CN106517230B - Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process - Google Patents
Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process Download PDFInfo
- Publication number
- CN106517230B CN106517230B CN201610956718.7A CN201610956718A CN106517230B CN 106517230 B CN106517230 B CN 106517230B CN 201610956718 A CN201610956718 A CN 201610956718A CN 106517230 B CN106517230 B CN 106517230B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sapo
- stage porous
- solid phase
- phase synthesis
- 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.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
- 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 81
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HLDZYRJADGAGSI-UHFFFAOYSA-N phosphoric acid;n-propylpropan-1-amine Chemical compound OP(O)(O)=O.CCCNCCC HLDZYRJADGAGSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000010703 silicon Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- -1 welding Substances 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)
-
- B01J35/60—
-
- 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
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- 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)
Abstract
The present invention provides a kind of multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process, the solid phase synthesis process includes, by solid silicon source, silicon source, mesoporous template, micropore template agent and phosphorus source mixed grinding, crystallization is carried out at 140-220 DEG C, reaction time is 12-72h, product centrifugation drying, roasting are gone after template agent removing up to multi-stage porous SAPO-11 molecular sieve.The multi-stage porous SAPO-11 molecular sieve prepared in the present invention is 83.5% to the conversion ratio of the hydroisomerizing reaction of hexadecane, and stereoselectivity is 82.1%(reaction condition: 290 DEG C, 6MPa, WHSV=1‑1, nH2: nC16=15).Compared with prior art, products obtained therefrom not only has the AEL structure and higher crystallinity of complete SAPO-11 molecular sieve, and there is meso-hole structure, in addition water is not used in sieve synthesis procedure, reduce the generation of waste water in production process, yield and one-pot yield are all enhanced.
Description
Technical field
The invention belongs to technical field of material chemistry, and in particular to multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process, and its
The application method of hydroisomerizing for long chain alkane.
Background technique
SAPO-11 molecular sieve is the means of nonzeolitic mesoporous molecular sieve of AEL structure, belongs to orthorhombic system, has one-dimensional ten
Membered ring channel structure, oval duct (0.64 × 0.39nm).Because having suitable acid site and cellular structure to make SAPO-
11 molecular sieves restore the petrochemical industries such as octane number and lubricating oil isomerization dewaxing in the isomerization of normal hydrocarbon class, alkylation, gasoline isomery
Field is widely applied.
The main component of wax is high-melting-point long-chain normal paraffin in lube base oil, and pour point is high, low temperature fluidity
Difference.Branched paraffin is converted by n-alkane by hydroisomerization reaction, these performances can be improved.In molecular sieve catalyst
On long-chain normal paraffin isomerization reaction occur mainly at the aperture of catalyst, only be located at molecular sieve aperture near work
Property center could really be utilized.Therefore the long-chain normal paraffin isomerization catalyst of high activity require molecular sieve used have compared with
More exposure aperture numbers.The SAPO-11 molecular sieve applied in isomerization reaction at present in isomerization reaction, reactant or
Diffusional resistance of person's product on molecular sieve crystal surface is big, and case depth is be easy to cause to react, and leads to the aperture carbon deposit of catalyst
Inactivation.Multistage porous molecular sieve is due to micropore and meso-hole structure, combining the acidity of micro porous molecular sieve, high stability and mesoporous
Mass transfer rate can be improved in the advantages that large aperture of material, improves catalytic activity, pays close attention to by researcher.
The primary synthetic methods of conventional multistage porous molecular sieve are hydrothermal synthesis, solvent-thermal process, dry gum method synthesis and ion
(Chem.Soc.Rev., the 2008,37,2530-2542 such as thermal method synthesis；Angew.Chem.,2006,118,3162-3165；
Science,333(6040),328-332).It needs to use a large amount of water as reaction dissolvent in these synthetic methods, so that silicon source
Assembling is able to silicon source to reset, and generates crystal structure of molecular sieve；The process can generate a large amount of waste water, welding, and molecular sieve
Yield only has 80% or so.Patent CN201410084067 reports the method that solid phase method prepares SAPO-11 molecular sieve, still
There is no synthesis multi-stage porous SAPO-11 molecular sieves, and are not applied to reality for the SAPO-11 molecular sieve of this method preparation
In the catalysis reaction on border.
Based on the above, a kind of method of synthesis in solid state multistage porous molecular sieve is provided, adds hydrogen different for long chain alkane
Structure reaction, to overcome the problems, such as that a large amount of waste water can be generated in existing multi-stage porous sieve synthesis procedure, low yield is necessary.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of multi-stage porous SAPO-11 molecules
Sieve and solid phase synthesis process can generate a large amount of waste water, yield in multi-stage porous sieve synthesis procedure in the prior art for solving
Low problem.
In order to achieve the above objects and other related objects, the present invention provides a kind of solid phase of multi-stage porous SAPO-11 molecular sieve
Synthetic method, the solid phase synthesis process include: to mix silicon source, silicon source, mesoporous template, micropore template agent and phosphorus source to grind
Mill carries out crystallization at 140-220 DEG C, and template agent removing is removed in roasting after product separation drying, obtains multi-stage porous SAPO-11 points
Son sieve.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, crystallization
Reaction time be 12-72h.
Further, the crystallization time of crystallization is 16-48h.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, crystallization
Range of reaction temperature be 160-200 DEG C.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, using centrifugation
Method separates product.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, the silicon source
For one of white carbon black, sodium metasilicate or two kinds of mixtures.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, source of aluminium
For the mixtures of the one or more of boehmite, aluminum sulfate, aluminium isopropoxide.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, the micropore
Template select be the di-n-propylamine that di-n-propylamine and phosphatase reaction are formed phosphate, di-n-propylamine and phosphoric acid react mole
Than for 1:1.0-1:1.2.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, it is described mesoporous
It is one of cetyl trimethylammonium bromide CTAB, PVAC polyvinylalcohol that template, which is selected,.
A kind of preferred embodiment of solid phase synthesis process as multi-stage porous SAPO-11 molecular sieve of the invention, the silicon source,
Molar ratio between silicon source, micropore template agent and mesoporous template are as follows: 0.12-0.48:1:0.7-1.2:0.01-0.2.
The present invention also provides a kind of multi-stage porous SAPO-11 molecular sieve, the multi-stage porous SAPO-11 molecular sieve is with micropore point
The AEL structure of son sieve SAPO-11, and the mesoporous pore size in the multistage porous molecular sieve is 30nm.
As a kind of preferred embodiment of multi-stage porous SAPO-11 molecular sieve of the invention, the multi-stage porous SAPO-11 molecular sieve
Partial size be 2 microns.
The present invention also provides a kind of application method of multi-stage porous SAPO-11 molecular sieve, the multi-stage porous SAPO-11 molecular sieve
Hydroisomerizing applied to long chain alkane reacts.
A kind of preferred embodiment of application method as multi-stage porous SAPO-11 molecular sieve of the invention, the long chain alkane
Including hexadecane.
As described above, multi-stage porous SAPO-11 molecular sieve of the invention and its solid phase synthesis process, have below beneficial to effect
Fruit:
The multi-stage porous SAPO-11 molecular sieve prepared in the present invention is to the conversion ratio of the hydroisomerizing of hexadecane reaction
83.5%, stereoselectivity be 82.1% (reaction condition: 290 DEG C, 6MPa, WHSV=1-1, nH2: nC16=15).With existing skill
Art is compared, and products obtained therefrom not only has the AEL structure and higher crystallinity of complete SAPO-11 molecular sieve, but also has and be situated between
In addition pore structure does not use water in sieve synthesis procedure, reduces the generation of waste water in production process, yield and one-pot
Yield is all enhanced.
Detailed description of the invention
Fig. 1 is shown as the XRD spectra of multi-stage porous SAPO-11 molecular sieve synthesized by embodiment 1.
Fig. 2 is shown as the stereoscan photograph of multi-stage porous SAPO-11 molecular sieve synthesized by embodiment 1.
Fig. 3 is shown as the nitrogen adsorption isotherm of multi-stage porous SAPO-11 molecular sieve synthesized by embodiment 1.
Fig. 4 is shown as the XRD spectra of multi-stage porous SAPO-11 molecular sieve synthesized by embodiment 3.
Fig. 5 is shown as the stereoscan photograph of multi-stage porous SAPO-11 molecular sieve synthesized by the present embodiment 3.
Fig. 6 is shown as the nitrogen adsorption isotherm of multi-stage porous SAPO-11 molecular sieve synthesized by embodiment 3.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to FIG. 1 to FIG. 6.It should be noted that diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shown in diagram then with related component in the present invention rather than package count when according to actual implementation
Mesh, shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its
Assembly layout kenel may also be increasingly complex.
Embodiment 1
The present embodiment provides a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve, the solid phase synthesis process packet
It includes: by silicon source, silicon source, mesoporous template, micropore template agent and phosphorus source mixed grinding, crystallization is carried out at 140-220 DEG C,
After product centrifugation drying, template agent removing is removed in roasting, obtains multi-stage porous SAPO-11 molecular sieve.
As an example, the reaction time of crystallization is 12-72h.Preferably, the crystallization time of crystallization is 16-
48h。
As an example, the range of reaction temperature of crystallization is 160-200 DEG C.
As an example, the silicon source is one of white carbon black, sodium metasilicate or two kinds of mixtures.Source of aluminium is thin to intend
The mixtures of the one or more of diaspore, aluminum sulfate, aluminium isopropoxide.The micropore template agent select be di-n-propylamine and
The phosphate for the di-n-propylamine that phosphatase reaction is formed, di-n-propylamine are 1:1.0-1:1.2 with the molar ratio of reacting of phosphoric acid.It is given an account of
It is one of cetyl trimethylammonium bromide CTAB, PVAC polyvinylalcohol that hole template, which is selected,.The silicon source, silicon source, micropore
Molar ratio between template and mesoporous template are as follows: 0.12-0.48:1:0.7-1.2:0.01-0.2.
In a specific implementation process, 0.14g white carbon black, 1.46g boehmite, 4.04g di-n-propylamine are weighed
Phosphate and 0.36g cetyl trimethylammonium bromide (CTAB) after mixing, grind 10 minutes, resulting powder are put into
In reaction kettle, for 24 hours, obtained product centrifuge washing is dried at a temperature of 80 DEG C and 600 for crystallization at a temperature of 200 DEG C
DEG C roasting 6h obtain final product.
Fig. 1 is shown as the XRD characterization result of multi-stage porous SAPO-11 molecular sieve synthesized by the present embodiment, it can be seen that produces
Product are typical AEL structure, have preferable crystallinity.Fig. 2 is shown as multi-stage porous SAPO-11 molecule synthesized by the present embodiment
The stereoscan photograph of sieve, it can be seen that the ball that product is about 2 microns of partial size, and be pure phase.Fig. 3 is shown as the present embodiment
The nitrogen adsorption isotherm of synthesized multi-stage porous SAPO-11 molecular sieve.The multi-stage porous SAPO-11 molecular sieve that the present embodiment obtains
Specific surface area be 132m2/ g, external surface area 35m2/ g, total pore volume 0.125cm3/ g, mesoporous Kong Rongwei 0.075cm3/
g。
The present embodiment also provides a kind of multi-stage porous SAPO-11 molecular sieve, and the multi-stage porous SAPO-11 molecular sieve has micropore
The AEL structure of molecular sieve SAPO-11, and the mesoporous pore size in the multistage porous molecular sieve is 30nm, the multi-stage porous SAPO-11
The partial size of molecular sieve is 2 microns.
The present embodiment also provides a kind of application method of multi-stage porous SAPO-11 molecular sieve, the multi-stage porous SAPO-11 molecule
The hydroisomerizing that sieve is applied to long chain alkane reacts.As an example, the long chain alkane includes hexadecane.It is prepared in the present invention
Multi-stage porous SAPO-11 molecular sieve be 83.5% to the conversion ratio of the hydroisomerizing of hexadecane reaction, stereoselectivity is
82.1% (reaction condition: 290 DEG C, 6MPa, WHSV=1-1, nH2: nC16=15).
Embodiment 2
The present embodiment provides a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve, specifically include: weighing 0.14g
White carbon black, 1.46g boehmite, 3.60g di-n-propylamine phosphate and 0.36g cetyl trimethylammonium bromide (CTAB),
After mixing, grind 10 minutes, resulting powder is put into reaction kettle, at 200 DEG C crystallization for 24 hours, by obtained product
Centrifuge washing dries at 80 DEG C and obtains final product in 600 DEG C of roasting 6h.
Embodiment 3
The present embodiment provides a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve, specifically include: weighing 0.14g
White carbon black, 1.46g boehmite, 3.14g di-n-propylamine phosphate and 0.36g cetyl trimethylammonium bromide (CTAB),
Mixing, grind 10 minutes, resulting powder is put into reaction kettle, 200 DEG C of crystallization for 24 hours, obtained product is centrifuged
Washing dries at 80 DEG C and obtains final product in 600 DEG C of roasting 6h.
Fig. 4 is shown as the XRD characterization result of multi-stage porous SAPO-11 molecular sieve synthesized by the present embodiment, it can be seen that produces
Product are typical AEL structure, have preferable crystallinity.Fig. 5 is shown as multi-stage porous SAPO-11 molecule synthesized by the present embodiment
The stereoscan photograph of sieve, it can be seen that product is made of ball and acicular substance.Fig. 6 is shown as more synthesized by the present embodiment
The nitrogen adsorption isotherm of grade hole SAPO-11 molecular sieve.The specific surface area for the multi-stage porous SAPO-11 molecular sieve that the present embodiment obtains
For 108m2/ g, external surface area 25m2/ g, total pore volume 0.124cm3/ g, mesoporous Kong Rongwei 0.081cm3/g。
Embodiment 4
The present embodiment provides a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve, specifically include: weighing 0.28g
White carbon black, 1.46g boehmite, 3.14g di-n-propylamine phosphate and 0.36g cetyl trimethylammonium bromide (CTAB),
Mixing, grind 10 minutes, resulting powder is put into reaction kettle, 200 DEG C of crystallization for 24 hours, obtained product is centrifuged
Washing dries at 80 DEG C and obtains final product in 600 DEG C of roasting 6h.
As described above, multi-stage porous SAPO-11 molecular sieve of the invention and its solid phase synthesis process, have below beneficial to effect
Fruit:
The multi-stage porous SAPO-11 molecular sieve prepared in the present invention is to the conversion ratio of the hydroisomerizing of hexadecane reaction
83.5%, stereoselectivity be 82.1% (reaction condition: 290 DEG C, 6MPa, WHSV=1-1, nH2: nC16=15).With existing skill
Art is compared, and products obtained therefrom not only has the AEL structure and higher crystallinity of complete SAPO-11 molecular sieve, but also has and be situated between
In addition pore structure does not use water in sieve synthesis procedure, reduces the generation of waste water in production process, yield and one-pot
Yield is all enhanced.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (4)
1. a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve, which is characterized in that the solid phase synthesis process includes:
Weigh 0.14g white carbon black, 1.46g boehmite, 4.04g di-n-propylamine phosphate and 0.36g cetyl trimethyl
Ammonium bromide, after mixing, grind 10 minutes, resulting powder is put into reaction kettle, at a temperature of 200 DEG C crystallization for 24 hours, by institute
Obtained product centrifuge washing is dried at a temperature of 80 DEG C and in 600 DEG C of roasting 6h.
2. multi-stage porous synthesized by a kind of solid phase synthesis process of multi-stage porous SAPO-11 molecular sieve as described in claim 1
SAPO-11 molecular sieve, which is characterized in that the multi-stage porous SAPO-11 molecular sieve is tied with the AEL of micro porous molecular sieve SAPO-11
Structure, and the mesoporous pore size in the multistage porous molecular sieve is 30nm.
3. multi-stage porous SAPO-11 molecular sieve as claimed in claim 2, which is characterized in that the multi-stage porous SAPO-11 molecular sieve
Partial size be 2 microns.
