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    • 专利摘要:
    A novel process for preparing a microporous crystalline solid, referred to as microporous solid IZM-2 or zeolite IZM-2, is described. This new process consists in carrying out the synthesis of zeolite IZM-2 by conversion / transformation under hydrothermal conditions of a zeolite of structural type FAU in a fluorinated medium. In particular, said new process consists in carrying out the synthesis of a zeolite IZM-2 in a fluorinated medium, from a zeolite of structural type FAU used as a source of silicon and aluminum and a specific organic or structuring molecule comprising two quaternary ammonium functions, 1,6-bis (methylpiperidinium) hexane dihydroxide.
    公开号:FR3064261A1
    申请号:FR1752472
    申请日:2017-03-24
    公开日:2018-09-28
    发明作者:Raquel MARTINEZ FRANCO；Nicolas Bats
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to a new process for the preparation of a microporous crystalline solid, called the microporous solid IZM-2 or zeolite IZM-2. This new process consists in carrying out the synthesis of the IZM-2 zeolite by conversion / transformation under hydrothermal conditions of a zeolite of structural type FAU. In particular, said new process consists in carrying out the synthesis of an IZM-2 zeolite in a fluorinated medium, from a zeolite of FAU structural type used as a source of silicon and aluminum and of a specific organic or structuring molecule comprising two quaternary ammonium functions, 1,6-bis (methylpiperidinium) hexane dihydroxide. Said IZM-2 microporous solid obtained according to the process of the invention advantageously finds its application as a catalyst, adsorbent or separation agent.
    Prior art
    Microporous crystallized materials, such as zeolites or silicoaluminophosphates, are solids widely used in the petroleum industry as a catalyst, catalyst support, adsorbent or separation agent. Although many microporous crystal structures have been discovered, the refining and petrochemical industry is always looking for new zeolitic structures which have particular properties for applications such as purification or separation of gases, conversion of carbonaceous or other species.
    The IZM-2 zeolite is a solid with an unknown structure. Model reactions have been used (meta-xylene isomerization and disproportionation and hydrocracking isomerization of n-decane) with the objective of predicting the topology of the microporous material IZM-2 (Fecant et al. In J. Catal., 20, ( 2013) 20-29). The results obtained for these reactions suggest that the structure of the IZM2 material consists of two types of pore size (10-MR and 12-MR).
    The IZM-2 zeolite has been synthesized in its aluminosilicate form (Fecant et al. US8361435 B2) and in its purely silicic form (Li et al. In Microporous Mesoporous Mater., 237 (2017) 222-227), using the quaternary ammonium ion 1,6-bis (methylpiperidinium) hexane as a structuring agent, in its hydroxide and bromide form. As far as our knowledge reaches, the IZM-2 zeolite was carried out using hydroxide anions as a mineralizing agent.
    Typically, zeolites are prepared by hydrothermal treatment of an aqueous gel containing a source of amorphous silicon and aluminum, a mineralizing agent and a structuring agent (Cundy et al. In Microporous Mesoporous Mater., 82 (2005) 1). Recently, a new zeolite synthesis procedure has been described. This makes it possible to prepare zeolitic structures by hydrothermal synthesis using as reagent source at least one zeolitic structure, which will be transformed into another zeolite during the synthesis process. Sano et al. in J.Jpn.Pet.Inst., 56 (2013) 183-197 proposes to carry out the synthesis of a zeolite of structural type BEA, RUT, CHA, LEV from a zeolite of structural type FAU using it as a molecule organic TEAOH (tetraethyl ammonium hydroxide), TMAOH (tetra methyl ammonium hydroxide), BTMAOH (benzyl triethylammonium hydroxide), Cholite (choline hydroxy), respectively; Shi et al. in Microporous Mesoporous Mater., 200 (2014) 269-278 proposes to carry out the synthesis of a zeolite of structural type MWW from a zeolite of structural type FAU using it as organic molecule HMI (hexamethyleneimine); Goel et al. in Chem. Mater., 27 (2015) 2056-2066 proposes to carry out the synthesis of a zeolite of structural type MFI from a zeolite of structural type FAU and also of a zeolite of structural type BEA using it as organic molecule TPABr ( tetrapropylammonium bromide).
    As regards ΓΙΖΜ-2, the only known methods of its preparation consist in carrying out a hydrothermal treatment of an aqueous gel containing a source of amorphous silicon and aluminum, an alkaline earth metal (Na2O) and a structuring agent (1, 6-bis (methylpiperidinium) hexane).
    The present invention relates to a new process for the preparation of an IZM-2 zeolite, by conversion / transformation under hydrothermal conditions of a zeolite of structural type FAU, in the presence of a specific nitrogenous organic or structuring compound, 1, 6-bis (methylpiperidinium) hexane in its dihydroxide form, and in the presence for the first time of at least one source of at least one fluoride anion in the synthesis of this zeolite.
    In particular, the Applicant has discovered that the nitrogenous or structuring organic compound 1,6-bis (methylpiperidinium) hexane in its dihydroxide form, mixed with a zeolite of structural type FAU having a molar ratio S1O2 (FAU / AI2O3 (fau) greater than or equal to 30, used as a source of silicon and aluminum, in the presence or not, of an additional supply, within said mixture, of at least one source of at least one tetravalent element XO 2 , and at at least one source of at least one fluoride anion, leads to the production of an IZM-2 zeolite precursor gel having a molar ratio of the total amount of tetravalent element / AI 2 C> 3 between 10 and 800, the total amount of tetravalent element representing the sum of the content of SiO 2 coming from the zeolite FAU and the content of XO2 coming from the additional source of an oxide XO2, in the case where an addition of at least one additional source of an oxide XO 2 is produced, then at the production of a high purity IZM-2 zeolite. Any other crystallized or amorphous phase is generally and very preferably absent from the crystallized solid consisting of IZM-2 zeolite obtained at the end of the preparation process.
    Description of the invention
    The subject of the present invention is therefore a new process for preparing an IZM-2 zeolite comprising at least the following steps:
    i) the mixture, in aqueous medium, of at least one zeolite of structural type FAU having a SiO 2 molar ratio (FAU / AI2O3 (F au)) greater than or equal to 30 of at least one additional source of an oxide XO2 of so that the XO 2 / SiO 2 molar ratio (fau) is between 0 and 4, at least one nitrogenous organic compound R, R being 1,6-bis (methylpiperidinium) hexane dihydroxide, at least one source of at minus one fluoride anion, the mixture having the following molar composition:
    (XO2 + S1O2 (fau)) / AI2C> 3 (fau) between 10 and 800, preferably between 30 and 600
    H2O / (XO2 + S1O2 (FAU))
    R / (XO 2 + S1O2 (FAU))
    BF / (XC> 2 + S1O2 (FAU)) between 1 and 100, preferably between 10 and 70, between 0.01 to 0.6, preferably between 0.05 and 0.45, between 0.005 to 0.75, preferably between 0.01 and 0.65, in which X is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, preferably silicon, S1O2 (fau) being the amount of S1O2 provided by the FAU zeolite, and AI 2 O 3 (fau) being the amount of AI 2 O 3 provided by the FAU zeolite, and in which BF is chosen from the salts of fluorine in which B is a cation chosen from the NH 4 + , Na + , K + and Li + cations and hydrofluoric acid in aqueous solution, ii) the hydrothermal treatment of the said mixture obtained at the end of the step i) at a temperature between 120 ° C and 200 ° C for a period of between 1 day and 12 days, until said zeolite IZM-2 is formed.
    An advantage of the present invention is therefore to provide a new preparation process allowing the formation of an IZM-2 zeolite, in fluorinated media, of high purity from a zeolite of structural type FAU, said process being implemented in the presence of a specific organic structuring agent, 1,6 bis dihydroxide (methylpiperidinium) hexane.
    Another advantage of the present invention is to provide a new process for the preparation of an IZM-2 zeolite precursor gel having a SiO 2 / AI 2 O 3 molar ratio identical to or greater than the SiO 2 (fau / AI2O 3 ( F au) of the starting FAU structural type zeolite. The preparation process according to the invention therefore makes it possible to adjust the S1O2 / AI2O3 ratio of the IZM-2 precursor gel obtained as a function of the additional supply or not, within the reaction mixture of at least one source of at least one tetravalent element XO 2 .
    Detailed description of the invention
    The subject of the present invention is a process for preparing an IZM-2 zeolite by the hydrothermal conversion / transformation of a zeolite of structural type FAU comprising at least the following steps:
    i) the mixture, in aqueous medium, of at least one zeolite of structural type FAU having a SiO 2 molar ratio (FAU / AI2O3 (F au)) greater than or equal to 30 of at least one additional source of an oxide XO2 of so that the XO 2 / SiO 2 molar ratio (fau) is between 0 and 4, at least one nitrogenous organic compound R, R being 1,6-bis (methylpiperidinium) hexane dihydroxide, at least one source of at minus one fluoride anion, the mixture having the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O 3 (fau) between 10 and 800, preferably between 30 and 600
    H 2 O / (XO2 + S1O2 (FAU))
    R / (XO 2 + S1O2 (FAU))
    BF / (XO2 + S1O2 (FAU)) between 1 and 100, preferably between 10 and 70, between 0.01 to 0.6, preferably between 0.05 and 0.45, between 0.005 and 0, 75, preferably between 0.01 and 0.65, in which X is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, preferably the silicon, SiO 2 (fau) being the amount of SiO 2 provided by the FAU zeolite, and AI 2 C> 3 (fau) being the amount of AI2O3 provided by the FAU zeolite, and in which BF is chosen from fluorine salts in which B is a cation chosen from the NH 4 + , Na + , K + and Li + cations and hydrofluoric acid in aqueous solution, ii) the hydrothermal treatment of said mixture obtained at the end of step i) at a temperature between 120 ° C and 200 ° C for a period between 1 day and 12 days, until said zeolite IZM-2 is formed.
    According to the invention, a zeolite of structural type FAU having a molar ratio S1O2 (fau) / AI2C> 3 (fau) greater than or equal to 30, preferably between 30 and 100 and preferably between 30 and 80, is incorporated in the mixture for the implementation of step (i) as a source of silicon and aluminum element. Preferably, said zeolite of structural type FAU is zeolite Y.
    According to the invention, the source of aluminum element is brought into the mixture for the implementation of said step (i) of the preparation process according to the invention, by the zeolite of structural type FAU which is used as source of element silicon and aluminum.
    According to the invention, R is the nitrogenous organic compound R, R being 1,6-bis (methylpiperidinium) hexane dihydroxide, said compound being incorporated into the mixture for carrying out step (i), as organic structuring. The anion associated with the quaternary ammonium cations present in the structuring organic species for the synthesis of the crystallized solid IZM-2 according to the invention is the hydroxide anion.
    According to the invention, at least one source of at least one fluoride anion called BF is added to said reaction mixture of step i), BF being chosen from fluorine salts in which B is a cation chosen from NH cations 4 + , Na + , K + and Li + , and the mixture of at least two of these salts and hydrofluoric acid in aqueous solution. Preferably, the source of at least one fluoride anion is NH 4 F in aqueous solution.
    According to the invention, 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, and preferably silicon, so that the XO 2 / SiO 2 molar ratio (fau) is between 0 and 4, and preferably between 0 and 3, the SiO 2 content in said ratio being provided by the FAU zeolite, is implemented in the mixture of step i).
    The addition or not of at least one additional source of an oxide XO 2 therefore makes it possible to adjust the SiO 2 / AI 2 O 3 ratio of the IZM-2 precursor gel obtained at the end of step i ) of mixing in the case where X = Si.
    The source (s) of said element (s) tetravalent (s) can be any compound comprising element X and which can release this element in aqueous solution in reactive form. When X is titanium, Ti (EtO) 4 is advantageously used as the source of titanium. In the preferred case where X is silicon, the source of silicon can be any one of said sources commonly used for the synthesis of zeolites, for example powdered silica, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS). Among the powdered silicas, it is possible to use precipitated silicas, in particular those obtained by precipitation from an alkali metal silicate solution, fumed silicas, for example CAB-O-SIL and silica gels. It is possible to use colloidal silicas having different particle sizes, for example of average equivalent diameter between 10 and 15 nm or between 40 and 50 nm, such as those sold under the registered trademarks such as LUDOX. Preferably, the source of silicon is LUDOX HS-40.
    In accordance with the invention, the reaction mixture obtained in step (i) has the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O 3 (fau) between 10 and 800, preferably between 30 and 600 and preferably between 80 and 450, between 1 and 100, preferably between 10 and 70, and preferably between 15 and 55
    H 2 O / (XO 2 + SiO 2 (fau))
    R / (XO 2 + SiO 2 (fau)) between 0.01 to 0.6, preferably between
    0.05 and 0.45, and preferably between 0.085 and 0.4
    BF / (XO 2 + SiO 2 (fau)) between 0.005 to 0.75, preferably between 0.01 and 0.65, and preferably between 0.02 and 0.55 in which R and BF have the same definition as above and in which X is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, preferably silicon, XO 2 being the quantity d '' at least one additional source of an oxide XO 2 , SiO 2 (fau) being the amount of SiO 2 provided by the zeolite FAU, and AI 2 C> 3 (fau) being the amount of AI 2 O 3 provided by the FAU zeolite.
    In a preferred embodiment, the mixture of step i) may also contain at least one source of at least one alkali and / or alkaline-earth metal M of valence η, n being an integer greater than or equal to 1, preferably chosen from lithium, potassium, sodium, magnesium and calcium and the mixture of at least two of these metals. Preferably, the source of at least one alkali and / or alkaline earth metal M is sodium hydroxide.
    In the preferred embodiment or the mixture of step i) also contains at least the source of at least one alkali and / or alkaline-earth metal, the reaction mixture has the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O3 (fau) between 10 and 800, preferably between 80
    H 2 O / (XO 2 + SîO 2 (fau))
    R / (XO 2 + SiO 2 (fau))
    BF / (XO 2 + SiO 2 (fau)) and 400 between 1 and 100, preferably between 10 and 70, between 0.01 to 0.6, preferably between 0.05 and 0.45, between 0.005 to 0.75, preferably between 0.01 and 0.65,
    Μ 2 / η 0 / (Χ02 + S1O2 (fau)) between 0.005 to 0.35, preferably between 0.01 and 0.3, in which X, M, BF, AI 2 C> 3 (fau), SîC> 2 (fau) and XO 2 have the above definition.
    Step (i) of the process according to the invention consists in preparing an aqueous reaction mixture called precursor gel of the zeolite IZM-2 and containing at least one zeolite of structural type FAU, optionally a source of an oxide XO 2 , at at least one nitrogenous organic compound R, R being dihydroxide of 1,6bis (methylpiperidinium) hexane in the presence of at least one source of one or more fluorine salts and / or hydrofluoric acid in aqueous solution. The amounts of said reagents are adjusted so as to give this gel a composition allowing its crystallization into an IZM-2 zeolite.
    It may be advantageous to add IZM-2 zeolite seeds to the reaction mixture during said step i) of the process of the invention in order to reduce the time necessary for the formation of the IZM-2 zeolite crystals and / or the total crystallization time. Said seeds also promote the formation of said IZM-2 zeolite to the detriment of impurities. Such seeds include crystallized solids, in particular crystals of zeolite IZM-2. The crystalline seeds are generally added in a proportion of between 0.01 and 10% of the mass of the source of at least one oxide of the said tetravalent element (s) used in the reaction mixture.
    In accordance with step (ii) of the process according to the invention, the gel obtained at the end of step i) is subjected to a hydrothermal treatment, preferably carried out at a temperature between 120 ° C and 200 ° C for a period of between 1 day and 12 days, until the IZM-2 zeolite is formed. The gel is advantageously placed under hydrothermal conditions under an autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature preferably between 120 ° C and 195 ° C, preferably between 150 ° C and 195 ° C, until the formation of the zeolite IZM-2 crèreaux. The time required to obtain crystallization varies according to the invention between 1 day and 12 days, preferably between 2 days and 11 days and more preferably between 3 days and 10 days. The reaction is generally carried out with stirring or in the absence of stirring, preferably in the presence of stirring.
    At the end of the reaction, when said zeolite IZM-2 is formed following the implementation of said step ii) of the preparation process according to the invention, the solid phase formed from zeolite IZM-2 is preferably filtered, washed and then dried. The drying is generally carried out at a temperature between 20 and 150 ° C, preferably between 60 and 100 ° C, for a period between 5 and 24 hours. The dried zeolite can then be advantageously calcined. The calcined IZM-2 zeolite is generally analyzed by X-ray diffraction, this technique also making it possible to determine the purity of said zeolite obtained by the process of the invention. Very advantageously, the process of the invention leads to the formation of an IZM-2 zeolite, in the absence of any other crystallized or amorphous phase. Said zeolite, after the drying step, is then ready for subsequent steps such as calcination and ion exchange. For these steps, all the conventional methods known to those skilled in the art can be used.
    The calcination step of the IZM-2 zeolite obtained according to the process of the invention is preferably carried out at a temperature between 500 and 700 ° C for a period of between 5 and 20 hours. The IZM-2 zeolite obtained at the end of the calcination step is devoid of any organic species and in particular of the organic structuring agent R.
    At the end of said calcination step, the X-ray diffraction makes it possible to verify that the solid obtained by the process according to the invention is indeed zeolite IZM-2. The solid obtained presents the X-ray diffraction diagram including at least the lines listed in Table 1.
    This diffraction diagram is obtained by radiocrystallographic analysis using a diffractometer using the conventional method of powders with the Kcq radiation of copper (λ = 1.5406Â). From the position of the diffraction peaks represented by the angle 2Θ, we calculate, by the Bragg relation, the reticular equidistances dhki characteristic of the sample. The measurement error A (dhki) on dhki is calculated using the Bragg relation as a function of the absolute error Δ (2Θ) assigned to the measurement of 2Θ. An absolute error Δ (2Θ) equal to ± 0.02 ° is commonly accepted. The relative intensity l re i assigned to each value of dhki is measured according to the height of the corresponding diffraction peak. The X-ray diffraction diagram of the crystallized solid IZM-2 according to the invention comprises at least the lines with the values of dhki given in table 1. In the column of dhki, the average values of the inter-reticular distances have been indicated in Angstroms (Â). Each of these values must be assigned the measurement error A (dhki) between ± 0.6Â and ± 0.01 Â.
    Table 1: Average values of dhki and relative intensities measured on an X-ray diffraction diagram of the calcined IZM-2 crystallized solid
    2 theta (°) dhkl (Â) Irel 2 theta (°) dhkl (Â) Irel 7.21 12.25 mf 24.24 3.67 ff 7.58 11.66 mf 26.24 3.39 ff 8.66 10.21 f 26.54 3.36 f 14.69 6.02 ff 27.63 3.23 ff 15.18 5.83 ff 29.18 3.06 ff 17.79 4.98 ff 32.78 2.73 ff 18.85 4.70 ff 36.22 2.48 ff 20.98 4.23 FF 38.02 2.36 ff 22.10 4.02 mf 42.63 2.12 ff 22.93 3.88 mf 43.57 2.08 f 23.34 3.81 f 44.31 2.04 ff
    where FF = very strong; F = strong; m = medium; mf = medium weak; f = weak; ff = very weak. The relative intensity l re i is given in relation to a relative intensity scale where a value of 100 is assigned to the most intense line of the X-ray diffraction diagram: ff <15; 15 <f <30; 30 <mf <50; 50 <m <65; 65 <F <85;FF> 85.
    It is also advantageous to obtain the hydrogen form of the IZM-2 zeolite obtained by the process according to the invention. 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 chloride, sulphate or ammonium nitrate . Ion exchange can be carried out by suspending said IZM-2 zeolite in one or more stages with the ion exchange solution. Said zeolite can be calcined before or after ion exchange, or between two stages of ion exchange. The zeolite is preferably calcined before the ion exchange, in order to remove any organic substance included in the porosity of the zeolite, insofar as the ion exchange is thereby facilitated.
    The IZM-2 zeolite obtained by the process of the invention can be used after ion exchange as an acid solid for catalysis in the fields of refining and petrochemistry. It can also be used as an adsorbent for pollution control or as a molecular sieve for separation.
    For example, when used as a catalyst, the zeolite prepared according to the process of the invention is calcined, exchanged and is preferably in hydrogen form, and can be associated with an inorganic matrix, which can be inert or catalytically active. , and a metallic phase. The inorganic matrix can be present simply as a binder to hold together the small particles of the zeolite in the various known forms of the catalysts (extrudates, pellets, balls, powders), or else can be added as diluent to impose the degree of conversion process which would otherwise progress at an excessively rapid rate, leading to fouling of the catalyst as a result of significant formation of coke. Typical inorganic matrices are in particular support materials for catalysts such as silica, the different forms of alumina, magnesia, zirconia, oxides of titanium, boron, titanium, zirconium, aluminum phosphates, kaolinic clays, bentonites, montmorillonites, sepiolite, attapulgite, fuller's earth, synthetic porous materials such as S1O2-AI2O3, SiO2-ZrC> 2, SiO2-ThC> 2, SiO 2 -BeO, SiO2- TiC> 2 or any combination of these compounds. The inorganic matrix can be a mixture of different compounds, in particular an inert phase and an active phase.
    The zeolite prepared according to the process of the invention can also be combined with at least one other zeolite and play the role of main active phase or additive.
    The metallic phase is introduced onto the zeolite alone, the inorganic matrix alone or the inorganic matrix-zeolite assembly by ion exchange or impregnation with cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and any other element of the periodic table. The metals can be introduced either all in the same way, or by different techniques, at any time of the preparation, before or after shaping and in any order. In addition, intermediate treatments such as for example calcination and / or reduction can be applied between the deposits of the different metals.
    The catalytic compositions comprising the zeolite IZM-2 prepared according to the process of the invention are generally suitable for the implementation of the main processes for the transformation of hydrocarbons and reactions for the synthesis of organic compounds such as ethers.
    Any shaping method known to a person skilled in the art is suitable for the catalyst comprising the zeolite IZM-2. We can use, for example, pelletizing or extrusion or the form of beads. The shaping of the catalyst containing the zeolite prepared according to the process of the invention and which is at least partly in acid form is generally such that the catalyst is preferably in the form of extrudates or of beads for its use.
    The invention is illustrated by the following examples which are in no way limiting in nature.
    Example 1: preparation of 1,6-bis (methylpiperidinium) hexane dibromide (structuring RBr ).
    g of 1,6-dibromohexane (0.20 mole, 99%, Alfa Aesar) are added to a 1 L flask containing 50 g of N-methylpiperidine (0.51 mole, 99%, Alfa Aesar) and
    200 ml of ethanol. The reaction medium is stirred and brought to reflux for 5 h. The mixture is then cooled to room temperature and then filtered. The mixture is poured into 300 ml of cold diethyl ether then the precipitate formed is filtered and washed with 100 ml of diethyl ether. The solid obtained is recrystallized from an ethanol / ether mixture. The solid obtained is dried under vacuum for 12 h. 71 g of a white solid are obtained (ie a yield of 80%).
    The product has the expected 1 H NMR spectrum. 1 H NMR (D 2 O, ppm / TMS): 1.27 (4H, m); 1.48 (4H, m); 1.61 (4H, m); 1.70 (8H, m); 2.85 (6H, s); 3.16 (12H, m).
    Example 2: preparation of 1,6-bis (methylpiperidinium) hexane dihydroxide (structuring R (OHb).
    18.9 g of Ag 2 O (0.08 mol, 99%, Aldrich) are added to a Teflon beaker of
    250 ml containing 30 g of the structuring agent of 1,6-bis dibromide (methylpiperidinium) (0.07 mol) prepared according to example 1 and 100 ml of deionized water. The reaction medium is stirred protected from light for 12 h. The mixture is then filtered. The filtrate obtained is composed of an aqueous solution of 1,620 bis (methylpiperidinium) hexane dihydroxide. The assay of this species is carried out by proton NMR using formic acid as a standard.
    Example 3: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O3 = 80, Zeolyst) were mixed with 1621.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20 , 04% by weight) prepared according to Example 2, the mixture is stirred for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 5 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 342.6 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 575 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 O 3 : 0.33 R (OH) 2 : 0.5 NH 4 F : 33.33 H 2 O, ie an SiO 2 / AI 2 O 3 ratio of 300. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle comprises a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to 'at 550 ° C followed by a palèr at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 4: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 1228.2 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane ( 20.04% by weight) prepared according to Example 2 and with 630 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 5 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 342.6 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 58 mg of an aqueous solution at 10% by weight of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 O 3 : 0.25 R (OH) 2 : 0.05 NH 4 F : 33.33 H 2 O, ie an SiO 2 / AI 2 O 3 ratio of 300. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 5: preparation of an IZM-2 solid according to the invention.
    mg of a zeolite of the structural type FAU (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 412 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20, 04% by weight) prepared according to Example 2 and with 513 mg of deionized water. The mixture obtained is maintained with stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 5 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 109 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 29 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture which is kept under stirring for the time necessary to evaporate the solvent until to obtain the desired gel concentration, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0066 AI 2 O 3 : 0.17 R (OH) 2 : 0.05 NH 4 F: 33.33 H 2 O, ie a SiO 2 / AI 2 O 3 ratio of 150. The mixture is then transferred, after homogenization in an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to ambient temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid. The diffraction diagram performed on the calcined IZM-2 solid is given in FIG. 1.
    Example 6: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO2 / AI 2 O3 = 80, Zeolyst) were mixed with 412 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20.04% by weight) prepared according to Example 2 and with 453 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the crystallized solid IZM-2, 5 mg of seeds of the zeolite IZM-2 are added to the synthesis mixture and kept under stirring for 5 minutes. 109 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 96 mg of an aqueous solution at 10% by weight of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture which is kept under stirring for the time necessary to evaporate the solvent until to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 S1O2: 0.0066 AI2O3: 0.17 R (OH) 2 : 0.17 NH 4 F: 33.33 H 2 O, ie an S1O2 / AI2O3 ratio of 150. The mixture is then transferred, after homogenization in an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to ambient temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 7: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O3 = 80, Zeolyst) were mixed with 485.1 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20 , 04% by weight) prepared according to Example 2 and with 649 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 55 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 34 mg of an aqueous solution at 10% by weight of ammonium fluoride (> 99.9% by weight Aldrich) were incorporated into the synthesis mixture, which is kept stirring for the time necessary to evaporate the solvent until to obtain the desired gel concentration, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.01 AI 2 O 3 : 0.17 R (OH) 2 : 0.05 NH 4 F: 33.33 H 2 O, ie an SiO 2 / AI 2 C> 3 ratio of 100. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to ambient temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 8: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 954.6 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane ( 20.04% by weight) prepared according to Example 2 and with 1 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 55 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 339 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 S1O2: 0.01 AI2O3: 0.33 R (OH) 2 : 0.5 NH 4 F: 33.33 H 2 O, ie a ratio δίΟ 2 / ΑΙ 2 Ο 3 of 100. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to ambient temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 9: preparation of an IZM-2 solid according to the invention.
    mg of a zeolite of the structural type FAU (CBV780, SiO2 / AI 2 O3 = 80, Zeolyst) were mixed with 723.2 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20, 04% by weight) prepared according to Example 2 and with 388 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 55 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 113 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is kept stirring for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 S1O2: 0.01 AI2O3: 0.25 R (OH) 2 : 0.17 NH 4 F: 33.33 H 2 O, ie a ratio δίΟ 2 / ΑΙ 2 Ο 3 of 100. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 10: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO2 / AI 2 O3 = 80, Zeolyst) were mixed with 436.7 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20, 04% by weight) prepared according to Example 2 and with 597 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 27.5 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 30 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, that is to say a molar composition of the following mixture: 1 S1O2: 0.011 AI2O3: 0.17 R (OH) 2 : 0.05 NH4F: 33.33 H 2 O, or a ratio δίΟ 2 / ΑΙ 2 Ο 3 of 90. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 11: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO2 / AI 2 O3 = 80, Zeolyst) were mixed with 436.7 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20, 04% by weight) prepared according to Example 2 and with 533 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 27.5 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 102 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 δίθ 2 : 0.011 AI2O3: 0.17 R (OH) 2 : 0.17 NH 4 F: 33.33 H 2 O, ie a ratio δίΟ 2 / ΑΙ 2 Ο 3 of 90. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 12: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O3 = 80, Zeolyst) were mixed with 859.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20 , 04% by weight) prepared according to Example 2 and with 14 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 27.5 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture which is stirred for 15 minutes. 305 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.011 AI 2 O 3 : 0.33 R (OH) 2 : 0.5 NH 4 F: 33 , 33 H 2 O, ie an SiO 2 / AI 2 C> 3 ratio of 90. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 13: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 388.2 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane ( 20.04% by weight) prepared according to Example 2 and with 488 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 90 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.013 AI 2 O 3 : 0.17 R (OH) 2 : 0.17 NH 4 F: 33 , 33 H 2 O, ie an SiO 2 / AI 2 C> 3 ratio of 80. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to ambient temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 14: preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 763.9 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane ( 20.04% by weight) prepared according to Example 2 and with 27 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. In order to promote the formation of the IZM-2 crystallized solid, 9 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 5 minutes. 271 mg of a 10% by weight aqueous solution of ammonium fluoride (> 99.9% by weight, Aldrich) were incorporated into the synthesis mixture, which is stirred for the time necessary to evaporate the solvent until '' to obtain the desired gel concentration, i.e. a molar composition of the following mixture: 1 S1O2: 0.013 AI2O3: 0.33 Ft (OH) 2 : 0.5 NH 4 F: 33.33 H 2 O, ie a ratio δίΟ 2 / ΑΙ 2 Ο 3 of 80. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 8 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. The balance is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle includes a rise in temperature up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a rise in temperature up to '' at 550 ° C followed by a plateau at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    Example 15: Preparation of an IZM-2 solid according to the invention.
    mg of a FAU structural type zeolite (CBV780, SiO2 / AI 2 O3 = 80, Zeolyst) were mixed with 650.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dihydroxide hexane (20, 04% by weight) prepared according to Example 2 and with 896 mg of deionized water. The mixture obtained is kept under stirring for 10 minutes. 82 mg of a 20% by weight aqueous solution of sodium hydroxide (98% by weight, Aldrich) are added. In order to promote the formation of the IZM-2 crystallized solid, 5 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 15 minutes. 362.7 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture. Finally, 305 mg of an aqueous solution at 10% by weight of ammonium fluoride (> 99.9% by weight Aldrich) are added and the mixture is stirred for the time necessary to evaporate the solvent until obtaining the desired gel concentration, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 O 3 : 0.125 R (OH) 2 : 0.0625 Na 2 O: 0.25 NH 4 F: 33.33 H 2 O, ie an S1O2 / AI2O3 ratio of 300. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 6 days at 170 ° C. with stirring. The crystallized product obtained is filtered, washed with water and then dried overnight at 100 ° C. The solid is then introduced into a muffle furnace where a calcination step is carried out: the calcination cycle comprises a rise in temperature up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a rise in temperature up to 'at 550 ° C followed by a palèr at 550 ° C maintained for 8 hours then a return to room temperature.
    The calcined solid product was analyzed by X-ray diffraction and identified as being made up of IZM-2 solid.
    权利要求:
    Claims (8)
    [1" id="c-fr-0001]
    1. Process for the preparation of an IZM-2 zeolite comprising at least the following steps:
    i) the mixture in aqueous medium, of at least one zeolite of structural type FAU having a molar ratio SiO 2 (fau) / AI 2 C> 3 (fau) greater than or equal to 30 of at least one additional source of an oxide XO 2 so that the molar ratio XO 2 / SiO 2 (fau) is between 0 and 4, at least one organic nitrogenous compound R, R being 1,6-bis (methylpiperidinium) dihydroxide hexane, at least a source of at least one fluoride anion, the mixture having the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O3 (fau) H 2 O / (XO 2 + SiO 2 (fau)) R / (XO 2 + SîO 2 (fau))
    BF / (XO 2 + SîO 2 (fau)) between 10 and 800, between 1 and 100, between 0.01 to 0.6, between 0.005 to 0.75, in which X is one or more elements (s) tetravalent (s) chosen from the group formed by the following elements: silicon, germanium, titanium, preferably silicon, SiO 2 (fau) being the amount of SiO 2 provided by the zeolite FAU, and AI 2 O 3 (F au) being the amount of AI 2 O 3 provided by the zeolite FAU, and in which BF is chosen from fluorine salts in which B is a cation chosen from the cations NH 4 + , Na + , K + and Li + , and hydrofluoric acid in aqueous solution, ii) hydrothermal treatment of said mixture obtained at the end of step i) at a temperature between 120 ° C and 200 ° C for a period of between 1 day and 10 days, until said zeolite IZM-2 is formed.
    [2" id="c-fr-0002]
    2. Method according to claim 1 wherein said zeolite of FAU structural type is zeolite Y.
    [3" id="c-fr-0003]
    3. Method according to one of claims 1 or 2 wherein the BF source of at least one anion is NH4F in aqueous solution.
    [4" id="c-fr-0004]
    4. Method according to one of claims 1 to 3 wherein X is silicon.
    [5" id="c-fr-0005]
    5. Method according to one of claims 1 to 4 wherein, the additional source of an oxide XO2 is added in step i) of mixing so that the molar ratio XO 2 / SiO 2 (fau) is between 0 and 3.
    Process according to one of Claims 1 to 5, in which the reaction mixture obtained in step (i) has the following molar composition:
    (XO2 + S1O2 (fau)) / AI2Û3 (fau) between 30 and 600,
    H 2 O / (XO 2 + SiO 2 (fau)) between 10 and 70,
    R / (XO 2 + S1O2 (fau)) between 0.05 and 0.45,
    BF / (XO 2 + SiO 2 ( FAU)) between 0.01 and 0.65.
    Process according to Claim 6, in which the reaction mixture obtained in step (i) has the following molar composition:
    (XO2 + S1O2 (fau)) / AI2Û3 (fau) between 80 and 450,
    H 2 O / (XO 2 + SiO 2 (fau)) between 15 and 55
    R / (XO 2 + S1O2 (fau)) between 0.085 and 0.4
    BF / (XO 2 + SiO 2 (fau)) between 0.02 and 0.55.
    [6" id="c-fr-0006]
    8. Method according to one of claims 1 to 7 wherein the mixture of step i) also contains at least one source of at least one alkali and / or alkaline earth metal M of valence η, n being an integer greater than or equal to 1, chosen from lithium, potassium, sodium, magnesium and calcium and the mixture of at least two of these metals.
    [7" id="c-fr-0007]
    9. Method according to one of claims 1 to 8 wherein the hydrothermal treatment of step ii) is carried out at a temperature between 120 ° C and 195 ° C.
    [8" id="c-fr-0008]
    10. Method according to one of claims 1 to 9 wherein the hydrothermal treatment of step ii) is carried out for a period of between 2 days and 11 days.
    1/1
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    FR2934796B1|2008-08-08|2010-09-03|Inst Francais Du Petrole|IZM-2 ZEOLITE CATALYST AND METHOD FOR HYDROCONVERSION / HYDROCRACKING HYDROCARBON LOADS|
    JP5351216B2|2010-07-01|2013-11-27|日本化学工業株式会社|Method for producing zeolite|
    US9156706B2|2012-07-03|2015-10-13|Chevron U.S.A. Inc.|Method for preparing high-silica LEV-type zeolites|
    US9802831B2|2014-07-23|2017-10-31|Chevron U.S.A. Inc.|Synthesis of high silica zeolite via interzeolite transformation without OSDAs|FR3095131B1|2019-04-19|2021-10-29|Ifp Energies Now|RAPID SYNTHESIS PROCESS OF AN AFX STRUCTURAL TYPE ZEOLITH BY SYNTHESIS IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURING|
    FR3101258B1|2019-09-30|2022-01-14|Ifp Energies Now|LOW TEMPERATURE SYNTHESIS OF HIGH PURITY AFX ZEOLITH|
    FR3101259A1|2019-09-30|2021-04-02|IFP Energies Nouvelles|LOW TEMPERATURE SYNTHESIS OF A ZEOLITHE AFX BASED CATALYST AND ITS APPLICATION IN NH3-SCR|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1752472A|FR3064261B1|2017-03-24|2017-03-24|PROCESS FOR THE SYNTHESIS OF IZM-2 ZEOLITE IN THE PRESENCE OF A 1,6-BISHEXANE DIHYDROXIDE STRUCTURER|
    FR1752472|2017-03-24|FR1752472A| FR3064261B1|2017-03-24|2017-03-24|PROCESS FOR THE SYNTHESIS OF IZM-2 ZEOLITE IN THE PRESENCE OF A 1,6-BISHEXANE DIHYDROXIDE STRUCTURER|
    ZA2018/01815A| ZA201801815B|2017-03-24|2018-03-19|Process for the synthesis of izm-2 zeolite in the presence of a template, 1,6-bishexane dihydroxide|
    JP2018050324A| JP2018162207A|2017-03-24|2018-03-19|Method of synthesizing izm-2 zeolite in the presence of 1,6-bishexanedihydroxide, template|
    EP18305312.3A| EP3378831B1|2017-03-24|2018-03-21|Method for synthesising zeolite izm-2 in the presence of 1,6-bishexane dihydroxide as a structuring agent|
    CN201810245306.1A| CN108622914A|2017-03-24|2018-03-23|The method that IZM-2 zeolites are synthesized in the presence of template 1,6- bis-hexane dihydroxides|
    US15/933,848| US10865116B2|2017-03-24|2018-03-23|Process for the synthesis of IZM-2 zeolite in the presence of a template, 1,6-bishexane dihydroxide|
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