 60~100 DEG C, and the time of the stirring is 0.5~5h.
9. the preparation method of as claimed in claim 2 nanometer of SAPO-34 molecular sieve, it is characterised in that in step 7), the water
Mass ratio with gel is (10~20) ︰ 1；The condition of the heating is in an oven in 170~220 DEG C of 6~96h of heating；Institute
Stating dry condition is to dry 6~12h at 80~120 DEG C in a vacuum drying oven；The roasting is roasted in Muffle furnace
It burns, wherein maturing temperature is 400~600 DEG C, and the rate of roasting is 2~3 DEG C/min, and the time of roasting is 2~8h.
10. as described in claim 1 nanometer of SAPO-34 molecular sieve is applied in the reaction for preparing light olefins from methanol, i.e. MTO
Reaction；The step of application, is as follows:
Nanometer SAPO-34 molecular sieve is fitted into fixed bed high pressure microreactor, MTO reaction, reaction condition are as follows: methanol are carried out
It is carried by nitrogen, methanol quality air speed is 2.0~4.0h-1, nitrogen volume space velocity is 5000~8000h-1, reaction temperature 400
~450 DEG C, the reaction time is 10h or more；The low-carbon alkene includes ethylene, propylene or butylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154321.1A CN109264740A (en) | 2018-09-30 | 2018-09-30 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154321.1A CN109264740A (en) | 2018-09-30 | 2018-09-30 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109264740A true CN109264740A (en) | 2019-01-25 |
Family
ID=65195337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811154321.1A Pending CN109264740A (en) | 2018-09-30 | 2018-09-30 | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109264740A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536040A (en) * | 2022-09-27 | 2022-12-30 | 厦门大学 | A kind of nano lotus leaf-shaped aluminum-rich mordenite molecular sieve and its synthesis method and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963907A (en) * | 2012-12-03 | 2013-03-13 | 华东师范大学 | Pentasil type zeolite molecular sieve synthetic method |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN104556092A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hierarchical porous structure SAPO molecular sieve material and preparation method thereof |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN105585022A (en) * | 2014-10-20 | 2016-05-18 | 中国科学院大连化学物理研究所 | Synthetic method of flaky nano-SAPO-34 molecular sieve |
| CN106928007A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Hydrogenation alkyne-removing method for methanol-to-olefin product |
| CN107601522A (en) * | 2017-09-22 | 2018-01-19 | 中国华能集团公司 | A kind of silicoaluminophosphamolecular molecular sieves and its synthetic method |
| CN107827121A (en) * | 2017-11-17 | 2018-03-23 | 陕西延长石油（集团）有限责任公司 | A kind of synthetic method of the molecular sieves of high-specific surface area SAPO 34 |
| CN107986297A (en) * | 2017-12-27 | 2018-05-04 | 厦门大学 | Metal-modified mesoporous SAPO-34 molecular sieves and preparation method and application |
| CN108250012A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Method for removing alkyne by selective hydrogenation of methanol-to-olefin product |
| CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
-
2018
- 2018-09-30 CN CN201811154321.1A patent/CN109264740A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963907A (en) * | 2012-12-03 | 2013-03-13 | 华东师范大学 | Pentasil type zeolite molecular sieve synthetic method |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN104556092A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Hierarchical porous structure SAPO molecular sieve material and preparation method thereof |
| CN105585022A (en) * | 2014-10-20 | 2016-05-18 | 中国科学院大连化学物理研究所 | Synthetic method of flaky nano-SAPO-34 molecular sieve |
| CN105585022B (en) * | 2014-10-20 | 2017-12-05 | 中国科学院大连化学物理研究所 | A kind of synthetic method of the molecular sieves of flake nano SAPO 34 |
| CN104973608A (en) * | 2015-06-16 | 2015-10-14 | 吉林大学 | SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof |
| CN106928007A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Hydrogenation alkyne-removing method for methanol-to-olefin product |
| CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
| CN108250012A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Method for removing alkyne by selective hydrogenation of methanol-to-olefin product |
| CN107601522A (en) * | 2017-09-22 | 2018-01-19 | 中国华能集团公司 | A kind of silicoaluminophosphamolecular molecular sieves and its synthetic method |
| CN107827121A (en) * | 2017-11-17 | 2018-03-23 | 陕西延长石油（集团）有限责任公司 | A kind of synthetic method of the molecular sieves of high-specific surface area SAPO 34 |
| CN107986297A (en) * | 2017-12-27 | 2018-05-04 | 厦门大学 | Metal-modified mesoporous SAPO-34 molecular sieves and preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536040A (en) * | 2022-09-27 | 2022-12-30 | 厦门大学 | A kind of nano lotus leaf-shaped aluminum-rich mordenite molecular sieve and its synthesis method and application |
| CN115536040B (en) * | 2022-09-27 | 2023-08-15 | 厦门大学 | Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthetic method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102616810B (en) | Cubic or sheet-shaped nano SAPO-34 molecular sieve and application thereof | |
| CN105016355B (en) | A kind of molecular sieves of FeZSM 5 and its synthetic method | |
| CN107986297A (en) | Metal-modified mesoporous SAPO-34 molecular sieves and preparation method and application | |
| CN101121529A (en) | A kind of rapid synthesis method of phosphorus silicon aluminum SAPO-34 molecular sieve | |
| CN106745035B (en) | A kind of multi-stage porous SSZ-13 molecular sieve and its synthetic method and application | |
| CN1107803A (en) | Process for preparing amorphous, catalytically active silico-aluminas | |
| CN101249452A (en) | A kind of supported solid base catalyst for synthesizing dimethyl carbonate and preparation method thereof | |
| CN102836741A (en) | SAPO-34 (Silicoaluminophosphate-34) molecular sieve catalyst and application thereof to preparation of low-carbon olefin from methanol | |
| CN102633282B (en) | Method for preparing mesoporous titanium silicon molecular sieve nanoparticles | |
| CN113353954B (en) | A kind of green synthetic graded pore SAPO-11 molecular sieve based on natural minerals and preparation method thereof | |
| CN103212435B (en) | Preparation method of microsphere titanium silicalite molecular sieve catalyst | |
| CN102188999B (en) | Preparation method and application of ionic liquid functionalized Al-MCM-41 mesoporous material | |
| CN102795638A (en) | Preparation method of nanometer Zn/Al ZSM-5 molecular sieve | |
| CN107827121B (en) | A kind of synthetic method of SAPO-34 molecular sieve with high specific surface area | |
| CN107138176A (en) | A kind of preparation method of middle micro-diplopore lamella MFI molecular sieve catalysts | |
| CN106477595B (en) | A kind of preparation method and application of sheet morphology SAPO-34 molecular sieve | |
| CN109264740A (en) | A kind of preparation method and application of nanometer of SAPO-34 molecular sieve | |
| CN102294258A (en) | Preparation method of Cu-SBA-15 mesoporous molecular sieve with high copper content | |
| CN107055563B (en) | A kind of nano whiskers SAPO-34 molecular sieve and its preparation and application | |
| CN1332761C (en) | Process for preparing load type silicon phoshporus aluminium molecular sieve | |
| CN106608632B (en) | The preparation and application thereof of hierarchical porous structure SAPO-34 molecular sieves | |
| CN102424398B (en) | Method for rapid synthesis of titanium silicate molecular sieve | |
| CN106467309A (en) | A kind of method of temperature programming synthesizing methanol propylene nano-ZSM-5 molecular sieve | |
| JP2010155759A (en) | Method for synthesizing mesoporous aluminosilicate | |
| CN106145155A (en) | A kind of prepare the method for high silica alumina ratio Y type molecular sieve, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190125 |
|
| RJ01 | Rejection of invention patent application after publication |