CN108264051A - The method of modifying of silicoaluminophosphamolecular molecular sieves, modified obtained silicoaluminophosphamolecular molecular sieves and application thereof - Google Patents
The method of modifying of silicoaluminophosphamolecular molecular sieves, modified obtained silicoaluminophosphamolecular molecular sieves and application thereof 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 83
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 229910002796 Si–Al Inorganic materials 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 241000269350 Anura Species 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- -1 source Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing 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]
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic 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)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of method of modifying of silicoaluminophosphamolecular molecular sieves, modified obtained silicoaluminophosphamolecular molecular sieves and application thereof.The method of modifying is included in be enough to deposit siliceous material on the silicoaluminophosphamolecular molecular sieves under conditions of, the step of silicoaluminophosphamolecular molecular sieves is made to be contacted with organo-silicon compound, in the industrial production available for silicoaluminophosphamolecular molecular sieves modification.
Description
Technical field
The present invention relates to a kind of method of modifying of silicoaluminophosphamolecular molecular sieves, modified obtained silicoaluminophosphamolecular molecular sieves 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.In order to further improve the ratio of ethylene in product, need
Surface chemical modification modification is carried out to SAPO-34 molecular sieves, to further reduce the aperture of molecular sieve, improves its selecting property
Can, and then improve yield of ethene.
At present, SAPO-34 framework of molecular sieve mainly is introduced by various metallic elements to the modification of SAPO-34 molecular sieves
On.For example, document CN101555022A discloses a kind of preparation method of metal-modified SAPO-34 molecular sieve, including by molecule
It sieves in original powder preparation process, template and metal salt solution is first mixed to form metal complex, then add silicon source, phosphorus
The materials such as source, silicon source are prepared into gel mixture, by aging, hydrothermal crystallizing, washing, drying and roasting etc. to get to metal
Modified SAPO-34 molecular sieves.Document CN102744102A discloses the nitrate solution dipping using iron, magnesium, cobalt, nickel and chromium
SAPO-34 molecular sieves, vacuum distillation, drying, roasting method it is modified.
In short, SAPO-34 molecular sieves play very important work as active component in entire carbon monoxide-olefin polymeric
With.Although the prior art has carried out the modification of SAPO-34 molecular sieves some researchs, the performance of SAPO-34 molecular sieves
The space also further improved particularly in methanol to olefins reaction, for the variation of industrial chemicals market conditions, needs
Prepare ethylene, the adjustable catalyst of propylene ratio.
Invention content
The present invention is intended to provide a kind of method of modifying of silicoaluminophosphamolecular molecular sieves.
For achieving the above object, the technical solution adopted by the present invention is as follows：A kind of modification of silicoaluminophosphamolecular molecular sieves
Method is included under conditions of being enough to deposit siliceous material on the silicoaluminophosphamolecular molecular sieves, makes the Silicoaluminophosphate molecular
The step of sieve is contacted with organo-silicon compound.
In above-mentioned technical proposal, the silicoaluminophosphamolecular molecular sieves only have microcellular structure.
In above-mentioned technical proposal, the organo-silicon compound are selected from methyl silicate, ethyl orthosilicate, silicon tetrachloride, poly- two
At least one of methyl-silicone oil and polyphenyl methyl-silicone oil；It is preferred that in methyl silicate, polydimethyl siloxane fluid and polyphenyl methyl-silicone oil
At least one.
In above-mentioned technical proposal, the condition for being enough to deposit siliceous material on the silicoaluminophosphamolecular molecular sieves includes：
15~35 DEG C of temperature, 0.5~24 hour time, silicoaluminophosphamolecular molecular sieves are counted with the weight ratio of organo-silicon compound using butt as (5
~50):(0.1~10).
In above-mentioned technical proposal, organo-silicon compound dissolving in a solvent, the solvent be selected from benzene, carbon tetrachloride,
At least one of hexamethylene, pentane and petroleum ether.
In above-mentioned technical proposal, the weight ratio of organo-silicon compound and solvent is (0.1~10):(10~200).
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 mixed after silicoaluminophosphamolecular molecular sieves are contacted with organo-silicon compound
The step of closing dry object, roasting.
Raw materials used silicoaluminophosphamolecular molecular sieves in the present invention, only with microcellular structure.Can be synthesized according to conventional hydrothermal
What prepared by method or business was purchased.Can be the molecular screen primary powder of non-removed template method after hydrothermal crystallizing, it can also
It is the fired molecular sieve being stripped of after template.Preferably, used silicoaluminophosphamolecular molecular sieves are removed template method.
The present invention also provides the silicoaluminophosphamolecular molecular sieves that a kind of method of modifying according to the silicoaluminophosphamolecular molecular sieves obtains.
The silicoaluminophosphamolecular molecular sieves micropore average pore size is not more than 0.4 nanometer.The silicoaluminophosphamolecular molecular sieves specific surface area is not less than
450 meters2/ gram, preferably 450~600 meters2/ gram；Wherein external surface area is 10~25 meters2/ gram.The silicoaluminophosphamolecular molecular sieves
Kong Rong is not less than 0.15 centimetre3/ gram, preferably 0.15~0.25 centimetre3/ gram.
The present invention also provides the silicoaluminophosphamolecular molecular sieves that a kind of method of modifying according to the silicoaluminophosphamolecular molecular sieves obtains
Application in methanol to olefins reaction.Reaction condition includes：390~515 DEG C of temperature, methanol Feed space velocities 1~100 hour-1。
The present invention modifies silicoaluminophosphamolecular molecular sieves using organosilicon, and the aperture of molecular sieve is effectively reduced, and aperture is not more than
0.4 nanometer.During modified silicoaluminophosphamolecular molecular sieves are used for methanol-to-olefins as the active component of catalyst, show
Good catalytic performance improves diene yield (ethylene+propylene), and the yield of ethylene improves 2 percentage points, and catalyst is steady
It is qualitative to also improve 25%, achieve preferable technique effect.
In the method for the present invention, XRD data are used to be measured with German Brooker AXS D8 Advance type X-ray diffractometers；
Specific surface area data and pore-size distribution are measured by U.S.'s Mike's ASAP-2020 adsorption instruments.
Description of the drawings
Fig. 1 is【Comparative example 1】、【Embodiment 1-4】The SAPO-34 molecular sieve-4 As of preparation, the XRD spectra of B, C, D, E.Wherein A
For SAPO-34 molecular sieves before modified, B, C, D, E are modified SAPO-34 molecular sieves.As seen from the figure, synthesis and it is modified
Molecular sieve be respectively provided with characteristic diffraction peak possessed by SAPO-34 molecular sieves.
The present invention will be further described below by way of examples.
Specific embodiment
【Comparative example 1】
Prepare the SAPO-34 molecular sieves (conventional SAPO molecular sieve) 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 Micropore volume of A is 0.27cm3/g；Micropore average pore size is 0.42nm；Specific surface area is 571m2/ g, China and foreign countries' ratio
Surface area is 5m2/g。
【Embodiment 1】
It weighs 3g polydimethyl siloxane fluids to be placed in the cyclohexane solution of 100mL, stirs 2h at room temperature, add in 20g molecules
Sieve A simultaneously stirs 5h, and product B is obtained after drying and roasting.
Product B relative crystallinities are 98%；Micropore volume is 0.23cm3/g；Micropore size is distributed in 0.3-0.4nm；Than
Surface area is 535m2/ g, wherein external surface area are 15m2/g。
【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 final product is denoted as C.
Products C relative crystallinity is 93%；Micropore volume is 0.20cm3/g；Micropore size is distributed in 0.3-0.4nm；Than
Surface area is 518m2/ g, wherein external surface area are 18m2/g。
【Embodiment 3】
Together【Embodiment 1】, only organo-silicon compound and solvent are respectively polyphenylene dimethicone and petroleum ether, dosage
Respectively 10g and 80mL, modified-reaction time are 12h, and products therefrom is denoted as D.
Product D relative crystallinities are 95%；Micropore volume is 0.18cm3/g；Micropore size is distributed in 0.3-0.4nm；Than
Surface area is 470m2/ g, wherein external surface area are 10m2/g。
【Embodiment 4】
10g molecular sieve-4 As are fitted into fixed bed reactors, 8g ethyl orthosilicates steam is introduced and divided as carrier gas by nitrogen
In son sieve, saturation balance is adsorbed to, is passed through steam treatment 2h, heating roasting 2h, products therefrom E.
Product E relative crystallinity is 92%；Micropore volume is 0.19cm3/g；Micropore size is distributed in 0.3-0.4nm；Than
Surface area is 483m2/ g, wherein external surface area are 15m2/g。
【Embodiment 5】
It will【Embodiment 1-4】The SAPO-34 molecular sieves B-E of gained is made anti-for MTO after carrying out calcination process and tabletting
The catalyst answered.Using fixed-bed catalytic reactor, reactor is stainless steel tube, investigates process conditions used and is：Catalysis
Agent loadings 2.0g, reaction temperature are 460 DEG C, weight space velocity 6h-1, pressure 0.1MPa, evaluation result is as shown in table 1.
【Comparative example 2】
It will【Comparative example 1】The SAPO-34 molecular sieve-4 As of gained are made what is reacted for MTO after carrying out calcination process and tabletting
Catalyst.Using fixed-bed catalytic reactor, reactor is stainless steel tube, investigates process conditions used and is：Catalyst fills
The amount of filling out 2.0g, reaction temperature are 460 DEG C, weight space velocity 6h-1, pressure 0.1MPa, evaluation result is as shown in table 1.
Table 1
By table 1 as it can be seen that the SAPO-34 molecular sieves after surface chemical modification are used in MTO reactions, more unmodified molecule
Sieve yield of ethene has 2 percentage points of promotion, and the service life of catalyst also has more than 25% promotion.
Claims (13)
1. a kind of method of modifying of silicoaluminophosphamolecular molecular sieves is included in and is enough to deposit siliceous material on the silicoaluminophosphamolecular molecular sieves
Under conditions of material, the step of silicoaluminophosphamolecular molecular sieves is made to be contacted with organo-silicon compound.
2. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that the silicoaluminophosphamolecular molecular sieves
Only there is microcellular structure.
3. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that the organo-silicon compound choosing
From at least one of methyl silicate, ethyl orthosilicate, silicon tetrachloride, polydimethyl siloxane fluid and polyphenyl methyl-silicone oil.
4. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 3, which is characterized in that the organo-silicon compound choosing
From at least one of methyl silicate, polydimethyl siloxane fluid and polyphenyl methyl-silicone oil.
5. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that described to be enough in the phosphoric acid
The condition that siliceous material is deposited on Si-Al molecular sieve includes：15~35 DEG C of temperature, 0.5~24 hour time, Silicoaluminophosphate molecular
Sieve is counted with the weight ratio of organo-silicon compound using butt as (5~50):(0.1~10).
6. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that the organo-silicon compound are molten
In a solvent, the solvent is selected from least one of benzene, carbon tetrachloride, hexamethylene, pentane and petroleum ether to solution.
7. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 6, which is characterized in that organo-silicon compound and solvent
Weight ratio be (0.1~10):(10~200).
8. the method for modifying of silicoaluminophosphamolecular molecular sieves according to claim 1, which is characterized in that the silicoaluminophosphamolecular molecular sieves
For SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40,
Single or composite molecular screen in SAPO-41, SAPO-42, SAPO-44, SAPO-46 and SAPO-56.
9. the silicoaluminophosphamolecular molecular sieves that the method for modifying of any silicoaluminophosphamolecular molecular sieves of claim 1~8 obtains.
10. silicoaluminophosphamolecular molecular sieves according to claim 9, which is characterized in that the silicoaluminophosphamolecular molecular sieves are averaged hole
Diameter is not more than 0.4 nanometer.
11. silicoaluminophosphamolecular molecular sieves according to claim 9, which is characterized in that the silicoaluminophosphamolecular molecular sieves specific surface
Product is not less than 450 meters2/ gram, wherein external surface area is 10~25 meters2/ gram；Kong Rong is not less than 0.15 centimetre3/ gram.
12. silicoaluminophosphamolecular molecular sieves according to claim 11, which is characterized in that the silicoaluminophosphamolecular molecular sieves specific surface
Product is 450~600 meters2/ gram；0.15~0.30 centimetre of Kong Rongwei3/ gram.
13. the silicoaluminophosphamolecular molecular sieves that the method for modifying of any silicoaluminophosphamolecular molecular sieves of claim 1~8 obtains are in methanol
Application in olefine reaction processed.
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