FR3059916B1 - PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS - Google Patents

PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS Download PDF

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Publication number
FR3059916B1
FR3059916B1 FR1662461A FR1662461A FR3059916B1 FR 3059916 B1 FR3059916 B1 FR 3059916B1 FR 1662461 A FR1662461 A FR 1662461A FR 1662461 A FR1662461 A FR 1662461A FR 3059916 B1 FR3059916 B1 FR 3059916B1
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France
Prior art keywords
metal
boxes
hollow nano
crystals
walls
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Expired - Fee Related
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FR1662461A
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French (fr)
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FR3059916A1 (en
Inventor
Ana Rita Morgado Prates
Alain Tuel
David Farrusseng
Nicolas Bats
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority to FR1662461A priority Critical patent/FR3059916B1/en
Priority to PCT/EP2017/082085 priority patent/WO2018108750A1/en
Publication of FR3059916A1 publication Critical patent/FR3059916A1/en
Application granted granted Critical
Publication of FR3059916B1 publication Critical patent/FR3059916B1/en
Expired - Fee Related legal-status Critical Current
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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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • 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
    • 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
    • B01J2229/60—Synthesis on support
    • B01J2229/62—Synthesis on support in or on other molecular sieves
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

On décrit un procédé de préparation du matériau comprenant au moins une zéolithe Beta dont les cristaux se présentent sous la forme de nano boites creuses, et au moins une ou plusieurs nanoparticule(s) métallique(s), la ou lesdites nanoparticule(s) métallique(s) étant située(s) à la fois sur la surface interne desdits nano boites et à l'intérieur des parois desdites nano boites creuses, le procédé comprenant au moins les étapes suivantes : i) la synthèse d'un zincosilicate microporeux CIT-6 de type structural *BEA ii) l'introduction de nanoparticules métalliques dans les cristaux de CIT-6 obtenues à l'issue de l'étape i), iii) le mélange dans une solution aqueuse des cristaux de CIT-6 obtenus à l'étape ii) avec au moins une source d'un oxyde XO2, au moins une source d'un oxyde Y2O3, et au moins une source d'au moins un métal alcalin et/ou alcalino-terreux M de valence n, n étant un entier supérieur ou égal à 1 pour obtenir un gel, le traitement hydrothermal du gel obtenu à l'issue de l'étape iii), à une température comprise entre 110°C et 180°C, de préférence entre130°C et 60° C, pendant une durée comprise entre 1 jours et 5 jours, de préférence entre 1 et 3 jours, pour synthétiser une zéolithe beta dont les cristaux se présentent sous la forme de nano boites creuses, et dans laquelle la ou lesdites nanoparticule(s) métallique(s) sont située(s) à la fois sur la surface interne des nano boites creuses et à l'intérieur de la cavité desdites nano boites creuses.A process for preparing the material comprising at least one Beta zeolite whose crystals are in the form of hollow nano-boxes, and at least one or more metallic nanoparticles, said nanoparticle (s) metal (s) being located at the same time on the inner surface of said nano boxes and inside the walls of said hollow nano boxes, the process comprising at least the following steps: i) the synthesis of a microporous zinc silicate CIT- 6 of structural type * BEA ii) the introduction of metal nanoparticles in the CIT-6 crystals obtained at the end of step i), iii) the mixing in an aqueous solution of the CIT-6 crystals obtained at the end of step ii) with at least one source of an oxide XO2, at least one source of a oxide Y2O3, and at least one source of at least one alkali metal and / or alkaline earth metal M of valence n, n being an integer greater than or equal to 1 to obtain a gel, the hydrothermal treatment gel obtained at the end of step iii), at a temperature of between 110 ° C. and 180 ° C., preferably between 130 ° C. and 60 ° C., for a duration of between 1 days and 5 days, preferably between 1 and 3 days, to synthesize a beta zeolite whose crystals are in the form of hollow nano boxes, and wherein the one or more metal nanoparticles are located on the inner surface at the same time hollow nano boxes and inside the cavity of said hollow nano boxes.

FR1662461A 2016-12-14 2016-12-14 PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS Expired - Fee Related FR3059916B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FR1662461A FR3059916B1 (en) 2016-12-14 2016-12-14 PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS
PCT/EP2017/082085 WO2018108750A1 (en) 2016-12-14 2017-12-08 Method for producing crystals of zeolite beta in the form of hollow boxes containing a metal on the inner surface thereof and in the walls thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1662461 2016-12-14
FR1662461A FR3059916B1 (en) 2016-12-14 2016-12-14 PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS

Publications (2)

Publication Number Publication Date
FR3059916A1 FR3059916A1 (en) 2018-06-15
FR3059916B1 true FR3059916B1 (en) 2019-05-10

Family

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FR1662461A Expired - Fee Related FR3059916B1 (en) 2016-12-14 2016-12-14 PROCESS FOR THE PREPARATION OF ZEOLITHE BETA CRYSTALS IN THE FORM OF A HOLLOW BOX CONTAINING A METAL ON ITS INTERNAL SURFACE AND IN ITS WALLS

Country Status (2)

Country Link
FR (1) FR3059916B1 (en)
WO (1) WO2018108750A1 (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010097108A1 (en) * 2009-02-27 2010-09-02 Haldor Topsøe A/S Process for the preparation of hybrid zeolite or zeolite-like materials
US9938157B2 (en) * 2014-07-23 2018-04-10 Chevron U.S.A. Inc. Interzeolite transformation and metal encapsulation in the absence of an SDA

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Publication number Publication date
FR3059916A1 (en) 2018-06-15
WO2018108750A1 (en) 2018-06-21

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