CN115010146A - Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof - Google Patents
Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN115010146A CN115010146A CN202110244821.XA CN202110244821A CN115010146A CN 115010146 A CN115010146 A CN 115010146A CN 202110244821 A CN202110244821 A CN 202110244821A CN 115010146 A CN115010146 A CN 115010146A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zsm
- pore
- sio
- nanoaggregate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 97
- 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 97
- 239000002149 hierarchical pore Substances 0.000 title claims description 40
- 238000002360 preparation method Methods 0.000 title description 6
- 239000011148 porous material Substances 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 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 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 150000001924 cycloalkanes Chemical class 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002159 nanocrystal Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The average particle size of the multistage-hole ZSM-5 nano aggregate molecular sieve particles is 0.5-0.7 mu m, blocky crystals are arranged in the middle of the particles, the average grain size of the grains is 30-80nm, and the most probable pore size of the multistage-hole ZSM-5 nano aggregate molecular sieve is 30-55nm and 150-190 nm. The synthesis method comprises the following steps: (1) the template agent, water and alkali metal hydroxide are added after the alkali metal hydroxide is completely dissolved, and an aluminum source is added and stirred for 0.5 to 5.0 hours at room temperature; (2) adding a silicon source into the first mixed solution obtained in the step (1) at the temperature of 30-50 ℃, and stirring for more than 0.5 hour; (3) crystallizing; (4) recovering the ZSM-5 molecular sieve. The ZSM-5 molecular sieve provided by the invention has a good effect when being used for converting larger cycloalkane.
Description
Technical Field
The invention relates to a ZSM-5 nano aggregate molecular sieve and a preparation method thereof.
Background
Zeolite molecular sieves are microporous crystalline materials with framework structures, have pore structures with specific sizes and shapes, large specific surface areas and strong adjustable acid properties, and are widely applied to petroleum refining and processing processes, such as catalytic cracking, alkane isomerization, catalytic reforming, toluene disproportionation and other catalytic reactions. The catalytic material is the core of a novel catalyst, and in order to realize the shape-selective performance of a molecular sieve catalyst, reduce the activity loss of the catalyst and realize high activity on the premise of high selectivity, the development of a shape-selective catalyst with better performance is urgently needed. ZSM-5 has a unique pore channel structure, has the characteristics of good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like.
The hierarchical pore ZSM-5 molecular sieve combines strong acidity and hydrothermal stability of a microporous molecular sieve and pore diameter advantages of a mesoporous molecular sieve, and becomes a hotspot of research in the fields of current catalysis, adsorption, separation and the like. The current methods for synthesizing the hierarchical pore ZSM-5 molecular sieve mainly comprise a template method, a post-treatment method, a template-free method and the like. CN108658093A discloses a method for preparing a multistage pore ZSM-5 molecular sieve, i.e. a cationic surfactant cetyl trimethyl ammonium bromide is used as a soft template agent, and a dry gel conversion method is used to synthesize the multistage pore ZSM-5 molecular sieve. Sashkina adopts polystyrene spheres as hard templates to prepare the hierarchical pore ZSM-5 zeolite through hydrothermal treatment, the preparation of the hierarchical pore ZSM-5 by the template method needs to add a large amount of mesoporous templates into a system, the cost is high, and the waste liquid is not beneficial to environmental protection. The post-treatment method generally comprises acid treatment, alkali treatment and the like, but the post-treatment method is easy to cause collapse of partial framework structure due to dealumination and desiliconization, and has low molecular sieve yield and certain limitation on industrial application.
The template-free method does not need to add a mesoporous template, thereby reducing the cost and avoiding environmental pollution. The template-free method is mainly used for preparing a hierarchical pore molecular sieve by nanocrystal accumulation or self-assembly, and the hierarchical pore molecular sieve synthesized by the prior art has the problems of smaller mesoporous aperture ratio, less quantity of large mesopores and less existence of macropores, and has low efficiency when being used for the conversion of naphthene rings with larger molecules.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano aggregate molecular sieve with a ZSM-5 structure.
In the invention, the grain size of the molecular sieve is the size of the widest part in the projection plane of the molecular sieve grains. The particle size is the widest point of the projected plane of the molecular sieve particles. Can be obtained by measuring the maximum circumcircle diameter of the crystal grains or particles of the molecular sieve by a projection electron microscope (TEM) image or a Scanning Electron Microscope (SEM). The average grain size is the average of 10 grain sizes measured randomly; the average particle size is the average of 10 particle sizes measured at random.
The invention provides a hierarchical pore ZSM-5 nano aggregate molecular sieve, wherein the average particle size of the hierarchical pore ZSM-5 nano aggregate molecular sieve particles is 0.5-0.7 mu m, the average grain size of the grains is 30-80nm, blocky crystals are arranged in the middle of the particles, and the most probable pore diameter of the hierarchical pore ZSM-5 nano aggregate molecular sieve is 30-55nm and 150-190 nm.
According to the technical scheme, the multistage pore ZSM-5 nano aggregate molecular sieve has one embodiment, bulk crystals are arranged in the middle of particles, the outer surface of the particles is formed by stacking nano crystals, the stacking among the nano crystals forms intercrystalline pores, and the average grain size of the nano crystal grains is preferably 30-80 nm; the ratio of the surface area of the intermediate blocky crystals to the surface area of the molecular sieve particles is 40-80%. The ratio of the surface area of the intermediate bulk crystal to the surface area of the molecular sieve particle is the ratio of the projected area of the bulk crystal part to the projected area of the molecular sieve particle in a TEM (projection electron microscope) image of the particle. The ratio of the surface area of the intermediate bulk crystals of 10 particles to the surface area of the molecular sieve particles was randomly measured, and the average value thereof was taken as the ratio of the surface area of the intermediate bulk crystals of the sample to the surface area of the molecular sieve particles. The intermediate bulk crystals are beneficial to improving the hydrothermal stability of the molecular sieve.
Preferably, the particles of the hierarchical porous ZSM-5 nanoaggregate molecular sieve present a spherical morphology. The ratio of the largest dimension to the shortest dimension of the center of the particles of the molecular sieve is about 1.0, for example, 0.98 to 1.0.
The hierarchical pore ZSM-5 nanoaggregate molecular sieve of any of the preceding claims, wherein the hierarchical pore ZSM-5 nanoaggregate molecular sieve has a relative crystallinity of 80.0-100.0%.
The hierarchical pore ZSM-5 nanoaggregate molecular sieve of any of the preceding claims, wherein the hierarchical pore ZSM-5 nanoaggregate molecular sieve has a mode of a most probable pore diameter of 30-55nm as measured by a low-temperature nitrogen adsorption capacity method. The pore diameter refers to the diameter. The method for measuring the pore size distribution by the low-temperature nitrogen adsorption volumetric method refers to the analysis method of RIPP151-90 (petrochemical analysis method, RIPP test method, scientific publishing company, 1990). The total cumulative pore volume is the total pore volume of pores having a pore diameter of 1 to 100 nm.
The multi-stage pore ZSM-5 nanoaggregate molecular sieve according to any of the preceding claims, wherein the pore volume of the pores within a pore diameter range of 24-51nm, as measured by low temperature nitrogen adsorption capacity method, is 25-55% of the total cumulative pore volume.
The hierarchical pore ZSM-5 nanoaggregate molecular sieve recited in any of the above scenarios, wherein the pore volume of the inner pores with a pore diameter in the range of 10-90nm as measured by low temperature nitrogen adsorption capacity method accounts for 30-75% of the total cumulative pore volume.
The hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any of the above schemes, wherein the mesopore volume measured by a low temperature nitrogen adsorption capacity method accounts for 15-40% of the total pore volume.
The hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above schemes, wherein the mesoporous area of the hierarchical pore ZSM-5 nanoaggregate molecular sieve accounts for 4-8% of the total specific surface area.
The hierarchical porous ZSM-5 nanoaggregate molecular sieve according to any one of the above schemes, having macropores with a pore size greater than 100 nm. The largest pore diameter of the hierarchical pore ZSM-5 nano-aggregate molecular sieve measured by a mercury intrusion method is 150-190nm, and the average pore diameter is 230-330 nm. The measurement of the large pore size distribution by the mercury intrusion method is disclosed in GB/T21650.1-2008 < determination of the pore size distribution and the porosity of a solid material by the mercury intrusion method and a gas adsorption method, the first part of mercury intrusion method.
The invention also provides a synthesis method of the hierarchical pore ZSM-5 nano aggregate molecular sieve, which comprises the following steps:
(1) mixing a template agent, water and alkali metal hydroxide, adding an aluminum source after the alkali metal hydroxide is completely dissolved, and stirring at room temperature for at least 0.5 hour to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 30-50 ℃, then adding a silicon source, and stirring for at least 0.5 hour; obtaining a precursor solution;
(3) crystallizing the precursor liquid;
(4) and after the crystallization is finished, recovering the ZSM-5 molecular sieve.
According to the synthesis method of the hierarchical pore ZSM-5 nano aggregate molecular sieve provided by the invention, the silicon source can be one or more of silica sol, water glass, methyl orthosilicate, ethyl orthosilicate and solid silica gel; the aluminum source can be one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum isopropoxide and aluminum sol, and is preferably aluminum chloride; the alkali metal hydroxide can be one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the template agent can be one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine.
The method for synthesizing the hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above technical solutions, wherein the ratio of the amount of the materials among the materials is such that in the precursor liquid: SiO 2 2 /Al 2 O 3 The molar ratio is 10 to 500, for example 20 to 300.
The method for synthesizing the hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above technical solutions, wherein in the precursor solution: R/SiO 2 The molar ratio is 0.05 to 0.5, for example 0.15 to 0.4 or 0.17 to 0.37. Wherein R represents a templating agent.
The method for synthesizing the hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above technical solutions, wherein, in the precursor solution: h 2 O/SiO 2 The molar ratio is 5 to 75, for example 30 to 75.
The method for synthesizing the hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above technical solutions, wherein in the precursor solution: alkali metal oxide/SiO 2 The molar ratio is 0.01 to 2, for example 0.04 to 0.4 or 0.049 to 0.34. The alkali metal oxide is preferably Na 2 O,Na 2 O/SiO 2 The molar ratio is 0.01-2, for example 0.04-0.4 or 0.049-0.34.
The method for synthesizing the hierarchical pore ZSM-5 nanoaggregate molecular sieve according to any one of the above technical solutions, wherein in the precursor solution: OH group - /SiO 2 The molar ratio is 0.1 to 3, for example 0.2 to 0.6.
According to any one of the above technical solutions, in the synthesis method of the hierarchical pore ZSM-5 nanoaggregate molecular sieve, preferably, the ratio of the amount of the precursor liquid is as follows: SiO 2 2 /Al 2 O 3 20-290 or 20-50, R/SiO 2 0.15-0.40 or 0.17-0.37, H 2 O/SiO 2 31-75, alkali metal oxide/SiO 2 0.04-0.4 or 0.04-0.35,OH -/ SiO 2 0.2 to 0.6, the alkali metal oxide is preferably Na 2 O。
According to the synthesis method of the hierarchical pore ZSM-5 nanoaggregate molecular sieve described in any of the above technical solutions, preferably, in the step (1), the template and water are uniformly mixed, the alkali metal hydroxide is added to the formed mixture, the aluminum source is added after the alkali metal hydroxide is completely dissolved, and the mixture is stirred for 0.5 hour or more, for example, 0.5 to 5 hours or 0.5 to 2.0 hours. Such as deionized water or decationized water.
According to any one of the above technical solutions, in the step (2), preferably, the temperature of the mixed solution is 30-50 ℃, then a silicon source is added, and the mixture is stirred at 30-50 ℃ for 0.5 hour or more, for example, 0.5-5.0 hours, so as to obtain a precursor solution.
According to the synthesis method of the hierarchical pore ZSM-5 nano-aggregate molecular sieve in any of the above technical solutions, preferably, the precursor is crystallized in step (3), and the crystallization is, for example, dynamic crystallization at 160-180 ℃ for 12-60h, and the dynamic crystallization is, for example, crystallization under stirring.
According to the synthesis method of the hierarchical pore ZSM-5 nanoaggregate molecular sieve in any of the above technical schemes, the hierarchical pore ZSM-5 nanoaggregate molecular sieve is recovered after crystallization is finished. Such recovery is well known to those skilled in the art and typically involves one or more of filtration, washing, drying and calcination. Such as centrifugal filtration, aluminum extraction, plate and frame filtration, as is well known to those skilled in the art. The washing may be performed by washing with water until the filtrate after washing is neutral, so as to wash away the unreacted template agent and sodium ions, and the drying may be performed by drying, air drying, flash drying, spray drying, and the calcination may be performed at, for example, 400-600 ℃ for 2-6 h.
In the invention, the room temperature is 15-30 ℃.
According to the hierarchical pore ZSM-5 nano aggregate molecular sieve provided by the invention, the center of a molecular sieve particle is provided with a blocky crystal, the outer surface of the molecular sieve particle is provided with ZSM-5 nano crystal grains, and the molecular sieve is rich in intercrystalline mesopores and macropores formed by stacking the ZSM-5 nano crystal grains, and has good hydrothermal stability. The ZSM-5 molecular sieve provided by the invention has a plurality of mesopores with larger aperture, which indicates that the molecular sieve has more mesopores. The ZSM-5 molecular sieve provided by the invention has good physicochemical property and catalytic performance, has good cracking performance, is particularly used for hydrocarbon conversion of macromolecular cycloalkane, and has good ring opening cracking performance.
The synthesis method of the hierarchical pore ZSM-5 nano aggregate molecular sieve provided by the invention can be used for preparing the ZSM-5 molecular sieve with specific mesopore and macropore distribution without using a mesopore template agent, and is simple to operate. The obtained molecular sieve has a blocky central body and an outer layer formed by stacking nano crystal grains, can have higher hydrothermal stability under the condition of having the nano crystal grains and mesoporous and macroporous structures, and can have good ring-opening cracking performance of macromolecular naphthenic rings.
Drawings
FIG. 1 is an SEM image of a sample of example 1;
FIG. 2 is a TEM image of a sample of example 1;
FIG. 3 is N of the sample of example 1 2 Adsorption and desorption curves.
FIG. 4 shows N of the sample of example 1 2 Desorption pore size distribution diagram.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the examples and comparative examples, the average crystal grain size of the molecular sieve samples was obtained by measuring the crystal grain size and particle size of the molecular sieve by SEM or TEM, and randomly measuring 10 crystal grain sizes, and averaging them. The average particle size of the molecular sieve samples was obtained by randomly measuring 10 particles and averaging them.
The mesoporous surface area, the specific surface area, the pore volume (total pore volume) and the pore size distribution are measured by a low-temperature nitrogen adsorption capacity method, a sample is subjected to vacuum degassing for 0.5h and 6h at 100 ℃ and 300 ℃ respectively by using an ASAP2420 adsorption instrument of Micromeritics company in America, and N is carried out at 77.4K 2 Adsorption and desorption test, namely testing the adsorption amount and desorption of the sample on nitrogen under different specific pressuresAmount of obtaining N 2 Adsorption-desorption isotherm curve. The BET specific surface area (total specific surface area) was calculated using the BET formula, and the micropore area was calculated using t-plot.
The macroporous PORE size distribution is determined by a mercury intrusion method, and the testing equipment is an AUTOPORE V9600 mercury intrusion instrument, the testing standard adopts GB/T21650.1-2008, and the average PORE diameter is 4 times of the PORE volume divided by the PORE surface area.
In the following examples, room temperature is 25 ℃.
Example 1
(1) 91.0 g of tetrapropylammonium hydroxide solution (25.0 wt% concentration) was weighed, 395 g of deionized water was added, and the mixture was stirred at room temperature for 10 min;
(2) then adding 1.8 g of sodium hydroxide particles to completely dissolve the sodium hydroxide, then adding 7.8 g of aluminum chloride hexahydrate, uniformly mixing, and stirring for 1.0h at room temperature;
(3) heating to 40 ℃, adding 94.7 g of tetraethoxysilane, and stirring for 2.0h under the condition of water bath at 40 ℃; obtaining a precursor solution;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing at 170 ℃ for 48 hours;
(5) after crystallization, the mixture is centrifugally filtered, washed, dried and roasted at 550 ℃ for 4 hours.
Example 2
(1) 39.0 g of tetrapropylammonium bromide aqueous solution (mass fraction: 98 wt%) was weighed, 314.0 g of deionized water was added thereto, and the mixture was stirred at room temperature for 30 min;
(2) then adding 9.7 g of sodium hydroxide particles to completely dissolve the sodium hydroxide, then adding 3.5 g of sodium aluminate, uniformly mixing, and stirring for 2.0h at room temperature;
(3) heating to 40 ℃, adding 84.5 g of methyl orthosilicate, and stirring for 2.0h under the condition of 40 ℃ water bath;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing at 170 ℃ for 48 hours;
(5) after crystallization, centrifugal filtration, washing, drying and roasting at 500 ℃ for 6 h.
Example 3
(1) 84.7 g of tetrapropylammonium hydroxide aqueous solution (the concentration is 25.0 weight percent) is weighed, 547.0 g of deionized water is added, and the mixture is stirred for 60min at room temperature;
(2) then adding 2.48 g of sodium hydroxide particles to completely dissolve the sodium hydroxide, then adding 7.0 g of aluminum isopropoxide, uniformly mixing, and stirring for 1.5h at room temperature;
(3) heating to 40 ℃, adding 97.8 g of tetraethoxysilane, and stirring for 4.0h at 40 ℃ under the condition of water bath; obtaining a precursor solution;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing at 170 ℃ for 48 hours;
(5) after crystallization, the mixture is centrifugally filtered, washed, dried and roasted at 550 ℃ for 4 hours.
Example 4
(1) 96.4 g of tetrapropylammonium hydroxide aqueous solution (concentration: 25.0 wt%) was weighed, 542 g of deionized water was added thereto, and the mixture was stirred at room temperature for 10 min;
(2) then 2.8 g of sodium hydroxide particles are added to completely dissolve the sodium hydroxide, 10.8 g of aluminum chloride hexahydrate is added to be uniformly mixed, and the mixture is stirred for 1.0h at room temperature;
(3) heating to 40 ℃, adding 121.1 g of tetraethoxysilane, and stirring for 2.0h under the condition of water bath at 40 ℃; obtaining a precursor solution;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing for 48 hours at 170 ℃;
(5) after crystallization, the mixture is centrifugally filtered, washed, dried and roasted at 550 ℃ for 4 hours.
Example 5
(1) 34.2 g of tetrapropylammonium bromide aqueous solution (mass fraction: 98 wt%) was weighed, 408.0 g of deionized water was added, and the mixture was stirred at room temperature for 30 min;
(2) then adding 8.45 g of sodium hydroxide particles to completely dissolve the sodium hydroxide, then adding 6.2 g of sodium aluminate, uniformly mixing, and stirring for 2.0h at room temperature;
(3) heating to 40 ℃, adding 157.8 g of methyl orthosilicate, and stirring for 2.0h under the condition of 40 ℃ water bath; obtaining a precursor solution;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing for 48 hours at 170 ℃;
(5) after crystallization, centrifugal filtration, washing, drying and roasting at 500 ℃ for 6 h.
Example 6
(1) 79.4 g of tetrapropylammonium hydroxide aqueous solution (concentration: 25.0 wt%) was weighed, 521.0 g of deionized water was added, and stirring was carried out at room temperature for 60 min;
(2) then adding 3.47 g of sodium hydroxide particles to completely dissolve the sodium hydroxide, then adding 9.0 g of aluminum chloride hexahydrate, uniformly mixing, and stirring for 1.5h at room temperature;
(3) heating to 40 ℃, adding 97.8 g of tetraethoxysilane, and stirring for 4.0h under the condition of 40 ℃ water bath; obtaining a precursor solution;
(4) transferring the precursor solution into a synthesis kettle, and dynamically crystallizing at 170 ℃ for 48 hours;
(5) after crystallization, centrifugal filtration, washing, drying and roasting at 550 ℃ for 4 h.
The properties and precursor ratios of the hierarchical pore ZSM-5 nanoaggregate molecular sieves obtained in examples 1-6 are shown in Table 1.
Evaluation of reaction
After ammonium exchange is performed on the hierarchical pore ZSM-5 nanoaggregate molecular sieves prepared in examples 1 to 6, the sodium oxide content is reduced to less than 0.1 wt%, and an H-type molecular sieve is obtained, where the ammonium exchange conditions are as follows: molecular sieve: ammonium chloride: h 2 O is 1:0.5:10, the ammonium exchange temperature is 85 ℃, and the ammonium exchange time is 1 h. After ammonium exchange, filtering, washing and drying, and then roasting for 2h at 550 ℃.
The obtained H-type molecular sieve sample is evaluated on a fixed bed micro-reaction device FB, the raw oil is a model compound decalin, and the evaluation conditions are as follows: the reaction temperature was 600 ℃, the agent-to-oil ratio (by weight) was 0.3, and the oil-feeding time was 75 seconds, and the results are shown in Table 2.
TABLE 1
TABLE 2
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Reaction temperature/. degree.C | 600 | 600 | 600 | 600 | 600 | 600 |
| Reaction pressure/MPa | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Reaction time/s | 75 | 75 | 75 | 75 | 75 | 75 |
| Agent to oil ratio/weight ratio | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Conversion rate/% | 24.7 | 23.0 | 23.8 | 25.4 | 22.7 | 24.5 |
| Product yield/% | ||||||
| Ethylene (CO) process | 3.02 | 2.86 | 2.90 | 3.15 | 2.87 | 3.08 |
| Propylene (PA) | 4.51 | 4.16 | 4.36 | 4.83 | 4.00 | 4.40 |
| Carbon tetraolefins | 2.23 | 1.87 | 1.96 | 2.34 | 1.84 | 2.18 |
As can be seen from Table 2, the ZSM-5 molecular sieve provided by the invention has higher decalin conversion activity, and the low-carbon olefin, especially the carbon tetraolefin (C) 4 ＝ ) The yield is higher, and in addition, the yields of ethylene and propylene are higher. Therefore, the ZSM-5 molecular sieve provided by the invention has higher ring-opening cracking activity and better cracking effect on cycloalkanes with larger molecules.
Claims (11)
1. A hierarchical pore ZSM-5 nanoagglomerate molecular sieve, wherein:
the average particle size of the multistage-pore ZSM-5 nano aggregate molecular sieve particles is 0.5-0.7 mu m, the average grain size of the grains is 30-80nm, the middle of the particles is provided with blocky crystals, and the most probable pore diameters of the multistage-pore ZSM-5 nano aggregate molecular sieve particles are 30-55nm and 150-190 nm.
2. The multi-stage pore ZSM-5 nanoaggregate molecular sieve of claim 1, wherein the multi-stage pore ZSM-5 nanoaggregate molecular sieve particles have bulk crystals in the middle, and the ratio of the surface area of the intermediate bulk crystals to the surface area of the multi-stage pore ZSM-5 nanoaggregate molecular sieve particles is 40-80%.
3. The multi-stage pore ZSM-5 nanoagglomerate molecular sieve of claim 1, wherein the relative crystallinity of the multi-stage pore ZSM-5 nanoagglomerate molecular sieve is between 80-100%.
4. The multi-stage pore ZSM-5 nanoagglomerate molecular sieve of claim 1, wherein the multi-stage pore ZSM-5 nanoagglomerate molecular sieve has a mode pore size of 30-55nm as measured by low temperature nitrogen adsorption capacity.
5. The multi-stage pore ZSM-5 nanoagglomerate molecular sieve of claim 1, wherein the pore volume of the multi-stage pore ZSM-5 nanoagglomerate molecular sieve having pore diameters in the range of 24-51nm accounts for 25-55% of the total cumulative pore volume, and the pore volume of the pores in the range of 10-90nm accounts for 30-75% of the total cumulative pore volume, as measured by low temperature nitrogen adsorption capacity method.
6. The hierarchical pore ZSM-5 nanoaggregate molecular sieve of claim 1, wherein the mesoporous area of the hierarchical pore ZSM-5 nanoaggregate molecular sieve measured by low temperature nitrogen adsorption volumetric method accounts for 4-8% of the total specific surface area, and the mesoporous volume accounts for 15-40% of the total pore volume.
7. The multi-stage pore ZSM-5 nanoaggregate molecular sieve of claim 1, wherein the multi-stage pore ZSM-5 nanoaggregate molecular sieve has a distribution of macropores having a largest possible pore diameter of 150-190nm and an average pore diameter of 230-330nm as measured by mercury intrusion method.
8. A method for synthesizing a hierarchical pore ZSM-5 nano aggregate molecular sieve comprises the following steps:
(1) mixing the template agent, water and alkali metal hydroxide, adding an aluminum source after the alkali metal hydroxide is completely dissolved, and stirring for more than 0.5h, such as 0.5-5h, at room temperature; obtaining a first mixed solution;
(2) adding a silicon source into the first mixed solution obtained in the step (1) at the temperature of 30-50 ℃, and stirring for more than 0.5 hour, such as 0.5-5 hours; obtaining a precursor solution; the material amount of the precursor liquid is SiO 2 /Al 2 O 3 ＝10-500，R/SiO 2 ＝0.05-0.5，H 2 O/SiO 2 ＝5-75，Na 2 O/SiO 2 ＝0.01-2，OH - /SiO 2 0.1-3; wherein R represents a templating agent;
(3) crystallizing the precursor liquid;
(4) and after the crystallization is finished, recovering the ZSM-5 molecular sieve.
9. The method according to claim 8, wherein the silicon source is one or more of silica sol, water glass, methyl orthosilicate, ethyl orthosilicate and solid silica gel; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum chloride, aluminum isopropoxide and aluminum sol, and preferably is aluminum chloride; the alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the template agent is one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylene diamine.
10. The method according to claim 8, wherein the precursor liquid is prepared by the following substances: SiO 2 2 /Al 2 O 3 ＝20-290，R/SiO 2 ＝0.15-0.4，H 2 O/SiO 2 ＝31-75，Na 2 O/SiO 2 ＝0.04-0.4，OH - /SiO 2 ＝0.2-0.7。
11. The method as claimed in claim 8, wherein the crystallization is dynamic crystallization at 160-180 ℃ for 12-60 h; the molecular weight recovery comprises filtration, washing, drying and roasting, wherein the roasting temperature is 400 ℃ for example, and the roasting time is 2-6h for example.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110244821.XA CN115010146B (en) | 2021-03-05 | 2021-03-05 | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110244821.XA CN115010146B (en) | 2021-03-05 | 2021-03-05 | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115010146A true CN115010146A (en) | 2022-09-06 |
| CN115010146B CN115010146B (en) | 2024-03-12 |
Family
ID=83064942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110244821.XA Active CN115010146B (en) | 2021-03-05 | 2021-03-05 | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115010146B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993008125A1 (en) * | 1991-10-23 | 1993-04-29 | Exxon Chemical Patents Inc. | Nanometer-sized molecular sieve crystals or agglomerates and processes for their production |
| US20120027673A1 (en) * | 2010-07-30 | 2012-02-02 | University Of Iowa Research Foundation | Synthesis of hierarchical nanocrystalline zeolites with controlled particle size and mesoporosity |
| CN104556135A (en) * | 2015-01-28 | 2015-04-29 | 中国石油大学(北京) | Hydrothermal synthesis system for synthesizing ZSM-5 zeolite molecular sieve and application thereof |
| CN106219569A (en) * | 2016-07-16 | 2016-12-14 | 太原理工大学 | A kind of method preparing porous zeotile without secondary template one step |
| CN106745055A (en) * | 2016-12-28 | 2017-05-31 | 河南大学 | A kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5 |
| CN108203101A (en) * | 2018-04-04 | 2018-06-26 | 江苏马庄文化旅游发展有限公司 | A kind of zeolite |
| US10343926B1 (en) * | 2016-08-22 | 2019-07-09 | Louisiana Tech Research Corporation | Synthesis of hierarchical zeolites by solid state crystallization of aluminosilicate nanogels |
-
2021
- 2021-03-05 CN CN202110244821.XA patent/CN115010146B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993008125A1 (en) * | 1991-10-23 | 1993-04-29 | Exxon Chemical Patents Inc. | Nanometer-sized molecular sieve crystals or agglomerates and processes for their production |
| US20120027673A1 (en) * | 2010-07-30 | 2012-02-02 | University Of Iowa Research Foundation | Synthesis of hierarchical nanocrystalline zeolites with controlled particle size and mesoporosity |
| CN104556135A (en) * | 2015-01-28 | 2015-04-29 | 中国石油大学(北京) | Hydrothermal synthesis system for synthesizing ZSM-5 zeolite molecular sieve and application thereof |
| CN106219569A (en) * | 2016-07-16 | 2016-12-14 | 太原理工大学 | A kind of method preparing porous zeotile without secondary template one step |
| US10343926B1 (en) * | 2016-08-22 | 2019-07-09 | Louisiana Tech Research Corporation | Synthesis of hierarchical zeolites by solid state crystallization of aluminosilicate nanogels |
| CN106745055A (en) * | 2016-12-28 | 2017-05-31 | 河南大学 | A kind of synthetic method of the molecular sieves of monoblock type multi-stage porous ZSM 5 |
| CN108203101A (en) * | 2018-04-04 | 2018-06-26 | 江苏马庄文化旅游发展有限公司 | A kind of zeolite |
Non-Patent Citations (3)
| Title |
|---|
| YANG, JH ET AL.: "Synthesis of ZSM-5 hierarchical microsphere-like particle by two stage varying temperature crystallization without secondary template", 《CHEMICAL ENGINEERING JOURNAL》, vol. 166, no. 3, pages 1083 - 1089, XP028136522, DOI: 10.1016/j.cej.2010.11.071 * |
| 岳元等: "纳米晶堆积多级结构ZSM-5分子筛的制备及表征", 《精细石油化工》, vol. 36, no. 05, pages 6 - 10 * |
| 王有和;王晓东;孙洪满;任子豪;阎子峰;季生福;: "单一模板剂两段变温法合成球状多级孔ZSM-5分子筛", 中国石油大学学报(自然科学版), no. 02, pages 159 - 165 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
| CN116119681B (en) * | 2023-01-11 | 2024-08-02 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115010146B (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107512728B (en) | Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores | |
| CN112110457B (en) | Preparation method of directionally stacked and grown ZSM-5 nanosheet aggregate | |
| CN108821304B (en) | High-activity hierarchical pore titanium silicalite molecular sieve and preparation method and application thereof | |
| CN106219569B (en) | A method of no one step of secondary template prepares porous zeotile | |
| CN107651693B (en) | A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve | |
| CN107020145B (en) | Mesoporous IM-5 molecular sieve and preparation method thereof | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN115010146B (en) | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof | |
| CN111056561B (en) | Small-grain SSZ-13 molecular sieve containing hierarchical pores and synthesis method thereof | |
| CN104760971A (en) | Beta molecular sieve alkali-free metal ion synthesis method | |
| CN108946756B (en) | Hierarchical pore EUO structure molecular sieve and synthesis method thereof | |
| CN110342533B (en) | Molecular sieve and preparation method and application thereof | |
| CN115196650B (en) | Metal modified mesoporous ZSM-5 molecular sieve and preparation method thereof | |
| CN108033462B (en) | Hierarchical porous LTL molecular sieve and synthesis method and application thereof | |
| CN111655370A (en) | Process for making hollow ZSM-5 and TS-1 zeolites | |
| CN115140745B (en) | Metal modified hierarchical pore ZSM-5 molecular sieve and preparation method thereof | |
| CN114804141B (en) | Nanocluster mesoporous ZSM-5 molecular sieve and preparation method thereof | |
| CN113830778B (en) | ZSM-5/beta core-shell molecular sieve and synthesis method and application thereof | |
| CN112456511B (en) | SAPO-34 molecular sieve, and preparation method and application thereof | |
| CN115140746B (en) | ZSM-5 molecular sieve with cascade hole distribution and preparation method thereof | |
| CN114988429B (en) | ZSM-5 molecular sieve rich in intergranular mesopores and preparation method thereof | |
| CN108996517B (en) | Hierarchical-pore wide-silica-alumina-ratio EU-1 molecular sieve and preparation method thereof | |
| CN108862314B (en) | Hierarchical-pore wide-silica-alumina-ratio EUO-structure molecular sieve and synthesis method thereof | |
| CN109052427B (en) | High-mesopore-degree H-ZSM-5 molecular sieve with uniformly distributed bulk mesopores, and preparation method and application thereof | |
| CN109607564B (en) | Preparation method of hollow microporous mesoporous ZSM-5 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |