CN106276970A - A kind of SAPO 34 molecular sieve utilizing big particle diameter aluminum source to synthesize and synthetic method thereof and application - Google Patents
A kind of SAPO 34 molecular sieve utilizing big particle diameter aluminum source to synthesize and synthetic method thereof and application Download PDFInfo
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- CN106276970A CN106276970A CN201610804674.6A CN201610804674A CN106276970A CN 106276970 A CN106276970 A CN 106276970A CN 201610804674 A CN201610804674 A CN 201610804674A CN 106276970 A CN106276970 A CN 106276970A
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- particle diameter
- sapo
- molecular sieve
- big particle
- aluminum source
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 74
- 239000002245 particle Substances 0.000 title claims abstract description 63
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 47
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 241000269350 Anura Species 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 101
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 21
- 102220043159 rs587780996 Human genes 0.000 description 17
- 238000001033 granulometry Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- -1 olefin hydrocarbon Chemical class 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004519 manufacturing process 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
- 238000011160 research Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WZGWWPARMFQTAY-UHFFFAOYSA-N ethene;methanol Chemical group OC.C=C WZGWWPARMFQTAY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- KTWPKIIYRIEILL-UHFFFAOYSA-M tetraethylazanium;hydroxide;hydrate Chemical compound O.[OH-].CC[N+](CC)(CC)CC KTWPKIIYRIEILL-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of SAPO 34 molecular sieve utilizing big particle diameter aluminum source to synthesize and synthetic method thereof and application, first the present invention by preparing big particle diameter aluminum source, the method preparing SAPO 34 molecular sieve by big particle diameter aluminum source again obtains SAPO 34 molecular sieve of a kind of high activity, big particle diameter, when using as MTO catalyst, diolefin selective can be made in higher level stable, and average diolefin selective significantly improves.
Description
Technical field
The present invention relates to the technical field of SAPO-34 molecular sieve.
Background technology
Ethylene and propylene are basic organic chemical raw materials important in chemical industry, rise in modern petroleum and chemical industry
Very important effect.In recent years, along with the day by day shortage of Global Oil resource, conventional petroleum route ethylene and third is produced
The disparities between supply and demand that alkene is brought tend to nervous, and various countries are devoted to develop the process route of new non-petroleum producing olefinic hydrocarbons.Wherein,
Coal or natural gas are by synthesis gas (CO+H2) it is the most application prospect generally acknowledged at present via the technique of preparing light olefins from methanol
Technology path.Rich coal resources in China, the energy resource structure that petroleum resources are relatively deficient also determines once olefin hydrocarbon making by coal
Process route is extensively applied, will be to expanding China's traditional coal chemical industry development space, it is ensured that national energy security has
Important and far-reaching meaning.At present, the coal gasification in olefin hydrocarbon making by coal technological process, synthesising gas systeming carbinol have developed into maturation
Coal chemical technology, the industrialization technology exploitation of methanol-to-olefins (MTO) is then the key link that this process route realizes.
Methanol-to-olefins technology it is crucial that: the activity and selectivity of catalyst and corresponding technical flow design.Its
Research emphasis is concentrated mainly on screening of catalyst and preparation.In numerous MTO molecular sieve catalysts, SAPO-34 molecule
The activity of sieve and the selectivity to low-carbon alkene are considered as best.In United States Patent (USP) US4440871, U.S.'s carbon compound
Company (UCC) develops novel SAPO Series Molecules sieve (SAPO-n).Wherein SAPO-34 molecular sieve be by
SiO2、AlO2 -、PO2 +Three kinds of tetrahedrons are connected with each other and form, and have the structure of class chabasie (CHA), are that octatomic ring is constituted
Elliposoidal cage and three-dimensional open-framework, window diameter is 0 .38 nanometer, and space symmetr group is R3m.SAPO-34 is to generally acknowledge at present
Be applied to MTO reaction optimal molecular sieve.
Finding in conventional research work, except specific surface area, acid site density, elementary composition and crystalline phase composition is right
Outside SAPO-34 molecular sieve has an impact as the catalytic performance of MTO catalyst, grain size and pattern are to SAPO-34 molecular sieve
MTO catalytic performance also has a great impact.
In conventional work, find that the small crystal grain molecular sieve of Nano grade has the advantage of himself in terms of diffusion absorption,
Little crystal grain or nano level SAPO-34 molecular sieve have superior MTO performance as MTO catalyst, therefore in conventional work
Work has in a large number about little crystal grain or nano level SAPO-34 molecular sieve as the research of MTO catalyst.
Patent CN101214974B discloses a kind of method preparing fine grain SAPO-34 molecular sieve, and this patent is ultrasonic
The fine grain SAPO-34 molecular sieve of 0.5 1.5 microns is synthesized, for low-carbon (LC)s such as methanol ethylene, propylene under aging condition
The reaction of alkene.
Patent CN103408034B discloses the preparation method of the little SAPO-34 molecular sieve of mean diameter, and the method is passed through
Aging Step is prepared has the SAPO-34 molecular sieve that the mean diameter of MTO performance of excellence is little.
Patent CN4340986A discloses method preparing fine grain SAPO-34 molecular sieve and products thereof and purposes, the party
The crystallization precursor synthesis of the low-crystallinity that method prepares with the SAPO-34 molecular sieve of 10 800 nm goes out the little crystalline substance of high catalytic performance
Grain SAPO-34 molecular sieve.
Patent CN104192860B discloses the synthetic method of a kind of thin layer pattern SAPO-34 molecular sieve, and the method is passed through
Add the SAPO-34 molecular sieve of the thin layer pattern of double end amine cationic surfactant synthesis thickness about 100 nm, in methanol system
Olefine reaction has higher selectivity of light olefin.
Patent CN102616810B discloses to be had the nanometer SAPO-34 molecular sieve of cube or thin layer pattern and answers
With, the method synthesizes the molecular sieve of 20 300 nm by adding feature solvent, has the feature of catalytic applications life-span length.
Patent CN105174280A discloses nanometer thin lamellar SAPO-34 molecular sieve, ultrafast preparation method and applications, should
Method synthesizes the laminar SAPO-34 molecular sieve of 50 200 nm by introducing crystal seed, has high low in MTO reacts
Carbon olefin selectivity.
Patent CN103011188A discloses nanometer SAPO-34 molecular sieve and the synthesis side thereof with spherical or sheet-like morphology
Method and catalyst prepared therefrom and application.The method by microwave synthetically prepared go out 30 below nm spherical or 70 below nm
Thin slice SAPO-34 molecular sieve, for the reaction of the low-carbon alkenes such as methanol ethylene, propylene.
Patent CN105460956A discloses a kind of method preparing rule isometric particle SAPO-34 molecular sieve and answers
With, the method prepares the SAPO-34 molecular sieve of rule isometric particle by vacuum ageing, introducing noble gas, urges as MTO
Agent catalytic performance is preferable.
In sum, have in conventional SAPO-34 Zeolite synthesis work and substantial amounts of prepare little crystal grain or nanometer
The work of SAPO-34 molecular sieve, conventional work shows that little crystal grain or lamellar SAPO-34 molecular sieve have as MTO catalyst
There is superior MTO catalytic performance.
Summary of the invention
It is an object of the invention to provide a kind of big particle diameter, be easily recycled, process costs is low, production efficiency is high and has high
The SAPO-34 molecular sieve of diolefin selective, other purpose of the present invention includes the synthetic method and methods for using them proposing it.
Technical scheme is as follows:
A kind of method utilizing big particle diameter aluminum source synthesis SAPO-34 molecular sieve, comprises the following steps:
(1) prepared by big particle diameter aluminum source:
Boehmite and water are formulated as the serosity of solid content 10% ~ 40%, stir at 20 ~ 40 DEG C, use thereafter all
Serosity, by serosity micronization processes, being 0.5 ~ 1.5 μm to median D50, then is spray-dried by matter machine, obtains middle position
Particle diameter D50 is the big particle diameter aluminum source of 10 ~ 100 μm；
(2) prepared by gel:
Phosphoric acid is mixed with distilled water, under 20 ~ 50 DEG C of water bath condition, is stirred with the speed of 100 ~ 500r/min, then adds
Enter silicon source, after stirring, be slowly added to above-mentioned big particle diameter aluminum source, continue stirring, be slow added into template, hereafter improve and stir
Mix speed to 700 ~ 900r/min, after stirring 5 ~ 20h, prepare homogeneous gel；
(3) crystallization:
Above-mentioned gel is proceeded to autoclave, with the stir speed (S.S.) of 200 ~ 500r/min, the heating rate of 20 ~ 35 DEG C/h,
165 ~ 185 DEG C it are warming up under stirring, crystallization 50 ~ 80h thereafter, after crystallization is complete, cooling down, filtering and washing, dry
To molecular screen primary powder；
(4) roasting:
Molecular screen primary powder is warming up to 500 ~ 700 DEG C with the heating rate of 100 ~ 200 DEG C/h, roasting 4 ~ 8h, i.e. obtain big particle diameter
Active SAPO-34 molecular sieve.
Its a kind of preferred embodiment is: described in described step (1), the median D50 of boehmite is 1 ~ 3 μ
m。
Its another kind of preferred embodiment is: the homogenizer used in described step (1) is that microjet nano-dispersed is equal
Matter machine, during preparation, pressure is 0.5 ~ 0.8Mpa.
Its another kind of preferred embodiment is: based on molal quantity, use 1 part of big particle diameter aluminum source in described step (2),
0.05 ~ 0.15 part of silicon source, 1 ~ 1.2 part of phosphoric acid, 30 ~ 50 parts of distilled water, 0.8 ~ 1.2 part of template.
The most preferably: described phosphoric acid is the orthophosphoric acid of mass concentration 70% ~ 85%.
It is another kind of the most preferably: described template is the tetraethyl ammonium hydroxide water of mass concentration 20% ~ 40%
Solution.
It is another kind of the most preferably: described silicon source is the neutral Ludox of mass concentration 30% ~ 50%.
Present invention further proposes a kind of SAPO-34 molecular sieve utilizing big particle diameter aluminum source to synthesize, it passes through above-mentioned
A kind of method utilizing big particle diameter aluminum source synthesis SAPO-34 molecular sieve or its preferred embodiment prepare.
The median D50 of this SAPO-34 molecular sieve is 1.2 ~ 8 μm, pattern rule.
Present invention further proposes a kind of application mode of this SAPO-34 molecular sieve, i.e. use this SAPO-34 molecular sieve
Methanol-to-olefins (MTO) reaction is carried out as catalyst.
Its preferred embodiment is: the process of described methanol-to-olefins is: pure methanol and distilled water are formulated as methanol
The methanol solution of concentration 90wt% ~ 99wt%, at mass space velocity 2 ~ 25 h-1, reaction temperature 440 ~ 480 DEG C, under conditions of normal pressure
Fixed bed reactors carry out methanol and prepares olefine reaction.
The present invention uses big particle diameter aluminum source, reduces the dissolution velocity of crystallization initial stage gel, reduces the one-tenth of crystallization process
Core speed and crystallization rate, it is to avoid the defect that SAPO-34 zeolite product causes because crystallization rate is too fast, position, active center exists
Framework of molecular sieve is uniformly distributed so that SAPO-34 molecular sieve prepared by the present invention is as the diolefin selective of MTO catalyst
Stable in higher level, average diolefin selective significantly improves, and in contrast, traditional method prepares
SAPO-34 molecular sieve diolefin selective concordance and less stable, though the SAPO-34 molecule that the highest selectivity is higher
Sieve, it maintains higher selective ability the most poor, causes average diene selective low.
The present invention uses big particle diameter aluminum source, reduces crystallization rate, improves the granularity of SAPO-34 zeolite product.
The big particle diameter aluminum source that the present invention prepares, can form regular microspheroidal, the molecular sieve prepared further
Having regular morphology, thus during MTO, the dispersibility of SAPO-34 molecular sieve is fabulous, significantly improves catalytic capability and urges
Change efficiency.
The present invention uses big particle diameter aluminum source, prepares the SAPO-34 zeolite product of big particle diameter, accelerates production SAPO-
The speed of solid-liquid separation during 34 molecular sieve, improves SAPO-34 molecular sieve production efficiency, reduces process costs, improve simultaneously
Mother solution recycle efficiency, decrease the discharge of waste water, alleviate environmental burden, reduce the one-tenth of Industrial Wastewater Treatment
This.
In addition to significantly improving average diolefin selective, the present invention synthesizes the SAPO-34 molecular sieve of big particle diameter and makees
Significantly reducing for MTO catalyst loss rate in use more conventional SAP-34 molecular sieve, the coefficient of waste of catalyst shows
Writing and reduce, catalyst is significantly improved the service life during industrial applications, reduces Catalystization fortune
Row cost.
Additionally, the present invention uses the aluminum source of big particle diameter, improve the uniform of position, SAPO-34 molecular sieve active center distribution
Degree, it is ensured that the SAPO-34 molecular sieve prepared is stable in higher level as the diolefin selective of MTO catalyst, thus
Not only increase the highest selectivity, significantly improve average diolefin selective simultaneously.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the SAPO-34 sieve sample of A ~ F in embodiment；
Fig. 2 is the sample of the SAPO-34 molecular sieve of A ~ F in embodiment change curve of reactivity in MTO course of reaction
Figure；
Fig. 3 is that the change of sample diolefin selective in MTO course of reaction of the SAPO-34 molecular sieve of A ~ F in embodiment is bent
Line chart.
Detailed description of the invention
The present invention is described in further detail by the following examples, but this should be interpreted as the scope of the present invention
It is only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill knowledge and
Various replacements that customary means is made or change, should be included in the scope of the present invention.
Embodiment 1
The preparation of comparative sample and application:
(1) prepared by gel: first joined in reactor by the phosphoric acid that 1347.5g concentration is 80wt%, adds 1474.8g and steams
Distilled water, mixing, 30 DEG C of water-baths, under the mixing speed of 300r/min, add the neutral silicon source that 75.1g concentration is 40%, stirring is all
Even, the most slowly add the boehmite of 708.3g median D50=2 μm, continue stirring, be slow added into 2455g concentration
It it is the tetraethyl ammonium hydroxide of 30%；Increasing mixing speed, to 800r/min, prepares homogeneous gel after stirring 15h；
(2) crystallization: proceed to gel, in 10 L autoclaves, under the stir speed (S.S.) of 400r/min, be warming up to 30 DEG C/h
175 DEG C, crystallization 60h, cool thereafter；Separating through sucking filtration, the washing that adds water, to pH=7.0, is divided then at 120 DEG C of drying
Son sieves former powder；
(3) roasting: the molecular screen primary powder prepared by step (2) is proceeded in Muffle furnace, is warming up to 600 DEG C with 150 DEG C/h, roasting
Burn 6h, i.e. obtain comparative sample small-particle diameter active SAPO-34 molecular sieve, numbered A；
The small-particle diameter active SAPO-34 molecular sieve prepared with the test of laser granulometry instrument, its median D50=0.83 μm,
Testing its specific surface area is 705.1/g；
The methanol solution of methanol concentration 95wt% it is formulated as, at mass space velocity 15 h with pure methanol and distilled water-1, reaction temperature
450 DEG C, under normal pressure, fixed bed reactors carry out methanol and prepare olefine reaction, its average diolefin selective only has 77.5
%。
Embodiment 2
(1) preparation in big particle diameter aluminum source: take the little granule boehmite of 1kgD50=3 μm, adding water preparation solid content is 20%
Serosity, at 30 DEG C stir 2h prepare uniform serosity, under pressure 0.8Mpa use microjet nano-dispersed homogenizer thin
Change processes, and by laser granulometry instrument test molecule sieve granule median D50=1.5 μm, stops micronization processes, is carried out by serosity
It is spray-dried, the dried microsphere big particle diameter aluminum source obtaining D50=52.8 μm；
(2) prepared by gel: is first joined in reactor by the orthophosphoric acid that 1152.9g concentration is 85wt%, adds 1580.4g
Distilled water, mixing, 50 DEG C of water-baths, 100r/min stir speed (S.S.) under, adding 60.08g concentration is the neutral silicon source of 40wt%,
Stir, be slowly added to the big particle diameter aluminum source that 708.3g is prepared by step (1) afterwards, continue stirring, be slow added into 2455g
Concentration is the tetraethyl ammonium hydroxide of 30wt%；Increasing mixing speed stirs 20 little h to 700r/min and prepares homogeneous gel；
(3) crystallization: proceeded to by gel in 10L autoclave, under low whipping speed 300r/min, with the heating rate of 20 DEG C/h
It is warming up to 165 DEG C, crystallization 80h, after crystallization is complete, cool；Separate through sucking filtration, the washing that adds water to pH=6.5, then at
140 DEG C of drying obtain molecular screen primary powder；
(4) roasting: proceeded to by molecular screen primary powder in Muffle furnace, is warming up to 600 DEG C of roasting 6h with 150 DEG C/h, obtains big particle diameter
Activity SAPO-34 molecular sieve, numbering B；
Test through laser granulometry instrument, D50=8 μm of B sample, specific surface area 631.7/g；
It is the methanol solution of 99% by pure methanol and distilled water compounding methanol mass concentration, at mass space velocity 20 h-1, reaction temperature
Spend 460 DEG C, under normal pressure, fixed bed reactors carry out methanol and prepares olefine reaction, test average diolefin selective and reach
82.6 %.
Embodiment 3
(1) preparation in big particle diameter aluminum source: take the little granule boehmite of 1kgD50=1 μm, adding water preparation solid content is 40%
Serosity, at 40 DEG C stir 5h prepare uniform serosity, under pressure 0.8Mpa use microjet nano-dispersed homogenizer thin
Change processes, and sieves granule median D50=0.5 μm with laser granulometry instrument test molecule, stops micronization processes, is carried out by serosity
It is spray-dried, obtains the microsphere big particle diameter aluminum source of D50=100 μm after drying；
(2) prepared by gel: is first joined in reactor by the orthophosphoric acid that 1347.5g mass concentration is 80%, adds
1874.6g distilled water, mixing, 40 DEG C of water-baths, mixing speed 400r/min, add the neutral silicon source that 60.08g concentration is 50%, stir
Mix uniformly, be slowly added to the big particle diameter aluminum source that 708.3g is prepared by step (1) afterwards, continue stirring, be slow added into 1473g dense
Degree is the tetraethyl ammonium hydroxide of 40%；Strengthen mixing speed and prepare homogeneous gel to 900r/min stirring 5h；
(3) crystallization: proceeded to by gel in 10 L autoclaves, mixing speed 400r/min, with the heating rate liter of 35 DEG C/h
Warm to 185 DEG C, crystallization 50h, cool；Separating through sucking filtration, the washing that adds water, to pH=7.5, is divided then at 150 DEG C of drying
Son sieves former powder；
(4) roasting: finally proceed in Muffle furnace by molecular screen primary powder, is warming up to 700 DEG C of roasting 4h with 100 DEG C/h, obtains big grain
The active SAPO-34 molecular sieve in footpath, numbering C；
Test C sample, its median D50=5.26 μm with laser granulometry instrument, test specific surface area 657.4/g；
It is the methanol solution of 97% by pure methanol and distilled water compounding methanol mass concentration, mass space velocity 2 h-1, reaction temperature
470 DEG C, reaction pressure is normal pressure, carries out methanol and prepare olefine reaction on fixed bed reactors, tests average diolefin and selects
Property has reached 83.4%.
Embodiment 4
(1) preparation in big particle diameter aluminum source: take the little granule boehmite of 1kgD50=2.3 μm, adding water preparation solid content is
The serosity of 10%, 20 stirring 3h prepare uniform serosity, use the refinement of microjet nano-dispersed homogenizer under pressure 0.5Mpa
Process, sieve granule median D50=1.25 μm with laser granulometry instrument test molecule, stop micronization processes, serosity is sprayed
Mist is dried, and obtains the microsphere big particle diameter aluminum source of D50=10 μm after drying；
(2) prepared by gel: is joined in reactor by the orthophosphoric acid that 1152.9g mass concentration is 85%, adds 758.6g
Distilled water, mixing, 20 DEG C of water-baths, mixing speed 500r/min, add the neutral silicon source that 50.07g concentration is 30%, stir,
Being slowly added to the big particle diameter aluminum source that 708.3g is prepared by step (1) afterwards, continue stirring, being slow added into 2525.1g concentration is
The tetraethyl ammonium hydroxide of 35%；Strengthen mixing speed and prepare homogeneous gel to 900r/min stirring 10h；
(3) crystallization: gel proceeds to 10 L autoclaves, mixing speed 500r/min, with the heating rate of 30 DEG C/h
Under the conditions of, it is warming up to crystallization temperature 180 DEG C, crystallization 60h, cools thereafter；Separate through sucking filtration, add water and wash to pH=8
.5, molecular screen primary powder is obtained then at 120 DEG C of drying；
(4) roasting: proceeded to by molecular screen primary powder in Muffle furnace, is warming up to 500 DEG C of roasting 8h with 180 DEG C/h, obtains big particle diameter
Activity SAPO-34 molecular sieve, numbering D；
Knowing its D50=1.2 μm with the test of laser granulometry instrument, test specific surface area is 683.6/g；
It is the methanol solution of 90% by pure methanol and distilled water compounding methanol mass concentration, mass space velocity 5 h-1, reaction temperature
440 DEG C, reaction pressure is normal pressure, carries out methanol and prepare olefine reaction on fixed bed reactors, tests average diolefin and selects
Property has reached 83.9 %.
Embodiment 5
(1) preparation in big particle diameter aluminum source: take 1kgD50=1.52 little granule boehmite, adding water preparation solid content is 30%
Serosity, 25 DEG C of stirring 4h prepare uniform serosity, use at microjet nano-dispersed homogenizer refinement under pressure 0.6 Mpa
Reason, sieves granule median D50=0.92 μm with laser granulometry instrument test molecule, stops micronization processes, is sprayed by serosity
It is dried, obtains the microsphere big particle diameter aluminum source of D50=81.3 μm after drying；
(2) prepared by gel: is first joined in reactor by the orthophosphoric acid that 1254.4g mass concentration is 75%, adds
841.4g distilled water, mixing, 35 DEG C of water-baths, mixing speed 200r/min, add the neutral silicon source that 103g concentration is 35%, stirring
Uniformly, it is slowly added to the big particle diameter aluminum source that 566.7g is prepared by step (1) afterwards, continues stirring, be slow added into 2592.5g dense
Degree is the tetraethyl ammonium hydroxide of 25%；Strengthen mixing speed and prepare homogeneous gel to 850r/min stirring 12h；
(3) crystallization: gel is proceeded to 10 L autoclaves, mixing speed 200r/min, heats up with the heating rate of 22/h
To 170 DEG C, crystallization 70h, cool thereafter；Separating through sucking filtration, the washing that adds water, to pH=8, is divided then at 100 DEG C of drying
Son sieves former powder；
(4) roasting: proceeded to by molecular screen primary powder in Muffle furnace, is warming up to 550 DEG C of roasting 7h with 120 DEG C/h, obtains big particle diameter
Activity SAPO-34 molecular sieve, numbering E；
Testing E sample with laser granulometry instrument, its D50=6.78 μm, test specific surface area is 644.8/g；
It is the methanol solution of 95% by pure methanol and distilled water compounding methanol mass concentration, mass space velocity 10 h-1, reaction temperature
480 DEG C, reaction pressure is normal pressure, carries out methanol and prepare olefine reaction on fixed bed reactors, tests average diolefin and selects
Property has reached 82.7 %.
Embodiment 6
(1) preparation in big particle diameter aluminum source: take the little granule boehmite of 1kgD50=2.02 μm, adding water preparation solid content is
The serosity of 15 %, 35 DEG C of stirring 3h prepare uniform serosity, use microjet nano-dispersed homogenizer thin under pressure 0.7 Mpa
Change processes, and sieves granule median D50=1.15 micron with laser granulometry instrument test molecule, stops micronization processes, by serosity
It is spray-dried, obtains the microsphere big particle diameter aluminum source of D50=23.4 μm after drying；
(2) prepared by gel: is first joined in reactor by the orthophosphoric acid that 1120g mass concentration is 70%, adds 1034g
Distilled water, mixing, 45 DEG C of water-baths, mixing speed 250r/min, add the neutral silicon source that 64.08g concentration is 45%, stir,
Being slowly added to the big particle diameter aluminum source that 566.7g is prepared by step (1) afterwards, continue stirring, being slow added into 2651.4g concentration is
The tetraethyl ammonium hydroxide of 20%；Strengthen mixing speed and prepare homogeneous gel to 750r/min stirring 18h；
(3) crystallization: gel is proceeded to 10 L autoclaves, mixing speed 500r/min, is warming up to 175 DEG C with 25 DEG C/h,
Crystallization 70h, cools down thereafter fall；Separating through sucking filtration, the washing that adds water, to pH=7, obtains molecular screen primary powder then at 110 DEG C of drying
(4) roasting: proceeded to by molecular screen primary powder in Muffle furnace, is warming up to 650 DEG C of roasting 5h with 200 DEG C/h, obtains big particle diameter
Activity SAPO-34 molecular sieve molecular sieve, numbering F；
Testing F sample with laser granulometry instrument, its D50=3.43 μm, test specific surface area is 675.3/g；
It is the methanol solution of 92% by pure methanol and distilled water compounding methanol mass concentration, mass space velocity 25 h-1, reaction temperature
455 DEG C, reaction pressure is normal pressure, carries out methanol and prepare olefine reaction on fixed bed reactors, tests average diolefin and selects
Property has reached 83.3 %.
The same condition test situation carrying out above-mentioned 5 kinds of samples is as shown in table one and table two:
Table a part sieve sample specific surface area result
Table two sieve sample methanol to olefins reaction result
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only the present invention relatively
Good embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should be appreciated that those skilled in the art can
To design a lot of other amendments and embodiment, these amendments and embodiment will fall at spirit disclosed in the present application
Within spirit.
Claims (10)
1. the method utilizing big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: comprise the following steps:
(1) prepared by big particle diameter aluminum source:
Boehmite and water are formulated as the serosity of solid content 10% ~ 40%, stir at 20 ~ 40 DEG C, use thereafter all
Serosity, by serosity micronization processes, being 0.5 ~ 1.5 μm to median D50, then is spray-dried by matter machine, obtains middle position
Particle diameter D50 is the big particle diameter aluminum source of 10 ~ 100 μm；
(2) prepared by gel:
Phosphoric acid is mixed with distilled water, under 20 ~ 50 DEG C of water bath condition, is stirred with the speed of 100 ~ 500r/min, then adds
Enter silicon source, after stirring, be slowly added to above-mentioned big particle diameter aluminum source, continue stirring, be slow added into template, hereafter improve and stir
Mix speed to 700 ~ 900r/min, after stirring 5 ~ 20h, prepare homogeneous gel；
(3) crystallization:
Above-mentioned gel is proceeded to autoclave, with the stir speed (S.S.) of 200 ~ 500r/min, the heating rate of 20 ~ 35 DEG C/h,
165 ~ 185 DEG C it are warming up under stirring, crystallization 50 ~ 80h thereafter, cooling down, filtering and washing, dry and obtain molecular screen primary
Powder；
(4) roasting:
Molecular screen primary powder is warming up to 500 ~ 700 DEG C with the heating rate of 100 ~ 200 DEG C/h, roasting 4 ~ 8h, i.e. obtain big particle diameter
Active SAPO-34 molecular sieve.
The method of utilization the most according to claim 1 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: institute
Stating the median D50 of boehmite described in step (1) is 1 ~ 3 μm.
The method of utilization the most according to claim 1 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: institute
Stating the homogenizer used in step (1) is microjet nano-dispersed homogenizer, and during preparation, pressure is 0.5 ~ 0.8Mpa.
The method of utilization the most according to claim 1 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: press
Molal quantity meter, uses 1 part of big particle diameter aluminum source, 0.05 ~ 0.15 part of silicon source, 1 ~ 1.2 part of phosphoric acid, 30 ~ 50 parts of steamings in described step (2)
Distilled water, 0.8 ~ 1.2 part of template.
The method of utilization the most according to claim 4 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: institute
State the orthophosphoric acid that phosphoric acid is mass concentration 70% ~ 85%.
The method of utilization the most according to claim 4 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: institute
State the tetraethyl ammonium hydroxide aqueous solution that template is mass concentration 20% ~ 40%.
The method of utilization the most according to claim 4 big particle diameter aluminum source synthesis SAPO-34 molecular sieve, it is characterised in that: institute
State the neutral Ludox that silicon source is mass concentration 30% ~ 50%.
8. one kind utilizes the SAPO-34 molecular sieve that big particle diameter aluminum source synthesizes, it is characterised in that: by any one of claim 1 ~ 7
The described method synthesis utilizing big particle diameter aluminum source synthesis SAPO-34 molecular sieve obtains.
9. the application process of the SAPO-34 molecular sieve utilizing big particle diameter aluminum source to synthesize, it is characterised in that: use this SAPO-
34 molecular sieves carry out methanol-to-olefins (MTO) reaction as catalyst.
The application process of the SAPO-34 molecular sieve of utilization the most according to claim 9 big particle diameter aluminum source synthesis, its feature
It is: the process of described methanol-to-olefins is: pure methanol and distilled water are formulated as the first of methanol concentration 90wt% ~ 99wt%
Alcoholic solution, at mass space velocity 2 ~ 25 h-1, reaction temperature 440 ~ 480 DEG C, on fixed bed reactors, carry out first under conditions of normal pressure
Olefine reaction prepared by alcohol.
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Effective date of registration: 20210421 Address after: No.1, 7th floor, No.66, Shenghe 1st Road, Chengdu hi tech Zone, China (Sichuan) pilot Free Trade Zone, Chengdu, Sichuan 610041 Patentee after: CHENGDU RUNHE SHENGJIAN PETROCHEMICAL ENGINEERING TECHNOLOGY Co.,Ltd. Address before: The three group of Jin Su Zhen Miao Er Cun, Wutongqiao District of Leshan City, Sichuan province 614000 Patentee before: Runhe catalyst Co.,Ltd. |