4. a kind of application method of the multi-stage porous SAPO-11 molecular sieve as described in any one of Claims 2 or 3 claim,
Be characterized in that: the hydroisomerizing that the multi-stage porous SAPO-11 molecular sieve is applied to long chain alkane reacts, and the long chain alkane includes
Hexadecane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610956718.7A CN106517230B (en) | 2016-10-27 | 2016-10-27 | Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610956718.7A CN106517230B (en) | 2016-10-27 | 2016-10-27 | Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106517230A CN106517230A (en) | 2017-03-22 |
| CN106517230B true CN106517230B (en) | 2019-08-23 |
Family
ID=58325874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610956718.7A Active CN106517230B (en) | 2016-10-27 | 2016-10-27 | Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106517230B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108128786B (en) * | 2018-01-09 | 2019-07-30 | 中国科学院上海高等研究院 | A kind of method that ultrasonic wave added prepares multi-stage porous SAPO-11 molecular sieve |
| CN109692705B (en) * | 2019-01-11 | 2022-04-22 | 中国石油大学(华东) | Method for synthesizing MeAPO-5 molecular sieve by solid-phase reaction method |
| CN112973783B (en) * | 2019-12-14 | 2022-06-03 | 中国科学院大连化学物理研究所 | Hierarchical pore catalyst, synthesis gas and C4Method for preparing low liquid fuel from components |
| CN112403511A (en) * | 2020-11-26 | 2021-02-26 | 中国科学院上海高等研究院 | Preparation method of limited-domain bifunctional catalyst |
| CN112456513B (en) * | 2020-12-10 | 2023-05-09 | 聊城大学 | Open system solid phase synthesis AEL structure aluminum phosphate based molecular sieve, preparation method and application |
| CN115043414B (en) * | 2022-06-09 | 2023-12-29 | 青岛科技大学 | Hierarchical pore molecular sieve and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913622B (en) * | 2010-08-25 | 2012-03-14 | 中国石油大学(北京) | Preparation method of multistage pore canal SAPO-11 (silicoaluminophosphate-11) molecular sieve and application thereof in gasoline modification |
| CN101913623B (en) * | 2010-08-25 | 2011-12-07 | 中国石油大学(北京) | Multilevel pore channel SAPO-11 molecular sieve and synthetic method of hydrocarbon isomerization catalyst |
| CN103864088B (en) * | 2014-03-07 | 2015-12-09 | 浙江大学 | By the method for solid-phase grinding synthesis of molecular sieve |
| CN105800632B (en) * | 2014-12-31 | 2018-03-13 | 中国石油天然气股份有限公司 | The molecular sieves of little crystal grain step hole SAPO 11 and hydrocarbon isomerization catalyst and preparation method |
-
2016
- 2016-10-27 CN CN201610956718.7A patent/CN106517230B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 通过固相合成方法对若干磷酸铝分子筛形貌的调控;陈鲜;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150515(第5期);54,56,59页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106517230A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106517230B (en) | Multi-stage porous SAPO-11 molecular sieve and solid phase synthesis process | |
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN108128786B (en) | A kind of method that ultrasonic wave added prepares multi-stage porous SAPO-11 molecular sieve | |
| CN101935053B (en) | ZSM-5 zeolite and synthesis method thereof | |
| CN102336413B (en) | Synthesis method of low-silicon SAPO-34 molecular sieves | |
| CN103435065B (en) | Preparation method of nano ZSM-12 molecular sieve | |
| CN109626394B (en) | Method for preparing SAPO-35 molecular sieve by using N-methylpiperidine as template agent | |
| CN110182823A (en) | A method of reducing aluminium phosphate molecular sieve size of microcrystal | |
| CN107487777A (en) | The synthetic method of the nanometer molecular sieve catalysts of HZSM 5 | |
| WO2016029591A1 (en) | Method for preparing y-type molecular sieve having high silica-alumina ratio | |
| CN103121698A (en) | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding | |
| JP2015533765A (en) | SAPO-34 molecular sieve and synthesis method thereof | |
| CN103663493A (en) | Preparation method of silicoaluminophosphate molecular sieve with mesoporous-microporous hierarchical structure | |
| CN109761243A (en) | A kind of preparation of low silicon small grain SAPO-34 molecular sieve and application method | |
| CN101508446B (en) | Production process of regulating and controlling SAPO-11 molecular sieve bore diameter | |
| CN102951656B (en) | Method for synthesizing even-grained ZSM-5 molecular sieves | |
| CN105597815B (en) | ZSM-5/ZnVPI-8 composite molecular sieves catalyst | |
| CN105645427B (en) | The preparation method of the molecular sieves of ZSM 22 with mesoporous micropore graded structure | |
| CN106564912A (en) | Double-micropore SAPO (silicoaluminophosphate)-34/SAPO-18 composite molecular sieve, and preparation method and application thereof | |
| CN106824262B (en) | SSZ-13/SCM-9 composite molecular sieve catalyst, preparation method and its usage | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN104355318B (en) | A kind of synthetic method of nano-ZSM-5 molecular sieve | |
| CN106185983A (en) | The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve | |
| CN105800635B (en) | The preparation method of ZSM-48 molecular sieves with mesoporous-micropore graded structure | |
| CN106582806A (en) | In-situ synthesis method for synthesizing composite carrier material SAPO-11@gamma-Al2O3 by using hydrous modified alumina as substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |