CN109796028B - Method for preparing silicoaluminophosphate molecular sieve, silicoaluminophosphate molecular sieve and method for preparing olefin from methanol - Google Patents
Method for preparing silicoaluminophosphate molecular sieve, silicoaluminophosphate molecular sieve and method for preparing olefin from methanol Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 105
- 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 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 67
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003292 glue Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 238000001994 activation Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000005216 hydrothermal crystallization Methods 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005406 washing Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- 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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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysis, and discloses a method for preparing a silicoaluminophosphate molecular sieve, the silicoaluminophosphate molecular sieve prepared by the method, and a method for preparing olefin from methanol. According to the method for preparing the silicoaluminophosphate molecular sieve, provided by the invention, silicoaluminophosphate dry glue powder is used as a molecular sieve crystallization initial raw material, the raw material is easy to store, and the problem that liquid raw materials such as silica sol, phosphoric acid and the like are difficult to store due to the influences of temperature and weather in the current industrial production is solved; meanwhile, the amount of water is reduced in the crystallization process, the yield of the molecular sieve is improved, the discharge amount of crystallized liquid sewage is greatly reduced, and the preparation cost of the silicoaluminophosphate molecular sieve is reduced. The silicoaluminophosphate molecular sieve prepared by the method shows excellent catalytic performance when used for catalyzing the reaction of preparing olefin from methanol.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a method for preparing a silicoaluminophosphate molecular sieve, the silicoaluminophosphate molecular sieve prepared by the method and a method for preparing olefin from methanol.
Background
The energy structure of China is characterized by more coal, poor oil and less gas, and is a country with relatively insufficient petroleum resources, and at present, China becomes the biggest coal producing country and consuming country in the world. This coal-based energy landscape does not change much over a considerable period of time in the future. The shortage of petroleum resources has become one of the major bottlenecks restricting the development of the olefin industry in China. Petrochemical routes using natural gas or coal as a raw material to develop various alternative petroleum resources have been ongoing. The technical progress of the MTO process is very beneficial to quickening the preparation of low-carbon olefin including propylene from methanol in China.
Mto (methane to olefin) refers to a chemical process technology for preparing low-carbon olefins (ethylene and propylene) from methanol. The successful development of MTO technology finds a new raw material route for olefin production. The method for producing olefin by using methanol as a raw material instead of petroleum not only can enable the olefin price to get rid of the influence of petroleum products and reduce the excessive dependence of China on petroleum resources, but also has very important strategic significance for promoting the industrial development of lean oil regions and balancing and reasonably utilizing the resources of China, and the research on the selection and preparation of the catalyst is the key point of the MTO industrialization.
In 1984, UCC company invented a silicoaluminophosphate non-zeolite molecular sieve (SAPO-34 molecular sieve for short) with a small pore diameter, which is similar to chabazite in structure, has three-dimensional cross pore channels with a pore diameter of 0.43nm, belongs to a cubic crystal system, and a shape-selective eight-membered ring channel of the molecular sieve can inhibit the generation of aromatic hydrocarbon. SAPO-34 molecular sieve with PO2+、A1O2-、SiO2+The three tetrahedrons are connected with each other, and have an ellipsoidal cage formed by oxygen-membered rings, a circular or corrugated structure, and the diameter of the orifice is kept between 0.43 and 0.50 nm. The molecular sieve pore volume is 1.42cm3/g, space symmetry group R3mBelongs to a trigonal system, has a structure similar to chabazite, has large available specific surface area, and when the SAPO-34 molecular sieve is used for preparing olefin by methanol conversion, the content of low-carbon olefin such as ethylene, propylene and the like in the product is obviously increased, and C5 +The content of the components is significantly reduced and almost no aromatic hydrocarbons are produced. Therefore, the SAPO-34 molecular sieve with excellent development performance and mild process conditions has very important research significance for the MTO process. In recent years, how to improve the performance and preparation conditions of SAPO-34 molecular sieve has been the subject of much research.
CN101121529A reports a method for preparing SAPO-34 molecular sieve by traditional hydrothermal synthesis, which comprises mixing a phosphorus source, a silicon source, an aluminum source, water and an organic amine template agent into gel, adding an organic amine accelerator to prepare a uniform initial gel mixture for synthesizing the SAPO-34 molecular sieve, and carrying out hydrothermal crystallization after aging treatment on the gel mixture to prepare the SAPO-34 molecular sieve. The traditional method for synthesizing the SAPO-34 molecular sieve by the hydrothermal method has the characteristics of poor repeatability, low yield and the like.
CN102372288A discloses a method for preparing SAPO-34 molecular sieve by a gas phase method, which prepares precursor compounds of silicon, phosphorus and aluminum, fluoride and an organic template agent into dry glue and arranges the dry glue on the upper part of a reaction kettle, arranges a mixed solution of water and organic amine on the lower part of the reaction kettle, and prepares the SAPO-34 molecular sieve catalyst under the reaction conditions of 140-. The SAPO-34 molecular sieve prepared by the gas phase method has the problems of low relative crystallinity of the molecular sieve, low activity when used for MTO reaction, high coking rate and the like.
CN104556091A discloses a preparation method of SAPO-34 molecular sieve, which is characterized in that: uniformly mixing a phosphorus source, an aluminum source and water according to a certain proportion, and drying to obtain a phosphorus-aluminum dry adhesive with the solid content of not less than 60%; contacting and mixing the phosphorus-aluminum dry glue with a template agent and a silicon source uniformly to prepare a mixture for hydrothermal crystallization. In the hydrothermal crystallization process, a special sectional crystallization process is combined to prepare the target molecular sieve.
The research has the problems of difficult storage of raw materials, large sewage discharge amount, low molecular sieve yield and the like, so how to further improve the preparation condition of the SAPO-34 molecular sieve and ensure the performance of the SAPO-34 molecular sieve is an urgent problem to be solved in the technical field of preparing low-carbon olefin by using methanol.
Disclosure of Invention
The invention aims to overcome the defects that in the industrial production of preparing a silicoaluminophosphate molecular sieve in the prior art, liquid raw materials such as silica sol, phosphoric acid and the like are difficult to store due to the influence of temperature and weather, the discharge amount of sewage is large, the yield of the molecular sieve is low and the like, and provides a method for preparing the silicoaluminophosphate molecular sieve, the silicoaluminophosphate molecular sieve prepared by the method and a method for preparing olefin from methanol. The silicoaluminophosphate molecular sieve prepared by the method shows excellent catalytic performance when used for catalyzing the reaction of preparing olefin from methanol.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a silicoaluminophosphate molecular sieve, characterized in that the method comprises the steps of:
(a) mixing and contacting an aluminum source, a silicon source, a phosphorus source and water to obtain a mixture A;
(b) drying and grinding the mixture A in sequence to obtain silicon-phosphorus-aluminum dry glue powder;
(c) activating the silicon-phosphorus-aluminum dry glue powder in the presence of phosphoric acid aqueous solution to obtain a mixture B;
(d) mixing and contacting the mixture B with a template agent to obtain a mixture C;
(e) crystallizing, filtering and drying the mixture C in sequence to obtain raw powder of the silicoaluminophosphate molecular sieve;
(f) and (3) carrying out demoulding agent treatment on the raw powder of the silicoaluminophosphate molecular sieve.
In a second aspect, the present invention provides a silicoaluminophosphate molecular sieve prepared by the foregoing method.
In a third aspect of the present invention, there is provided a method for producing olefins from methanol, the method comprising: under the reaction condition of preparing olefin from methanol, in the presence of a catalyst, the methanol is subjected to the reaction of preparing olefin, wherein the catalyst is the silicoaluminophosphate molecular sieve prepared by the method provided by the invention.
According to the method for preparing the silicoaluminophosphate molecular sieve, provided by the invention, silicoaluminophosphate dry glue powder is used as a molecular sieve crystallization initial raw material, the raw material is easy to store, and the problem that liquid raw materials such as silica sol, phosphoric acid and the like are difficult to store due to the influences of temperature and weather in the current industrial production is solved; meanwhile, the amount of water is reduced in the crystallization process, the yield of the molecular sieve is improved, the discharge amount of crystallized liquid sewage is greatly reduced, and the preparation cost of the silicoaluminophosphate molecular sieve is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample synthesized in examples 1 to 5 and comparative examples 1 to 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing a silicoaluminophosphate molecular sieve, wherein the method comprises the following steps:
(a) mixing and contacting an aluminum source, a silicon source, a phosphorus source and water to obtain a mixture A;
(b) drying and grinding the mixture A in sequence to obtain silicon-phosphorus-aluminum dry glue powder;
(c) activating the silicon-phosphorus-aluminum dry glue powder in the presence of phosphoric acid to obtain a mixture B;
(d) mixing and contacting the mixture B with a template agent to obtain a mixture C;
(e) crystallizing, filtering and drying the mixture C in sequence to obtain raw powder of the silicoaluminophosphate molecular sieve;
(f) and (3) carrying out demoulding agent treatment on the raw powder of the silicoaluminophosphate molecular sieve.
In the method provided by the invention, the silicon-phosphorus-aluminum dry glue powder is used as the initial raw material for molecular sieve crystallization, and the raw material is easy to store, so that the problem that liquid raw materials such as silica sol, phosphoric acid and the like are difficult to store due to the influence of temperature and weather in the current industrial production is effectively avoided; meanwhile, the water consumption can be greatly reduced in the crystallization process, the yield of the silicoaluminophosphate molecular sieve is improved, the discharge amount of crystallized liquid sewage is greatly reduced, the preparation cost of the silicoaluminophosphate molecular sieve is reduced, and the economy is good.
In the method of the present invention, the types of the aluminum source, the silicon source, and the phosphorus source are not particularly limited, and may be selected conventionally in the art as long as they are water-soluble. For example, the aluminum source may be at least one of pseudoboehmite, aluminum sol, and aluminum isopropoxide; the silicon source can be at least one of ethyl orthosilicate, silica sol and white carbon black; the phosphorus source may be phosphoric acid and/or phosphorous acid.
According to the present invention, the amounts of the aluminum source, the silicon source and the phosphorus source can be selected according to the structure type of the desired silicoaluminophosphate molecular sieve, and can vary within a wide range, for example, the molar ratio of the amounts of the aluminum source, the silicon source and the phosphorus source, respectively, in terms of their respective oxides, can be 1: 0.1-1.5: 0.01-1.5; the amount of water used is not particularly limited, and may vary within a wide range as long as the aluminum source, the silicon source and the phosphorus source can be dissolved, and it is preferable that the molar ratio of the amount of water used to the amount of aluminum source used in terms of its oxide is 5 to 30: 1.
according to the present invention, the contact manner between the aluminum source, the silicon source, the phosphorus source and the water is not particularly limited, and for example, the four substances may be simultaneously mixed and contacted, or several of them may be mixed and contacted first, and then the remaining substances may be added to the obtained mixture to continue mixing and contacting. The mixing contact is preferably carried out under stirring conditions. In a preferred embodiment, the contacting is performed by first mixing the aluminum source and the water with stirring, then adding the silicon source and the phosphorus source, and continuing to mix with stirring.
According to the invention, in order to obtain solid silicoaluminophosphate dry glue, in step (b), the drying conditions may include: the drying temperature is 25-150 ℃, and the drying time is 6-48 h.
According to the present invention, in the step (b), the grinding manner is not particularly limited, and may be a grinding manner that is conventional in the art.
According to the invention, the silicoaluminophosphate dry glue powder can be activated under the action of phosphoric acid. The activation degree of the silicoaluminophosphate dry glue powder is increased along with the increase of the using amount of the phosphoric acid, but when the using amount of the phosphoric acid is increased to a certain degree, the activation effect of the phosphoric acid on the silicoaluminophosphate dry glue powder becomes no longer significant, and even the pore development of the silicoaluminophosphate dry glue powder is not facilitated, preferably, in order to ensure that the activated mixture B has a higher activation degree, in the step (c), the using amount of the phosphoric acid can be such that the molar ratio of the content of the phosphoric acid to the content of aluminum element in the silicoaluminophosphate dry glue powder, calculated as oxide thereof, is 0.1-1: 1.
according to the invention, the phosphoric acid used for activating the silicoaluminophosphate dry glue powder is preferably used in the form of an aqueous solution. Preferably, the molar ratio of the content of phosphoric acid to water in the phosphoric acid aqueous solution is 1: 5-300.
According to the invention, the temperature and time of the activation treatment also affect the activation degree of the silicon-phosphorus-aluminum dry glue powder, and in order to further increase the activation degree of the mixture B obtained by the activation treatment, in step (c), the conditions of the activation treatment may include: the activation temperature is 25-120 ℃, and the activation time is 1-24 h.
In the method, the template agent plays a role in template, structure guiding, space filling and skeleton charge balancing, and has great influence on the shape and structure of the finally obtained silicoaluminophosphate molecular sieve. The pore size and the degree of pore development of the finally obtained silicoaluminophosphate molecular sieve increase with the increase of the amount of the template agent, but when the amount of the template agent is increased to a certain degree, the promotion effect of the template agent on the pore structure of the mixture B becomes no longer significant, and even the development of pores is not facilitated, preferably, in order to ensure that the finally obtained silicoaluminophosphate molecular sieve has a highly developed pore structure, in the step (d), the mixture B and the template agent are used in amounts such that the molar ratio of the content of aluminum element in the mixture B in terms of oxide thereof to the content of the template agent is 1: 1-5.
In the method, the selection of the template plays a crucial role in the morphology and structure of the finally obtained silicoaluminophosphate molecular sieve, and can even determine the type of the finally obtained silicoaluminophosphate molecular sieve. In order to ensure that the finally obtained silicoaluminophosphate molecular sieve has a long-range ordered topological structure and a large specific surface area and obtain the SAPO-34 molecular sieve, in the step (d), the template agent is preferably at least one of triethylamine, diethylamine, tetraethylammonium hydroxide, N-butylamine, morpholine and N, N-diisopropylethylamine.
According to the present invention, in the step (e), the crystallization conditions may include: the crystallization temperature is 150-210 ℃, and the crystallization time is 10-24 h. If the crystallization temperature is too low, a crystalline substance consisting of silicon, phosphorus and aluminum with unknown crystal phases can be formed, and if the crystallization temperature is too high, the influence on the crystallinity of the finally obtained silicoaluminophosphate molecular sieve is not large; if the crystallization time is too short, the silicon is not beneficial to entering the molecular sieve framework, and if the crystallization time is too long, the influence on the crystallinity of the finally obtained silicoaluminophosphate molecular sieve is also not great. According to a preferred embodiment, the crystallization is performed by a hydrothermal crystallization method, and since water is added in the activation process in the step (c), no water is added in the crystallization process, so that compared with the crystallization step of preparing the silicoaluminophosphate molecular sieve by the traditional hydrothermal synthesis method, the water consumption is greatly reduced, and simultaneously, the generation of a large amount of waste liquid in the subsequent separation and washing process is effectively avoided.
According to the present invention, in the above process for preparing a silicoaluminophosphate molecular sieve, the process for obtaining raw powder of a silicoaluminophosphate molecular sieve by filtration may include: after centrifugal separation to obtain solid product, repeatedly washing with deionized water to neutrality (washing times can be 2-10), and then carrying out suction filtration.
According to the present invention, in order to obtain a raw powder of silicoaluminophosphate molecular sieve, in step (e), the drying conditions may include: the drying temperature is 80-120 ℃, and the drying time is 2-24 h.
According to the invention, the method for removing the template agent is generally a calcination method. Preferably, the conditions for removing the template agent may include: roasting for 2-12h at 400-700 ℃. If the roasting temperature is too high and the roasting time is too long, the molecular sieve framework is easy to be dealuminized seriously and part of the framework is easy to collapse, so that the crystallinity is greatly reduced, and if the roasting temperature is too low and the roasting time is too short, the template agent is easy to be removed incompletely.
The invention also provides a silicoaluminophosphate molecular sieve prepared by the method.
The invention also provides a method for preparing olefin from methanol, which comprises the following steps: under the reaction condition of preparing olefin from methanol, in the presence of a catalyst, the methanol is subjected to the reaction of preparing olefin, wherein the catalyst is the silicoaluminophosphate molecular sieve prepared by the method provided by the invention.
The reaction conditions for producing olefins from methanol are not particularly limited in the present invention, and may be conventionally selected in the art, and for example, the reaction conditions for producing olefins from methanol may include: the reaction is carried out in the nitrogen atmosphere, the reaction temperature is 450-500 ℃, and the weight space velocity of the methanol is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following experimental examples and experimental comparative examples, analysis of reaction product composition was performed on an off-line gas chromatograph available from Agilent under model 7890B;
in the following experimental examples and experimental comparative examples, the catalyst service life was calculated as the time from the start of the reaction to the time at which the conversion of methanol was 99%.
Example 1
1) Adding 7.25g of pseudo-boehmite into 9.89g of deionized water, stirring uniformly, respectively dropwise adding 5.41g of phosphoric acid (85%) and 5.63g of silica sol, and stirring for 1h to obtain a mixtureThe molar ratio of the materials of the components is Al2O3：P2O5：SiO2：H2O is 1: 0.5: 0.6: 20. the mixture was dried in an oven at 80 ℃ overnight.
2) And grinding the dried silicon-phosphorus-aluminum dry glue to obtain silicon-phosphorus-aluminum dry glue powder. The obtained silicon-phosphorus-aluminum dry glue powder is mixed with 3.73g of phosphoric acid and 20.03g of deionized water, and is activated for 4 hours at the temperature of 60 ℃.
3) And cooling the treated mixed solution to room temperature, adding 10.00g of triethylamine, stirring for 1h, and transferring into a hydrothermal crystallization kettle for hydrothermal crystallization at 190 ℃ for 24 h. And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the sample synthesized in example 1 is the SAPO-34 molecular sieve.
Example 2
1) Adding 7.25g of pseudo-boehmite into 15.60g of deionized water, stirring uniformly, then respectively dropwise adding 10.82g of phosphoric acid (85%) and 4.69g of silica sol, and continuing stirring for 1h to obtain a mixture, wherein the molar ratio of each component in the mixture is Al2O3：P2O5：SiO2：H2O is 1: 1: 0.5: 27. the mixture was dried in an oven at 60 ℃ overnight.
2) And grinding the dried silicon-phosphorus-aluminum dry glue to obtain silicon-phosphorus-aluminum dry glue powder. The obtained silicon-phosphorus-aluminum dry glue powder is mixed with 1.12g of phosphoric acid and 15.70g of deionized water, and is activated for 4 hours at the temperature of 80 ℃.
3) And cooling the treated mixed solution to room temperature, adding 13.85g of triethylamine, stirring for 1h, and transferring into a hydrothermal crystallization kettle for hydrothermal crystallization at 200 ℃ for 24 h. And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the sample synthesized in example 2 is the SAPO-34 molecular sieve.
Example 3
1) Respectively mixing and stirring 9.58g of aluminum isopropoxide, 13.38g of phosphoric acid (85%) and 13.25g of deionized water, dropwise adding 5.63g of silica sol after uniformly stirring, and continuously stirring for 1h to obtain a mixture with the molar ratio of each component to material of Al2O3：P2O5：SiO2：H2O is 1: 1.2: 0.6: 23. the mixture was dried in an oven at 60 ℃ overnight.
2) And grinding the dried silicon-phosphorus-aluminum dry glue to obtain silicon-phosphorus-aluminum dry glue powder. The obtained silicon-phosphorus-aluminum dry glue powder is mixed with 2.46g of phosphoric acid and 18.19g of deionized water, and is activated for 4 hours at the temperature of 80 ℃.
3) And cooling the treated mixed solution to room temperature, adding 11.25g of triethylamine and 1.55g of diethylamine, stirring for 1h, and transferring into a hydrothermal crystallization kettle for hydrothermal crystallization at 200 ℃ for 24 h. And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the sample synthesized in example 3 is the SAPO-34 molecular sieve.
Example 4
1) Adding 7.25g of pseudo-boehmite into 13.11g of deionized water, stirring uniformly, then respectively dropwise adding 7.63g of phosphoric acid (85%) and 2.84g of silica sol, and continuing stirring for 1h to obtain a mixture, wherein the molar ratio of each component in the mixture is Al2O3：P2O5：SiO2：H2O is 1: 0.7: 0.3: 22. the mixture was dried in an oven at 80 ℃ overnight.
2) And grinding the dried silicon-phosphorus-aluminum dry glue to obtain silicon-phosphorus-aluminum dry glue powder. The obtained silicon-phosphorus-aluminum dry glue powder is mixed with 1.59g of phosphoric acid and 17.39g of deionized water, and is activated for 4 hours at the temperature of 60 ℃.
3) And cooling the treated mixed solution to room temperature, adding 20.74g of tetraethylammonium hydroxide (20%), stirring for 1h, and transferring the mixture into a hydrothermal crystallization kettle for hydrothermal crystallization for 48h at the temperature of 180 ℃. And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the sample synthesized in example 4 is the SAPO-34 molecular sieve.
Example 5
1) Adding 7.25g of pseudo-boehmite into 16.89g of deionized water, stirring uniformly, then respectively dropwise adding 5.41g of phosphoric acid (85%) and 5.63g of silica sol, and continuing stirring for 1h to obtain a mixture, wherein the molar ratio of each component in the mixture is Al2O3：P2O5：SiO2：H2O is 1: 0.5: 0.6: 29. the mixture was dried in an oven at 50 ℃ overnight.
2) And grinding the dried silicon-phosphorus-aluminum dry glue to obtain silicon-phosphorus-aluminum dry glue powder. The obtained silicon-phosphorus-aluminum dry glue powder is mixed with 3.73g of phosphoric acid and 21.51g of deionized water, and is activated for 4 hours at the temperature of 90 ℃.
3) And cooling the treated mixed solution to room temperature, adding 10g of triethylamine, stirring for 1h, and transferring into a hydrothermal crystallization kettle for hydrothermal crystallization at 200 ℃ for 24 h. And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the sample synthesized in example 5 is the SAPO-34 molecular sieve.
Comparative example 1
Comparative example to illustrate a reference silicoaluminophosphate molecular sieve and method of making the same
Traditional hydrothermal synthesis of SAPO-34
1) 9.86g of pseudo-boehmite, 13.84g of phosphoric acid (85%) and 55.73g of deionized water were mixed and stirred with strong forceAfter stirring for 1 hour, 7.13g of silica sol (30%) is added dropwise, after stirring uniformly, 18.20g of Triethylamine (TEA) as a template is added, stirring is continued for 2 hours, and aging is carried out for 2 hours at room temperature. The molar ratio of each component in the obtained mixture is Al2O3：P2O5：SiO2：TEA：H2O is 1: 0.9: 0.6: 2.8: 58. and (3) putting the gel into a reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization at 200 ℃ for 24 hours.
2) And centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product for 8 hours at 550 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the synthesized sample of comparative example 1 is the SAPO-34 molecular sieve.
Comparative example 2
Comparative example to illustrate a reference silicoaluminophosphate molecular sieve and method of making the same
Dry glue method for synthesizing SAPO-34 molecular sieve
1) Adding 23.00g of phosphoric acid (85%) and 28.20g of silica sol (30%) into deionized water under stirring, fully mixing uniformly, then adding 14.60g of pseudo-boehmite, stirring for 2h at room temperature, then adding tetraethyl ammonium hydroxide (TEAOH), and adding the components according to the molar ratio of Al2O3：P2O5：SiO2：H2O：TEAOH＝1：1：1.2：75：1；
2) Stirring at room temperature for 24 hr, gradually raising the temperature to 80 deg.C, stirring for 5 hr, and gradually increasing the viscosity of the system with the evaporation of water during the reaction to form colloid. Putting the colloid into an oven, heating at 120 ℃ for more than 12h, and completely evaporating water to obtain dry colloid;
3) grinding the dry glue into powder, placing 6.5g of the dry glue on the upper part of a reaction kettle, and placing the lower part of the reaction kettle into a mixed solution of 7.5g of triethylamine and 15g of water. And (3) crystallizing the reaction kettle for 48 hours at 180 ℃ after sealing, fully washing the obtained product after cooling, drying the product for 5 hours at 120 ℃ after filtering, and roasting the product for 8 hours at 550 ℃ to obtain the SAPO-34 molecular sieve. The XRD spectrum of the sample is shown in figure 1.
As can be seen from fig. 1, characteristic diffraction peaks of the SAPO-34 molecular sieve at 2 θ ═ 9.5 ± 0.1 °, 15.9 ± 0.1 °, 20.5 ± 0.1 ° and the like appear in the XRD spectrum, which proves that the synthesized sample of comparative example 2 is the SAPO-34 molecular sieve.
Test example
The silicoaluminophosphate molecular sieves prepared in the examples and the comparative examples are used for catalyzing the reaction of preparing olefin from methanol by adopting a fixed bed catalytic reaction evaluation device for evaluation.
The reaction conditions for preparing the olefin from the methanol are as follows: respectively weighing 0.2g of the silicoaluminophosphate molecular sieve samples prepared in the above examples and comparative examples, placing the samples into a reactor, introducing nitrogen at 500 ℃ for activation for 0.5h, then cooling to 450 ℃, mixing a raw material methanol solution with a carrier gas-nitrogen gas after passing through a flow metering pump, feeding the mixture into a preheating furnace, vaporizing the mixture into gas in the preheating furnace, and feeding the gas into the reactor for reaction, wherein the nitrogen flow rate is 200mL/min, and the methanol weight space velocity is 3h-1The product after the reaction was analyzed by off-line gas chromatography, and the analysis results are shown in table 1. The time from the start of the reaction to 99% conversion of methanol was used as the catalyst life.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| CH4(wt%) | 1.37 | 1.38 | 1.31 | 1.69 | 1.54 | 1.32 | 0.82 |
| C2H4(wt%) | 44.81 | 43.89 | 48.58 | 49.85 | 44.82 | 42.71 | 48.10 |
| C3H6(wt%) | 37.28 | 38.10 | 34.92 | 34.04 | 37.79 | 37.28 | 32.97 |
| C2H4+C3H6(wt%) | 82.09 | 81.99 | 83.50 | 83.89 | 82.61 | 79.99 | 81.07 |
| C4 +(wt%) | 9.76 | 10.05 | 8.42 | 7.99 | 9.81 | 10.10 | 9.41 |
| C5 +(wt%) | 3.76 | 5.04 | 3.66 | 3.75 | 3.69 | 4.48 | 4.22 |
| Life span (min) | 185 | 179 | 193 | 197 | 181 | 154 | 145 |
As can be seen from the results in Table 1, the silicoaluminophosphate molecular sieve catalyst prepared by the method of the invention has higher selectivity of low-carbon olefin and longer catalytic life. In addition, the preparation method reduces the water consumption in the crystallization process, reduces the problem of generating a large amount of waste liquid in the subsequent separation and washing process, and avoids generating a large amount of waste water; meanwhile, the yield of the molecular sieve is obviously improved, and the production cost of the catalyst is effectively reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method of preparing a silicoaluminophosphate molecular sieve, comprising the steps of:
(a) mixing and contacting an aluminum source, a silicon source, a phosphorus source and water to obtain a mixture A;
(b) drying and grinding the mixture A in sequence to obtain silicon-phosphorus-aluminum dry glue powder;
(c) activating the silicon-phosphorus-aluminum dry glue powder in the presence of phosphoric acid to obtain a mixture B;
(d) mixing and contacting the mixture B with a template agent to obtain a mixture C;
(e) crystallizing, filtering and drying the mixture C in sequence to obtain raw powder of the silicoaluminophosphate molecular sieve;
(f) and (3) carrying out demoulding agent treatment on the raw powder of the silicoaluminophosphate molecular sieve.
2. The method of claim 1, wherein the aluminum source is at least one of pseudoboehmite, aluminum sol, and aluminum isopropoxide;
the silicon source is at least one of tetraethoxysilane, silica sol and white carbon black;
the phosphorus source is phosphoric acid and/or phosphorous acid.
3. The process of claim 1 or 2, wherein the aluminum source, the silicon source and the phosphorus source are used in a molar ratio of 1: 0.1-1.5: 0.01-1.5.
4. The method of claim 1, wherein in step (b), the drying conditions comprise: the drying temperature is 25-150 ℃, and the drying time is 6-48 h.
5. The method according to claim 1, wherein in step (c), the amount of the phosphoric acid aqueous solution is such that the molar ratio of the content of phosphoric acid to the content of aluminum element in the silicoaluminophosphate dry glue powder calculated as the oxide thereof is from 0.1 to 1: 1.
6. the method according to claim 1, wherein in step (c), the conditions of the activation treatment comprise: the activation temperature is 25-120 ℃, and the activation time is 1-24 h.
7. The method according to claim 1, wherein in step (d), the mixture B and the template are used in such an amount that the molar ratio of the content of the aluminum element in the mixture B in terms of the oxide thereof to the content of the template is 1: 1-5.
8. The method of claim 1, wherein the templating agent is at least one of triethylamine, diethylamine, tetraethylammonium hydroxide, N-butylamine, morpholine, and N, N-diisopropylethylamine.
9. The method of claim 1, wherein in step (e), the crystallization conditions comprise: the crystallization temperature is 150-210 ℃, and the crystallization time is 10-24 h.
10. The method of claim 1, wherein in step (e), the drying conditions comprise: the drying temperature is 80-120 ℃, and the drying time is 2-24 h.
11. The method of claim 1 wherein in step (f), the conditions of the stripper plate agent treatment include: roasting for 2-12h at 400-700 ℃.
12. A silicoaluminophosphate molecular sieve whenever prepared by a process as claimed in any one of claims 1 to 11.
13. A method for producing olefins from methanol, the method comprising: the method for preparing olefin from methanol under the reaction condition of preparing olefin from methanol in the presence of a catalyst, wherein the catalyst is the silicoaluminophosphate molecular sieve of claim 12.
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Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |