CN108264058A - The preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves, the molecular sieve prepared and its purposes - Google Patents
The preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves, the molecular sieve prepared and its purposes Download PDFInfo
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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 127
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 126
- 210000001367 artery Anatomy 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 5
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 claims 2
- 229910002796 Si–Al Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 31
- 235000015165 citric acid Nutrition 0.000 abstract description 4
- 238000005287 template synthesis Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 241000269350 Anura Species 0.000 description 17
- 239000011799 hole material Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 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
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves, the molecular sieve prepared and its purposes, mainly solve the problem of that the prior art is cumbersome of high cost using the existing operating process of mesoporous template synthesis.The present invention is by using including making the step of only silicoaluminophosphamolecular molecular sieves with microcellular structure are contacted with the solution containing modifying agent；The technical solution that the modifying agent is selected from least one of ammonium hydroxide, oxalic acid, acetic acid, ethanedioic acid, citric acid, sodium carbonate, sodium acetate, sodium acetate, sodium hypochlorite, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide preferably solves the problems, such as this, in the industrial production available for preparing multi-stage artery structure silicoaluminophosphamolecular molecular sieves.
Description
Technical field
The present invention relates to a kind of preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves, the molecular sieve prepared and its use
On the way.
Background technology
1984, silicoaluminophosphamolecular molecular sieves of the aperture in 0.4nm or so were invented by U.S. combinating carbide company (UCC)
(abbreviation SAPO molecular sieve).SAPO molecular sieve is by AlO4、SiO4And PO4The crystal network structure that tetrahedron is formed, in crystal
Duct is because of Si4+Replace P5+Or Al3+The acidity of generation is replaced with metal and generated acid.In SAPO Series Molecules sieve,
SAPO-34 molecular sieves because its with good thermal stability and hydrothermal stability, moderate acid, higher specific surface area and
The micropore canals of high-sequential, and be widely used in modern petroleum processing industry.Most noticeable is the molecular sieve application
In methanol-to-olefins (MTO) reaction, the conversion ratio of methanol can be made to reach 100%, the selectivity of ethylene and propylene can be more than
70%, C5+The content of component is less, and is generated almost without aromatic hydrocarbons.But the relatively long and narrow duct of SAPO molecular sieve shows seriously
Shape-selective limitation, on the one hand hinder the contact in activated centre inside raw molecule and its duct, on the other hand can make reactant,
The diffusion of middle transition product and final product and mass transfer are restricted, and easily because carbon deposit causes duct to be blocked, cause to urge
The inactivation of agent limits the performance of its catalytic performance.
In order to overcome the shortcomings of single microcellular structure molecular screen material, many researchers have been prepared with reference to multiple hole road advantage
Novel molecular sieve, i.e. hierarchical porous structure molecular sieve.According to pore passage structure type, multistage porous molecular sieve can be divided into two categories below：
One kind is micropore-mesoporous-microporous composite molecular sieve that two-phase cocrystallization molecular sieve is formed, and this kind of material is answered by two or more
Close micropore canals composition；Another kind of is mesopore/macropore-mesoporous-microporous composite molecular sieve, and this kind of material has micropore and mesoporous/big simultaneously
Two kinds of hole pore canal system can greatly improve the diffusion of material, improve the catalytic performance of material, in the reaction for being related to macromolecular
And it needs to show good catalyzed conversion performance in the reaction quickly spread.
For this purpose, there has been proposed by adding in preparation side of the mesoporous template through hydrothermal synthesis and after in gel rubber system
Method.It is template that Choi etc., which is reported using the long chain alkyl ammonium salt of silanization, and mesoporous knot has been provided through a step hydrothermal synthesis
The AlPO of structure4- n Series Molecules sieve (Choi M, Srivastava R, Ryoo R.Chemical Communications,
2006；(42):4380-4382.)；Then, Danilina and Chen Lu etc. is using a kind of multi-functional long chain silicone as silicon source, respectively
Hydrothermal synthesis provides SAPO-5 (Danilina N, Krumeich F, the van Bokhoven J.Journal of hierarchical porous structure
of Catalysis,2010,272(1):37-43.) and SAPO-34 molecular sieves (Chen Lu, Wang Runwei, Ding Shuandeng institutions of higher education
Journal, 2010；31(9):1693-1696.)；Fan etc. is used as mesoporous template by adding in long-chain organic phosphine, can be in routine
Synthesize SAPO-11 molecular sieves (Fan Y, Xiao H, Shi G, et with abundant meso-hole structure under hydrothermal condition
al.Journal of Catalysis,2012,285(1):251-259.)；Cui etc. is using polyethylene glycol (PEG) as mesoporous mould
Plate agent, synthesizes the SAPO-34 molecular sieves with hierarchical porous structure under hydrothermal conditions, and can by the amount of modulation PEG come
Change mesoporous size (Cui Y, Zhang Q, He J, et al.Particuology, 2013；11(4):468-474.).
Yang etc. synthesizes hierarchical porous structure SAPO- using the surfactant of silanization as mesoporous template in the case of microwave radiation technology
34, the results showed that, the introducing of microwave can not only effectively shorten crystallization time (only small crystallization process need to can be completed at present 2),
And synthesized product has higher specific surface area and mesoporous Kong Rong (Yang S, Kim J, Chae H, et
al.Materials Research Bulletin,2012；47(11):3888-3892.).Although by the synthesis process will
Mesoporous template is introduced into the SAPO-34 molecular sieves that can be prepared in the synthetic system of molecular sieve with hierarchical porous structure, but
Suitable template is not only expensive, but also the process for removing template is also difficult to control.
To solve the above-mentioned problems, poplar He Qin etc. is prepared a kind of with hierarchical porous structure using the method for gas phase crystallization
Silicoaluminophosphate SAPO molecular sieve integral material, the material are shown more in MTO reactions compared to conventional SAPO-34 molecular sieves
High catalytic activity (CN102219237A；Yang H,Liu Z,Gao H,et al.Journal of Materials
Chemistry,2010；20(16):3227-3231.).Recently, silicon source, silicon source, phosphorus source and morpholine are uniformly mixed by Jin etc.
And after grinding, directly the solid mixture is directly placed into baking oven, crystallization 8-24 is small at 200 DEG C under solvent-free conditions
When, products therefrom is washed, after dry, roasting, you can obtains SAPO-34 molecular sieves (Jin Y, Sun with meso-hole structure
Q,Qi G,et al.Angewandte Chemie International Edition,2013；125(35):9342-
9345.), which equally shows preferable catalytic performance in MTO reactions.
It is prepared about the method using post processing modified (roasting, hydro-thermal or chemical treatment) with hierarchical porous structure
Molecular sieve has been widely used in the binary molecules such as Y, ZSM-5 and Beta sieve.The soda acid particularly developed in recent years processes
Journey so that the aluminium silicon species on molecular sieve are selectively removed, and the specific surface area of products molecule sieve increases and formed a large amount of secondary
Hole, while the microcellular structure of molecular sieve in itself is retained.But up to the present not yet there is the method system using post processing
The relevant report of standby hierarchical porous structure SAPO-34 molecular sieves.
In conclusion although the preparation of multilevel hole material at present is the hot spot of numerous scientific research personnel research, existing system
All there is operating process is cumbersome and the shortcomings of cost is higher for the method for standby multi-stage porous SAPO molecular sieve.In consideration of it, reduce system
Standby cost, simplifies procedures, develops the multi-stage porous SAPO molecular sieve preparation route being simple and efficient and have important practical significance.
In addition, methanol-to-olefins technology is developed so far, diene yield (ethylene+propylene) has reached 80~83%, on this basis, yield
If improving 0.5 percentage point, for the device of 10,000 tons, economic benefit is considerable；Meanwhile catalyst stability
It improves and people is of interest.
Invention content
The technical problems to be solved by the invention are the prior arts using the existing operating process of mesoporous template synthesis
It is cumbersome, it is of high cost the problem of, a kind of preparation method of new multi-stage artery structure silicoaluminophosphamolecular molecular sieves is provided.This method has
The characteristics of easy to operate and of low cost.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of multi-stage artery structure silicoaluminophosphate
The preparation method of molecular sieve, including making the step that only silicoaluminophosphamolecular molecular sieves with microcellular structure are contacted with the solution containing modifying agent
Suddenly；The modifying agent be selected from ammonium hydroxide, oxalic acid, acetic acid, ethanedioic acid, citric acid, sodium carbonate, sodium acetate, sodium acetate, sodium hypochlorite,
At least one of tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
In above-mentioned technical proposal, it is preferable that the modifying agent is selected from ammonium hydroxide, oxalic acid, citric acid, sodium carbonate and tetrapropyl hydrogen
At least one of amine-oxides.
In above-mentioned technical proposal, the solution containing modifying agent is the aqueous solution containing modifying agent.
In above-mentioned technical proposal, a concentration of 0.02~1 mol/L of the modifying agent in aqueous solution, preferably 0.05~
0.5 mol/L.
In above-mentioned technical proposal, the mass ratio of solution and silicoaluminophosphamolecular molecular sieves butt containing modifying agent is (10~100):
1, preferably (25~70):1.
In above-mentioned technical proposal, the temperature that silicoaluminophosphamolecular molecular sieves are contacted with the solution containing modifying agent is 20~95 DEG C, excellent
Select 45~85 DEG C；Time is 0.5~24 hour, preferably 1~16 hour.
In above-mentioned technical proposal, the silicoaluminophosphamolecular molecular sieves for SAPO-5, SAPO-11, SAPO-17, SAPO-18,
SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-46 and
Single or composite molecular screen in SAPO-56.
In above-mentioned technical proposal, the method further includes silicoaluminophosphamolecular molecular sieves are contacted with the aqueous solution containing modifying agent after
Mixture washing, dry, roasting the step of.
Raw materials used silicoaluminophosphamolecular molecular sieves in the present invention, only with microcellular structure.Can not remove after hydrothermal crystallizing
The molecular screen primary powder of template or the fired molecular sieve being stripped of after template.Preferably, used silicon phosphate
Aluminum molecular screen is removed template method.
It, can be to modified after being handled using inorganic base or strong base weak acid salting liquid molecular sieve in the method for the present invention
Silicoaluminophosphamolecular molecular sieves with hierarchical porous structure implement ammonium ion exchange processing, and this method is that those of ordinary skill in the art say
Well known, there is no particular limitation to it by the present invention, it is preferable that the ammonium ion exchange process is：It will treated molecule
Sieve is with 1：10 ratio is added in ammonium salt solution progress ammonium ion exchange, and the pH value of regulation system is in the range of 2.0-7.0,
Slurries are filtered, washing, roast.
The present invention also provides a kind of according to the more of the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves preparation
Grade pore passage structure silicoaluminophosphamolecular molecular sieves.The molecular sieve has micropore, mesoporous and macropore simultaneously；Wherein, micropore size is little
In 1 nanometer, mesoporous pore size is distributed in 5~30 nanometers, and macropore diameter is distributed in 50~350 nanometers；The Kong Rongwei of micropore contribution
0.05~0.30 centimetre3/ gram, 0.15~0.40 centimetre of the Kong Rongwei of mesoporous contribution3/ gram, the Kong Rongwei 0.25 that macropore is contributed~
0.60 centimetre3/ gram.
The present invention also provides a kind of according to the more of the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves preparation
Application of the grade pore passage structure silicoaluminophosphamolecular molecular sieves in methanol to olefins reaction.Reaction condition includes：390~515 DEG C of temperature,
Methanol Feed space velocities 1~100 hour-1。
It is modified in the prior art using post processing, such as roasting, hydro-thermal or chemically treated method are prepared with more
The molecular sieve of grade pore structure has been widely used in the binary molecules such as Y, ZSM-5 and Beta sieve, had particularly developed in recent years
Strong acid, highly basic processing procedure so that the aluminium silicon species on molecular sieve are selectively removed, and the specific surface area of products molecule sieve increases
Greatly and a large amount of secondary pores are formed, while the microcellular structure of molecular sieve in itself is retained.But for SAPO molecular sieve,
Since the acid source of molecular sieve replaces the phosphorus or aluminium species in molecular sieve in the silicon species being introduced into, the silicon of molecular sieve in itself contains
Amount is very low, and a large amount of silicon species that remove will certainly significantly reduce the Acidity of molecular sieve；Secondly, SAPO molecular sieve belongs to CHA structure,
The basic component units of the structure are four-membered rings, for the ZSM-5 molecular sieve with five-membered ring structure, the drawing of four-membered ring
Power is higher than pentacyclic, after the point of some position in structure is destroyed, also easily causes caving in for skeleton.Cause
This, highly basic, strong acid method applied to Y, ZSM-5 and Beta molecular sieve are not particularly suited for SAPO molecular sieve.
Based on the so sensitive design feature of SAPO molecular sieve, the present invention uses mild soda acid processing method, selects ammonia
Water, oxalic acid, acetic acid, ethanedioic acid, citric acid, sodium carbonate, sodium acetate, sodium acetate, sodium hypochlorite, tetraethyl ammonium hydroxide, 4 third
As modifying agent, control changes at least one of base ammonium hydroxide and tetrabutylammonium hydroxide weak acid, weak base and strong base-weak acid salt
Property agent aqueous solution concentration keep relatively low level, only 0.02~1 mol/L, synthesis has obtained having multi-stage artery structure
SAPO molecular sieve.The method of the present invention can not only be solved effectively in the prior art using the existing behaviour of mesoporous template synthesis
Make the problem of process is cumbersome, of high cost, the SAPO molecular sieve with multi-stage artery structure of gained is also steady with good hydro-thermal
It is qualitative.
SAPO molecular sieve with multi-stage artery structure prepared according to the methods of the invention is used as catalyst activity component
During methanol-to-olefins, good catalytic performance is shown, while yield of light olefins is improved, diene (ethylene+the third
Alkene) yield can improve 2.1 percentage points, moreover it is possible to the reaction stability of catalyst is dramatically increased, achieves preferable technology effect
Fruit.
In the method for the present invention, XRD data are used to be measured with German Brooker AXS D8 Advance type X-ray diffractometers；
N2Adsorption-desorption data and pore-size distribution are measured by U.S.'s Mike's ASAP-2020 adsorption instruments；SEM pictures are by Dutch FEI
Quanta200F field emission scanning electron microscopes obtain.
Description of the drawings
Fig. 1 is【Comparative example 1】、【Embodiment 1-3】The SAPO-34 molecular sieve-4 As of preparation, the XRD spectra of B, C, D.Wherein A is
The SAPO-34 molecular sieves of micropore are contained only, B, C, D is have micropore, mesoporous and macropore SAPO-34 molecular sieves simultaneously.It can by figure
See, synthesis and modified molecular sieve is respectively provided with characteristic diffraction peak possessed by SAPO-34 molecular sieves.
Fig. 2 is【Comparative example 1】The SEM photograph of SAPO-34 molecular sieves that is conventional, containing only micropore of preparation.As seen from the figure,
Conventional molecular sieve is regular cube pattern, and surface compact is smooth.
Fig. 3 is【Embodiment 1】SEM photograph with micropore, mesoporous and macropore SAPO-34 molecular sieves while preparation.
As seen from the figure, multi-stage artery structure molecular sieve is cube pattern, and a large amount of holes occurs in surface.
The present invention will be further described below by way of examples.
Specific embodiment
【Comparative example 1】
Prepare the SAPO-34 molecular sieves for containing only micropore.
With Ludox (30 weight %SiO2), boehmite (70 weight %Al2O3) and phosphoric acid (85 weight %H3PO4)
Respectively silicon, aluminium and phosphorus source, triethylamine NEt3For template, according to SiO2：Al2O3：P2O5：NEt3：H2O=1.0：1.0：0.6：
3：50 molar ratio is mixed, and mixture is in 200 DEG C of crystallization.After crystallization, crystallization product is cooled down, filtered, is washed
It washs, 120 DEG C of dryings are denoted as A in 6 hours to get to conventional, to contain only micropore SAPO-34 molecular sieves.
