CN111924856B - ZSM-57 molecular sieve and preparation method thereof - Google Patents
ZSM-57 molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- 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 38
- 238000002360 preparation method Methods 0.000 title description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 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
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- -1 add T element source Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229940044658 gallium nitrate Drugs 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel 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
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 23
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
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Abstract
本申请公开了一种ZSM‑57分子筛，所述ZSM‑57分子筛为纳米晶粒堆叠的规则的片状。所述ZSM‑57分子筛不仅具有规整的孔道排列且有较短的扩散程，极高的结晶度和较为充裕的接触面积提高了此类沸石的利用效率。The present application discloses a ZSM-57 molecular sieve, the ZSM-57 molecular sieve is in the form of a regular sheet with stacked nano-crystal grains. The ZSM-57 molecular sieve not only has regular channel arrangement and short diffusion path, but also has extremely high crystallinity and relatively abundant contact area, which improves the utilization efficiency of this type of zeolite.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a ZSM-57 molecular sieve single crystal sheet.
Background
ZSM-57 zeolite is a microporous crystalline zeolite having a two-dimensional ten-membered ring and eight-membered ring channel structure. Meanwhile, the ZSM-57 zeolite also has higher thermal stability, hydrothermal stability and adjustable acidity. Therefore, ZSM-57 zeolites have shown high utility in small molecule shape selective catalysis, aromatic alkylation, toluene disproportionation, and long paraffin isomerization.
The ZSM-57 zeolite reported at present has irregular appearance and nonuniform grain size, so that the ten-membered ring channel structure is in disordered stacking arrangement and often has higher mass transfer resistance. The preparation of regular shape and uniform nano zeolite crystal grain is one of the effective approaches to solve the above problems. Compared with conventional disordered ZSM-57 zeolite crystal grains, the ZSM-57 zeolite with regular pore channel arrangement and single crystal disc sheet shape has the advantages of wider mass transfer orientation, high activity, high mechanical strength and the like, so the application of the ZSM-57 zeolite in the chemical industry is increasingly wide.
Usually, more additives, such as amino acids or polyhydroxy high molecular polymers, are required to be introduced to adjust the structure and morphology of the zeolite, which increases the cost and pollutes the environment.
Disclosure of Invention
According to one aspect of the present application, there is provided a ZSM-57 molecular sieve characterized in that,
the ZSM-57 molecular sieve is a regular sheet with stacked nano crystal grains.
Optionally, the ZSM-57 molecular sieve morphology is a pentagonal star-like regular single crystal disc.
Optionally, the particle size of the zsm-57 molecular sieve is 0.2-1 μm.
Optionally, the length-diameter ratio of the ZSM-57 molecular sieve is 1-100; the thickness of the ZSM-57 molecular sieve is 20-300 nm.
Alternatively, the ZSM-57 molecular sieve pore channels are oriented.
Optionally, the ZSM-57 molecular sieve has a silicon-aluminum atomic ratio of 15-40.
Optionally, the XRD pattern of the ZSM-57 molecular sieve contains diffraction peaks at the following positions:
optionally, the specific surface area of the ZSM-57 molecular sieve is 400-500 m2/g；
The specific surface area of the micropores of the ZSM-57 molecular sieve is 300-400 m2/g；
The micropore volume of the ZSM-57 molecular sieve is 0.1-0.5 m3/g。
According to one aspect of the application, a preparation method of a directional pore channel arranged ZSM-57 molecular sieve sheet single crystal with low pollution and high efficiency is provided. The preparation method is simple, high in efficiency, convenient to operate, low in pollution and suitable for industrial production.
The method for preparing the ZSM-57 molecular sieve is characterized by comprising the following steps of:
(1) the method comprises the steps of providing a source containing T element, a source containing A element and an alkali source OH-Mixing the raw materials of the organic template agent R and water to obtain an initial mixture;
(2) carrying out hydrothermal crystallization on the initial mixture obtained in the step (1) to obtain the ZSM-57 molecular sieve;
wherein the T element source is selected from at least one of group IV A elements;
the A element source is selected from at least one of group IIIA elements;
the alkali source OH-Is a source of an alkali metal and/or a source of an alkaline earth metal;
the organic template R is selected from at least one of compounds with a chemical structural formula shown in formula I:
in the formula I, n is 3-10; r1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of the hydrocarbon groups of (a); x1 -、X2 -Independently selected from OH-And a halogen element anion.
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of linear alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C6At least one of the alkyl groups having a branch.
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of linear alkyl groups of (a).
Alternatively, R1，R2，R3，R4，R5，R6Independently selected from C1～C5At least one of the alkyl groups having a branch.
Optionally, the lower limit of the hydrothermal crystallization temperature is selected from 140 ℃, 145 ℃, 150 ℃, 155 ℃. 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 195 ℃; the upper limit is selected from 145 deg.C, 150 deg.C, 155 deg.C. 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃.
Optionally, the lower limit of the hydrothermal crystallization time is selected from 24 hours, 48 hours, 72 hours, 96 hours, 120 hours, 144 hours, 168 hours, 192 hours, 216 hours, 240 hours, 264 hours, 288 hours, 312 hours, 336 hours, 360 hours, 384 hours, 408 hours, 432 hours, or 456 hours; the upper limit is selected from 48 hours, 72 hours, 96 hours, 120 hours, 144 hours, 168 hours, 192 hours, 216 hours, 240 hours, 264 hours, 288 hours, 312 hours, 336 hours, 360 hours, 384 hours, 408 hours, 432 hours, 456 hours, or 480 hours.
Specifically, the method comprises the following steps:
(1) TO is a tetravalent oxide2Of a trivalent oxide A2O3OH as a source of alkali-Mixing an organic template agent R and water to obtain an initial mixture;
(2) placing the mixture obtained in the step (1) at 140-200 ℃ for hydrothermal crystallization for 24-480 hours to obtain the ZSM-57 molecular sieve with the directional pore channel arrangement;
wherein TO in the initial mixture2、A2O3OH as a source of alkali-R and H2The molar ratio of O is: TO2/Y2O3Is in the range of 10 to 999,
OH-/TO2is in the range of 0.01 to 1.0,
H2O/TO2is in the range of 10 to 120,
R/TO20.05 to 1.0;
r is selected from at least one of the compounds with the chemical structural formula shown in the formula I:
wherein n is 3-10.
Optionally, a source of T element, a source of A element, a source of an alkali OH in the initial mixture-Organic templating agents R and H2The molar ratio of O is:
TO2/A2O3is in the range of 10 to 999,
OH-/TO2is in the range of 0.01 to 1.0,
H2O/TO2is in the range of 10 to 120,
R/TO20.05 to 1.0;
wherein, T element is sourced from TO2Based on the mole number of the element A, the source of the element A is A2O3Based on the mole number of the alkali source OH-With OH contained therein-In moles of the organic template R, H in moles of the organic template R itself2O is in moles on its own.
Optionally, R/TO in the initial mixture2The lower limit of the molar ratio range of (a) is selected from 0.06: 1. 0.07: 1. 0.08: 1. 0.09: 1. 0.1: 1 or 0.12: 1, upper limit selected from 0.15: 1. 0.2: 1. 0.3: 1. 0.4: 1. 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1 or 1.0: 1.
optionally, R/TO in the initial mixture2The molar ratio of (A) to (B) is: 0.08-0.8: 1.
optionally, OH in the initial mixture-/TO2The lower limit of the molar ratio range of (a) is selected from 0.01: 1. 0.02: 0.03, 0.04: 1. 0.045: 1 or 0.05: 1, upper limit selected from 0.5: 1. 0.6: 1. 0.65: 1. 0.7: 1 or 0.8: 1.
optionally, TO in the initial mixture2/A2O3The lower limit of the molar ratio range of (a) is selected from 10, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, 200, 250, 300, 400, 500, 600, 700, 800 or 900; the upper limit is selected from 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 180, 200, 250, 300, 400, 500, 600, 700, 800, 900, or 999.
Alternatively, H in the initial mixture2O/TO2The lower limit of the molar ratio range of (a) is selected from 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 110; the upper limit is selected from 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120.
Optionally, the T element source is selected from at least one of a silicon source, a germanium source and a tin source;
the A element source is at least one selected from aluminum source, boron source and gallium source;
the alkali source OH-At least one selected from alkali metal hydroxides and alkaline earth metal hydroxides.
Optionally, the silicon source is selected from at least one of tetraethoxysilane, silica gel, silicic acid, white carbon black, silica sol, water glass and diatomite;
the germanium source is germanium oxide;
the tin source is at least one of tin oxide and tin chloride;
the aluminum source is selected from at least one of aluminum isopropoxide, sodium aluminate, aluminum foil, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide and pseudo-boehmite;
the boron source is at least one of boric acid, sodium borate and boron oxide;
the gallium source is selected from at least one of gallium nitrate and gallium trichloride;
the alkali source OH-At least one selected from sodium hydroxide, potassium hydroxide and cesium hydroxide.
Alternatively, in formula I, n ═ 3-7; r1，R2，R3，R4，R5，R6Independently selected from C1～C3At least one of alkyl groups of (a).
Optionally, the organic template agent R is 1, 5-hexaethyl pentanediammonium bromide.
Optionally, step (1) comprises: to A element source and alkali source OH-And adding a T element source into the mixture of the organic template agent R and the water, and mixing to obtain an initial mixture.
Optionally, step (1) comprises: to A element source and alkali source OH-And adding a T element source into the mixture of the organic template agent R and the water, and mixing to obtain an initial mixture.
Optionally, step (2) comprises: and (2) carrying out hydrothermal crystallization on the initial mixture obtained in the step (1) at the temperature of 140-200 ℃ for 24-480 hours, and separating, washing and drying the obtained product to obtain the ZSM-57 molecular sieve.
Based on the principle of zeolite preparation, framework four connecting atoms in zeolite can be replaced by other metals (germanium source, tin source, aluminum source and gallium source) or non-metal atoms (silicon source and boron source) and the framework structure of zeolite crystal is kept the same.
All conditions in this application that relate to a numerical range can be independently selected from any point within the numerical range.
In this application "C1～C6"and the like refer to the number of carbon atoms which a group contains.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound.
In this application, a "hydrocarbyl group" is a group formed by the loss of one hydrogen atom on a carbon atom in a hydrocarbon molecule. The hydrocarbon is a carbohydrate, for example, the alkane, alkene, alkyne are all hydrocarbons.
The beneficial effects that this application can produce include:
1) according to the method provided by the application, the prepared ZSM-57 has a regular appearance and a directionally distributed zeolite pore channel structure;
2) according to the method provided by the application, the prepared ZSM-57 has extremely high crystallinity and relatively abundant contact area, so that the sieving utilization efficiency of the zeolite is improved;
3) the ZSM-57 prepared by the method has extremely high length-diameter ratio and shorter diffusion path, thereby improving the film forming efficiency of the zeolite sheets.
Drawings
Figure 1 is an XRD spectrum of the sample of example 1.
FIG. 2 is a SEM photograph of a sample of example 1.
FIG. 3 is a transmission electron micrograph of a selected area of the sample of example 1.
FIG. 4 is a scanning electron micrograph of a sample of comparative example 1.
Detailed Description
The invention is illustrated by the following examples, which are not intended to limit the scope of the invention. The starting materials, templating agents and solvents in the examples of the present invention were all purchased commercially, unless otherwise specified.
The molar ratio of Si to Al in the product is Si/Al atomic ratio in the examples.
The analysis method in the examples of the present invention is as follows:
x-ray powder diffraction phase analysis (XRD) was performed using X' Pert PRO X-ray diffractometer [ Cu target, ka radiation source (λ ═ 0.15418nm), voltage 40kV, current 40mA ], of pananace (PANalytical), netherlands.
SEM topography analysis was performed using a Hitachi (SU8020) scanning electron microscope.
Selective electron diffraction analysis was performed using a JEOL (2100) type transmission electron microscope.
Example 1
The initial gel was formulated in the following molar ratios: SiO 22/Al2O3＝100，OH-/SiO2＝0.4，R/SiO2＝0.2，H2O/SiO2Sodium aluminate, potassium hydroxide and 1, 5-hexaethyl pentanediammonium bromide are respectively dissolved in deionized water, and then white carbon black is added under the condition of continuous stirring. Then the mixture is put into a 100ml crystallization kettle to react for 168 hours at 160 ℃.
And (3) placing the cooled reaction liquid into a water bath, standing for 5 hours to generate obvious layering, wherein beige solid at the lower layer is ZSM-57 zeolite, separating, washing, drying and roasting (the roasting temperature is 550 ℃ and the roasting time is 8 hours) to obtain a sample, wherein the number of the sample is ZSM-57-1, and the yield of the ZSM-57-1 is 91% based on the weight of the added silicon dioxide.
XRD analysis (XRD spectrogram is shown in figure 1) shows that the sample is ZSM-57 zeolite, and the molar ratio of silicon to aluminum is 21; SEM characterization (the SEM image is shown in FIG. 2) confirmed that the sample morphology is pentagonal disk-shaped with nano-small crystal grain stacking, the particle size is 2 μm, and the thickness is about 20 nm.
Examples 2 to 5
The specific compounding ratio and crystallization conditions are shown in table 1, and the specific compounding process is the same as that of example 1.
XRD analysis is carried out on the prepared sample, the data result is similar to that of the sample shown in the table 2, namely, the position and the shape of the peak are the same, and the relative kurtosis of the peak fluctuates within the range of +/-10% according to the change of the preparation conditions, which shows that the prepared product has the characteristics of a ZSM-57 structure.
TABLE 1 ingredient and crystallization conditions for molecular sieve preparation
Table 2 XRD results for the sample of example 1
Comparative example 1
Mixing sodium hydroxide, 1, 5-hexaethyl pentanediammonium bromide, sodium aluminate, water and white carbon black, and preparing according to the following molar ratio: SiO 22/Al2O3＝60，OH-/SiO2＝0.6，R/SiO2＝0.15，H2O/SiO 240. The mixture was then stirred in a 50 ℃ water bath to a homogeneous gel and aged for 12 hours while stirring. And transferring the gel into a hydrothermal crystallization kettle, heating to 160 ℃, carrying out hydrothermal crystallization for 168 hours, then naturally cooling, filtering and drying to obtain zeolite raw powder, and marking the zeolite raw powder as a sample ZSM-57-D1. XRD tests prove that the ZSM-57-D1 sample is ZSM-57 zeolite, small-grain aggregates are observed in a low-power SEM, and a ZSM-57 pentagonal disc with a regular surface is not formed, as shown in figure 4. The yield of ZSM-57 was 86% based on the weight of silica charged. Comparative example description: the aging of the gel affects the morphology of the ZSM-57 molecular sieve, and the obtained ZSM-57 sample does not form a regular single crystal disc and only presents a small particle aggregation state with the same crystal orientation.
Experimental example 6
The sample obtained in example 1 is calcined at 550 ℃ for 8 hours by introducing air to remove the template agent, and then the specific surface area and the pore volume of the sample are tested, wherein the sample has high BET specific surface area of 456m2The specific surface area and the volume of each micropore calculated according to the t-plot method are 316m2G and 0.16cm3/g。
The samples prepared in examples 2 to 5 have similar BET specific surface areas to those tested for the sample of example 1.
Experimental example 7
And (3) introducing air into the sample obtained in the example 1 at 550 ℃ to roast for 8 hours to remove the template agent, and then testing the crystal plane orientation of the sample by adopting a transmission electron microscope. From the selected area electron diffraction pattern (FIG. 3), it can be found that the zeolite sheet orientation of ZSM-57 is [100], i.e. the ten-member ring channel orientation of the zeolite.
The samples prepared in examples 2-5 were similar to the transmission electron mirror image obtained from the sample testing of example 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
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