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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 particular, said new process consists in carrying out the synthesis of an IZM-2 zeolite from a zeolite of structural type FAU used as a source of silicon and aluminum and of a specific organic or structuring molecule comprising two ammonium functions quaternary dibromide of 1,6-bis (methylpiperidinium) hexane.
    公开号:FR3064262A1
    申请号:FR1752473
    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 from a zeolite of structural type FAU used as a source of silicon and aluminum and of a specific organic or structuring molecule comprising two ammonium functions quaternary, 1,6bis dibromide (methylpiperidinium) hexane. 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 IZM-2 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.
    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 by 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 (tetra ethyl ammonium hydroxide), TMAOH (tetra methyl ammonium hydroxide), BTMAOH (benzyl tri methyl ammonium 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 consists in carrying out a hydrothermal treatment of an aqueous gel containing a source of amorphous silicon and aluminum, an alkaline earth metal (Na 2 O) and a structuring agent ( 1,6-bis (methylpiperidinium) hexane).
    The Applicant has discovered 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 organic nitrogenous or structuring compound, 1,6-bis (methylpiperidinium) hexane in its dibromide form.
    In particular, the applicant has discovered that the organic nitrogenous or structuring compound 1,6-bis (methylpiperidinium) hexane in its dibromide form, mixed with a zeolite of structural type FAU having a molar ratio SiO 2 (fau / AI 2 O 3 (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 least one source of at least one alkali and / or alkaline earth metal of valence n, leads to the production of a zeolite IZM-2 precursor gel having a molar ratio of the total amount of tetravalent element / AI 2 O 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 XO 2 coming from the additional source of an oxide XO 2 , in the case where an addition of at least one additional source the of an oxide XO 2 is produced, then in the production of a zeolite IZM-2 of high purity. 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 molar ratio SiO 2 (fau) / AI 2 O 3 (fau) greater than or equal to 30 of at least one additional source of a oxide XO 2 so that the molar ratio XO 2 / SiO 2 (fau) is between 0 and 4, at least one nitrogenous organic compound R, R being the dibromide of 1,6-bis (methylpiperidinium) hexane, at least one alkali metal and / or an alkaline earth metal of valence η, n being an integer greater than or equal to 1, the mixture having the following molar composition:
    (XO 2 + S1O2 (FAU)) / Al2O3 (FAU) H 2 O / (XO2 + SiO 2 (fau)) R / (XO 2 + SiO 2 (FAU)) M2 / n O / (XO2 + SiO 2 ( FAU)) between 10 and 800, between 1 and 100, between 0.01 to 0.6, between 0.005 to 0.35, in which X is one or more tetravalent element (s) chosen ( s) in the group formed by the following elements: silicon, germanium, titanium, SiO 2 (fau) being the amount of SiO 2 provided by the zeolite FAU, and AI2O3 (fau) being the amount of AI 2 O 3 provided by the FAU zeolite, 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 IZM-2 zeolite is formed.
    An advantage of the present invention is therefore to provide a new preparation process allowing the formation of a high purity IZM-2 zeolite from a zeolite of structural type FAU, said process being carried out in the presence of a specific organic structuring agent, 1.6bis dibromide (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 molar ratio
    S1O2 / AI2O3 identical to or greater than the SiO 2 molar ratio (FAU / AI2O3 (fau) 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 precursor gel d 'IZM-2 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 molar ratio SiO 2 (fau / AI 2 O 3 (F au) greater than or equal to 30 of at least one additional source of a oxide XO 2 so that the molar ratio XO 2 / SiO 2 (fau) is between 0 and 4, at least one nitrogenous organic compound R, R being the dibromide of 1,6-bis (methylpiperidinium) hexane, at least one alkali metal and / or an alkaline earth metal of valence η, n being an integer greater than or equal to 1, the mixture having the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O 3 (fau) H 2 O / (XO 2 + SiO 2 (fau)) R / (XO 2 + SîO 2 (fau)) M 2 / n O / (XO 2 + SîO 2 (fau)) between 10 and 800, between 1 and 100, between 0.01 to 0.6, between 0.005 to 0.35, in which X is one or more element (s) ) tetravalent (s) chosen from the group formed by the following elements: silicon, germanium, titanium, 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 FAU zeolite, 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 10 days, until said zeolite IZM-2 is formed.
    In accordance with the invention, a zeolite of the FAU structural type having a SiO 2 (fau / AI 2 O 3 (F au)) molar ratio greater than or equal to 30 preferably between 30 and 100 and preferably between 30 and 80 is incorporated into 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.
    In accordance with the invention, R is the nitrogenous organic compound R, R being 1,6-bis (methylpiperidinium) hexane dibromide, 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 bromide anion.
    According to the invention, 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, and preferably sodium, is used in the mixture of step i). Preferably, the source of at least one alkali and / or alkaline earth metal M is sodium hydroxide.
    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 molar ratio XO 2 / SiO 2 (fau) is between 0 and 4, and preferably between 0 and 3, the content of S1O2 in said ratio being provided by the zeolite FAU is set work in the mixture of step i).
    The addition or not of at least one additional source of an oxide XO2 therefore makes it possible to adjust the ratio δίΟ 2 / ΑΙ 2 Ο 3 of the precursor gel of IZM-2 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:
    (XO2 + S1O2 (fau)) / AI2O3 (fau) between 10 and 800, preferably between 20 and 600 and preferably between 25 and 450,
    H2O / (XO2 + SiO2 (FAU))
    R / (XO2 + SiO2 (FAU))
    M2 / nO / (XO2 + SiO2 (FAU)) between 1 and 100, preferably between 10 and 70, and preferably between 15 and 55 between 0.01 and 0.6, preferably between 0.05 and 0.45, and preferably between 0.085 and 0.4 between 0.005 and 0.35, preferably between 0.008 and 0.3, and preferably between 0.01 and 0.25 in which R and M 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 S1O2 provided by the FAU zeolite, and AI 2 O3 (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 fluoride anion BF 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.
    Preferably, the source of at least one fluoride anion is NH 4 F in aqueous solution.
    In the preferred embodiment or the mixture of step i) also contains at least one source of fluoride anion, the reaction mixture has the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI2O 3 (fau) between 10 and 800, preferably between 200 and 340,
    H 2 O / (XO 2 + SiO 2 (fau))
    R / (XO 2 + SîO 2 (fau))
    M 2 / n O / (XO 2 + SîO 2 ( fau))
    BF / (XO 2 + SîO 2 (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 0.35, preferably between 0.01 and 0.3, between 0.01 and 0.33, preferably between 0.01 and 0.25, in which X, M, BF, AI 2 O 3 (fau ), SîO 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 the dibromide of 1,6bis (methylpiperidinium) hexane in the presence of at least one source of one or more metal (s) alkali (s) and / or alkaline earth. 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 10 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 10 days, preferably between 2 days and 9 days and more preferably between 3 days and 8 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 7.23 12.21 mf 24.34 3.65 ff 7.60 11.62 mf 25.78 3.45 ff 8.70 10.16 f 26.36 3.38 ff 12.09 7.32 ff 26.64 3.34 mf 14.56 6.08 ff 27.74 3.21 ff 14.73 6.01 ff 28.46 3.13 ff 15.25 5.80 ff 29.30 3.05 ff 17.88 4.96 ff 32.90 2.72 ff 18.88 4.70 ff 35.67 2.51 ff 21.00 4.23 FF 36.09 2.49 ff 21.77 4.08 mf 36.51 2.46 ff 22.01 4.03 mf 38.40 2.34 ff 23.01 3.86 F 42.47 2.13 ff 23.44 3.79 f 44.48 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 d 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 1 H NMR spectrum expected. 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 an IZM-2 solid according to the invention.
    316 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 7121.7 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1. 3583 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 1270 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 crystallized solid IZM-2, 116 mg of zeolite seeds IZM-2 are added to the synthesis mixture and maintained with stirring for 15 minutes. Subsequently, 2116.6 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, the latter is stirred for the time necessary to evaporate the solvent until the concentration is obtained of the desired gel, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 O 3 : 0.17 RBr 2 : 0.165 Na 2 O: 33.33 H 2 O, i.e. a ratio
    SiO 2 / AI 2 C> 3 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 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 paler 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. The diffraction diagram performed on the calcined IZM-2 solid is given in FIG. 1.
    Example 3: preparation of an IZM-2 solid according to the invention.
    303 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 C> 3 = 80, Zeolyst) were mixed with 6848 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane ( 20.04% by weight) prepared according to Example 1.3682 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 925 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, 112 mg of IZM2 zeolite seeds are added to the synthesis mixture and kept stirring for 15 minutes. Subsequently, 2035.4 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, which is kept stirred for the time necessary to evaporate the solvent until the concentration of the desired gel, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 O 3 : 0.17 RBr 2 : 0.125 Na 2 O: 33.33 H 2 O, i.e. an SiO 2 / AI 2 C> 3 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 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 paler 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.
    1803 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 20 636.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1. 11,754 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 3680 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, 334 mg of IZM2 zeolite seeds are added to the synthesis mixture and kept stirring for 15 minutes. Subsequently, 3847.2 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, which is kept stirring for the time necessary to evaporate the solvent until the concentration is obtained of the desired gel, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0066 AI 2 O 3 : 0.17 RBr 2 : 0.165 Na 2 O: 33.33 H 2 O, i.e. a SiO 2 / AI 2 O 3 ratio of 150. 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 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 paler 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.
    1803 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 20 636.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1. 12467 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 2788 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 crystallized solid IZM-2, 334 mg of the zeolite seeds IZM2 are added to the synthesis mixture and kept stirring for 15 minutes. Subsequently, 3847.2 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, the latter is stirred for the time necessary to evaporate the solvent until the concentration is obtained of the desired gel, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0066 AI 2 O 3 : 0.17 RBr 2 : 0.125 Na 2 O: 33.33 H 2 O, i.e. a SiO 2 / AI 2 O 3 ratio of 150. 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 chamber where a calcination step is carried out: the calcination cycle includes a temperature rise up to 200 ° C., a plateau at 200 ° C. maintained for 2 hours, a temperature rise 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 6: preparation of an IZM-2 solid according to the invention.
    3005 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 26916.9 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1.5881 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 2439 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 crystallized solid IZM-2, 300 mg of the zeolite seeds IZM2 are added to the synthesis mixture, the mixture and kept stirring for the time necessary to evaporate the solvent until the desired gel concentration is obtained, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.0125 AI 2 O 3 : 0.25 RBr 2 : 0.125 Na 2 O: 33.33 H 2 O, i.e. an SiO 2 / ratio AI 2 O 3 of 80. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 6 days at 170 ° C with agitation. 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 in 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 7: preparation of an IZM-2 solid according to the invention.
    3005 mg of a FAU structural type zeolite (CBV780, SiO 2 / AI 2 O 3 = 80, Zeolyst) were mixed with 18055.9 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1. 12928 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 2439 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, 300 mg of IZM2 zeolite seeds are added to the synthesis mixture, the latter is stirred for the time necessary to evaporate the solvent until the desired gel concentration is obtained , i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0125 AI 2 O 3 : 0.17 RBr 2 : 0.125 Na 2 O: 33.33 H 2 O, i.e. an SiO 2 ratio / AI 2 O 3 of 80. The mixture is then transferred, after homogenization, to an autoclave. The autoclave is closed and then heated for 6 days at 170 ° C with agitation. 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 in 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 8: preparation of an IZM-2 solid according to the invention.
    781 mg of a FAU structural type zeolite (CBV720, SiO 2 / AI 2 O 3 = 30, Zeolyst) were mixed with 6076.6 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to example 1.4203 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 548 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 crystallized solid IZM-2, 103 mg of IZM2 zeolite seeds are added to the synthesis mixture and kept stirring for 15 minutes. Subsequently, 610.3 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture, the latter being stirred for the time necessary to evaporate the solvent until the desired gel concentration, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.025 AI 2 C> 3: 0.17 RBr 2 : 0.0835 Na 2 O: 33.33 H 2 O, or an SiO 2 / AI 2 O 3 ratio of 40. 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 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 9: preparation of an IZM-2 solid according to the invention.
    781 mg of a FAU structural type zeolite (CBV720, SiO 2 / AI 2 C> 3 = 30, Zeolyst) were mixed with 6076.6 mg of an aqueous solution of 1,6-bis dibromide (methylpiperidinium) hexane (20.04% by weight) prepared according to example 1.3985 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 821 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, 103 mg of IZM2 zeolite seeds are added to the synthesis mixture and kept under stirring for 15 minutes. Subsequently, 610.3 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, which is kept stirring for the time necessary to evaporate the solvent until the concentration is obtained of the desired gel, that is to say a molar composition of the following mixture: 1 SiO 2 : 0.025 AI 2 O 3 : 0.17 RBr 2 : 0.125 Na 2 O: 33.33 H 2 O, i.e. an SiO ratio 2 / AI 2 O 3 of 40. 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 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 10: preparation of an IZM-2 solid according to the invention.
    150 mg of a FAU structural type zeolite (CBV720, SiO 2 / AI 2 O 3 = 30, Zeolyst) were mixed with 1043.3 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20.04% by weight) prepared according to Example 1. 742 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 94 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 crystallized solid IZM-2, 18 mg of zeolite germ IZM-2 are added to the synthesis mixture, the latter and maintained under stirring for 15 minutes. Subsequently, 70.4 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, the latter is stirred for the time necessary to evaporate the solvent until the concentration of the desired gel, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0278 AI 2 O 3 : 0.17 RBr 2 : 0.0835 Na 2 O: 33.33 H 2 O, i.e. an SiO 2 / AI 2 O 3 ratio of 36. 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 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 11: preparation of an IZM-2 solid according to the invention.
    150 mg of a FAU structural type zeolite (CBV720, SiO2 / AI 2 O3 = 30, Zeolyst) were mixed with 2053.1 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20 , 04% by weight) prepared according to Example 1. The mixture is stirred for 10 minutes. 94 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, 18 mg of IZM-2 zeolite seeds are added to the synthesis mixture and kept stirring for 15 minutes. Subsequently, 70.4 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) are incorporated into the synthesis mixture, the latter is stirred for the time necessary to evaporate the solvent until the concentration of the desired gel, i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0278 AI 2 O 3 : 0.33 RBr 2 : 0.0835 Na 2 O: 33.33 H 2 O, i.e. an S1O2 / AI2O3 ratio of 36. 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 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 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 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 1219.1 mg of an aqueous solution of 1,6-bis (methylpiperidinium) dibromide hexane (20 , 04% by weight) prepared according to Example 1. 558 mg of deionized water are added to the preceding mixture, the preparation obtained is kept under stirring for 10 minutes. 217 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 crystallized solid IZM-2, 5 mg of the zeolite seeds IZM-2 are added to the synthesis mixture maintained with stirring for 15 minutes. Subsequently, 362.7 mg of colloidal silica (Ludox HS40, 40% by weight, Aldrich) were incorporated into the synthesis mixture. Finally, 61 mg of a 10% by weight aqueous solution of ammonium fluoride (Aldrich) are added to the synthesis mixture and kept stirring for the time necessary to evaporate the solvent until the desired gel concentration is obtained. , i.e. a molar composition of the following mixture: 1 SiO 2 : 0.0033 AI 2 C> 3: 0.17 RBr 2 : 0.165 Na 2 O: 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 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 temperature rise up to 200 ° C., in step at 200 ° C. maintained for 2 hours, a temperature rise 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.
    权利要求:
    Claims (10)
    [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 an aqueous medium, of at least one zeolite of structural type FAU having a molar ratio S1O2 (fau) / AI2C> 3 (fau) greater than or equal to 30 of at least one additional source of an oxide XO 2 so that the molar ratio XO2 / S1O2 (fau) is between 0 and 4, at least one nitrogenous organic compound R, R being the dibromide of 1,6-bis (methylpiperidinium) hexane, at least one alkali metal and / or an alkaline earth metal of valence η, n being an integer greater than or equal to 1, the mixture having the following molar composition:
    (XO2 + S1O2 (FAU)) / Al2O3 (FAU) H2O / (XO2 + S1O2 (FAU)) R / (XO 2 + S1O2 (FAU) M2 / n O / (XO2 + S1O2 (FAU)) between 10 and 800, between 1 and 100, between 0.01 to 0.6, between 0.005 and 0.35, in which X is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, S1O2 (fau) being the amount of SiO 2 provided by the FAU zeolite, and AI 2 O 3 (fau) being the amount of AI2O3 provided by the FAU zeolite, 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 source of at least one alkali and / or alkaline earth metal M is sodium hydroxide.
    [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 XO2 / SÎO2 (FAU) is between 0 and 3.
    [6" id="c-fr-0006]
    6. Method according to one of claims 1 to 5 wherein the reaction mixture 5 obtained in step (i) has the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O 3 (fau) between 20 and 600,
    H 2 O / (XO 2 + SiO 2 (fau)) between 10 and 70,
    R / (XO 2 + SiO 2 (fau) between 0.05 and 0.45,
    M 2 / n O / (XO 2 + SiO 2 (fau)) between 0.008 and 0.3.
    10
    [7" id="c-fr-0007]
    7. The method of claim 6 in which the reaction mixture obtained in step (i) has the following molar composition:
    (XO 2 + SiO 2 (fau)) / AI 2 O 3 (fau) between 25 and 450,
    H 2 O / (XO 2 + SiO 2 (fau)) between 15 and 55,
    R / (XO 2 + SiO 2 (fau) between 0.085 and 0.4,
    15 M 2 / n O / (XO 2 + SiO 2 (fau)) between 0.01 and 0.25.
    [8" id="c-fr-0008]
    8. Method according to one of claims 1 to 7 wherein the mixture of step i) also contains at least one source of fluoride anion BF chosen from fluorine salts in which B is a cation chosen from NH4 + cations , Na +, K + and Li +, and hydrofluoric acid in aqueous solution.
    20
    [9" id="c-fr-0009]
    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.
    [10" id="c-fr-0010]
    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
    25 and 9 days.
    1/1
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    同族专利:
    公开号 | 公开日
    FR3064262B1|2019-03-22|
    JP2018162206A|2018-10-18|
    ZA201801813B|2019-01-30|
    US20180273393A1|2018-09-27|
    CN108622915A|2018-10-09|
    EP3378830B1|2019-10-16|
    US10875778B2|2020-12-29|
    EP3378830A1|2018-09-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2170769B1|2007-06-29|2011-03-30|IFP Energies nouvelles|Crystalline solid izm-2 and method for the preparation thereof|
    US8361435B2|2007-06-29|2013-01-29|IFP Energies Nouvelles|IZM-2 crystalline solid and process for its preparation|WO2020212356A1|2019-04-19|2020-10-22|IFP Energies Nouvelles|Method for fast synthesis of an afx-structure zeolite with a faujasite source|
    EP3798189A1|2019-09-26|2021-03-31|IFP Energies nouvelles|Method for synthesising zeolite izm-2 in the presence of a nitrogen-containing organic structuring agent in the hydroxide form and of an alkali metal chloride, in a fluorinated or not fluorinated medium|
    FR3101342A1|2019-09-26|2021-04-02|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A ZEOLITH IZM-2 IN THE PRESENCE OF A MIXTURE OF ORGANIC NITROGEN STRUCTURANTS IN HYDROXIDE AND BROMIDE FORM AND OF A METAL ALKALINE CHLORIDE|US3222583A|1962-03-23|1965-12-07|Gen Electric|Control systems|
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    US9802831B2|2014-07-23|2017-10-31|Chevron U.S.A. Inc.|Synthesis of high silica zeolite via interzeolite transformation without OSDAs|
    CN110540215A|2014-11-21|2019-12-06|三菱化学株式会社|AEI-type aluminosilicate zeolite, catalyst and exhaust gas treatment method|FR3095967A1|2019-05-16|2020-11-20|IFP Energies Nouvelles|Process for preparing a MER-structural-type zeolite|
    FR3109103A1|2020-04-08|2021-10-15|IFP Energies Nouvelles|Method for the synthesis of zeolite mordenitewith a high Si / Al ratio|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1752473|2017-03-24|
    FR1752473A|FR3064262B1|2017-03-24|2017-03-24|PROCESS FOR THE SYNTHESIS OF IZM-2 ZEOLITE IN THE PRESENCE OF A DIBROMIDE STRUCTURER OF 1,6-BISHEXANE|FR1752473A| FR3064262B1|2017-03-24|2017-03-24|PROCESS FOR THE SYNTHESIS OF IZM-2 ZEOLITE IN THE PRESENCE OF A DIBROMIDE STRUCTURER OF 1,6-BISHEXANE|
    JP2018050318A| JP7005399B2|2017-03-24|2018-03-19|Method for synthesizing IZM-2 zeolite in the presence of template 1,6-bishexanedibromid|
    ZA2018/01813A| ZA201801813B|2017-03-24|2018-03-19|Process for the synthesis of izm-2 zeolite in the presence of a template, 1,6-bishexane dibromide|
    EP18305310.7A| EP3378830B1|2017-03-24|2018-03-21|Method for synthesising zeolite izm-2 in the presence of 1,6-bishexane dibromide as a structure directing agent|
    CN201810245524.5A| CN108622915A|2017-03-24|2018-03-23|The method that IZM-2 zeolites are synthesized in the presence of template 1,6- bis-hexane dibromide|
    US15/935,946| US10875778B2|2017-03-24|2018-03-26|Process for the synthesis of IZM-2 zeolite in the presence of a template, 1,6-bishexane dibromide|
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