CN110857218A - Nano-flake ZSM-5 molecular sieve and preparation method and application thereof - Google Patents
Nano-flake ZSM-5 molecular sieve and preparation method and application thereof Download PDFInfo
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- CN110857218A CN110857218A CN201810969700.XA CN201810969700A CN110857218A CN 110857218 A CN110857218 A CN 110857218A CN 201810969700 A CN201810969700 A CN 201810969700A CN 110857218 A CN110857218 A CN 110857218A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 176
- 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 175
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002060 nanoflake Substances 0.000 title description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 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 23
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 50
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 35
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000010703 silicon Substances 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 8
- 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 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- -1 more preferably Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 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 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 21
- 229910002651 NO3 Inorganic materials 0.000 description 19
- 239000013078 crystal Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 125000003636 chemical group Chemical group 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention relates to the field of molecular sieves used for preparing olefin catalysts through methanol conversion, and discloses a nano flaky ZSM-5 molecular sieve and a preparation method thereofAnd applications. The thickness of the nano flaky ZSM-5 molecular sieve is 20-70nm, the length is 200-800nm, the length-width ratio is 2-10, and SiO is2/Al2O3The molar ratio is 10-200: 1. the ZSM-5 molecular sieve has a two-dimensional ultrathin nano structure, can shorten a diffusion path, reduces the probability of side reaction and improves the selectivity of a catalyst for preparing olefin from methanol.
Description
Technical Field
The invention relates to the field of molecular sieves used for catalysts for preparing olefins by converting methanol, in particular to a nano flaky ZSM-5 molecular sieve and a preparation method and application thereof.
Background
Propylene is an important organic chemical raw material, and with the rapid increase of the demand of derivatives such as polypropylene and the like, the demand of propylene also rises year by year. The development of preparing low-carbon olefins such as ethylene, propylene and the like by a non-petroleum route finds a new raw material route for olefin production, and greatly relieves the energy crisis caused by the problem of petroleum and natural gas resources. Among them, a process of preparing methanol from a coal or natural gas raw material and then converting the methanol into propylene (MTP) has been widely noticed. The high-performance ZSM-5 molecular sieve catalyst is one of the core technologies of the MTP technology, and the selectivity of propylene is one of the important indexes of the MTP catalyst. It is known that the olefin side reactions-hydrogen transfer and aromatization-are consumed in the conversion of methanol to olefins as secondary reactions, and thus the probability of side reactions occurring can be reduced by accelerating the diffusion of olefin products, i.e., the diffusion path is shortened. That is, the shorter the diffusion path of the olefin product, the better the diffusion of the olefin is accelerated, thereby reducing the occurrence of side reactions consuming the olefin, and further improving the selectivity of the olefin, especially the selectivity of the target product propylene.
Disclosure of Invention
The invention aims to provide a novel ZSM-5 molecular sieve and a preparation method and application thereof, wherein the novel ZSM-5 molecular sieve has a two-dimensional ultrathin nanostructure, can shorten a diffusion path, reduce the probability of side reaction and improve the selectivity of a catalyst for preparing olefin from methanol.
The inventor of the invention discovers through intensive research that when the molecular sieve is acted by mechanical force, the material is damaged and generates a new surface, and due to the action of high energy, the material generates a series of microstructure change and non-equilibrium state phase change under the action of mechanical external force, so that various non-equilibrium state structures are formed, such as nanocrystalline, amorphous, metastable phase, supersaturated solid solution and the like; the material treated by mechanical force becomes more active and unstable; when it is used as a seed crystal, the crystal nucleation rate is greatly promoted, and the resulting crystal is thinner or smaller, thereby completing the present invention.
In order to achieve the above object, the present invention provides, in a first aspect, a nanosheet-shaped ZSM-5 molecular sieve, wherein the nanosheet-shaped ZSM-5 molecular sieve has a thickness of 20-70nm, a length of 200-800nm, an aspect ratio of 2-10, and SiO2/Al2O3The molar ratio is 10-200: 1.
preferably, the thickness of the nano-sheet ZSM-5 molecular sieve is 30-60nm, the length is 300-700nm, the aspect ratio is 4-7, and SiO is2/Al2O3The molar ratio is 15-150: 1.
the second aspect of the invention provides a preparation method of a nano flaky ZSM-5 molecular sieve, wherein the method comprises the following steps: sequentially mixing, aging and hydro-thermal synthesis crystallization of a silicon source, an aluminum source, molecular sieve crushed fine powder, a template agent, alkali, urea and water, wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The mixing ratio of the raw materials meets the following requirements: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (5-500): (0.25-25): (0.2-20): (1.5-2000): (40-4000), the molecular sieve crushed fine powder and SiO in the silicon source2(1-10): 100.
preferably, the mixing ratio of the raw materials further satisfies: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (10-200): (0.5-20): (0.3-10): (10-800): (50-2500), and the molecular sieve pulverizing fine powder and solid siliconSiO in source2(3-7): 100.
preferably, the molecular sieve crushed fine powder is at least one of SAPO-34 molecular sieve crushed fine powder, ZSM-5 molecular sieve crushed fine powder, Y-type molecular sieve crushed fine powder and β molecular sieve crushed fine powder.
Preferably, the molecular sieve finely divided powder is obtained by a ball milling process and/or a high-speed shearing process.
Preferably, the ball milling process is performed by a ball mill under the conditions including: the rotation speed of the ball mill is 100-.
Preferably, the molecular sieve finely pulverized powder has an average particle diameter of 1 to 2 um.
Preferably, the hydrothermal synthesis crystallization conditions include: the temperature is 120 ℃ and 180 ℃, and the time is 10-80 h; more preferably, the hydrothermal synthesis crystallization conditions include: the temperature is 130-160 ℃, and the time is 24-48 h.
Preferably, the aging time is 8-24 h.
Preferably, the method further comprises: and washing, drying and roasting the product obtained by hydrothermal synthesis crystallization in sequence.
Preferably, the silicon source is at least one of silica sol, water glass, ethyl silicate and white carbon black.
Preferably, the aluminum source is at least one of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate and kaolin, and more preferably, the aluminum source is at least one of kaolin, sodium aluminate and aluminum nitrate.
Preferably, the template agent is at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide and tetramethylammonium hydroxide, and more preferably, the template agent is tetrapropylammonium bromide and/or tetrapropylammonium hydroxide.
Preferably, the base is a sodium base, more preferably, the base is sodium hydroxide.
The third aspect of the invention provides the nano flaky ZSM-5 molecular sieve prepared by the preparation method.
The fourth method of the invention provides the application of the nano flaky ZSM-5 molecular sieve in the preparation of olefin by methanol conversion.
Through the technical scheme, the novel ZSM-5 molecular sieve provided by the invention has a two-dimensional ultrathin nanostructure, can shorten a diffusion path, reduces the probability of side reaction and improves the selectivity of a methanol-to-olefin catalyst. In addition, the two-dimensional ultrathin nanostructure also facilitates molecular sieve washing and filtration.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a ZSM-5 molecular sieve product prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of the ZSM-5 molecular sieve prepared in example 1.
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 nano flaky ZSM-5 molecular sieve, wherein the thickness of the nano flaky ZSM-5 molecular sieve is 20-70nm, the length is 200-800nm, the length-width ratio is 2-10, and SiO is2/Al2O3The molar ratio is 10-200: 1.
preferably, the thickness of the nano-sheet ZSM-5 molecular sieve is 30-60nm, the length is 300-600nm, the length-width ratio is 4-7, and SiO is2/Al2O3The molar ratio is 15-150: 1.
specific examples of the thickness of the nanosheet-shaped ZSM-5 molecular sieve of the present invention include: 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, 35nm, 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42nm, 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm, 60nm, 61nm, 62nm, 63nm, 64nm, 65nm, 66nm, 67nm, 68nm, 69nm, 70nm, etc.
Specific examples of the length of the nanosheet-like ZSM-5 molecular sieve of the present invention include: 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 29nm, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm, 510nm, 520nm, 530nm, 540nm, 550nm, 560nm, 570nm, 580nm, 590nm, 600nm, 61nm, 620nm, 630nm, 640nm, 650nm, 660nm, 670nm, 680nm, 690nm, 700nm, and the like.
Specific examples of the aspect ratio of the nanosheet-like ZSM-5 molecular sieve of the present invention include: 2. 3, 4, 5, 6, 7, 8, 9, and 10, etc.
SiO as the nano-flake ZSM-5 molecular sieve of the invention2/Al2O3Specific examples of the molar ratio include: 10. 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, etc.
Compared with the ZSM-5 molecular sieve in the prior art, the ZSM-5 molecular sieve provided by the invention is thinner and smaller, has a two-dimensional ultrathin nanostructure, can shorten a diffusion path, reduce the probability of side reaction, improve the selectivity of the methanol-to-olefin catalyst, and prolong the service life of the catalyst.
The invention provides a preparation method of a nano flaky ZSM-5 molecular sieve, wherein the method comprises the following steps: sequentially mixing, aging and hydro-thermal synthesis crystallization of a silicon source, an aluminum source, molecular sieve crushed fine powder, a template agent, alkali, urea and water, wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The mixing ratio of the raw materials meets the following requirements: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (5-500): (0.25-25): (0.2-20): (1.5-2000): (40-4000), the molecular sieve crushed fine powder and SiO in the silicon source2(1-10): 100.
according to the process of the present invention, preferably, the mixing ratio of the raw materials is further oneThe method comprises the following steps: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (10-200): (0.5-20): (0.3-10): (10-800): (50-2500), and the molecular sieve is used for crushing the fine powder and SiO in the solid silicon source2(3-7): 100, respectively; more preferably, the mixing ratio of the raw materials further satisfies: 1: (30-150): (3.5-15): (2-7.5): (30-350): (50-2000), and the molecular sieve is used for crushing the SiO in the fine powder and the solid silicon source2(4-5): 100. by setting the molar ratio of the aluminum source, the silicon source, the template, the alkali, the urea and the water within the above range, the selectivity of the catalyst for producing olefins by converting methanol when the ZSM-5 molecular sieve is used as a catalytically active component can be further improved.
The inventor of the invention discovers through intensive research that when the molecular sieve is acted by mechanical force, the material is damaged and generates a new surface, and due to the action of high energy, the material generates a series of microstructure change and non-equilibrium state phase change under the action of mechanical external force, so that various non-equilibrium state structures are formed, such as nanocrystalline, amorphous, metastable phase, supersaturated solid solution and the like; the material treated by mechanical force becomes more active and unstable; when used as a seed crystal, the rate of crystal nucleation is greatly enhanced and the resulting crystals are thinner or smaller.
In accordance with the above, the method of the present invention employs a molecular sieve-pulverized fine powder in which a molecular sieve is destroyed by mechanical force, preferably, the molecular sieve-pulverized fine powder is at least one of a SAPO-34 molecular sieve-pulverized fine powder, a ZSM-5 molecular sieve-pulverized fine powder, a Y-type molecular sieve-pulverized fine powder and an β molecular sieve-pulverized fine powder, and more preferably, the molecular sieve-pulverized fine powder is a ZSM-5 molecular sieve-pulverized fine powder.
As a method for obtaining the molecular sieve pulverized fine powder, only a method satisfying the generation of a new surface by the destruction by mechanical force is sufficient, and preferably, the molecular sieve pulverized fine powder may be obtained by a ball milling process and/or a high-speed shearing process.
The ball milling step may be performed by a ball mill under conditions including: the rotation speed of the ball mill is 100-.
Preferably, the average particle size of the molecular sieve pulverized fine powder is 1-2 um; more preferably, the molecular sieve finely pulverized powder has an average particle diameter of 1 to 1.5 um.
According to the method provided by the invention, the silicon source can be various existing silicon sources which can be used for the molecular sieve, and preferably at least one of silica sol, water glass, ethyl silicate and white carbon black; more preferably a silica sol.
According to the method of the present invention, the aluminum source may be various aluminum sources conventional in the art, preferably, the aluminum source is at least one of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate and kaolin, and more preferably, the aluminum source is at least one of kaolin, sodium aluminate and aluminum nitrate.
According to the method of the present invention, the templating agent may be any of various templating agents conventional in the art, preferably, the templating agent is at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide and tetramethylammonium hydroxide, and more preferably, the templating agent is tetrapropylammonium bromide and/or tetrapropylammonium hydroxide.
According to the method of the present invention, the base may be any conventional base, preferably, the base is a sodium base, and more preferably, the base is sodium hydroxide.
According to the method of the invention, there is no special requirement on the mixing sequence of the silicon source, the aluminum source, the ZSM-5 molecular sieve seed crystal, the template agent, the alkali, the urea and the water, as long as the raw materials are uniformly mixed before the aging stage, for example, the urea and the molecular sieve crushed fine powder are mixed with the water, the alkali and the template agent are sequentially added after the uniform stirring, the aluminum source is added after the stirring, the silicon source is added after the continuous stirring. The stirring time is not particularly limited as long as the raw materials can be uniformly mixed.
The ageing time may be an ageing treatment time conventional in the art, according to the method of the present invention, and may be, for example, 8 to 24 hours. The temperature of the aging treatment is not particularly limited, and the aging treatment is preferably carried out at room temperature, and may be carried out at 10 to 45 ℃.
According to the method of the present invention, the conditions for hydrothermal synthesis crystallization may be crystallization conditions conventional in the art, and preferably, the conditions for hydrothermal synthesis crystallization include: the temperature is 120-: the temperature is 130-160 ℃, and the time is 24-48 h.
According to the method of the present invention, the hydrothermal synthesis crystallization can be performed in various conventional crystallization equipment, for example, in a high pressure reaction kettle.
According to the method of the present invention, the method may further include: and washing, drying and roasting the product obtained by hydrothermal synthesis crystallization in sequence. The washing method may be a conventional method, and for example, the crystallized product may be washed 4 to 8 times with deionized water. The conditions for drying may include: the temperature is 80-120 ℃, and the time is 4-12 h. The conditions for calcination may include: the temperature is 500-650 ℃, and the time is 4-12 h.
The third aspect of the invention provides the nano flaky ZSM-5 molecular sieve prepared by the method.
According to the invention, the thickness of the nano-sheet ZSM-5 molecular sieve is 20-70nm, the length is 200-800nm, the length-width ratio is 2-8, and SiO is2/Al2O3The molar ratio is 10-200: 1.
preferably, the thickness of the nano-sheet ZSM-5 molecular sieve is 30-60nm, the length is 300-600nm, the length-width ratio is 4-7, and SiO is2/Al2O3The molar ratio is 15-150: 1.
specific examples of the thickness of the nanosheet-like ZSM-5 molecular sieve include: 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, 35nm, 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42nm, 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm, 60nm, 61nm, 62nm, 63nm, 64nm, 65nm, 66nm, 67nm, 68nm, 69nm, 70nm, etc.
Specific examples of the length of the nanosheet-like ZSM-5 molecular sieve include: 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 29nm, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm, 510nm, 520nm, 530nm, 540nm, 550nm, 560nm, 570nm, 580nm, 590nm, 600nm, 61nm, 620nm, 630nm, 640nm, 650nm, 660nm, 670nm, 680nm, 690nm, 700nm, and the like.
Specific examples of the aspect ratio of the nanosheet-like ZSM-5 molecular sieve include: 2. 3, 4, 5, 6, 7, 8, 9, and 10, etc.
SiO as the nano-flake ZSM-5 molecular sieve2/Al2O3Specific examples of the molar ratio include: 10. 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, etc.
Compared with the ZSM-5 molecular sieve in the prior art, the ZSM-5 molecular sieve provided by the invention is thinner and smaller, has a two-dimensional ultrathin nanostructure, can shorten a diffusion path, reduce the probability of side reaction, improve the selectivity of the methanol-to-olefin catalyst, and prolong the service life of the catalyst.
The fourth aspect of the invention provides an application of the nano flaky ZSM-5 molecular sieve in the preparation of olefin by methanol conversion.
According to the application of the invention, the nano flaky ZSM-5 molecular sieve is further treated by NH before use4 +The alkali metal ions contained in the solution are replaced by ions to perform hydrogen type exchange modification, for example, the alkali metal ions can be sodium ions, and the hydrogen type exchange method can be a method conventional in the art, and for example, the method can comprise the following steps: impregnating ZSM-5 molecular sieve in NH4NO3Stirring the solution at 25-90 deg.C for 4-14h, washing, filtering, and sequentially drying and calcining the filtered product. Wherein the washing may include: washing with deionized water for 4-8 times; the conditions for drying may include: the temperature is 80-120 ℃, and the time is 4-12 h; the conditions for calcination may include: the temperature is 500-650 ℃, and the time is 4-12 h. Wherein NH4NO3The concentration of the solution can be 0.5-5mol/L, and the moleculesSieve and NH4NO3NH in solution4NO3The weight ratio of (A) may be 1: 5-15.
According to the application of the present invention, the nano-flake ZSM-5 molecular sieve is modified by hydrogen type exchange, and then the step of shaping the nano-flake ZSM-5 molecular sieve is included, for example, the nano-flake ZSM-5 molecular sieve is tableted and sieved to obtain the shaped hydrogen type nano-flake ZSM-5 molecular sieve, and the tabletting and sieving can be a method conventional in the art.
Examples
In the following examples, the determination of the X-ray diffraction (XRD) morphogram was carried out on an X-ray diffractometer of the Bruker D8 ADVANCE type; the scanning electron microscope used was a FEI Company Nova NanoSEM 450 model.
Preparation example 1
And (2) carrying out ball milling on a ZSM-5 molecular sieve (purchased from catalyst works of southern Kai university) at the rotating speed of 300r/min for 1h to obtain crushed fine powder of the ZSM-5 molecular sieve, wherein the average particle size of the crushed fine powder is 1.2 um.
Preparation example 2
The SAPO-34 molecular sieve (purchased from Shanghai Song chemical Co., Ltd.) is subjected to ball milling at the rotating speed of 300r/min for 1h to obtain SAPO-34 molecular sieve crushed fine powder with the average particle size of 1.4 um.
Preparation example 3
And (3) carrying out ball milling on a Y-type molecular sieve (NaY type, catalyst works of southern Kai university) at the rotating speed of 300r/min for 1h to obtain crushed fine powder of the Y-type molecular sieve, wherein the average particle size of the crushed fine powder is 1.2 um.
Example 1
This example is used to illustrate the nano-flake ZSM-5 molecular sieve of the present invention, and its preparation method and application.
(1) Weighing 20g of urea (AR national chemical group chemical Co., Ltd.) and 0.9g of ZSM-5 molecular sieve crushed fine powder obtained in preparation example 1, adding 54g of deionized water, mixing, stirring uniformly, sequentially adding 0.84g of NaOH (AR national chemical group chemical Co., Ltd.) and 12.2g of tetrapropylammonium hydroxide template (25 wt% aqueous solution, industrial grade), stirring for 1h, adding 0.4g of sodium aluminate (AR national chemical group chemical Co., Ltd.), and continuously stirring for 10min60.8g of silica sol (30% by weight in water, technical grade), i.e.a source of aluminium (in Al)2O3Calculated), silicon source (in terms of SiO)2Calculated), the molar ratio of the template agent, the base, the urea and the water is 1: 30: 1.5: 2: 33: 300, ZSM-5 molecular sieve crushed fine powder and SiO in silicon source2The weight ratio of (1) to (0.05): 1. aging the obtained mixed solution at room temperature for 16h, transferring the aged reaction solution into a high-pressure reaction kettle, crystallizing at 165 ℃ for 48h, taking out, washing for 5 times, and filtering; finally drying at 110 deg.C for 5h, and calcining at 600 deg.C for 6h to obtain ZSM-5 molecular sieve A1 (SiO)2/Al2O3The molar ratio is 30: 1). FIG. 2 is an X-ray diffraction (XRD) pattern of the ZSM-5 molecular sieve prepared in example 1, which was analyzed by X-ray diffraction to be a pure crystalline phase ZSM-5 molecular sieve. FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the ZSM-5 molecular sieve product prepared in example 1, which is observed by an electron scanning microscope and has a lamellar structure with a length of 300-700nm, a thickness of 40-60nm and an aspect ratio of about 5.
(2) Impregnating the prepared ZSM-5 molecular sieve A1 in 1mol/L NH4NO3In solution (ZSM-5 molecular sieve and NH)4NO3NH in solution4NO3The weight ratio of (1): 10) then stirring the solution in a water bath at 70 ℃ for 14h, washing (washing with deionized water for 4 times) and filtering, drying the filtered product at 110 ℃ for 5h, roasting at 600 ℃ for 6h to obtain a hydrogen-type ZSM-5 molecular sieve, tabletting and screening the hydrogen-type exchange modified nano-flake-shaped ZSM-5 molecular sieve, and selecting particles of 20-40 meshes for reaction evaluation of preparing propylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Example 2
This example is used to illustrate the nano-flake ZSM-5 molecular sieve of the present invention, and its preparation method and application.
(1) 20g of urea (manufactured by AR national chemical Co., Ltd.) and 0.9g of ZSM-5 molecular sieve-pulverized fine powder obtained in preparation example 1 were weighed, 72g of deionized water was added thereto, and mixed, followed by stirring to be uniform, and then 0.84g of NaOH (manufactured by AR national chemical Co., Ltd.) and 12.2g of tetrapropylammonium hydroxide template (25 wt% of tetrapropylammonium hydroxide) were sequentially addedAqueous solution, technical grade), stirring for 1h, adding 0.16g of sodium aluminate (AR national chemical group chemical agent limited), stirring for 10min, adding 60.8g of silica sol (30 wt% aqueous solution, technical grade), i.e., aluminum source (as Al)2O3Calculated), silicon source (in terms of SiO)2Calculated), the molar ratio of the template agent, the base, the urea and the water is 1: 75: 3.75: 5: 82.5: 1000, ZSM-5 molecular sieve crushed fine powder and SiO in silicon source2The weight ratio of (1) to (0.05): 1. aging the obtained mixed solution at room temperature for 16h, transferring the aged reaction solution into a high-pressure reaction kettle, crystallizing at 145 ℃ for 70 h, taking out, washing for 5 times, and filtering; finally drying at 110 deg.C for 5h, and calcining at 600 deg.C for 6h to obtain ZSM-5 molecular sieve A2 (SiO)2/Al2O3The molar ratio is 75: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length is 300-600nm, the thickness is 30-60nm, and the aspect ratio is about 5.
(2) Impregnating the prepared ZSM-5 molecular sieve A2 in 1mol/L NH4NO3In solution (ZSM-5 molecular sieve and NH)4NO3NH in solution4NO3The weight ratio of (1): 10) then stirring the solution in a water bath at 50 ℃ for 14h, washing (washing with deionized water for 4 times) and filtering, drying the filtered product at 110 ℃ for 5h, roasting at 600 ℃ for 6h to obtain a hydrogen-type ZSM-5 molecular sieve, tabletting and screening the hydrogen-type exchange modified nano-flake-shaped ZSM-5 molecular sieve, and selecting particles of 20-40 meshes for reaction evaluation of preparing propylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Example 3
This example is used to illustrate the nano-flake ZSM-5 molecular sieve of the present invention, and its preparation method and application.
(1) Weighing 20g of urea (AR national chemical group chemical Co., Ltd.) and 0.9g of ZSM-5 molecular sieve crushed fine powder obtained in preparation example 1, adding 54g of deionized water, mixing, stirring uniformly, adding 0.3g of NaOH (AR national chemical group chemical Co., Ltd.) and 7.3g of tetrapropylammonium hydroxide template (25 wt% aqueous solution, industrial grade),stirring for 1 hr, adding 0.15g Kaolin (China Kaolin Co., Ltd., industrial grade), stirring for 10min, adding 60.8g silica sol (30 wt% water solution, industrial grade), which is aluminum source (Al2O3Calculated), silicon source (in terms of SiO)2Calculated), the molar ratio of the template agent, the base, the urea and the water is 1: 150: 9: 7.4: 330: 2000, ZSM-5 molecular sieve crushed fine powder and SiO in silicon source2The weight ratio of (1) is 0.04: 1. aging the obtained mixed solution at room temperature for 16h, transferring the aged reaction solution into a high-pressure reaction kettle, crystallizing at 145 ℃ for 70 h, taking out, washing for 5 times, and filtering; finally drying at 110 deg.C for 5h, and calcining at 600 deg.C for 6h to obtain ZSM-5 molecular sieve A3 (SiO)2/Al2O3The molar ratio is 150: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length is 300-600nm, the thickness is 40-60nm, and the aspect ratio is about 7.
(2) Impregnating the prepared ZSM-5 molecular sieve A3 in 1mol/L NH4NO3In solution (ZSM-5 molecular sieve and NH)4NO3NH in solution4NO3The weight ratio of (1): 10) then stirring the solution in a water bath at 90 ℃ for 14h, washing (washing with deionized water for 4 times) and filtering, drying the filtered product at 110 ℃ for 5h, roasting at 600 ℃ for 6h to obtain a hydrogen-type ZSM-5 molecular sieve B3, tabletting and screening the hydrogen-type exchange-modified nano-flake-shaped ZSM-5 molecular sieve, and selecting 20-40 mesh particles for reaction evaluation of preparing propylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Example 4
This example is used to illustrate the nano-flake ZSM-5 molecular sieve of the present invention, and its preparation method and application.
(1) 40g of urea (AR national chemical group chemical Co., Ltd.) and 0.9g of ZSM-5 molecular sieve fine powder obtained in preparation example 1 were weighed, 54g of deionized water was added and mixed, 0.67g of NaOH (AR national chemical group chemical Co., Ltd.) and 12.2g of tetrapropylammonium hydroxide template (25 wt% aqueous solution, technical grade) were sequentially added after stirring uniformly, and 0 was added after stirring for 1 hour.45g of aluminum nitrate (chemical reagent of AR national medicine group Co., Ltd.), and 60.8g of silica sol (30% by weight aqueous solution, industrial grade) as an aluminum source (Al) was added thereto under stirring for 10 minutes2O3Calculated), silicon source (in terms of SiO)2Calculated), the molar ratio of the template agent, the base, the urea and the water is 1: 125: 6.3: 7: 275: 1250, ZSM-5 molecular sieve crushed fine powder and SiO in silicon source2The weight ratio of (1) to (0.05): 1. aging the obtained mixed solution at room temperature for 16h, transferring the aged reaction solution into a high-pressure reaction kettle, crystallizing at 140 ℃ for 70 h, taking out, washing for 5 times, and filtering; finally drying at 110 deg.C for 5h, and calcining at 600 deg.C for 6h to obtain ZSM-5 molecular sieve A4 (SiO)2/Al2O3The molar ratio is 125: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length is 300-600nm, the thickness is 40-60nm, and the aspect ratio is about 7.
(2) Impregnating the prepared ZSM-5 molecular sieve A4 in 1mol/L NH4NO3In solution (ZSM-5 molecular sieve and NH)4NO3NH in solution4NO3The weight ratio of (1): 15) then stirring the solution in a water bath at 90 ℃ for 14h, washing (washing with deionized water for 4 times) and filtering, drying the filtered product at 110 ℃ for 5h, roasting at 600 ℃ for 6h to obtain a hydrogen-type ZSM-5 molecular sieve B4, tabletting and screening the hydrogen-type exchange-modified nano-flake-shaped ZSM-5 molecular sieve, and selecting 20-40 mesh particles for reaction evaluation of preparing propylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Example 5
This example is used to illustrate the nano-flake ZSM-5 molecular sieve of the present invention, and its preparation method and application.
(1) Weighing 40g of urea (AR national chemical group chemical Co., Ltd.) and 0.9g of ZSM-5 molecular sieve crushed fine powder obtained in preparation example 1, adding 72g of deionized water, mixing, stirring uniformly, sequentially adding 0.59g of NaOH (AR national chemical group chemical Co., Ltd.) and 12.2g of tetrapropylammonium hydroxide template (25 wt% aqueous solution, industrial grade), stirring for 1h, and adding 0.08g of sodium aluminate (AR national chemical group chemical Co., Ltd.)Group chemical Co., Ltd.), and stirring was continued for 10min to add 60.8g of silica sol (30 wt% aqueous solution, technical grade), i.e., aluminum source (as Al)2O3Calculated), silicon source (in terms of SiO)2Calculated), the molar ratio of the template agent, the base, the urea and the water is 1: 150: 7.5: 7: 330: 2000, ZSM-5 molecular sieve crushed fine powder and SiO in silicon source2The weight ratio of (1) to (0.05): 1. aging the obtained mixed solution at room temperature for 16h, transferring the aged reaction solution into a high-pressure reaction kettle, crystallizing at 165 ℃ for 32 h, taking out, washing for 5 times, and filtering; finally drying at 110 deg.C for 5h, and calcining at 600 deg.C for 6h to obtain ZSM-5 molecular sieve A5 (SiO)2/Al2O3The molar ratio is 150: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length of the molecular sieve is 300-600nm, the thickness of the molecular sieve is 30-60nm, and the aspect ratio of the molecular sieve is about 4.
(2) Impregnating the prepared ZSM-5 molecular sieve A4 in 1mol/L NH4NO3In solution (ZSM-5 molecular sieve and NH)4NO3NH in solution4NO3The weight ratio of (1): 15) then stirring the solution in a water bath at 90 ℃ for 14h, washing (washing with deionized water for 4 times) and filtering, drying the filtered product at 110 ℃ for 5h, roasting at 600 ℃ for 6h to obtain a hydrogen-type ZSM-5 molecular sieve B5, tabletting and screening the hydrogen-type exchange-modified nano-flake-shaped ZSM-5 molecular sieve, and selecting 20-40 mesh particles for reaction evaluation of preparing propylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Example 6
ZSM-5 molecular sieve A6 (SiO) was obtained in the same manner as in example 1, except that the SAPO-34 molecular sieve prepared in preparation example 2 was used as a finely pulverized powder2/Al2O3The molar ratio is 150: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length is 400-600nm, the thickness is 40-60nm, and the aspect ratio is about 5. In addition, the reaction for converting methanol to propylene was evaluated as shown in Table 1 below.
Example 7
ZSM-5 molecular sieve and hydrogen type molecular sieve were prepared by the same method as in example 1, except that the Y type molecular sieve prepared in preparation example 3 was used as a finely pulverized powder, and ZSM-5 molecular sieve A7 (SiO)2/Al2O3The molar ratio is 150: 1) and the pure crystal phase ZSM-5 molecular sieve is analyzed by X-ray diffraction. The prepared molecular sieve is observed by an electron scanning microscope and has a sheet structure, the length of the molecular sieve is 500-700nm, the thickness of the molecular sieve is 40-60nm, and the aspect ratio of the molecular sieve is about 4. In addition, the reaction for converting methanol to propylene was evaluated as shown in Table 1 below.
Comparative example 1
The ZSM-5 molecular sieve and the hydrogen type molecular sieve were prepared according to the method of example 1, except that the ZSM-5 molecular sieve was prepared using the ZSM-5 molecular sieve without ball milling as a seed crystal, and the prepared molecular sieve was observed by an electron scanning microscope and had a lamellar structure with a length of 4 to 7 μm, a thickness of 200 and 300nm, an aspect ratio of 3 to 5: tabletting and screening a hydrogen type exchange modified nano flaky ZSM-5 molecular sieve, and selecting 20-40 mesh particles for reaction evaluation of preparing propylene and butylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
Compared with the method of the invention, the comparative example 1 adopts the molecular sieve which does not undergo ball milling as the seed crystal, and the grain size, no matter the length, the width and the thickness of the prepared ZSM-5 flaky molecular sieve are obviously larger than the grain size of the ZSM-5 flaky molecular sieve prepared by the method of the invention.
Comparative example 2
Sodium aluminate 3.16 g (Al)2O352.0 wt.% Na2O35.8 wt.%) was dissolved in 1000 g of water, 25 g of ammonium tetrapropyl bromide as a template and 20g of KOH were added under stirring, and 804 g of silica Sol (SiO) was added after complete dissolution 240 wt%). Stirring for 2 hours, putting into a stainless steel reaction kettle, stirring at 150-200 rpm, crystallizing at 110 ℃ for 6 hours, heating to 150 ℃ for crystallizing for 15 hours, filtering, washing and drying the obtained product, wherein the obtained crystal is ZSM-5 with the average grain diameter of 250 nanometers and SiO measured by an X-ray diffractometer2/Al2O3150: 1. tabletting and screening a ZSM-5 flaky molecular sieve obtained by hydrogen modification, and selecting 20-40-mesh particles for reaction evaluation of preparing propylene and butylene by methanol conversion, wherein the test conditions are as follows: the test temperature is 480 ℃, and the space velocity is 3h-1The test results are shown in table 1 below.
In contrast to the process of the present invention, comparative example 2 adopts a process in which urea and ZSM-5 molecular sieve fine powder are not added, and the process does not obtain flaky crystals although fine-grained ZSM-5 molecular sieve crystals are obtained.
TABLE 1
| Propylene selectivity (%) | |
| Example 1 | 47 |
| Example 2 | 49 |
| Example 3 | 53 |
| Example 4 | 52 |
| Example 5 | 53 |
| Example 6 | 52 |
| Example 7 | 51 |
| Comparative example 1 | 45 |
| Comparative example 2 | 43 |
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 (14)
1. The nano flaky ZSM-5 molecular sieve is characterized in that the thickness of the nano flaky ZSM-5 molecular sieve is 20-70nm, the length of the nano flaky ZSM-5 molecular sieve is 200-800nm, the length-width ratio of the nano flaky ZSM-5 molecular sieve is 2-10, and SiO is2/Al2O3The molar ratio is 10-200: 1.
2. the nanosheet ZSM-5 molecular sieve of claim 1, wherein the nanosheet ZSM-5 molecular sieve has a thickness of 30-60nm, a length of 300-700nm, an aspect ratio of 4-7, and a SiO2/Al2O3The molar ratio is 15-150: 1.
3. a preparation method of a nano flaky ZSM-5 molecular sieve is characterized by comprising the following steps: sequentially mixing, aging and hydro-thermal synthesis crystallization of a silicon source, an aluminum source, molecular sieve crushed fine powder, a template agent, alkali, urea and water, wherein the silicon source is SiO2The aluminum source is calculated as Al2O3The mixing ratio of the raw materials meets the following requirements: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (5-500): (0.25-25): (0.2-20): (1.5-2000): (40-4000), the molecular sieve pulverized fine powder and theSiO in silicon source2(1-10): 100.
4. the method of claim 3, wherein the mixing ratio of the feedstock further satisfies: the molar ratio of the aluminum source to the silicon source to the template agent to the alkali to the urea to the water is 1: (10-200): (0.5-20): (0.3-10): (10-800): (50-2500), and the molecular sieve is used for crushing the fine powder and SiO in the solid silicon source2(3-7): 100.
5. the method of claim 3, wherein the molecular sieve fines are at least one of SAPO-34 molecular sieve fines, ZSM-5 molecular sieve fines, Y-type molecular sieve fines, and β molecular sieve fines.
6. The method of claim 3, wherein the molecular sieve finely divided powder is obtained by a ball milling process and/or a high speed shearing process;
preferably, the ball milling process is performed by a ball mill under the conditions including: the rotation speed of the ball mill is 100-.
7. The method of any one of claims 3-6, wherein the molecular sieve finely divided powder has an average particle size of 1-2 um.
8. The method of any one of claims 3-6, wherein the hydrothermal synthesis crystallization conditions comprise: the temperature is 120 ℃ and 180 ℃, and the time is 10-80 h;
preferably, the hydrothermal synthesis crystallization conditions include: the temperature is 130-160 ℃, and the time is 24-48 h.
9. The method according to any one of claims 3-6, wherein the aging time is 8-24 h.
10. The method of any of claims 3-6, wherein the method further comprises: and washing, drying and roasting the product obtained by hydrothermal synthesis crystallization in sequence.
11. The method according to any one of claims 3 to 6, wherein the silicon source is at least one of silica sol, water glass, ethyl silicate and white carbon black;
preferably, the aluminum source is at least one of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum nitrate and kaolin, more preferably, the aluminum source is at least one of kaolin, sodium aluminate and aluminum nitrate;
preferably, the template agent is at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide and tetramethylammonium hydroxide, more preferably, the template agent is tetrapropylammonium bromide and/or tetrapropylammonium hydroxide;
preferably, the base is a sodium base, more preferably, the base is sodium hydroxide.
12. A nanosheet ZSM-5 molecular sieve produced by the process of any one of claims 3 to 11.
13. Use of a nanosheet ZSM-5 molecular sieve as defined in any one of claims 1, 2 and 12 in the conversion of methanol to olefins.
14. The use of claim 13, wherein the nanosheet-shaped ZSM-5 molecular sieve is treated with NH prior to use4 +The alkali metal ions contained in the solution are replaced by ions, and hydrogen type exchange modification is performed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114405534A (en) * | 2022-02-10 | 2022-04-29 | 上海骏恺环境工程股份有限公司 | Method for synthesizing ZSM-5 catalyst based on kaolin raw material, ZSM-5 catalyst and application |
| CN116351458A (en) * | 2023-03-28 | 2023-06-30 | 中化泉州石化有限公司 | Preparation method of catalyst for preparing low-carbon olefin by co-cracking C4-C6 olefin coupling oxygen-containing compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191660A1 (en) * | 2006-02-14 | 2007-08-16 | Johnson Ivy D | High throughput process for manufacturing molecular sieves |
| CN101954291A (en) * | 2010-09-26 | 2011-01-26 | 华中科技大学 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
| CN107285339A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | A kind of high silica ZSM-5 molecular sieve and its preparation method and application |
| CN107902667A (en) * | 2017-11-17 | 2018-04-13 | 清华大学 | The method for preparing small particle molecular sieve |
| CN108275697A (en) * | 2018-03-13 | 2018-07-13 | 南开大学 | The method that ultra-thin ZSM-5 molecular sieve nanometer sheet is synthesized under low-temperature atmosphere-pressure state |
-
2018
- 2018-08-23 CN CN201810969700.XA patent/CN110857218A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070191660A1 (en) * | 2006-02-14 | 2007-08-16 | Johnson Ivy D | High throughput process for manufacturing molecular sieves |
| CN101954291A (en) * | 2010-09-26 | 2011-01-26 | 华中科技大学 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
| CN107285339A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | A kind of high silica ZSM-5 molecular sieve and its preparation method and application |
| CN107902667A (en) * | 2017-11-17 | 2018-04-13 | 清华大学 | The method for preparing small particle molecular sieve |
| CN108275697A (en) * | 2018-03-13 | 2018-07-13 | 南开大学 | The method that ultra-thin ZSM-5 molecular sieve nanometer sheet is synthesized under low-temperature atmosphere-pressure state |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114405534A (en) * | 2022-02-10 | 2022-04-29 | 上海骏恺环境工程股份有限公司 | Method for synthesizing ZSM-5 catalyst based on kaolin raw material, ZSM-5 catalyst and application |
| CN116351458A (en) * | 2023-03-28 | 2023-06-30 | 中化泉州石化有限公司 | Preparation method of catalyst for preparing low-carbon olefin by co-cracking C4-C6 olefin coupling oxygen-containing compound |
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