The XRD spectra of A is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieves to be had
There is diffraction maximum at 9.5 °, 15.9 °, 20.5 °, 26 ° and 31 ° in some characteristic diffraction peaks, 2 θ, and it is pure to illustrate synthesized product
SAPO-34 molecular sieves, relative crystallinity is defined as 100%.
The SEM photograph of A is as shown in Fig. 2, surface is very smooth, for regular cube pattern, 3-5 μm of Product size.
The Micropore volume of A is 0.28cm3/ g, micropore size are distributed in 0.3~0.5nm.
【Embodiment 1】
Prepare have multi-stage artery structure SAPO-34 molecular sieves, raw material be taken from according to【Comparative example 1】The routine of preparation
, the SAPO-34 molecular sieve-4 As for containing only micropore.
It weighs 30g molecular sieve-4 As and places it in the citric acid solution of 0.05M, the dosage of wherein citric acid solution is
After being stirred 3 hours at 75 DEG C, product B is obtained after filtered, washing, dry, roasting by 0.9L.
The XRD spectra of B is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieves to be had
Some characteristic diffraction peaks illustrate synthesized product for pure SAPO-34 molecular sieves, relative crystallinity 95%.
The SEM photograph of B is as shown in figure 3, apparent pore space structure occurs in molecular sieve surface.
The micropore size of B is distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 5~18nm, and macropore diameter is distributed in 50~
200 nanometers；The Kong Rongwei 0.23cm of micropore contribution3/ g, the Kong Rongwei 0.17cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.15cm3/g。
It is multi-stage artery structure point according to prepared by the hole appearance that SEM photograph and physical absorption characterize as a result, sufficing to show that
Son sieve.
【Embodiment 2】
Together【Embodiment 1】, only used raw material be according to【Comparative example 1】Method prepare it is conventional, contain only it is micro-
Product after the SAPO-34 molecular sieve-4 As roasting in hole.Gained finally there is multi-stage artery structure SAPO-34 molecular sieves to be denoted as C.
The XRD spectra of C is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieves to be had
Some characteristic diffraction peaks illustrate synthesized product for pure SAPO-34 molecular sieves, relative crystallinity 92%.
The SEM photograph of C is similar with Fig. 3.
C micropore sizes are distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 8~28nm, and macropore diameter is distributed in 50~250
Nanometer；The Kong Rongwei 0.21cm of micropore contribution3/ g, the Kong Rongwei 0.25cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.18cm3/g。
It is multi-stage artery structure point according to prepared by the hole appearance that SEM photograph and physical absorption characterize as a result, sufficing to show that
Son sieve.
【Embodiment 3】
Together【Embodiment 1】, the only a concentration of 0.1M of citric acid, the dosage of citric acid is 0.6L, and reaction temperature is 65 DEG C,
Reaction time is 6 hours, and products therefrom is denoted as D.
The XRD spectra of D is as shown in Figure 1, it will be seen from figure 1 that there is synthesized molecular sieve SAPO-34 molecular sieves to be had
Some characteristic diffraction peaks illustrate synthesized product for pure SAPO-34 molecular sieves, relative crystallinity 89%.
The SEM photograph of D is similar with Fig. 3.
D micropore sizes are distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 5~30nm, and macropore diameter is distributed in 50~250
Nanometer；The Kong Rongwei 0.20cm of micropore contribution3/ g, the Kong Rongwei 0.25cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.19cm3/g。
It is multi-stage artery structure point according to prepared by the hole appearance that SEM photograph and physical absorption characterize as a result, sufficing to show that
Son sieve.
【Embodiment 4】
Together【Embodiment 1】, only used solution be sodium carbonate liquor, a concentration of 0.05M, dosage 0.6L, instead
It is 55 DEG C to answer temperature, and the reaction time is 2 hours, and products therefrom is denoted as E.
The XRD spectra of E is similar with Fig. 1, relative crystallinity 90%.
The SEM photograph of E is similar with Fig. 3.
E micropore sizes are distributed in 0.3~0.5nm, and mesoporous pore size is distributed in 6~20nm, and macropore diameter is distributed in 50~280
Nanometer；The Kong Rongwei 0.15cm of micropore contribution3/ g, the Kong Rongwei 0.18cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.20cm3/g。
It is multi-stage artery structure point according to prepared by the hole appearance that SEM photograph and physical absorption characterize as a result, sufficing to show that
Son sieve.
【Embodiment 5】
Present embodiments provide a kind of multi-stage artery structure SAPO-11 molecular sieves, be according to【Embodiment 1】Method system
Standby, the difference is that in the present embodiment, used raw material is with Ludox (30wt.%SiO2), boehmite
(70wt.%Al2O3) and phosphoric acid (85wt.%) be respectively silicon, aluminium and phosphorus source, di-n-propylamine (DPA) is template, according to
SiO2：Al2O3：P2O5：DPA：H2O=1.0：2.15：2.5：2.75：SAPO-11 through hydrothermal synthesis after 70 molar ratio mixing
Molecular sieve, the product multi-stage artery structure SAPO-11 molecular sieves of final gained are denoted as F.
The XRD spectra of F shows the SAPO-11 molecular sieves that synthesized molecular sieve is high-purity.
The SEM photograph of F shows that apparent pore space structure occurs in molecular sieve surface.
F micropore sizes are distributed in 0.3~0.8nm, and mesoporous pore size is distributed in 5~25nm, and macropore diameter is distributed in 50~300
Nanometer；The Kong Rongwei 0.08cm of micropore contribution3/ g, the Kong Rongwei 0.32cm of mesoporous contribution3/ g, the Kong Rongwei of macropore contribution
0.20cm3/g。
It is multi-stage artery structure point according to prepared by the hole appearance that SEM photograph and physical absorption characterize as a result, sufficing to show that
Son sieve.
【Embodiment 6-11】
Together【Embodiment 1】Hierarchical porous structure molecular screen material is made, unlike raw material, molten is changed in following embodiment
The factors such as liquid type and concentration, solid-to-liquid ratio, reaction temperature and time, are specifically listed in table 1.Products therefrom illustrates its result through characterization
With with【Embodiment 1-5】Similar pore passage structure feature, specific data are shown in Table 2.
Table 1
| Embodiment | Raw material | Solution type and concentration | Reaction temperature, DEG C | Reaction time, h | Products nr |
| 6 | SAPO-34 | Nitric acid/0.05M | 55 | 5 | G |
| 7 | SAPO-34 | Ammonium hydroxide/0.08M | 60 | 2 | H |
| 8 | SAPO-34 | Tetrapropylammonium hydroxide/0.5M | 75 | 8 | I |
| 9 | SAPO-31 | Citric acid/0.06M | 75 | 3 | J |
| 10 | SAPO-5 | Oxalic acid/0.1M | 80 | 1 | K |
| 11 | SAPO-44 | Citric acid/0.05M | 65 | 2 | L |
Table 2
【Comparative example 2】
Together【Embodiment 1】, only used solution is hydrochloric acid solution, and products therefrom is denoted as A2.
The XRD spectra of A2 is similar with Fig. 1, but its relative crystallinity is only 50%.
Though the SEM photograph of A2 is similar with Fig. 3, there is apparent pore space structure in surface, and broken molecular sieve is more, explanation
Processing, which is carried out, with strong acid causes caving in for framework of molecular sieve.
【Comparative example 3】
Together【Embodiment 1】, only used solution is sodium hydroxide solution, and products therefrom is denoted as A3.
The XRD spectra of A3 is similar with Fig. 1, but its relative crystallinity is only 35%.
Though the SEM photograph of A3 is similar with Fig. 3, there is apparent pore space structure in surface, and broken molecular sieve is more, explanation
Processing, which is carried out, with highly basic causes caving in for framework of molecular sieve.
