CN111495421A - Method for directly preparing M-HZSM-5 molecular sieve - Google Patents
Method for directly preparing M-HZSM-5 molecular sieve Download PDFInfo
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- CN111495421A CN111495421A CN202010345056.6A CN202010345056A CN111495421A CN 111495421 A CN111495421 A CN 111495421A CN 202010345056 A CN202010345056 A CN 202010345056A CN 111495421 A CN111495421 A CN 111495421A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- 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 76
- 238000000034 method Methods 0.000 title claims abstract description 62
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 27
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 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
- 125000004429 atom Chemical group 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 abstract description 28
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000002194 synthesizing effect Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 10
- 238000005342 ion exchange Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 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 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- Chemical Kinetics & Catalysis (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for directly preparing an M-HZSM-5 molecular sieve, which comprises the steps of mixing a silicon source, a heteroatom source and seed crystals according to a certain proportion, grinding or forming, adding a certain amount of template agent and auxiliary agent, crystallizing for a period of time, and directly roasting the obtained sample at high temperature to obtain M-HZSM-5 molecular sieve powder or a formed catalyst. The invention relates to a method for directly preparing H-type heteroatom ZSM-5 molecular sieve, which can be used without introducing solvent and Na+Alkali metal ions and corrosive F‑The synthesis is directly carried out under the working conditions of ions and the like, so that links such as washing, filtering, drying, ion exchange and the like are not needed, the energy consumption is greatly reduced, and the zero discharge of waste water is realized; the obtained sample can be directly used as a catalyst, and the acidity is easy to modulate. The method has simple process and high synthesis efficiency, does not generate a large amount of wastewater, and provides a simple, convenient, economic and environment-friendly new method for synthesizing the heteroatom molecular sieve.
Description
Technical Field
The invention belongs to a method for synthesizing a ZSM-5 molecular sieve in the field of petrochemical industry, and particularly relates to a method for directly synthesizing an M-HZSM-5 molecular sieve by a solid phase method.
Background
The introduction of the heteroatom further widens the application range of ZSM-5, and the heteroatom HZSM-5 molecular sieve has many special performances, such as adjustable ion exchange sites, adjustable acid quantity, adjustable acid strength, adjustable catalytic cracking performance, adjustable catalytic oxidation performance and the like, is widely used as a catalyst in coal chemical industry and petrochemical industry, and can also be used as an excellent adsorbent, an ion exchange material and the like.
The traditional HZSM-5 molecular sieve synthesis method adopts a hydrothermal method, and the main process is to dissolve a silicon source, an aluminum source, a template agent and other auxiliary agents in a large amount of water to form gel, and then to obtain product powder through the lengthy steps of aging, crystallization, filtration, washing, drying, roasting and the like; and the obtained NaZSM-5 can be changed into the HZSM-5 molecular sieve only by ion exchange, the process is complex, the energy consumption is high, a large amount of waste water is generated, the synthesis efficiency is low, and the economic cost is high.
To solve the problem of hydrothermal synthesis, many new processes have been developed, such as: dry gel and solvent-free synthesis. CN104724720A discloses a method for mixing silicon source, aluminum source, template agent, water and the like into glue, and HZSM-5 is prepared by adopting a dry glue gel method, ion exchange is not needed in the method, the dry glue gel method mainly improves the yield of the molecular sieve, but a large amount of water is still needed to be introduced in the glue forming process, so that the process is complex and the energy consumption is high; CN102627287A discloses a method for preparing a silicon source, an aluminum source, a template agent and an alkalinity regulatorMixing and grinding to synthesize the ZSM-5 molecular sieve, the method solves the problem of introducing a large amount of wastewater in the synthesis process, and improves the yield of the molecular sieve, but the synthesized Na-ZSM-5 molecular sieve still needs an ion exchange step and can introduce a large amount of wastewater; and the process uses ammonium fluoride as alkalinity regulator, F-The introduction of (2) causes severe corrosion of industrial equipment.
The method for synthesizing the M-HZSM-5 molecular sieve containing other heteroatoms is also mainly an in-situ hydrothermal method, the process is complex, a large amount of wastewater is generated, particularly when some heavy metal ions are introduced, the treatment cost is high, and serious harm is brought to the environment and human health. Such as: hu and the like mix and dissolve a silicon source, an aluminum source, boric acid, KF, a template agent and the like in water, and synthesize a B-HZSM-5 molecular sieve by a hydrothermal method, wherein Na ions, F ions and a large amount of solvents are introduced in the process, the process is complex, the yield of the molecular sieve is low, and the energy consumption is high (high stable boron-modified high molecular sieve ZSM-5zeolite for the molecular to propylene reaction [ J ]. Catalysis science & technology. 2014, 4(9): 2891 + 2895.); CN110642265A discloses a method for synthesizing a ZSM-5 molecular sieve with a framework containing heteroatoms (Fe, V, Ga, Ge, Co, Sn, Ni and Bi) by a hydrothermal method, wherein a silicon source, an aluminum source and a heteroatom source are dissolved in water, and then a solution of an organic template agent is poured, fully mixed and adjusted in pH, crystallized for a period of time and separated to obtain a sample. The method introduces a large amount of water in the synthesis, and has low yield and high water treatment cost.
The invention discloses a simple, economic and environment-friendly direct preparation method for directly synthesizing an M-HZSM-5 molecular sieve.
Disclosure of Invention
Based on the defects of the prior art, the invention is a method for directly synthesizing the M-HZSM-5 molecular sieve, wherein M refers to heteroatom. The method can directly obtain the H-type ZSM-5 molecular sieve, does not need ion exchange, can be directly used as a catalyst of an acid catalytic reaction system, and is easy to adjust the acidity. The method has simple process and high synthesis efficiency, does not generate a large amount of waste water, and provides a simple, economic and environment-friendly new method for directly synthesizing the heteroatom molecular sieve.
The method of the invention uses a compound containing at least one element of hetero atoms B, Al, Ga, Fe, P, Ti and the like as a hetero atom source, at least one of gas-phase silicon dioxide, silica gel, amorphous silica, TEOS and silica sol as a silicon source, and aluminum nitrate, aluminum sulfate, Al2O3、Al(OH)3Pseudo-boehmite, AlCl3And aluminum isopropoxide as an aluminum source; mixing and ball-milling a heteroatom source, a silicon source, an aluminum source and HZSM-5; adding a template agent and an auxiliary agent NH3·H2O、NH4At least one of Cl and urea solution is crystallized and roasted in a reaction kettle to obtain the M-HZSM-5 catalyst with the heteroatom doped into the molecular sieve framework.
The invention adopts a solid phase crystallization method, HZSM-5 molecular sieve is used as seed crystal, raw materials are ground and mixed under the alkaline condition, at least one element of hetero atoms B, Al, Ga, Fe, P, Ti and the like enters a molecular sieve framework after crystallization, an alkaline auxiliary agent can be added to adjust the pH, a template agent can be fully absorbed by the mixed raw materials, a crystallization system is alkalescent, and the hetero atoms are embedded in the HZSM-5 molecular sieve framework under a series of actions.
In the invention, the molar ratio of the reactants is SiO2:M2OnD is A =1: 1-0: 0.2-0.01: 1-0, wherein M is2OnRepresents a heteroatom oxide form, D represents a templating agent, A represents an adjuvant; to account for SiO2The addition amount of the HZSM-5 seed crystal is 0.5-10 wt% in mass fraction.
In the scheme, the raw material with the heteroatom B is boric acid or an oxide thereof; the raw material of the P atom is ammonium hydrogen phosphate or ammonium dihydrogen phosphate; ga. The raw material of Fe is nitrate or chloride corresponding to Ga and Fe; the raw material of Ti atom is salt corresponding to Ti element, i.e. TiCl3·6H2O or TiCl4(ii) a The template agent is at least one of TPAOH, ethylenediamine, ethylamine, triethylamine, n-butylamine and TPABr.
In the scheme, the crystallization time is 0.5-72 h, the crystallization temperature is 120-250 ℃, the roasting temperature is 550 ℃, and the roasting time is 6 h. The crystallization time is preferably 12-48 h; the crystallization temperature is preferably 170 ℃ and 210 ℃.
The invention provides a method for directly synthesizing M-HZSM-5, which improves the synthesis efficiency. The molecular sieve synthesized by the method is an H-type molecular sieve, ion exchange is not needed, and waste water and extra energy consumption generated in the process are avoided. The molecular sieve synthesized by the method can be directly applied to an acid catalysis system, the acidity of the molecular sieve is easy to modulate, and the method is applicable to a wide range of catalytic reactions. The invention directly introduces hetero atoms into the molecular sieve framework by a solid phase method, and regulates the acidity of the molecular sieve. The method for synthesizing the M-HZSM-5 molecular sieve is a solid phase method, and no additional solvent (such as H) is required to be added in the synthesis process2O), a large amount of waste water generated in the synthesis process is avoided, and the environmental pollution and the cost for treating the waste water are reduced. The M-HZSM-5 molecular sieve synthesized by the method has high yield which is close to 100%.
The molecular sieve prepared by the invention can be used for heterogeneous catalysts in the fields of thermal catalytic reactions such as MTP, MTO, MTA, MTG, MTH, catalytic cracking, catalytic oxidation and the like, photoelectric catalytic reactions and the like; can also be used as an adsorbent for organic matters, gases, radioactive pollution sources and heavy metal ions; it can also be used as carrier of other catalysts.
The molar ratio of silicon to heteroatoms in the process of the invention is between 1 and 3, the molecular sieve B acid increases with increasing molar ratio of silicon to heteroatoms, the molar ratio of aluminum element to heteroatoms is between 0.2 and 5, and the molecular sieve L acid increases with increasing molar ratio of aluminum to heteroatoms.
It is worth mentioning that in the method, part of the heteroatoms are embedded into the molecular sieve framework before the template agent is added, and M-HZSM-5 crystal grains are preliminarily formed. The method can also directly prepare the molded catalyst, namely, before adding the template agent, molding other materials, putting the materials into a reaction kettle, adding the template agent, and crystallizing and roasting the materials to obtain the industrial M-HZSM-5 catalyst. The size and shape of the granules can be determined according to the industrial requirements. The simple process can directly synthesize the formed catalyst required by industry, is suitable for industrial application and has certain industrial value.
The heteroatoms involved In the method are not limited to those described herein, and do not preclude application to the direct synthesis of M-HZSM-5 molecular sieves containing other heteroatoms, including V, In, Ti, Ge, Co, Sn, Ni, Bi, Zn, Cr, and the like.
Drawings
FIG. 1 is an XRD pattern of M-HZSM-5 molecular sieve synthesized in example 1
FIG. 2 is an SEM photograph of M-HZSM-5 molecular sieve synthesized in example 1
FIG. 3 shows the synthesis of molecular sieves of example 111B-NMR chart
FIG. 4 is an XRD pattern of Al-HZSM-5 molecular sieve synthesized in example 2
FIG. 5 is an SEM picture of Al-HZSM-5 molecular sieve synthesized in example 2
Figure 6 is an XRD pattern of the shaped molecular sieve synthesized in example 14.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the specific examples, but is not limited to any of the methods reported herein and the processing approaches that are close thereto.
Example 1
SiO coarse pores2Mixing aluminum sulfate octadecahydrate, boric acid and ZSM-5 seed crystal, grinding for 10min, fully grinding, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: B2O3: TPAOH: NH3=1: 0.005: 0.0025: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve. The sample XRD is shown in fig. 1, and distinct characteristic peaks of the MFI structure ZSM-5 molecular sieve appear at 2 θ = 7.9 °, 8.8 °, 23.1 °, 23.9 °, 24.4 °. A Scanning Electron Micrograph (SEM) image of the sample is shown in fig. 2. As can be seen from fig. 2, the sample is discoidal and shows a relatively uniform particle size (500 nm). The relative crystallinity of the obtained sample can reach 141%, and the yield is close to 100%. The BET surface area and micropore volume of the sample were 415 m, respectively2G and 0.17 cm3(ii)/g; of samples11The B MAS NMR spectrum is shown in FIG. 3, and a sharp and highly symmetrical peak was observed at-3.2 ppm, which is a characteristic signal of tetrahedrally coordinated framework boron. In addition, in the range of 0-10 ppm and 10-20No peak appears at ppm, and the two-order quadrupole broadening triangular coordination framework boron and the triangular coordination non-framework boron respectively belong to. Indicating that the B substance can be directly introduced into the framework of the molecular sieve by a solid phase method.
Example 2
SiO coarse pores2Grinding pseudoboehmite and ZSM-5 seed crystal for 10min, fully grinding, placing the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2And O, crystallizing at 180 ℃ for 12h, calcining the solid product at 550 ℃ for 6h, and removing the template agent to obtain the HZSM-5 molecular sieve. The sample XRD is shown in fig. 4, and distinct characteristic peaks of the MFI structure ZSM-5 molecular sieve appear at 2 θ = 7.9 °, 8.8 °, 23.1 °, 23.9 °, 24.4 °. A Scanning Electron Micrograph (SEM) image of the sample is shown in fig. 5. As can be seen in FIG. 5, the sample is a round cake and shows a relatively uniform particle size (300-1000 nm). The relative crystallinity of the obtained sample can reach 141%, and the yield is close to 100%. The BET surface area and micropore volume of the sample were 429.41 m, respectively2G and 0.16 cm3/g。
Example 3
SiO coarse pores2Mixing aluminum sulfate and ZSM-5 seed crystal, grinding for 10min, fully grinding, placing into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2O, initial molar ratio of reactants of SiO2:Al2O3:TPAOH:NH3And (3) crystallizing at 200 ℃ for 12h by using the ratio of 1: 0.01: 0.05: 0.88, and calcining the solid product at 550 ℃ for 6h to remove the template agent to obtain the HZSM-5 molecular sieve. The BET surface area and micropore volume of the sample were 435.59 m, respectively2G and 0.17 cm3/g。
Example 4
Mixing fumed silica, aluminum sulfate octadecahydrate, ammonium dihydrogen phosphate and ZSM-5 seed crystal, grinding for 10min, fully grinding, placing the raw materials into a 100m L polytetrafluoroethylene-lined high-pressure reaction kettle, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: P2O5: TPAOH: NH3=1: 0.005: 0.005: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the P-HZSM-5 molecular sieve.
Example 5
SiO coarse pores2Aluminum sulfate octadecahydrate, boric acid and NH4Mixing Cl and ZSM-5 seed crystal, grinding for 10min, fully grinding, placing the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH with certain mass, and the initial molar ratio of reactants SiO2: Al2O3: B2O3: TPAOH: NH4 +=1: 0.005: 0.0025: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve.
Example 6
SiO coarse pores2Mixing and grinding aluminum sulfate octadecahydrate, ferric nitrate nonahydrate and ZSM-5 seed crystal for 10min, fully grinding, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: Fe2O3: TPAOH: NH3=1: 0.005: 0.005: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template agent to obtain the Fe-HZSM-5 molecular sieve.
Example 7
SiO coarse pores2Mixing and grinding aluminum sulfate octadecahydrate, gallium nitrate and ZSM-5 seed crystal for 20 min, fully grinding, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: Ga2O3: TPAOH: NH3=1: 0.005: 0.005: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the Ga-HZSM-5 molecular sieve.
Example 8
SiO coarse pores2Eighteen, eighteenMixing aluminum sulfate, titanium trichloride and ZSM-5 seed crystal, grinding for 20 min, fully grinding, placing into 100m L polytetrafluoroethylene lined high pressure reaction kettle, adding TPAOH and NH3·H2O; initial molar ratio of reactants SiO2: Al2O3: TiO2: TPAOH: NH3=1: 0.005: 0.005: 0.05: 0.45. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the Ti-HZSM-5 molecular sieve.
Example 9
SiO coarse pores2Mixing and grinding aluminum sulfate octadecahydrate, boric acid, TPABr and ZSM-5 seed crystal for 5 min, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L after full grinding, and adding a certain mass of NH3·H2O; initial molar ratio of reactants SiO2: Al2O3: B2O3: TPA+: NH3=1: 0.005: 0.005: 0.08: 1. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve.
Example 10
SiO coarse pores2Mixing and grinding pseudo-boehmite, boric acid and ZSM-5 seed crystal for 20 min, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L after full grinding, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: B2O3: TPA+: NH3=1: 0.005: 0.005: 0.08: 1. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve.
Example 11
SiO coarse pores2Grinding pseudoboehmite, boric acid and ZSM-5 seed crystal for 20 min, fully grinding, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH with certain mass, and obtaining the initial molar ratio of reactants SiO2:Al2O3: B2O3: TPAOH: NH3=1: 0.005: 0.005: 0.05:0. At 180 °And crystallizing at the temperature of 550 ℃ for 48h, calcining the solid product at the temperature of 550 ℃ for 6h, and removing the template agent to obtain the B-HZSM-5 molecular sieve.
Example 12
SiO coarse pores2Grinding pseudoboehmite, boric acid, urea and ZSM-5 seed crystal for 20 min, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L after full grinding, adding TPAOH with certain mass, and adding SiO in the initial molar ratio of reactants2: Al2O3: B2O3: TPAOH: NH4 +=1: 0.005: 0.005: 0.05: 0.3. Crystallizing at 180 ℃ for 48h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve.
Example 13
SiO coarse pores2Mixing aluminum sulfate octadecahydrate, boric acid and ZSM-5 seed crystal, grinding for 10min, fully grinding, putting the raw materials into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100m L, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: B2O3: TPAOH: NH3=1: 0.005: 0.0025: 0.05: 0.45. Crystallizing at 200 ℃ for 12h, calcining the solid product at 550 ℃ for 6h, and removing the template to obtain the B-HZSM-5 molecular sieve.
Example 14
SiO coarse pores2Placing aluminum sulfate octadecahydrate and ZSM-5 crystal seeds into a forming machine, mixing and stirring, gradually dropwise adding silica sol until a sample is fully mixed into a dough, extruding the raw materials, drying the obtained strip raw materials at 100 ℃ overnight, cutting the dried strip raw materials into small particles (the particle diameter is about 3 mm), finally placing the raw material particles into a reaction kettle, adding TPAOH and NH with certain mass3·H2O; initial molar ratio of reactants SiO2: Al2O3: TPAOH: NH3=1: 0.005: 0.0025: 0.05: 0.45. Crystallizing at 180 ℃ for 12h, calcining the solid product at 550 ℃ for 6h, and removing the template agent to obtain the granular Al-HZSM-5 molecular sieve.
TABLE 1 Synthesis of M-HZSM-5 examples
Examples | Sample name | Auxiliary agent | Crystallization time (h) | Crystallization temperature (C.) | Degree of crystallinity (%) | Yield (%) |
1 | B-HZSM-5 | NH3·H2O | 48 | 180 | 141 | 99.8 |
2 | Al-HZSM-5 | NH3·H2O | 12 | 180 | 141 | 99.8 |
3 | Al-HZSM-5 | NH3·H2O | 12 | 200 | 150 | 100 |
4 | P-HZSM-5 | NH3·H2O | 48 | 180 | 135 | 99 |
5 | B-HZSM-5 | NH4Cl | 48 | 180 | 138 | 99 |
6 | Fe-HZSM-5 | NH3·H2O | 48 | 180 | 130 | 98 |
7 | Ga-HZSM-5 | NH3·H2O | 48 | 180 | 137 | 99.2 |
8 | Ti-HZSM-5 | NH3·H2O | 48 | 180 | 135 | 99.5 |
11 | B-HZSM-5 | Without adding | 48 | 180 | 120 | 97 |
12 | B-HZSM-5 | Urea | 48 | 180 | 130 | 98 |
13 | B-HZSM-5 | NH3·H2O | 12 | 200 | 139 | 99.5 |
14 | Al-HZSM-5 | NH3·H2O | 12 | 180 | 130 | 100 |
Table 1 summarizes the crystallinity and yield of the M-HZSM-5 molecular sieve synthesized under different conditions in the example, and it can be seen that the relative crystallinity (compared with seed crystal) of the M-HZSM-5 molecular sieve synthesized by the method is high, the yield is substantially close to 100%, and the yield of the molecular sieve synthesized by the traditional hydrothermal method is substantially about 20%, which shows that the method has significant advantages and good industrial application prospects compared with the traditional method.
Claims (5)
1. A method for directly preparing M-HZSM-5 molecular sieve, which is characterized in that the method comprises the following steps: using a compound containing at least one element of hetero atoms B, Al, Ga, Fe, P, Ti and the like as a hetero atom source, at least one of gas-phase silica, silica gel, amorphous silica, TEOS and silica sol as a silicon source, and aluminum nitrate, aluminum sulfate, Al2O3、Al(OH)3Pseudo-boehmite, AlCl3And aluminum isopropoxide as an aluminum source; by NH3·H2O、NH4At least one of Cl and urea is taken as an auxiliary agent; mixing a heteroatom source, a silicon source, an aluminum source, an auxiliary agent and seed crystal HZSM-5, and carrying out ball milling or molding; putting the mixture into a reaction kettle, adding a template agent, crystallizing, and directly roasting to obtain heteroatom molecular sieve M-HZSM-5 molecular sieve powder or a molded catalyst; in the method, partial heteroatoms are embedded into a molecular sieve framework before a template agent is added to form M-HZSM-5 crystal grains; the molar ratio of reactants in the method is SiO2:M2OnD is A =1: 1-0: 0.2-0.01: 1-0, wherein M is2OnRepresents a heteroatom oxide form, D represents a templating agent, A represents an adjuvant; to account for SiO2The mass fraction of the HZSM-5 seed crystal is SiO20.5 to 10 wt% of the total amount.
2. The method of claim 1, wherein the M-HZSM-5 molecular sieve is prepared by a solid phase crystallization method, wherein the raw materials are ground and mixed, and at least one element of hetero atoms B, Al, Ga, Fe, P, Ti and the like enters the molecular sieve framework after crystallization.
3. The method for directly preparing the M-HZSM-5 molecular sieve according to claim 1, wherein the other raw materials are formed before adding the template; putting the obtained molded sample into a reaction kettle, adding a template agent, crystallizing and roasting at high temperature to obtain the industrial M-HZSM-5 molded catalyst.
4. The method for directly preparing the M-HZSM-5 molecular sieve according to claim 1, wherein the raw material with the heteroatom B in the method is at least one of boric acid or an oxide thereof; the raw material of the P atom is at least one of ammonium hydrogen phosphate or ammonium dihydrogen phosphate; ga. The raw material of Fe is at least one of nitrate or chloride corresponding to Ga and Fe; the raw material of Ti atom is salt corresponding to Ti element, i.e. TiCl3·6H2O or TiCl4At least one of; the template agent is at least one of TPAOH, ethylenediamine, ethylamine, triethylamine, n-butylamine and TPABr.
5. The method for directly preparing the M-HZSM-5 molecular sieve according to claim 1, wherein the crystallization time in the method is 0.5 to 72 hours; the crystallization temperature is 90-250 ℃.
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