CN109796027B - SAPO-34 molecular sieve aggregate, preparation method thereof and method for preparing olefin from methanol - Google Patents
SAPO-34 molecular sieve aggregate, preparation method thereof and method for preparing olefin from methanol Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 142
- 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 142
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 230000004931 aggregating effect Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 17
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 239000002159 nanocrystal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 230000000717 retained effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group 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 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000009260 qiming Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the field of SAPO-34 molecular sieves, and discloses an SAPO-34 molecular sieve aggregate, a preparation method thereof and a method for preparing olefin from methanol. The preparation method comprises the following steps: (1) mixing an aluminum source, a phosphorus source, a silicon source, triethylamine hydrochloride and water to obtain a solution, and carrying out hydrothermal crystallization; wherein, in the solution, the aluminum source is Al2O3Calculating phosphorus source as P2O5The silicon source is calculated by SiO2The aluminum source, the phosphorus source, the silicon source, triethylamine hydrochloride and water are in the following molar ratio: al (Al)2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O is 1: (0.9-1.1): (0.1-0.5): (1.5-3): (0.1-0.5): (15-50); (2) and (2) performing solid-liquid separation on the product obtained by the hydrothermal crystallization in the step (1), and washing, drying and roasting the obtained solid to obtain the SAPO-34 molecular sieve aggregate. The catalyst is used for the reaction of preparing the olefin from the methanol, so that the selectivity of the low-carbon olefin can be improved, the generation of carbon deposition can be inhibited, and the service life of the catalyst can be prolonged.
Description
Technical Field
The invention relates to the field of SAPO-34 molecular sieves, in particular to a preparation method of an SAPO-34 molecular sieve aggregate, the SAPO-34 molecular sieve aggregate prepared by the method and a method for preparing olefin from methanol by using the SAPO-34 molecular sieve aggregate.
Background
The Silicoaluminophosphate (SAPO) series of molecular sieves was a new type of molecular sieve developed by united states carbide corporation (UCC) in 1984, of which SAPO-34 is a member. The crystal structure is chabazite type (CHA), the pore opening size is 0.43nm, the water absorption performance and the proton acidity are special, and the catalyst can be used as an adsorbent, a catalyst and a catalyst carrier. Because of the unique small-pore structure and the proper moderate-strength acidity of the SAPO-34, the SAPO-34 has high activity and selectivity in the reaction (MTO) for preparing low-carbon olefin from methanol/dimethyl ether, the selectivity of the low-carbon olefin in the product is higher than 80%, the selectivity of ethylene can reach more than 50%, and almost no products with more than C6 exist. Catalysts with SAPO-34 as the active component have been successfully applied in MTO processes.
However, SAPO-34 belongs to a small pore molecular sieve with 8-membered rings, and is very easy to be deactivated by carbon deposition in the methanol conversion process, so that a circulating regeneration fluidized bed reactor is generally adopted in industry. Improving the selectivity and service life of the catalyst is the key point of research and development of the SAPO-34 molecular sieve.
Organic amines such as morpholine, triethylamine and the like are commonly used as template agents for synthesizing the SAPO-34 molecular sieve, the prepared crystal is of a typical micron-sized cubic crystal appearance, and due to the fact that diffusion paths of reactants and product molecules are long, carbon deposition is easily generated in pore channels of the molecular sieve to deactivate.
The preparation of SAPO-34 using tetraethylammonium hydroxide as a template has been reported in Ultrafast synthesis of nano-sized zeolite SAPO-34with excellent mesoporous MTOcatalytic performance (Qiming Sun, Ning Wang, Guanqi Guo and Jihong Yu, chemical communications 2015,51,16397), and can synthesize nanoscale flaky SAPO-34 molecular sieves, effectively reduce diffusion paths and prolong the catalyst life. However, tetraethyl ammonium hydroxide is expensive, and nanocrystals are not easily separated from a synthesis system, so that the cost of synthesized SAPO-34 is high, and the industrial application is not facilitated.
The synthesis of SAPO-34 molecular sieve hierarchical structures with nanosheet-like structures from natural zeolite has been reported in Direct synthesis of hierarchical structures of SAPO-34 molecular sieves (Zhu J, Cui Y, Wang Y, Wei F, Chemical Communications 2009, 3282-. However, the kaolin has high silicon content, so that the prepared molecular sieve has very high acidity, is easy to deposit carbon and deactivate in methanol conversion reaction, and is not suitable for industrial application.
The prior art does not have a suitable method for preparing the commercially desirable SAPO-34 molecular sieves.
Disclosure of Invention
The invention aims to solve the problems of low selectivity and easy generation of carbon deposit of a conventional SAPO-34 molecular sieve for a methanol-to-olefin product, and provides an SAPO-34 molecular sieve aggregate, a preparation method thereof and a methanol-to-olefin method, wherein the SAPO-34 molecular sieve aggregate is a microcube formed by tightly stacking and laminating a plurality of nano flaky SAPO-34 molecular sieve grains, so that the advantages of nanocrystals in the aspect of reducing internal diffusion can be retained, and the advantage of larger dimension of a gathered micron-sized structure can be utilized, so that the molecular sieve product is easy to separate, and the production cost of the molecular sieve is effectively reduced.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing SAPO-34 molecular sieve aggregates, comprising:
(1) mixing an aluminum source, a phosphorus source, a silicon source, triethylamine hydrochloride and water to obtain a solution, and carrying out hydrothermal crystallization; wherein,
in the solution, the aluminum source is Al2O3Calculating phosphorus source as P2O5The silicon source is calculated by SiO2The aluminum source, the phosphorus source, the silicon source, triethylamine hydrochloride and water are in the following molar ratio:
Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：(0.9～1.1)：(0.1～0.5)：(1.5～3)：(0.1～0.5)：(15～50)；
(2) And (2) performing solid-liquid separation on the product obtained by the hydrothermal crystallization in the step (1), and washing, drying and roasting the obtained solid to obtain the SAPO-34 molecular sieve aggregate.
In a second aspect, the invention provides a SAPO-34 molecular sieve aggregate prepared by the method, wherein the SAPO-34 molecular sieve aggregate is a micron cube with a rough surface and formed by aggregating a plurality of nano flaky SAPO-34 molecular sieve grains.
Preferably, the grain size of the nano flaky SAPO-34 molecular sieve grains is 20-100 nm.
Preferably, the edge length of the microcubes is 3-20 μm.
Preferably, the specific surface area of the SAPO-34 molecular sieve aggregate is 600-800 m2/g。
The third aspect of the present invention provides a method for preparing olefins from methanol, comprising: under the reaction condition of preparing olefin from methanol, the methanol is contacted with the SAPO-34 molecular sieve aggregate.
According to the technical scheme, the SAPO-34 molecular sieve aggregate prepared by adopting the method provided by the invention and taking the aluminum source, the phosphorus source and the silicon source as raw materials, triethylamine and triethylamine hydrochloride as a template agent and water as a solvent and carrying out hydrothermal crystallization is a micron cube formed by closely stacking and gathering a plurality of nano flaky SAPO-34 molecular sieve grains, so that the advantages of nano grains in the aspect of reducing internal diffusion can be retained, the advantage of larger micron-scale structure size gathered together can be utilized, the molecular sieve product is easy to separate, and the production cost of the molecular sieve is effectively reduced. The SAPO-34 molecular sieve aggregate is used as a catalyst for the reaction of preparing the olefin from the methanol, so that the selectivity of the low-carbon olefin can be improved, the generation of carbon deposition can be inhibited, and the service life of the catalyst can be prolonged.
Drawings
FIG. 1 is an XRD spectrum of SAPO-34 molecular sieves prepared in example 1 and comparative example 1;
FIG. 2a is a scanning electron micrograph of nanocrystals of SAPO-34 molecular sieve aggregates prepared according to example 1;
FIG. 2b is a scanning electron micrograph of SAPO-34 molecular sieve aggregates prepared according to example 1;
FIG. 3 is a scanning electron micrograph of SAPO-34 molecular sieve prepared according to comparative example 1;
FIG. 4a is a plot of methanol conversion and olefin selectivity versus reaction time for a methanol to olefin reaction of example 7 using the SAPO-34 molecular sieve aggregate prepared in example 1 as the catalyst;
FIG. 4b is a graph of methanol conversion and olefin selectivity versus reaction time for the methanol to olefin reaction of example 7 using the SAPO-34 molecular sieve prepared in comparative example 1 as the catalyst.
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 preparation method of SAPO-34 molecular sieve aggregate, which comprises the following steps:
(1) mixing an aluminum source, a phosphorus source, a silicon source, triethylamine hydrochloride and water to obtain a solution, and carrying out hydrothermal crystallization; wherein,
in the solution, the aluminum source is Al2O3Calculating phosphorus source as P2O5The silicon source is calculated by SiO2The aluminum source, the phosphorus source, the silicon source, triethylamine hydrochloride and water are in the following molar ratio:
Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：(0.9～1.1)：(0.1～0.5)：(1.5～3)：(0.1～0.5)：(15～50)；
(2) And (2) performing solid-liquid separation on the product obtained by the hydrothermal crystallization in the step (1), and washing, drying and roasting the obtained solid to obtain the SAPO-34 molecular sieve aggregate.
According to the invention, Triethylamine (TEA) and triethylamine hydrochloride (TEA.HCl) are combined to be used as a template agent, so that nano-flaky SAPO-34 molecular sieve grains with a microstructure can be prepared, and a plurality of grains are closely stacked to form a micron cubic SAPO-34 molecular sieve aggregate. The SAPO-34 molecular sieve aggregate obtained by the method can retain the advantage of reducing the internal diffusion of the nano crystal grains, and can improve the selectivity of low-carbon olefin and reduce carbon deposition during the reaction of preparing olefin from methanol by utilizing the advantage of larger dimension of the micron-sized cubic structure of the aggregate, thereby prolonging the service life of the SAPO-34 molecular sieve aggregate as a catalyst.
In the invention, the aluminum source, the phosphorus source and the silicon source are raw materials for preparing the SAPO-34 molecular sieve, and the raw materials for conventionally synthesizing the SAPO-34 molecular sieve can be used, and preferably, the aluminum source is selected from at least one of pseudo-boehmite, sodium aluminate, aluminum nitrate and aluminum sulfate; the phosphorus source is selected from phosphoric acid and/or ammonium dihydrogen phosphate; the silicon source is at least one selected from silica sol, sodium silicate, ethyl orthosilicate and white carbon black.
More preferably, the aluminum source is pseudo-boehmite, the phosphorus source is phosphoric acid, and the silicon source is silica sol.
In the invention, the step (1) is used for preparing the solution for hydrothermal crystallization, preferably, the mixing is performed under closed stirring at room temperature (generally 10-40 ℃), the mixing stirring speed is 100-500 rpm, and the mixing time is 1-4 h, preferably 3-4 h.
In the invention, the hydrothermal crystallization is used for synthesizing the raw materials of the aluminum source, the phosphorus source and the silicon source into the SAPO-34 molecular sieve in the presence of the template agents of triethylamine and triethylamine hydrochloride, and preferably, the hydrothermal crystallization is carried out for 12-48 h at the temperature of 190-200 ℃ and the pressure of 2-3 MPa. The hydrothermal crystallization is carried out in a high-pressure reaction kettle in a closed way.
In the present invention, the solid-liquid separation in step (2) may be carried out by a conventional separation method to separate the solids therein. According to the method of the invention, solid-liquid separation can be realized by adopting filtration.
In the invention, the solid obtained by solid-liquid separation can be washed by water, and then dried and roasted under the conventional conditions to obtain the SAPO-34 molecular sieve aggregate. Specifically, the drying is carried out at the temperature of 80-120 ℃ for 1-2 h, and the roasting is carried out at the temperature of 500-600 ℃ for 3-5 h. The purpose of the calcination is mainly to remove substances, such as a template, remaining in the pore channels of the molecular sieve during the synthesis process of the molecular sieve. The calcination is generally carried out in an air atmosphere.
In a second aspect, the invention provides a SAPO-34 molecular sieve aggregate prepared by the method, wherein the SAPO-34 molecular sieve aggregate is a micron cube with a rough surface and formed by aggregating a plurality of nano flaky SAPO-34 molecular sieve grains.
In the invention, the SAPO-34 molecular sieve aggregate can be obtained through hydrothermal crystallization by the method, wherein the synthesized SAPO-34 molecular sieve crystal grows into nano-sheet-shaped crystal grains (as shown in figure 2 a), and the crystal grains are tightly packed to form a micro-cubic SAPO-34 molecular sieve aggregate (as shown in figure 2 b).
In the invention, the grain size of the nano flaky SAPO-34 molecular sieve grains is preferably 20-100 nm.
In the present invention, preferably, the edge length of the microcubes is 3 to 20 μm.
In the invention, the SAPO-34 molecular sieve aggregate can also retain nano-crystalline grains, and the surface of the aggregate is rough, thereby providing larger specific surface area. Preferably, the specific surface area of the SAPO-34 molecular sieve aggregate is 600-800 m2/g。
The third aspect of the present invention provides a method for preparing olefins from methanol, comprising: under the reaction condition of preparing olefin from methanol, the methanol is contacted with the SAPO-34 molecular sieve aggregate.
Specifically, the conditions for performing methanol-to-olefins may include: the temperature is 400-500 ℃, the pressure is 0.1-0.2 MPa, the raw material is an aqueous solution containing 95 weight percent of methanol, and the weight hourly space velocity of the raw material is 3-5 h-1。
The present invention will be described in detail below by way of examples.
In the following examples, the microscopic morphology of the SAPO-34 molecular sieve aggregate is measured by a scanning electron microscope of the type Nova Nano SEM450 from FEI company; x-ray diffraction analysis (XRD) was carried out on an X-ray diffractometer model D/max-2600/pc, available from Rigaku; the specific surface area of the SAPO-34 molecular sieve aggregates was measured by the low temperature nitrogen adsorption method using a Micromeritics model number tristarII 3020-M nitrogen physisoreter.
The grain size of SAPO-34 molecular sieve grains in the SAPO-34 molecular sieve aggregate and the cubic edge length of the SAPO-34 molecular sieve aggregate are measured by a scanning electron microscope;
the composition of the product obtained by the reaction of preparing olefin from methanol is measured on a self-made micro reactor, and the conversion rate of methanol and the selectivity of ethylene and propylene are calculated by the following formula:
percent methanol conversion ═ [ (inlet methanol moles-outlet methanol moles)/inlet methanol moles ] × 100%
Ethylene and propylene selectivity ═ carbon number of ethylene + carbon number of propylene/carbon number of all products ] × 100%.
In the following examples, pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride were all commercially available products, and pseudo-boehmite was obtained from Shandong aluminum industries, Inc., Al2O3Dry basis content 70 wt%; the pH of the silica sol is 9-10, SiO2The dry content was 30% by weight.
Example 1
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 4 hours at room temperature (25 ℃) at a stirring speed of 500rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：1.0：0.25：1.5：0.5：20。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 24 hours at the temperature of 200 ℃ and under the pressure of 2 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 120 ℃ for 2h, and roasting at 550 ℃ for 3h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and the obtained XRD spectrum is shown as SAPO-34 crystals in figure 1.
And (2) observing the SAPO-34 molecular sieve aggregate by a scanning electron microscope, wherein a picture in figure 2a is an electron microscope photo of nano crystal grains, the SAPO-34 molecular sieve crystal grains are nano-flaky, and the grain size is 50-80 nm. FIG. 2b is an electron microscope photograph of the SAPO-34 molecular sieve aggregate, wherein a plurality of nano flaky SAPO-34 molecular sieve grains in FIG. 2a are closely stacked to form the SAPO-34 molecular sieve aggregate with a micron cubic structure, the aggregate has a rough surface, and the cubic edge length is 10-15 μm.
The specific surface area of the SAPO-34 molecular sieve aggregate is determined to be 655m2/g。
Example 2
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 3 hours at room temperature (40 ℃) and at the stirring speed of 100rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：0.9：0.12：2.0：0.4：50。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 12 hours at the temperature of 190 ℃ and the pressure of 3 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 100 ℃ for 1.5h, and roasting at 500 ℃ for 5h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and is shown as SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve aggregate by using a scanning electron microscope, wherein the grain size of the nano crystal grain is 20-50 nm. A plurality of nano flaky SAPO-34 molecular sieve grains are closely stacked to form a micron cubic SAPO-34 molecular sieve aggregate, and the cubic edge length is 15-20 microns.
The specific surface area of the SAPO-34 molecular sieve aggregate is 682m2/g。
Example 3
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 3.5 hours at room temperature (10 ℃) and at the stirring speed of 200rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：1.1：0.5：3.0：0.25：30。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 48 hours at the temperature of 195 ℃ and the pressure of 2.5 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 80 ℃ for 3h, and roasting at 600 ℃ for 4h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and is shown as SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve aggregate by using a scanning electron microscope, wherein the grain size of the nano crystal grain is 80-100 nm. A plurality of nano flaky SAPO-34 molecular sieve grains are closely stacked to form a micron cubic SAPO-34 molecular sieve aggregate, and the cube edge length is 3-10 mu m.
The specific surface area of the SAPO-34 molecular sieve aggregate is determined to be 628m2/g。
Example 4
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 4 hours at room temperature (25 ℃) at a stirring speed of 500rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：1.0：0.2：1.5：0.5：40。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 24 hours at the temperature of 200 ℃ and the pressure of 3 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and is shown as SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve aggregate by using a scanning electron microscope, wherein the grain size of the nano crystal grains is 30-60 nm. A plurality of nano flaky SAPO-34 molecular sieve grains are closely stacked to form an SAPO-34 molecular sieve aggregate with a micron cubic structure, and the edge length of the cube is 5-10 mu m.
The specific surface area of the SAPO-34 molecular sieve aggregate is determined to be 657m2/g。
Example 5
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 4 hours at room temperature (25 ℃) at a stirring speed of 500rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：1.0：0.3：1.8：0.1：30。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 48 hours at the temperature of 190 ℃ and under the pressure of 3 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and is shown as SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve aggregate by using a scanning electron microscope, wherein the grain size of the nano crystal grain is 50-80 nm. A plurality of nano flaky SAPO-34 molecular sieve grains are closely stacked to form a micron cubic SAPO-34 molecular sieve aggregate, and the cube edge length is 3-5 microns.
The specific surface area of the SAPO-34 molecular sieve aggregate is 675m2/g。
Example 6
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine hydrochloride and deionized water into a reaction kettle, stirring for 4 hours at room temperature (25 ℃) at a stirring speed of 500rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochlorideSalt: h2O＝1：0.95：0.1：2.0：0.3：20。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 12 hours at the temperature of 200 ℃ and the pressure of 3 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the SAPO-34 molecular sieve aggregate.
The SAPO-34 molecular sieve aggregate is subjected to XRD spectrum analysis, and is shown as SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve aggregate by using a scanning electron microscope, wherein the grain size of the nano crystal grain is 60-80 nm. A plurality of nano flaky SAPO-34 molecular sieve grains are closely stacked to form a micron cubic SAPO-34 molecular sieve aggregate, and the cubic edge length is 15-20 microns.
The specific surface area of the SAPO-34 molecular sieve aggregate is determined to be 668m2/g。
Comparative example 1
Adding pseudo-boehmite, phosphoric acid, silica sol, triethylamine and deionized water into a reaction kettle, stirring for 4 hours at room temperature (25 ℃) and a stirring speed of 500rpm, wherein the molar ratio of the components in the obtained solution is Al2O3：P2O5：SiO2: triethylamine: h2O＝1：1.0：0.25：3.0：50。
Carrying out hydrothermal crystallization at the temperature of the reaction kettle, and carrying out crystallization for 24 hours at the temperature of 200 ℃ and the pressure of 3 MPa.
And filtering and separating a product after crystallization is finished, and washing an obtained solid by deionized water. Drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the SAPO-34 molecular sieve.
The SAPO-34 molecular sieve is subjected to XRD spectrum analysis, as shown in figure 1, and shows SAPO-34 crystals.
And (3) observing the SAPO-34 molecular sieve by a scanning electron microscope, wherein as shown in figure 3, the microscopic morphology of the SAPO-34 molecular sieve has no nano flaky crystal grains, and is of a cubic structure with a smooth surface, and the edge length of the cube is 5-10 mu m.
The specific surface area of the SAPO-34 molecular sieve is 565m2/g。
Example 7
The SAPO-34 molecular sieves prepared in each of example 1 and comparative example 1 were subjected to a methanol to olefin reaction.
The reaction conditions of the methanol to olefin are 450 ℃, 0.1MPa, the weight hourly space velocity (CH) of the raw material which contains 95 weight percent methanol water solution as the raw material3OH+H2O)＝3.5h-1。
The methanol conversion and olefin selectivity over reaction time during the methanol to olefin reaction were plotted as shown in FIG. 4a (SAPO-34 molecular sieve of example 1) and FIG. 4b (SAPO-34 molecular sieve of comparative example 1).
As can be seen from the above examples and comparative examples, the method provided by the invention adopts a template agent combining triethylamine and triethylamine hydrochloride, and can obtain an SAPO-34 molecular sieve aggregate through hydrothermal crystallization from an aluminum source, a phosphorus source and a silicon source, wherein the molecular sieve can have nano flaky SAPO-34 molecular sieve grains with the grain size of 20-100 nm; the nano flaky SAPO-34 molecular sieve crystal grains are tightly stacked and laminated into a micron cube, and the edge length of the cube is 3-20 microns. The molecular sieve may have a greater specific surface area. All the nano flaky SAPO-34 grains in the molecular sieve aggregate can effectively shorten the diffusion of product molecules in crystal pore canals, effectively inhibit the generation of carbon deposition and prolong the service life of the catalyst.
As shown in FIG. 4a, when the molecular sieve is used as a catalyst for methanol-to-olefin reaction, dimethyl ether (DME) is detected in the product after the SAPO-34 molecular sieve aggregate prepared in example 1 reacts for 185min, which indicates that the catalyst starts to deactivate. The selectivity to ethylene and propylene was 78%. After 90min of reaction of the SAPO-34 molecular sieve prepared in comparative example 1, the appearance of dimethyl ether (DME) in the product was detected, indicating that the catalyst began to deactivate. The selectivity to ethylene and propylene was 73%. Therefore, the selectivity of the low-carbon olefin of the SAPO-34 molecular sieve aggregate provided by the invention is obviously higher than that of the micron-sized cubic SAPO-34 molecular sieve prepared in the comparative example 1 (the template does not contain triethylamine hydrochloride). Moreover, the service time of the SAPO-34 molecular sieve aggregate for methanol-to-olefin reaction is doubled compared with that of the SAPO-34 molecular sieve aggregate in the comparison with the ratio 1.
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 (8)
1. A method for preparing SAPO-34 molecular sieve aggregate comprises the following steps:
(1) mixing an aluminum source, a phosphorus source, a silicon source, triethylamine hydrochloride and water to obtain a solution, and carrying out hydrothermal crystallization; wherein,
in the solution, the aluminum source is Al2O3Calculating phosphorus source as P2O5The silicon source is calculated by SiO2The aluminum source, the phosphorus source, the silicon source, triethylamine hydrochloride and water are in the following molar ratio:
Al2O3：P2O5：SiO2: triethylamine: triethylamine hydrochloride salt: h2O＝1：(0.9～1.1)：(0.1～0.5)：(1.5～3)：(0.1～0.5)：(15～50)；
(2) Performing solid-liquid separation on the product obtained by hydrothermal crystallization in the step (1), and washing, drying and roasting the obtained solid to obtain the SAPO-34 molecular sieve aggregate;
wherein the aluminum source is selected from at least one of pseudo-boehmite, sodium aluminate, aluminum nitrate and aluminum sulfate;
the phosphorus source is selected from phosphoric acid and/or ammonium dihydrogen phosphate;
the silicon source is at least one of silica sol, sodium silicate, ethyl orthosilicate and white carbon black;
the hydrothermal crystallization is carried out for 12-48 h at the temperature of 190-200 ℃ and the pressure of 2-3 MPa.
2. The preparation method according to claim 1, wherein the mixing is performed under closed stirring at room temperature, the mixing stirring rate is 100-500 rpm, and the mixing time is 1-4 hours.
3. The method according to claim 1, wherein the drying is performed at a temperature of 80 to 120 ℃ for 1 to 2 hours, and the baking is performed at a temperature of 500 to 600 ℃ for 3 to 5 hours.
4. The SAPO-34 molecular sieve aggregate prepared by the method of any one of claims 1 to 3, wherein the SAPO-34 molecular sieve aggregate is a micro-cube with a rough surface formed by aggregating a plurality of nano-sheet SAPO-34 molecular sieve grains.
5. The SAPO-34 molecular sieve aggregate of claim 4, wherein the nano-platelet SAPO-34 molecular sieve grains have a grain size of 20 to 100 nm.
6. The SAPO-34 molecular sieve aggregate of claim 4, wherein the microcubes have a ridge length of 3-20 μm.
7. The SAPO-34 molecular sieve aggregate of claim 4, wherein the SAPO-34 molecular sieve aggregate has a specific surface area of 600 to 800m2/g。
8. A method for preparing olefins from methanol, comprising: contacting methanol with the SAPO-34 molecular sieve aggregate of any one of claims 4-7 under methanol to olefin reaction conditions.
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