【Comparative example 4】
Together【Embodiment 1】, only used solution is the citric acid solution of 2.5M, and molecular sieve powder is by High Content Citric Acid
It is completely dissolved, can not detach, illustrate that the acid of high concentration not only damages the skeleton of molecular sieve or even can be to silicoaluminophosphate object
Kind plays complete destruction.【Embodiment 12】【Embodiment 12】
It will【Embodiment 1-11】After the SAPO molecular sieve of gained carries out calcination process, the Hydrogen with hierarchical porous structure is made
The catalyst reacted for MTO is made in SAPO-34 molecular sieves after tabletting.Using fixed-bed catalytic reactor, reactor is not
Become rusty steel pipe, investigates process conditions used and is：Loaded catalyst 2.0g, reaction temperature are 460 DEG C, weight space velocity 6h-1, pressure
0.1MPa, evaluation result are as shown in table 3.It can be seen that the SAPO molecular sieve with the hierarchical porous structure of higher crystallinity is used for
In MTO reactions, diene yield can be significantly improved, and catalyst has preferable stability.
【Comparative example 5】
It will【Comparative example 1-4】After the SAPO molecular sieve of gained carries out calcination process, the Hydrogen with hierarchical porous structure is made
The catalyst reacted for MTO is made in SAPO-34 molecular sieves after tabletting.Using fixed-bed catalytic reactor, reactor is not
Become rusty steel pipe, investigates process conditions used and is：Loaded catalyst 2.0g, reaction temperature are 460 DEG C, weight space velocity 6h-1, pressure
0.1MPa, evaluation result are as shown in table 3.
Table 3
Claims (10)
1. a kind of preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves, including the silicoaluminophosphate for making only there is microcellular structure
The step of molecular sieve is contacted with the solution containing modifying agent；The modifying agent be selected from ammonium hydroxide, oxalic acid, acetic acid, ethanedioic acid, citric acid,
In sodium carbonate, sodium acetate, sodium acetate, sodium hypochlorite, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide
At least one.
2. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that described to change
Property agent be selected from least one of ammonium hydroxide, oxalic acid, citric acid, sodium carbonate and tetrapropylammonium hydroxide.
3. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that described to contain
The solution of modifying agent is the aqueous solution containing modifying agent；A concentration of 0.02~1 mol/L of the modifying agent in aqueous solution, contains
The aqueous solution of modifying agent is (10~100) with the mass ratio of silicoaluminophosphamolecular molecular sieves butt:1.
4. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 3, which is characterized in that described to change
Property agent a concentration of 0.05~0.5 mol/L in aqueous solution, aqueous solution and silicoaluminophosphamolecular molecular sieves butt containing modifying agent
Mass ratio is (25~70):1.
5. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that silicon phosphate
The temperature that aluminum molecular screen is contacted with the solution containing modifying agent is 20~95 DEG C, and the time is 0.5~24 hour.
6. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 5, which is characterized in that silicon phosphate
The temperature that aluminum molecular screen is contacted with the solution containing modifying agent is 45~85 DEG C, and the time is 1~16 hour.
7. the preparation method of multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that the phosphorus
Sour Si-Al molecular sieve for SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37,
Single or composite molecular screen in SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-46 and SAPO-56.
8. multistage pore canal prepared by the preparation method of any multi-stage artery structure silicoaluminophosphamolecular molecular sieves of claim 1~7
Structure silicoaluminophosphamolecular molecular sieves.
9. multi-stage artery structure silicoaluminophosphamolecular molecular sieves according to claim 8, which is characterized in that the molecular sieve has simultaneously
There are micropore, mesoporous and macropore；Wherein, micropore size is not more than 1 nanometer, and mesoporous pore size is distributed in 5~30 nanometers, macropore diameter point
It is distributed in 50~350 nanometers；0.05~0.30 centimetre of the Kong Rongwei of micropore contribution3/ gram, the Kong Rongwei 0.15~0.40 of mesoporous contribution
Centimetre3/ gram, 0.25~0.60 centimetre of the Kong Rongwei of macropore contribution3/ gram.
10. multistage pore canal prepared by the preparation method of any multi-stage artery structure silicoaluminophosphamolecular molecular sieves of claim 1~7
Application of the structure silicoaluminophosphamolecular molecular sieves in methanol to olefins reaction.
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