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  • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
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  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
  • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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  • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
• • 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
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  • 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
  • C01B39/026—After-treatment
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
  • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
  • C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
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  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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  • 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

Definitions

• the present invention relates to a new process for preparing an AFX structural type zeolite.
• This new process makes it possible to carry out the synthesis of an AFX structural zeolite by conversion / transformation under hydrothermal conditions of a zeolite of structural type FAU.
• said novel process makes it possible to synthesize an AFX-structural zeolite from a FAU structural zeolite used as a source of silicon and aluminum and a specific organic or structuring molecule comprising two quaternary ammonium functions, selected from 1,5-bis (methylpiperidinium) pentane 1, 6-bis (methylpiperidinium) hexane or 1,7-bis (methylpiperidinium) heptane in its dihydroxide form.
• Said AFX structural type zeolite obtained according to the process of the invention is advantageously used as a catalyst, adsorbent or separating agent.
• Crystallized microporous materials such as zeolites or silicoaluminophosphates, are solids widely used in the petroleum industry as catalyst, catalyst support, adsorbent or separating agent. Although many microporous crystalline structures have been discovered, the refining and petrochemical industry is still searching for new zeolitic structures that have particular properties for applications such as gas purification or separation, conversion of carbon species or others.
• the AFX structural type zeolites comprise in particular the zeolite SSZ-16, and the SAPO-56 and MEAPSO-56 zeolites.
• the structural type zeolite AFX has a three-dimensional system of pores delimited by eight tetrahedra and is formed by two types of cages: gmelinite (GME cage) and a large AFT cage ( ⁇ 8.3 x 13.0 ⁇ ). Numerous methods for synthesizing AFX structural zeolites, in particular zeolite SSZ-16, are known.
• the zeolite SSZ-16 has been synthesized using nitrogenous organic species derived from 1,4-di (1-azoniabicyclo [2.2.2] octane) lower alkanes (US Patent No. 4,508,837). Chevron Research and Technology Company has prepared zeolite SSZ-16 in the presence of DABCO-C n -diquat cations, where DABCO represents 1,4-diazabicyclo [2.2.2] octane and n is 3, 4 or 5 (US Patent No. .5, 194, 235).
• SB Hong et al used the diquaternary alkylammonium ion Et6-diquat-n, where Et6-diquat represents N ', N'-bis-triethylpentanediammonium and n is 5, as structural agents for the synthesis of zeolite SSZ-16. (Micropor, Mesopor, Mat., 60 (2003) 237-249). Mention may also be made of the use of 1,3-bis (adamantyl) imidazolium cations as a structuring agent for the preparation of AFX structural type zeolites (RHArcher et al in Microp, Mesopor, Mat., 130 (2010) 255-2265.
• Chevron USA (WO2017 / 200607 A1) proposes to carry out the synthesis of a zeolite SSZ-16 using the dications: 1, 1 '- (1,4-cyclohexylenedimethylene) bis [1-methylpiperidinium], 1, 1' - ( 1,4-cyclohexylenedimethylene) bis [1-methylpyrrolidinium], 1,1- (1,4-cyclohexylenedimethylene) bis [1-ethylpyrrolidinium].
• the invention relates to a method for preparing an AFX structural zeolite comprising at least the following steps:
• a zeolite of structural type FAU having a molar ratio S10 2 (FAU AI 2 O 3 (FAUJ between 6.00 and 200, inclusive limits, of a nitrogenous organic compound R, R being selected from 1,5-bis (methylpiperidinium) pentane dihydroxide, 1,6-bis (methylpiperidinium) hexane dihydroxide, or dihydroxide of
• S1O 2 designates the amount of S1O 2 provided by the FAU zeolite
• AI 2 O 3 designates the quantity of AI 2 O 3 supplied by the FAU zeolite, until obtaining a homogeneous precursor gel
• step ii) the hydrothermal treatment of said precursor gel obtained after step i) at a temperature between 120 ° C and 220 ° C for a period of between 12 hours and 15 days.
• R is 1,6-bis (methylpiperidinium) hexane dihydroxide.
• the molar ratio S102 / Al2O3 of the zeolite AFX obtained is between 4.00 and 100, preferably between 6.00 and 80, inclusive.
• M is sodium.
• the source of at least one alkali metal and / or alkaline earth metal M is sodium hydroxide.
• the reaction mixture of step i) may comprise at least one additional source of an oxide XO2, X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, so that the molar ratio XO2 / S102 (FAUJ is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01 inclusive), S1O2 content (FAUJ in said ratio being the content provided by the zeolite of structural type FAU.
• X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, so that the molar ratio XO2 / S102 (FAUJ is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01 inclusive), S1O2 content (FAUJ in said ratio being the content provided by the zeolite of structural type FAU.
• reaction mixture of step i) can have the following molar composition:
• R / (X0 2 + S1O2 (FAU)) between 0.01 to 0.6, preferably between 0.05 and 0.5 M 2 / n0 / (X0 2 + SiO 2 (FAU)) between 0.005 to 0.45, preferably between 0.05 and 0.25 inclusive.
• the reaction mixture of step i) may comprise at least one additional source of an oxide Y 2 O 3 , Y being one or more trivalent element (s) chosen from the group formed by the following elements: aluminum, boron, gallium, so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAUJ is between 0.001 and 10, and preferably between 0.001 and 8, limits included, the content of AI 2 O 3 (FAUJ in said ratio being the content provided by the zeolite of structural type FAU.
• the reaction mixture of step i) preferably has the following molar composition:
• H2O / S1O2 (FAU) between 1 and 100, preferably between 5 and 60
• R / SiO 2 (FAU) of from 0.01 to 0.6, preferably from 0.05 to 0.5
• S1O 2 (FAU) being the amount of S1O 2 provided by the zeolite FAU
• Al 2 O 3 (FAU) being the amount of Al 2 O 3 provided by the zeolite FAU.
• Y is aluminum
• reaction mixture of step i) may contain: at least one additional source of an oxide XO 2
• the FAU zeolite representing between 5 and 95% by weight, preferably between 50 and 95% by weight, very preferably between 60 and 90% by weight, and even more preferably between 65 and 85% by weight relative to the total amount of trivalent and tetravalent elements SiO 2 (FAU), XO 2 , Al 2 O 3 (FAU) and Y 2 O 3 of the reaction mixture, and the reaction mixture having the following molar composition: (XO 2 + SiO 2 (FAU)) / (AI203 (FAU) + Y 2 O 3) between 6.00 and 200, preferably between 6.00 and 100
• Fi 2 0 / (X0 2 + Si0 2 (FAU)) between 1 and 100, preferably between 5 and 60
• R / (X0 2 + S1O2 (FAU)) between 0.01 to 0.6, preferably between 0.05 and 0.5
• M 2 / n 0 / (X0 2 + S1O 2 (FAU)) between 0.005 to 0.45, preferably between 0.05 and 0.25, inclusive.
• the precursor gel obtained at the end of step i) has a molar ratio of the total amount expressed as tetravalent element oxides to the total amount expressed as trivalent oxides between 6.00 and 100. , terminals included.
• the zeolite of structural type FAU has a molar ratio S102 / Al2O3 of between 6.00 and 100 inclusive.
• Crystalline seeds of an AFX structural zeolite can be added to the reaction mixture of step i), preferably in an amount of between 0.01 and 10% by weight relative to the total mass of the sources of the tetravalent and trivalent elements. in anhydrous form present in said mixture, said seed crystals not being taken into account in the total mass of the sources of the tetravalent and trivalent elements.
• Step i) may comprise a step of maturing the reaction mixture at a temperature between 20 and 100 ° C, with or without stirring, for a period of between 30 minutes and 48 hours.
• the hydrothermal treatment of step ii) can be carried out under autogenous pressure at a temperature of between 120 ° C. and 220 ° C., preferably between 150 ° C. and 195 ° C., for a period of between 12 hours and 12 days. preferably between 12 hours and 8 days.
• the solid phase obtained at the end of stage ii) can be filtered, washed and dried at a temperature of between 20 and 150 ° C., preferably between 60 and 100 ° C., for a period of between 5 and 24 hours. hours to obtain a dried zeolite.
• the dried zeolite can then be calcined at a temperature between 450 and 700 ° C for a period of between 2 and 20 hours, the calcination may be preceded by a gradual temperature rise.
• the invention also relates to an AFX structural zeolite of S1O2 / Al2O3 ratio of between 4.00 and 100 inclusive, which can be obtained by the preparation method described above.
• the invention also relates to an AFX structural zeolite of S1O2 / Al2O3 ratio of between 4.00 and 100 inclusive, which can be obtained by the previously described and calcined preparation process, for which the average values of the dh w and relative intensities measured on an X-ray diffraction pattern are as follows:
• FIG. 1 represents the chemical formulas of the nitrogenous organic compounds that may be chosen as structuring agent used in the synthesis process according to the invention.
• FIG. 2 represents the X-ray diffraction pattern of the AFX zeolite obtained according to Example 7.
• FIG. 3 represents a Scanning Electron Microscope (SEM) shot of the AFX zeolite obtained according to Example 7.
• the subject of the present invention is a new process for the preparation of a zeolite of AFX structural type, by conversion / transformation under hydrothermal conditions of a zeolite of structural type FAU, in the presence of a specific nitrogenous or structuring organic compound chosen from the following compounds
• a zeolite of structural type FAU having a molar ratio S1O2 (FAU AI2O3 (FAUJ greater than or equal to 6.00 and less than or equal to 200, used as a source of silicon and aluminum, in the presence or absence of an additional supply, within said mixture, of at least one source of at least one tetravalent element X0 2 , and or at least one source of at least one element trivalent Y 2 O 3 , leads to the production of a precursor gel of a zeolite AFX structural type having a molar ratio of the total amount expressed as tetravalent element oxides on the total amount expressed as oxides of trivalent elements included between 6.00 and 200, then to the production of a zeolite of structural type AFX of very high purity, the total amount of tetravalent element representing the sum of the content
• any other crystallized or amorphous phase is generally and very preferably absent from the crystalline solid consisting of the zeolite of AFX structural type obtained at the end of the preparation process.
• the AFX zeolite obtained has a ratio SiO 2 / Al 2 O 3 of between 4.00 and 100, preferably between 6.00 and 80, inclusive.
• the subject of the present invention is more specifically a novel process for preparing an AFX structural zeolite comprising at least the following steps:
• S1O 2 (FAUJ being the amount of S1O 2 provided by the zeolite FAU
• Al 2 O 3 (FAU) being the amount of Al 2 O 3 provided by the zeolite FAU
• HI 2 0 the molar amount of water present in the reaction mixture
• R is the molar amount of said nitrogenous organic compound
• M 2 / n 0 the molar amount expressed in oxide form of M 2 / n O by the source of alkali metal and / or alkaline earth metal
• M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and a mixture of at least two of these metals very preferably M is sodium, step i) being conducted for a time to obtain a homogeneous mixture called precursor gel;
• step ii) the hydrothermal treatment of said precursor gel obtained after step i) at a temperature between 120 ° C and 220 ° C for a period of between 12 hours and 15 days, until said zeolite of AFX structural type is formed.
• An advantage of the present invention is therefore to provide a new preparation process for the formation of a zeolite of AFX structural type of very high purity from a zeolite of structural type FAU, said method being implemented in the presence of a specific organic structurant chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, the dihydroxide of
• Another advantage of the present invention is to enable the preparation of a gel precursor of a structural AFX type zeolite having a molar ratio S1O 2 / Al 2 O 3 the same, greater or less than 2 molar ratio S1O (FAU Al 2 O 3 (FAUJ of zeolite of structural type FAU starting.
• the starting structural type zeolite FAU having a molar ratio Si0 2 / Al 2 O 3 of between 6 and 200, inclusive limits can be obtained by any method known to those skilled in the art such as, for example, by treatment with steam (steaming) and acid washes on a zeolite of structural type FAU of molar ratio SiO 2 / Al 2 O 3 less than 6.00.
• the sources of FAU with a S1O2 / Al2O3 ratio greater than or equal to 6.00 the commercial zeolites CBV712, CBV720, CBV760 and CBV780 produced by Zeolyst, the commercial zeolites HSZ-350HUA, HSZ-360HUA and HSZ-385HUA produced by TOSOH.
• the preparation process according to the invention therefore allows to adjust the ratio S1O 2 / Al 2 O 3 precursor gel containing a zeolite with structure type FAU depending on the zeolite chosen FAU structural type and the additional input or not within the reaction mixture of at least one source of at least one tetravalent element XO 2 and / or at least one source of at least one trivalent element Y 2 O 3 .
• Step i) comprises the mixing in an aqueous medium of a zeolite of structural type FAU having an SiO 2 molar ratio (FAU Al 2 O 3 (FAUJ between 6 and 200, inclusive limits), of a nitrogenous organic compound R, R being 1,5-bis (methylpiperidinium) pentane dihydroxide, 1,6-bis (methylpiperidinium) hexane dihydroxide, or dihydroxide of
• reaction mixture having the following molar composition:
• M 2 / n 0 / (SiO 2 (FAU) ) between 0.005 to 0.45, preferably between 0.05 and 0.25 in which S102 (FAUJ is the amount of S102 provided by the FAU zeolite, and Al2O3 (FAU ) is the amount of Al 2 O 3 provided by the FAU zeolite, and M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture of at least two of these metals, very preferably M is sodium.
• S102 FAUJ is the amount of S102 provided by the FAU zeolite
• Al2O3 (FAU ) is the amount of Al 2 O 3 provided by the FAU zeolite
• M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture of at least two of these metals, very preferably M is sodium.
• the reaction mixture of step i) also comprises at least one additional source of an oxide XO 2 so that the molar ratio XO 2 / SiO 2 (FAU) is between 0.001 and 1, the mixture having advantageously the following molar composition: (XO2 + S1O2 (FAU)) / AI203 (FAU) between 6.00 and 200, preferably between 6.00 and 100
• R / (X0 2 + Si0 2 ( FAU ) ) between 0.01 to 0.6, preferably between 0.05 and 0.5 M 2 / n 0 / (X0 2 + S 1O 2 (FAU)) between 0.005 to 0.45, preferably between 0.05 and
• X is one or more tetravalent element (s) selected from the group consisting of silicon, germanium, titanium, preferably X is silicon, S10 2 (FAU) being the amount of S1O 2 provided by the zeolite FAU, and Al 2 O 3 (FAU) being the amount of Al 2 O 3 provided by the zeolite FAU, R being the dihydroxide of 1, 5-bis (methylpiperidinium) pentane, the dihydroxide of
• M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture at least two of these metals, very preferably M is sodium.
• the reaction mixture of step i) also comprises at least one additional source of a Y 2 O 3 oxide so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAU) is between 0.001 and 10, the mixture advantageously having the following molar composition:
• R / S1O2 (FAU) between 0.01 to 0.6, preferably between 0.05 and 0.5
• M 2 / n 0 / SiO 2 (FAU) between 0.005 to 0.45, preferably between 0.05 and 0.25 in which Y is one or more trivalent element (s) chosen from group consisting of the following elements: aluminum, boron, gallium, preferably Y is aluminum, S1O 2 (FAU) is the amount of S1O 2 provided by the FAU zeolite and Al 2 O 3 (FAU) is the amount of AI 2 O 3 provided by the zeolite FAU, R being the dihydroxide of 1,5-bis (methylpiperidinium) pentane, the dihydroxide of 1,6-bis (methylpiperidinium) hexane or the dihydroxide of 1, 7-bis (methylpiperidinium) heptane, and M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture of at least two of these metals, very preferably M is sodium.
• Y is
• the reaction mixture of step i) contains a percentage between 5 and 95% by weight, preferably between 50 and 95% by weight, very preferably between 60 and 90% by weight and still most preferred between 65 and 85% by weight of a zeolite of structural type FAU with respect to the total amount of the sources of the trivalent and tetravalent elements of the mixture and also comprises at least one additional source of an oxide XO 2 and at least one additional source an oxide Y 2 O 3 , the reaction mixture having the following molar composition:
• X is one or more tetravalent element (s) selected from the group consisting of silicon, germanium, titanium, preferably X is silicon
• Y is one or more element (s) trivalent (s) chosen from the group formed by the following elements: aluminum, boron, gallium, preferably aluminum, Si0 2 (FAU) being the amount of SiO 2 provided by the zeolite FAU, and AI 2 0 3 (FAU) being the amount of AI 2 O 3 provided by the FAU zeolite, R being the dihydroxide of
• Step i) makes it possible to obtain a homogeneous precursor gel.
• Step ii) comprises a hydrothermal treatment of said precursor gel obtained at the end of step i) which is carried out at a temperature of between 120 ° C. and 220 ° C. for a duration of between 12 hours and 15 days, up to said structural zeolite AFX crystallizes.
• a zeolite of structural type FAU having a molar ratio S102 (FAU Al2O3 (FAUJ between 6 and 200 inclusive, preferably between 6.00 and 100 inclusive) is incorporated into the reaction mixture.
• FAU Al2O3 FAUJ between 6 and 200 inclusive, preferably between 6.00 and 100 inclusive
• step (i) as a source of silicon and aluminum elements.
• R is a nitrogenous organic compound chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, the dihydroxide of
• the anion associated with the quaternary ammonium cations present in the structuring organic species for the synthesis of an AFX structural zeolite according to the invention is the hydroxide anion.
• At least one source of at least one alkali metal and / or alkaline earth metal M of valence n is used in the reaction mixture of step i), n being an integer greater than or equal to at 1, M being preferably selected from lithium, potassium, sodium, magnesium and calcium and the mixture of at least two of these metals. Most preferably, M is sodium.
• the source of at least one alkali metal and / or alkaline earth metal M is sodium hydroxide.
• X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, and preferably X is silicon, so that the molar ratio XO 2 / S 10 2 (FAUJ is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and and 0.01, the content of Si0 2 (FAU) in said ratio being the content provided by the
• the addition of at least one additional source of an oxide XO 2 makes it possible in particular to adjust the ratio XO 2 / Y 2 O 3 of the precursor gel of a zeolite of structural type AFX obtained at the end of the step i).
• the source (s) of said tetravalent element (s) may be any compound comprising element X and capable of releasing this element in aqueous solution in reactive form.
• Ti (EtO) 4 is advantageously used as a source of titanium.
• the silicon source may be any of the sources commonly used for the synthesis of zeolites, for example powdered silica, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS).
• zeolites for example powdered silica, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS).
• TEOS tetraethoxysilane
• precipitated silicas especially those obtained by precipitation from an alkali metal silicate solution, pyrogenic silicas, for example "CAB-O-SIL" and silica gels.
• Colloidal silicas having different particle sizes for example having a mean equivalent diameter of between 10 and 15 nm or between 40 and 50 nm, such as those sold under registered trademarks such as "LUDOX", may be used.
• the silicon source is CAB-O-SIL.
• Y is aluminum, so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAUJ is between 0.001 and 10, and preferably between 0.001 and 8, the content of Al 2 O 3 (FAU)). in said ratio being the content provided by the zeolite of structural type FAU.
• the addition of at least one additional source of a Y 2 O 3 oxide therefore makes it possible to adjust the XO 2 / Y 2 O 3 ratio of the precursor gel of an AFX structural type zeolite obtained at the end of the step i).
• the source (s) of said trivalent element (s) Y may be any compound comprising element Y and capable of releasing this element in aqueous solution in reactive form.
• Element Y may be incorporated into the mixture in an oxidized form YO b with 1 ⁇ b ⁇ 3 (b being an integer or a rational number) or in any other form.
• the aluminum source is preferably aluminum hydroxide or an aluminum salt, for example chloride, nitrate, or sulphate, sodium aluminate, an aluminum alkoxide, or alumina proper, preferably in hydrated or hydratable form, such as for example colloidal alumina, pseudoboehmite, gamma alumina or alpha or beta trihydrate. It is also possible to use mixtures of the sources mentioned above.
• Step (i) of the process according to the invention consists in preparing an aqueous reaction mixture containing a zeolite of structural type FAU, optionally a source of an oxide XO 2 OR a source of a oxide Y 2 O 3 , at least one nitrogen-containing organic compound R, R being chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, 1,6-bis (methylpiperidinium) hexane dihydroxide or 1,7-bis (methylpiperidinium) heptane dihydroxide; in the presence of at least one source of one or more alkali metal (s) and / or alkaline earth metal, to obtain a precursor gel of an AFX structural type zeolite.
• the amounts of said reagents are adjusted as indicated above so as to confer on this gel a composition allowing the crystallization of a zeolite of AFX structural type.
• the crystalline seeds are generally added in a proportion of between 0.01 and 10% of the total anhydrous mass of the sources of said tetravalent (s) and trivalent (s) element (s) used in the reaction mixture, said crystalline seeds not being not taken into account in the total mass of the sources of the tetravalent and trivalent elements. Said seeds are also not taken into account to determine the composition of the reaction mixture and / or gel, defined further, that is to say in the determination of the different molar ratios of the composition of the reaction mixture.
• the mixing step i) is carried out until a homogeneous mixture is obtained, preferably for a period greater than or equal to 15 minutes, preferably with stirring by any system known to those skilled in the art at low or high shear rate.
• the precursor gel obtained at the end of step i) is subjected to a hydrothermal treatment, preferably carried out at a temperature of between 120 ° C. and 220 ° C. for a period of between 12 hours and 15 days, until said zeolite AFX structural type is formed.
• the precursor gel is advantageously placed under hydrothermal conditions under an autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature of preferably between 120 ° C. and 220 ° C., preferably between 150 ° C. and 195 ° C, until the complete crystallization of a zeolite AFX structural type.
• the reaction is generally carried out with stirring or without stirring, preferably with stirring.
• stirring system can be used any system known to those skilled in the art, for example, blades inclined with counterpanes, stirring turbines, screws Archimedes.
• loss on ignition of said zeolite AFX structural type obtained after drying and before calcination is generally between 5 and 15% by weight.
• loss of ignition on fire is defined as the percentage of mass loss suffered by a solid compound, a mixture of solid compounds or a paste, preferably in the case of the present invention by said prepared AFX zeolite, during a treatment. heat at 1000 ° C for 2 hours, in a static furnace (muffle furnace type), with respect to the mass of the solid compound, the mixture of solid compounds or the initial paste (e), preferably in the case of the the present invention with respect to the dried AFX zeolite mass tested.
• the loss on ignition generally corresponds to the loss of solvent (such as water) contained in the solids, but also to the elimination of organic compounds contained in the mineral solid constituents.
• the zeolite of AFX structural type obtained at the end of the calcination step is devoid of any organic species and in particular of the organic template R.
• the X-ray diffraction pattern of the AFX structural type crystallized solid according to the invention comprises at least the lines at the dhki values given in Table 1.
• Table 1 the average values of inter-reticular distances in Angstroms (A) have been indicated.
• Each of these values shall be assigned the measurement error A (d hki ) between ⁇ 0,6 and ⁇ 0,01 A.
• Table 1 Mean values of dh w and relative intensities measured on an X-ray diffraction diagram of crystallized solid AFX calcined structural solid
• Said hydrogen form can be obtained by carrying out an ion exchange with an acid, in particular a strong mineral acid such as hydrochloric, sulfuric or nitric acid, or with a compound such as ammonium chloride, sulphate or nitrate .
• the ion exchange can be carried out by suspending said AFX structural type zeolite in one or more times with the ion exchange solution.
• Said zeolite can be calcined before or after the ion exchange, or between two ion exchange steps. The zeolite is preferably calcined prior to the ion exchange, to remove any organic substance included in the zeolite porosity, as ion exchange is facilitated.
• Example 1 Preparation of 1,6-bis (methylpiperidinium) hexane dihydroxide (structuring R)
• the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C. maintained during 2 hours, a rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours and a return to room temperature.
• the crystallized product obtained is filtered off, washed with deionized water and then dried overnight at 100 ° C.
• the loss on ignition of the dried solid is 9.5%.
• the solid is then introduced into a muffle furnace where a calcination step is carried out: the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C. maintained during 2 hours, a rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours and a return to room temperature
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural zeolite with a purity greater than 99% by weight.
• PAF 6.63%) were mixed with 2.204 g of an aqueous solution of 1,6-bis (methylpiperidinium) hexane dihydroxide (21.56% by weight) prepared according to Example 1. 3.164 g of water Deionized are added to the above mixture, the resulting preparation is stirred for 10 minutes. 600 mg of an aqueous solution containing 20% by weight of sodium hydroxide (98% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for half an hour.
• the molar composition of the precursor gel is as follows: 1 SiO 2 : 0.03 Al 2 O 3 : 0.17 R: 0.17 Na 2 0: 34 Fl 2 0, ie a SiO 2 / Al 2 O 3 ratio of 33.33.
• the precursor gel is then transferred, after homogenization, into an autoclave.
• the autoclave is closed and heated for 24 hours at 180 ° C with stirring at 35 rpm with a spit system.
• the crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C.
• the loss on ignition of the dried solid is 10%.
• the solid is then introduced into a muffle furnace where a calcination step is carried out: the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C.
• the molar composition of the precursor gel is as follows: 1 SiO 2: 0.025 Al 2 O 3 : 0.17 R: 0.16 Na 2 O: 36 HI 2 0, ie a SiO 2 / Al 2 O 3 ratio of 40.
• the precursor gel is then transferred, after homogenization in an autoclave. The autoclave is closed and then heated for 4 days at 180 ° C. with stirring at 35 rpm with a spit-roaster system. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C.
• a zeolite of AFX structural type prepared according to Example 10 In order to promote the formation of an AFX structural type zeolite, 571 mg of seeds (10% relative to the mass of CBV720 zeolite) of a zeolite of AFX structural type prepared according to Example 10 are added to the mixture of synthesis and stirred for 5 minutes. 7.117 g of an aqueous solution containing 20% by weight of sodium hydroxide (98% by weight, Aldrich) is added to the synthesis mixture and stirred for 15 minutes.
• the precursor gel is then transferred, after homogenization in a 160 mL stainless steel reactor equipped with a stirring system with four inclined blades
• the reactor is closed and then heated for 30 hours at 180 ° C. with stirring at 250-300 rpm
• the crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C.
• the loss on ignition of the dried solid is 9.6%.
• the calcination cycle comprises a rise of 1.5 ° C / min in temperature up to 200 ° C, a plateau at 200 ° C maintained for 2 hours, a rise from 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours then a return to the ambient temperature.
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural zeolite with a purity greater than 99% by weight.
• the product has a SiO 2 / Al 2 O 3 molar ratio of 12.85 as determined by X-ray fluorescence.
• the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C. held for 2 hours, rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours and a return to ambient temperature.
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural zeolite, with a purity greater than 99% by weight.
• the X-ray diffraction pattern performed on the calcined solid is given in FIG. 2.
• the scanning electron microscopy (SEM) image on the calcined AFX structural type solid is given in FIG. product has a S1O2 / Al2O3 molar ratio of 13.26 as determined by X-ray fluorescence.
• the loss on ignition of the dried solid is 9.5%
• the solid is then introduced into a muffle furnace where a calcination step is carried out: the cycle of ca
• the invention comprises a rise of 1.5 ° C / min in temperature up to 200 ° C, a plateau at 200 ° C maintained for 2 hours, a rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours and a return to room temperature.
• amorphous gel of aluminum hydroxide (Al (OFi) 3 amorphous gel, 58.55% by weight of Al 2 O 3 , Merck), corresponding to a molar ratio (Al 2 O 3 (amorphous gel) / AI 2 O 3 (FAU) of 6.68 are incorporated in the synthesis mixture, which is stirred for half an hour to evaporate the solvent until the desired precursor gel composition is obtained; ie a molar composition of the following mixture: 1 SiO 2: 0.05 Al 2 O 3 : 0.17 R: 0.083 Na 2 0: 34 hi 2 0, ie a SiO 2 / Al 2 O 3 ratio of 20.
• the calcination cycle comprises a rise of 1.5 ° C / min in temperature up to 200 ° C, a plateau at 200 ° C maintained for 2 hours, a rise from 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours then a return to the ambient temperature.
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural type zeolite, with a purity greater than 99% by weight.
• the product has an SiO 2 / Al 2 O 3 molar ratio of 12.6 as determined by X-ray fluorescence.
• EXAMPLE 10 Preparation of an AFX Structural Type Zeolite According to the Invention
• amorphous aluminum hydroxide gel Al (OH) 3 amorphous gel, 58.55% by weight of Al 2 O 3 , Merck
• Al 2 O 3 ( amorphous gel) / Al 2 O 3 (FAU) amorphous aluminum hydroxide gel
• the molar composition of the precursor gel is as follows: 1 SiO 2 : 0.05 Al 2 O 3 : 0.17 R: 0.08 Na 2 O: 34 H 2 O, ie a SiO 2 / Al 2 O 3 ratio of 20.
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural zeolite with a purity greater than 99% by weight.
• the product has an SiO 2 / Al 2 O 3 molar ratio of 18.5 as determined by X-ray fluorescence.
• EXAMPLE 11 Preparation of an AFX Structural Type Zeolite According to the Invention
• amorphous gel of aluminum hydroxide (Al (OH) 3 amorphous gel, 58.55% by weight of Al 2 O 3 , Merck) are incorporated and the synthesis gel is stirred for 15 minutes.
• 180 mg of Cab-O-Sil M5 smoked silica (100% by weight SiO 2 , Cabot) were incorporated in the synthesis mixture which is stirred for half an hour.
• the molar composition of the precursor gel is as follows: 1 SiO 2 : 0.05 Al 2 O 3 : 0.167 R: 0.083 Na 2 O: 36.7H 2 O, ie a SiO 2 / Al 2 O 3 ratio of 20.
• the reaction mixture thus contains 74% by weight of anhydrous FAU zeolite relative to the total anhydrous mass of the sources of the trivalent and tetravalent elements of the mixture.
• the precursor gel is then transferred, after homogenization, into an autoclave.
• the autoclave is closed and then heated for 24 hours at 170 ° C with stirring at 35 rpm with a spit system.
• the crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The loss on ignition of the dried solid is 9.9%.
• the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural type zeolite, with a purity greater than 99% by weight.
• the product has an SiO 2 / Al 2 O 3 molar ratio of 14.8 as determined by X-ray fluorescence.
• the molar composition of the precursor gel is as follows: 1 SiO 2: 0.05 Al 2 O 3: 0.167 R: 0.093 Na 2 O: 36.7 H 2 O, ie a ratio SiO 2 / Al 2 O 3 of 20.
• the precursor gel is then transferred, after homogenization, in a 25 liter stainless steel reactor.
• the calcined solid product was analyzed by diffraction of X-ray and identified as consisting of a zeolite AFX structural type, with a purity greater than 99% by weight.
• the product has an SiO 2 / Al 2 O 3 molar ratio of 14 as determined by X-ray fluorescence.

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