CN113398984A - Preparation method and application of metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve - Google Patents
Preparation method and application of metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve Download PDFInfo
- Publication number
- CN113398984A CN113398984A CN202110685199.6A CN202110685199A CN113398984A CN 113398984 A CN113398984 A CN 113398984A CN 202110685199 A CN202110685199 A CN 202110685199A CN 113398984 A CN113398984 A CN 113398984A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hierarchical pore
- nickel
- metallic nickel
- encapsulated
- 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
- 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 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 80
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004806 packaging method and process Methods 0.000 title claims description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000006229 carbon black Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003077 lignite Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 150000001721 carbon Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 claims description 16
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 238000001833 catalytic reforming Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011286 gas tar Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
-
- 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
Abstract
The invention discloses a preparation method and application of a metal nickel-encapsulated and embedded multistage-hole ZSM-5 molecular sieve, a preparation method of metal nickel-supported modified carbon black and a preparation method of steam-assisted encapsulated metal nickel. The method comprises the synthesis of an H-type hierarchical pore molecular sieve, the synthesis of a metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve (metallic nickel is fixed in a molecular sieve mesoporous structure in an in-situ growth mode), and the synthesis of a hierarchical pore ZSM-5 molecular sieve embedded by metallic nickel as a core (metallic nickel is embedded in the mesoporous structure in a mode of epitaxial crystallization to form a shell as the core). The preparation process of the metal nickel-encapsulated and embedded hierarchical pore ZSM-5 catalyst has the advantages of low cost, high activity of the prepared Ni-HeZ5 catalyst, high efficiency of converting lignite pyrolysis volatile components into light aromatic hydrocarbons when coupling hydrogen is used as a reaction auxiliary agent, high selectivity, high yield and good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a metal nickel-encapsulated and embedded hierarchical pore ZSM-5 molecular sieve.
Background
The ZSM-5 molecular sieve is an important microporous material and is widely applied to the fields of petrochemical industry, oil refining, fine chemistry and the like. Molecular sieve catalysis has a unique position in environmentally friendly chemical processing because it can provide specific pathways for hydrocarbon processing and chemical synthesis.
However, for many chemical reactions, the space requirements for reactants and products exceed the pore size, and in particular the narrow pore size of microporous ZSM-5 has a repulsive effect on lignite pyrolysis derived heavy volatile components with molecular sizes larger than the characteristic pore size. The multistage pore ZSM-5 molecular sieve can give consideration to the pore property of the catalyst and the synergistic effect of the active sites, and has good diffusion performance. The metal-loaded ZSM-5 molecular sieve catalyst has high metal utilization rate and shows special activity in certain specific reactions.
However, the stability of these catalytic materials in heterogeneous catalytic systems is difficult to ensure, and under heating or H2 or Ar atmosphere, the metals will gradually agglomerate to form larger particles, and the deactivation is serious. The hierarchical pore ZSM-5 is a material with a micro-mesoporous structure, metal particles are filled in a molecular sieve, and the metal is stabilized by using pore channels of the molecular sieve, so that researchers have prepared various metal materials wrapped by the molecular sieve by methods such as ion exchange, in-situ synthesis of metal and molecular sieve precursors, and the like. However, it is still a well-known difficulty to construct ordered micro-mesoporous gradient multi-level pore ZSM-5, overcome the limitation of pore channel transport of molecular sieve, and improve the accessibility of its active site.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve, and solves the technical problems in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a metal nickel-encapsulated and embedded hierarchical pore ZSM-5 molecular sieve comprises the synthesis of an H-type hierarchical pore molecular sieve (HeZ5), the synthesis of a metal nickel-encapsulated hierarchical pore ZSM-5 molecular sieve (Ni-HeZ5) (namely, metal nickel in Ni-HeZ5 is fixed in a molecular sieve mesoporous structure in an in-situ growth mode), the synthesis of a metal nickel-core-embedded hierarchical pore ZSM-5 molecular sieve (Ni @ HeZ5) (namely, metal nickel in Ni @ HeZ5 is embedded in the mesoporous structure in a mode of epitaxial crystallization and shell formation as a core),
synthesis of the H-type hierarchical pore molecular sieve (HeZ 5):
s1, taking HNO3Adding carbon black into the solution, and stirring, washing, filtering and drying to obtain carbon black powder subjected to oxidation modification;
s2, mixing tetraethyl orthosilicate (TEOS) serving as a silicon source, aluminum sulfate octadecahydrate serving as an aluminum source, tetrapropylammonium hydroxide (TPAOH) serving as a structure directing agent and modified carbon black serving as a hard template agent according to a ratio to prepare a synthetic liquid, and performing hydrothermal crystallization treatment to obtain a solid-liquid mixed state;
s3, washing and filtering the solid-liquid mixed state to obtain filter residue, and drying and roasting the filter residue to obtain the Na-type molecular sieve;
s4, use of NH4Carrying out ion exchange on the Na-type molecular sieve by using a Cl solution, and drying and air roasting to obtain an H-type hierarchical pore molecular sieve;
synthesizing the metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve (Ni-HeZ 5):
s5, weighing nickel nitrate hydrate by adopting a wet impregnation method, adding the nickel nitrate hydrate into deionized water for ultrasonic reaction until the nickel nitrate hydrate is completely dissolved, then adding the oxidized and modified carbon black powder obtained in S1, and obtaining nickel-supported oxidized carbon black powder after stirring, vacuum standing, drying and roasting; wherein: the loading amount of metallic Ni in the nickel-supported oxidized carbon black is 1.2%;
s6 carbon black oxide (Ni/HNO) supported by nickel3-CB) is used as a hard template agent and a metal source, the synthetic material ratio of synthetic liquid phase in S2 is the same, and the synthetic material ratio is according to SiO2Molar ratio of/Ni 507: 1, preparing a synthetic liquid A by a one-step hydrothermal synthesis method, and carrying out hydrothermal crystallization, washing, drying, roasting and ion exchange treatment on the synthetic liquid A to obtain a high-dispersion metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve;
the synthesis of the multi-stage pore ZSM-5 molecular sieve (Ni @ HeZ5) embedded by taking metallic nickel as a core comprises the following steps:
s7, weighing nickel nitrate hydrate by adopting a wet impregnation method, adding the nickel nitrate hydrate into deionized water for ultrasonic reaction until the nickel nitrate hydrate is completely dissolved, then adding the H-type hierarchical pore molecular sieve prepared in S4, stirring, standing in vacuum and drying to obtain solid powder B, and calcining the solid powder B at high temperature to obtain Ni/HeZ5 powder;
s8, putting the Ni/HeZ5 powder prepared in the previous step into a tetrapropyl ammonium hydroxide solution, drying, then carrying out hydrothermal crystallization treatment, and then carrying out washing, drying, roasting and ion exchange treatment to obtain Ni @ HeZ 5; wherein: SiO 22Tetrapropylammonium hydroxide 1:0.42, SiO2The molar ratio/Ni was 370.
Further, HNO in S13Oxidizing agent in solution: water 1: 4.
Further, the mixture ratio of each material in the synthetic liquid in the S2 is SiO2:Al2O3:Na2O:TPAOH:H2O1: 0.02:0.09:0.2: 35; wherein: SiO 22/C(HNO3-CB)＝0.52。
Further, the hydrothermal crystallization treatment in S2 specifically includes: and (3) crystallizing the synthetic solution for 72 hours in a hydrothermal environment with a polytetrafluoroethylene lining at the temperature of 170 ℃.
Further, in the S6, the nickel-supported carbon black oxide (Ni/HNO)3-CB) was mixed with ethanol.
Further, in S7, the high-temperature calcination of the solid powder B is specifically performed by: the solid powder B was calcined in an Ar atmosphere at 2 ℃/min from room temperature to 600 ℃ for 2 h.
Further, the metallic nickel packaged hierarchical pore ZSM-5 molecular sieve is applied to the aspect of upgrading light aromatic hydrocarbons by catalytically reforming lignite pyrolysis volatile matters.
The preparation method of the metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve comprises the following specific steps of:
weighing lignite particles, placing the lignite particles in a feeding device, connecting the lignite particles with a reaction tube, then adding metal nickel for packaging and embedding the hierarchical pore ZSM-5 catalyst particles, carrying out pyrolysis reaction on the reaction tube, and carrying out catalytic reforming to generate light aromatic hydrocarbon;
wherein: the total selectivity of light aromatics is greater than 91.7%.
Further, the pyrolysis reaction is carried out in the presence of H2While the thermal temperature and the catalytic temperature are 600 ℃, lignite is delivered to a pyrolysis zone at 600 ℃ with a feed rate of 0.1g/min, and subsequently pyrolysis volatiles are H2The gas flow is swept to 600 ℃ and contains a metal nickel packaging and embedding multistage hole ZSM-5 catalyst bed layer for catalytic reforming to generate light aromatic hydrocarbon.
Further, the Ni-HeZ5 catalyzed carbon deposit content is as low as 2.39%.
The invention has the beneficial effects that:
1. the invention provides two different preparation methods for encapsulating and embedding the multi-level pore ZSM-5 by using metal nickel, and the preparation process of the catalyst is unique, wherein firstly, the metal nickel supports the modified carbon black in-situ synthesized molecular sieve to realize the encapsulation of a nickel species structure, and secondly, the steam assists in fixing the metal by taking the metal nickel as a core and forming a shell through epitaxial crystallization, so that the recrystallization of the peripheral molecular sieve of the metal supported multi-level pore ZSM-5 is realized. Overcomes the defects of high aggregation of metal particles and poor thermal stability of the metal particles caused by using a conventional post-treatment method for reaming and modifying the ZSM-5 molecular sieve by a metal surface modification method.
2. The preparation process of the metal nickel-encapsulated and embedded hierarchical pore ZSM-5 catalyst has the advantages of low cost, high activity of the prepared Ni-HeZ5 catalyst, high efficiency of converting lignite pyrolysis volatile components into light aromatic hydrocarbons when coupling hydrogen is used as a reaction auxiliary agent, high selectivity, high yield and good application prospect.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an SEM image of multi-level well HeZ5(a), Ni @ HeZ5(b), and Ni-HeZ5(c) made in accordance with an example of the present invention;
FIG. 2 is a graph of pore size distribution for multilevel pore HeZ5, Ni-HeZ5, and Ni @ HeZ5 made using a DFT process according to an embodiment of the present invention;
FIG. 3 is an XPS plot of Ni @ HeZ5 and Ni-HeZ5 produced in accordance with an example of the present invention;
FIG. 4 shows NH of Ni @ HeZ5 and Ni-HeZ5 prepared in accordance with an example of the present invention3-a TPD spectrum;
FIG. 5 is a graph showing the carbon yield and carbon selectivity profiles of BTEXN obtained in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: the embodiment of the invention provides a preparation method of a metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve, which comprises the synthesis of an H-type hierarchical pore molecular sieve (HeZ5), the synthesis of a metallic nickel packaging hierarchical pore ZSM-5 molecular sieve (Ni-HeZ5) and the synthesis of a metallic nickel core embedding hierarchical pore ZSM-5 molecular sieve (Ni @ HeZ 5).
Synthesis of H-type hierarchical pore molecular sieve (HeZ 5):
s1, taking 100mL of HNO with the content concentration of 25%3Adding 3g of commercial carbon black into the solution (i.e. oxidant: water ═ 1:4), placing into a polytetrafluoroethylene cup, mechanically stirring for 24h, washing, suction filtering, then placing into a forced air drying oven, drying at 60 ℃ for 4h, and drying at 100 ℃ for 24h to obtain the oxidation modified carbon black powder (HNO)3-CB) for use.
S2, adopting a hard template method, taking tetraethyl orthosilicate (TEOS) as a silicon source, taking aluminum sulfate octadecahydrate as an aluminum source, and taking tetrapropylammonium hydroxide (TPAOH) as a structureThe guiding agent and the modified carbon black are used as hard template agents according to the initial molar material ratio (SiO)2:Al2O3:Na2O:TPAOH:H2O＝1:0.02:0.09:0.2:35；SiO2/C(HNO3-CB) ═ 0.52) to prepare a synthetic solution, and then the synthetic solution is placed in a hydrothermal kettle with a polytetrafluoroethylene lining to be crystallized for 72 hours at the temperature of 170 ℃ to obtain a solid-liquid mixed state.
S3, washing and filtering the solid-liquid mixed state to obtain filter residue (namely a filter cake shape), then placing the filter residue in a blast drying oven to dry at 100 ℃ overnight, and then placing the filter residue in a muffle furnace to bake at 550 ℃ for 5 hours to obtain the Na-type molecular sieve.
S4, NH with the mass concentration of the used substance being 1.0mol/L4And (3) carrying out ion exchange on the Cl solution Na type molecular sieve, and drying (110 ℃, 24H) and roasting in air (550 ℃, 5H) to obtain the H type hierarchical pore molecular sieve (HeZ 5).
Synthesis of metallic nickel-encapsulated hierarchical pore ZSM-5(Ni-HeZ5) molecular sieve:
s5, weighing 0.0923g of nickel nitrate hydrate by a wet impregnation method, adding into deionized water, and performing ultrasonic treatment for 10min until the nickel nitrate hydrate is completely dissolved. Followed by the addition of the oxidatively modified carbon black powder (HNO) as prepared in S13-CB), after stirring, vacuum standing (24h) and drying (12h), the powder mixture obtained is placed in a tube furnace and calcined in an Ar atmosphere at 2 ℃/min from room temperature to 600 ℃ for 2h, obtaining a nickel-supported carbon black oxide (Ni/HNO)3-CB) powder.
S6, wetting Ni/HNO with 3g of ethanol solution3-the CB powder is pre-treated for future use. Ni/HNO prepared in S5 by one-step hydrothermal synthesis method3-CB as hard template agent and metal source, SiO in initial molar mass ratio2:Al2O3:Na2O:TPAOH:H2O＝1:0.02:0.09:0.2:35，SiO2The mol ratio of Ni to the solid is 507, synthetic liquid A is prepared, and the synthetic liquid A is transferred to a hydrothermal kettle with a polytetrafluoroethylene lining to be crystallized for 72 hours at 170 ℃, so that a solid-liquid mixture is obtained. After washing and suction filtration of the solid-liquid mixture, the filter cake was dried overnight at 100 ℃ in a forced air drying oven. Then, the sample was placed in a horseRoasting the mixture for 5 hours at 550 ℃ in a muffle furnace to obtain the Na-type molecular sieve. Subsequently, 1.0mol/L NH was used4And (3) carrying out ion exchange on the Na-type molecular sieve for 3 times by using a Cl solution in a water bath kettle at the temperature of 80 ℃, and then drying (110 ℃, 24 hours) and roasting (550 ℃, 5 hours) a filtered filter cake to obtain the high-dispersion metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve (Ni-HeZ 5).
The synthesis of the metallic nickel core-embedded hierarchical pore ZSM-5(Ni @ HeZ5) molecular sieve:
s7, weighing 0.2104g of nickel nitrate hydrate, adding into deionized water, and carrying out ultrasonic treatment for 10min until the nickel nitrate hydrate is completely dissolved. Subsequently, the H-type hierarchical pore molecular sieve (HeZ5) prepared in S4 was added, and after stirring, vacuum standing (24H) and drying (12H), solid powder B was obtained, and the solid powder B was calcined in a tube furnace at 2 ℃/min from room temperature to 600 ℃ for 2H in an Ar atmosphere to obtain Ni/HeZ5 powder.
S8, taking 4g of prepared Ni/HeZ5 and putting the Ni/HeZ5 into a beaker according to the molar ratio of materials to SiO2:TPAOH＝1:0.42，SiO2The molar ratio of Ni/tetrapropylammonium hydroxide (TPAOH) was added to the mixture at a molar ratio of 370, followed by drying at room temperature for a while, and then Tetraethylorthosilicate (TEOS) was added and drying at room temperature was continued overnight to obtain a mixture. The mixture was transferred to a teflon liner and crystallized in an outer liner containing 100mL of water at 170 ℃ for 72 hours. After washing and suction filtration of the solid-liquid mixture, the filter cake was dried overnight in a forced air drying oven at 100 ℃. Then, the sample is placed in a muffle furnace to be roasted for 5 hours at the temperature of 550 ℃, and the Na-type molecular sieve is obtained. Subsequently, 1.0mol/L NH was used4And (3) carrying out ion exchange on the Na-type molecular sieve for 3 times by using a Cl solution in a water bath kettle at the temperature of 80 ℃, and then drying (110 ℃, 24 hours) and roasting (550 ℃, 5 hours) a filtered filter cake to obtain the metallic nickel core embedded hierarchical pore ZSM-5(Ni @ HeZ5) molecular sieve.
FIG. 1 is an SEM image of multi-level hole HeZ5(a), Ni @ HeZ5(b), and Ni-HeZ5(c) made in accordance with an embodiment of the present invention; as shown in fig. 1a, the synthesized hierarchical pores HeZ5 are intracrystalline mesopores, which can fill metal particles into the molecular sieve and stabilize the metal; the metal of Ni-HeZ5 in fig. 1b is attached to and highly dispersed in the hierarchical pore molecular sieve structure; in FIG. 1c, the metallic nickel of Ni @ HeZ5 is used as a core, and the molecular sieve which is externally arranged is embedded in the multilevel pore structure in an internal manner in a recrystallization mode.
FIG. 2 is a graph of pore size distributions of multi-level pores HeZ5, Ni-HeZ5, and Ni @ HeZ5 made in accordance with an embodiment of the present invention; as shown in fig. 2, HeZ5 is a hierarchical pore channel with micro-mesoporous gradient, the metal species remains in the molecular sieve structure after being baked by attaching carbon black, and part of the metal species can block the mesoporous pore channel with the pore diameter ranging from 50nm to 60nm to generate more micropores, and at the same time, the addition of nickel and carbon black generates larger mesopores ranging from 11 nm to 50 nm.
FIG. 3 is an XPS plot of Ni-HeZ5 and Ni @ HeZ5 prepared in accordance with examples of the present invention; as shown in FIG. 3, most of the metallic nickel species in Ni-HeZ5 is NiO. The metallic nickel species of Ni @ HeZ5 recrystallized to produce lone electron nickel species, and the aluminum species of Ni @ HeZ5 was lower. Illustrating that different encapsulation and embedding regimes are different for the immobilization of metallic nickel species.
FIG. 4 shows NH of Ni-HeZ5 and Ni @ HeZ5 prepared in examples of the present invention3-a TPD spectrum; as can be seen from FIG. 3, recrystallization shifts the strong acid in Ni @ HeZ5 to the super acid and the content is high.
Example 2: the application of the metallic nickel encapsulated and embedded hierarchical pore ZSM-5(Ni-HeZ5 and Ni @ HeZ5) prepared by the method in the aspect of upgrading light aromatic hydrocarbon by catalytically reforming lignite pyrolysis volatile matters is realized by carrying out catalytic reforming reaction on the lignite pyrolysis volatile matters by utilizing Ni-HeZ5 and Ni @ HeZ5, and the method specifically comprises the following steps:
(1) the method is carried out in a normal-pressure falling bed pyrolysis device. Proper amount of lignite particles are weighed and placed in a feeding hopper and connected to a reaction tube. In a quartz reaction tube (the length of the tube is 360mm, the inner diameter is 22mm), a proper amount of metallic nickel packaging multistage hole ZSM-5 catalyst particles are poured into the quartz reaction tube by a funnel, a certain amount of quartz wool is put into the quartz reaction tube to be used as a partition, then the reaction tube is put into a pyrolysis furnace, and all paths of gas are connected and the gas tightness of the reaction tube is checked.
(2) The experimental conditions were: h2The pyrolysis temperature and the catalytic temperature were 600 ℃ and the space velocity was 1.5s under the atmosphere. 2.0g of lignite was delivered to a pyrolysis zone at 600 ℃ at a feed rate of 0.1 g/min. Subsequently, the pyrolysis volatiles are H2The air flow is swept to the temperature of 600 DEG CContains 3.0g of metallic nickel to encapsulate a multistage pore ZSM-5 catalyst bed layer, and carries out catalytic reforming to generate light aromatic hydrocarbon.
The upgraded gas tar enters a trapping system (a cold trap containing 100mL of methanol), the chemical components of the tar are analyzed in an off-line mode by a gas chromatography-mass spectrometer, the content of light aromatic hydrocarbons (BTEXN) in the tar is quantitatively analyzed by the gas chromatography through an external standard method, the generated non-condensable gas is collected through an air bag, and pyrolysis gases (CO and CO) are subjected to pyrolysis through the gas chromatography through the external standard method2、C1-C4Alkane and C1-C3Olefins) were analyzed off-line quantitatively. After the experiment is finished, the pyrolytic coke and the used catalyst are separated, and the carbon element content and the carbon deposit content of the pyrolytic coke are measured by an element analyzer and a synchronous thermal analyzer.
FIG. 5 is a graph showing the carbon selectivity profile of light aromatic hydrocarbons (BTEXN) produced in example 2 of the present invention; as can be seen from FIG. 5, compared with the yield of light aromatics produced by catalytic reforming with multi-stage pore HeZ5, the carbon yield of BETXN obtained by Ni-HeZ5 catalysis was 28.7%, and the selectivity was as high as 91.7%.
In conclusion, the preparation process of the metallic nickel-encapsulated and embedded hierarchical pore ZSM-5 catalyst has the advantages of low cost, high activity of the prepared Ni-HeZ5 catalyst, high efficiency of converting lignite pyrolysis volatile components into light aromatic hydrocarbons when coupling hydrogen is used as a reaction auxiliary agent, high selectivity, high yield and good application prospect.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve comprises the synthesis of an H-type hierarchical pore molecular sieve, the synthesis of the metallic nickel packaging hierarchical pore ZSM-5 molecular sieve, and the synthesis of the metallic nickel core embedding hierarchical pore ZSM-5 molecular sieve, which is characterized in that,
the synthesis of the H-type hierarchical pore molecular sieve comprises the following steps:
s1, taking HNO3Adding carbon black into the solution, and stirring, washing, filtering and drying to obtain carbon black powder subjected to oxidation modification;
s2, mixing tetraethyl orthosilicate as a silicon source, aluminum sulfate octadecahydrate as an aluminum source, tetrapropylammonium hydroxide as a structure directing agent and modified carbon black as a hard template agent according to a ratio to prepare a synthetic liquid, and performing hydrothermal crystallization treatment to obtain a solid-liquid mixed state;
s3, washing and filtering the solid-liquid mixed state to obtain filter residue, and drying and roasting the filter residue to obtain the Na-type molecular sieve;
s4, use of NH4Carrying out ion exchange on the Na-type molecular sieve by using a Cl solution, and drying and air roasting to obtain an H-type hierarchical pore molecular sieve;
synthesizing the metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve:
s5, weighing nickel nitrate hydrate by adopting a wet impregnation method, adding the nickel nitrate hydrate into deionized water for ultrasonic reaction until the nickel nitrate hydrate is completely dissolved, then adding the oxidized and modified carbon black powder obtained in S1, and obtaining nickel-supported oxidized carbon black powder after stirring, vacuum standing, drying and roasting; wherein: the loading amount of metallic Ni in the nickel-supported oxidized carbon black is 1.2%;
s6, mixing the synthetic materials with the nickel-supported oxidized carbon black as the hard template agent and the metal source in the same proportion of the synthetic liquid phase in S2 according to SiO2Ni MoThe molar ratio is 507: 1, preparing a synthetic liquid A by a one-step hydrothermal synthesis method, and carrying out hydrothermal crystallization, washing, drying, roasting and ion exchange treatment on the synthetic liquid A to obtain a high-dispersion metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve;
the synthesis of the multilevel pore ZSM-5 molecular sieve with the metal nickel as the core comprises the following steps:
s7, weighing nickel nitrate hydrate by adopting a wet impregnation method, adding the nickel nitrate hydrate into deionized water for ultrasonic reaction until the nickel nitrate hydrate is completely dissolved, then adding the H-type hierarchical pore molecular sieve prepared in S4, stirring, standing in vacuum and drying to obtain solid powder B, and calcining the solid powder B at high temperature to obtain Ni/HeZ5 powder;
s8, putting the Ni/HeZ5 powder prepared in the previous step into a tetrapropyl ammonium hydroxide solution, drying, then carrying out hydrothermal crystallization treatment, and then carrying out washing, drying, roasting and ion exchange treatment to obtain Ni @ HeZ 5; wherein: SiO 22Tetrapropylammonium hydroxide 1:0.42, SiO2The molar ratio/Ni was 370.
2. The method for preparing metallic nickel encapsulated embedded hierarchical pore ZSM-5 molecular sieve according to claim 1, wherein the HNO in S1 is HNO3Oxidizing agent in solution: water 1: 4.
3. The method for preparing the metallic nickel-encapsulated embedded hierarchical pore ZSM-5 molecular sieve of claim 1, wherein the ratio of the materials in the synthetic solution in S2 is SiO2:Al2O3:Na2O:TPAOH:H2O1: 0.02:0.09:0.2: 35; wherein: SiO 22/C(HNO3-CB)＝0.52。
4. The preparation method of the metallic nickel-encapsulated embedded hierarchical pore ZSM-5 molecular sieve according to claim 1, wherein the hydrothermal crystallization treatment in S2 comprises the following specific operations: and (3) crystallizing the synthetic solution for 72 hours in a hydrothermal environment with a polytetrafluoroethylene lining at the temperature of 170 ℃.
5. The method for preparing the metallic nickel-encapsulated, embedded hierarchical pore ZSM-5 molecular sieve as claimed in claim 1, wherein in S6, the nickel-supported carbon black oxide is mixed with ethanol.
6. The method for preparing the metallic nickel-encapsulated, embedded hierarchical pore ZSM-5 molecular sieve according to claim 1, wherein in S7, the high temperature calcination of solid powder B is specifically operated as follows: the solid powder B was calcined in an Ar atmosphere at 2 ℃/min from room temperature to 600 ℃ for 2 h.
7. The preparation method of the metallic nickel-encapsulated embedded hierarchical pore ZSM-5 molecular sieve according to any one of claims 1-6, wherein the metallic nickel-encapsulated hierarchical pore ZSM-5 molecular sieve is applied to upgrading of light aromatic hydrocarbons by catalytic reforming of lignite pyrolysis volatiles.
8. The application of the preparation method of the metallic nickel encapsulated and embedded hierarchical pore ZSM-5 molecular sieve according to claim 7,
the specific steps of utilizing metallic nickel to encapsulate the hierarchical pore ZSM-5 molecular sieve and embedding the hierarchical pore ZSM-5 molecular sieve by taking the metallic nickel as a core to carry out catalytic reforming reaction comprise:
weighing lignite particles, placing the lignite particles in a feeding device, connecting the lignite particles with a reaction tube, then adding metal nickel for packaging and embedding the hierarchical pore ZSM-5 catalyst particles, carrying out pyrolysis reaction on the reaction tube, and carrying out catalytic reforming to generate light aromatic hydrocarbon;
wherein: the total selectivity of light aromatics is greater than 91.7%.
9. The use of the metallic nickel encapsulated, embedded hierarchical pore ZSM-5 molecular sieve of claim 8 in the preparation method of the molecular sieve, wherein the pyrolysis reaction is carried out in the presence of H2While the thermal temperature and the catalytic temperature are 600 ℃, lignite is delivered to a pyrolysis zone at 600 ℃ with a feed rate of 0.1g/min, and subsequently pyrolysis volatiles are H2ZSM-5 containing metal nickel encapsulation and embedding multistage holes and allowing air flow to sweep to 600 DEG CAnd the catalyst bed layer is used for carrying out catalytic reforming to generate light aromatic hydrocarbon.
10. The use of the metallic nickel encapsulated, embedded hierarchical pore ZSM-5 molecular sieve as claimed in claim 9, in which the Ni-HeZ5 catalysed soot content is as low as 2.39%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110685199.6A CN113398984B (en) | 2021-06-21 | 2021-06-21 | Application of metal nickel encapsulated hierarchical pore ZSM-5 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110685199.6A CN113398984B (en) | 2021-06-21 | 2021-06-21 | Application of metal nickel encapsulated hierarchical pore ZSM-5 molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113398984A true CN113398984A (en) | 2021-09-17 |
| CN113398984B CN113398984B (en) | 2024-03-22 |
Family
ID=77681853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110685199.6A Active CN113398984B (en) | 2021-06-21 | 2021-06-21 | Application of metal nickel encapsulated hierarchical pore ZSM-5 molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113398984B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113813987A (en) * | 2021-09-30 | 2021-12-21 | 太原理工大学 | Preparation method and application of chain Ni/ZSM-5-V catalyst |
| CN114345396A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Molecular sieve in-situ packaging active component type oxygen carrier and preparation method and application thereof |
| CN115814847A (en) * | 2022-12-10 | 2023-03-21 | 南京工程学院 | Preparation method of SSZ-39 molecular sieve morphology-controllable encapsulated metal catalytic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086362A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing multilevel pore zsm-5 zeolite |
| CN109078652A (en) * | 2018-08-31 | 2018-12-25 | 中国矿业大学 | A kind of preparation method and application of the multi-stage porous ZSM-5 molecular sieve of W metal doping |
| CN109368657A (en) * | 2018-08-22 | 2019-02-22 | 中国矿业大学 | Framework metal high dispersive type multi-stage porous H-ZSM-5 molecular sieve preparation method |
| CN111250152A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Packaging method of Ni @ ZSM-5 bifunctional catalyst |
-
2021
- 2021-06-21 CN CN202110685199.6A patent/CN113398984B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086362A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing multilevel pore zsm-5 zeolite |
| CN109368657A (en) * | 2018-08-22 | 2019-02-22 | 中国矿业大学 | Framework metal high dispersive type multi-stage porous H-ZSM-5 molecular sieve preparation method |
| CN109078652A (en) * | 2018-08-31 | 2018-12-25 | 中国矿业大学 | A kind of preparation method and application of the multi-stage porous ZSM-5 molecular sieve of W metal doping |
| CN111250152A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Packaging method of Ni @ ZSM-5 bifunctional catalyst |
Non-Patent Citations (2)
| Title |
|---|
| KRISTOFFER H. RASMUSSEN ET AL.: ""Stabilization of metal nanoparticle catalysts via encapsulation in mesoporous zeolites by steam-assisted recrystallization"" * |
| 任雪宇: ""ZSM-5分子筛的孔道调控及褐煤催化热解制芳烃的研究"" * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113813987A (en) * | 2021-09-30 | 2021-12-21 | 太原理工大学 | Preparation method and application of chain Ni/ZSM-5-V catalyst |
| CN113813987B (en) * | 2021-09-30 | 2023-05-05 | 太原理工大学 | Preparation method and application of chain-shaped Ni/ZSM-5-V catalyst |
| CN114345396A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Molecular sieve in-situ packaging active component type oxygen carrier and preparation method and application thereof |
| CN115814847A (en) * | 2022-12-10 | 2023-03-21 | 南京工程学院 | Preparation method of SSZ-39 molecular sieve morphology-controllable encapsulated metal catalytic material |
| CN115814847B (en) * | 2022-12-10 | 2023-09-08 | 南京工程学院 | Preparation method of SSZ-39 molecular sieve morphology controllable encapsulated metal catalytic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113398984B (en) | 2024-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113398984A (en) | Preparation method and application of metallic nickel packaging and embedding hierarchical pore ZSM-5 molecular sieve | |
| Álvaro-Muñoz et al. | Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reaction | |
| Julian et al. | Supercritical solvothermal synthesis under reducing conditions to increase stability and durability of Mo/ZSM-5 catalysts in methane dehydroaromatization | |
| Soh et al. | Catalytic ethylene production from ethanol dehydration over non-modified and phosphoric acid modified Zeolite HY (80) catalysts | |
| Askari et al. | Rapid synthesis of SAPO-34 nanocatalyst by dry gel conversion method templated with morphline: investigating the effects of experimental parameters | |
| KR102048913B1 (en) | Zeolite and method for producing same, and cracking catalyst for paraffin | |
| Zhang et al. | Na 2 HPO 4-modified NaY nanocrystallites: efficient catalyst for acrylic acid production through lactic acid dehydration | |
| Hajfarajollah et al. | Effects of micro and nano-sized SAPO-34 and SAPO-5 catalysts on the conversion of methanol to light olefins | |
| KR101743760B1 (en) | Method for manufacturing of SSZ-13 zeolite catalyst and the SSZ-13 zeolite catalyst thereby | |
| WO2021169028A1 (en) | Method for preparing hierarchical pore zsm-5 molecular sieve and method for preparing bis-(5-formylfurfuryl)ether | |
| Pan et al. | A highly active and stable Zn@ C/HZSM-5 catalyst using Zn@ C derived from ZIF-8 as a template for conversion of glycerol to aromatics | |
| Tzeng et al. | Zn-based metal–organic frameworks as sacrificial agents for the synthesis of Zn/ZSM-5 catalysts and their applications in the aromatization of methanol | |
| CN102285669A (en) | Method for preparing SAPO-34 molecular sieve with rich Si(4Al) structures and product and application thereof | |
| JP6265354B2 (en) | Bismuth molybdate catalyst having zeolite coating layer, method for producing the same, and method for producing 1,3-butadiene using the same | |
| Baracchini et al. | Structured catalysts for the direct synthesis of dimethyl ether from synthesis gas: A comparison of core@ shell versus hybrid catalyst configuration | |
| Mhamdi et al. | Influence of the Co/Al ratio and the temperature of thermal treatment on cobalt speciation and catalytic properties of Co-ZSM-5 prepared by solid-state ion exchange | |
| Hou et al. | Highly selective synthesis of large aromatic molecules with nano-zeolite: beyond the shape selectivity effect | |
| Wang et al. | Synthesis of submicron-sized SAPO-34 as efficient catalyst for olefin generation from CH3Br | |
| Vosmerikova et al. | Conversion of dimethyl ether to liquid hydrocarbons over Zn-isomorphously substituted HZSM-5 | |
| Sumi et al. | Mg and Zn co-doped mesoporous ZSM-5 as an ideal catalyst for ethane dehydroaromatization reaction | |
| Zhao et al. | SAPO-34 crystals with nanosheet morphology synthesized by pyrophosphoric acid as new phosphorus source | |
| CN109529921B (en) | Preparation method of hierarchical pore Beta molecular sieve and Ni type catalyst for hydrogen production by ethanol steam reforming | |
| JP5131624B2 (en) | Paraffin catalytic cracking process | |
| Liu et al. | Bifunctional catalysts composed of low silicon‐content SAPO‐34 nanosheets and In2O3/ZrO2 with improved performance for CO2 hydrogenation | |
| JP2010042343A (en) | Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst |
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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cao Jingpei Inventor after: Ren Xueyu Inventor after: Zhao Xiaoyan Inventor after: Liu Tianlong Inventor after: He Zimeng Inventor before: Cao Jingpei |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |