• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The invention describes a process for the preparation of a nanometric zeolite of structural type FAU having a crystal size of less than 100 nm and an Si / Al ratio greater than 2 comprising mixing, in an aqueous medium, at least one source AO2 of at least one tetravalent element A chosen from among silicon, germanium, titanium alone or as a mixture of at least one source BOb of at least one trivalent element B chosen from aluminum, boron and iron , indium, gallium, alone or as a mixture, of at least one C2 / mO source of an alkali or alkaline earth metal C selected from lithium, sodium, potassium, calcium, magnesium alone or in a mixture, said source C2 / mO also comprising at least one source of hydroxide ions to obtain a gel, the ripening of the gel obtained at the end of step (i) at a temperature of between -15 ° C. and 60 ° C. ° C, with or without agitation, for a period between 1 and 60 days, after at least 3 days of murisse the single or repeated addition of at least one source of at least one tetravalent element A and the hydrothermal treatment of the gel obtained at the end of step (iii) at a temperature of between 20 ° C. and 200 ° C. ° C, under autogenous reaction pressure, for a period of between 1 hour and 14 days, to obtain the crystallization of said nanometric zeolite Y structural FAU type.
    公开号:FR3031513A1
    申请号:FR1550149
    申请日:2015-01-08
    公开日:2016-07-15
    发明作者:Mathias Dodin；Nicolas Bats
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a new process for the preparation of a zeolite Y of structural type FAU whose crystal size is less than 100 nm, which is called throughout the rest of the text "nanoscale zeolite" and having an Si / Al ratio of structure greater than 2, in the absence of organic structuring species, and with addition during the ripening step of a source of a tetravalent element A (A = Si). Said nanometric zeolite of structural type FAU advantageously finds its application as a catalyst, adsorbent or separating agent.
    [0002] Prior art Zeolites, or molecular sieves, are crystalline materials consisting of a three-dimensional arrangement of interconnected TO4 tetrahedra (T may be Si, Al, B, P, Ge, Ti, Ga, Fe, for example). The organization of elements TO4 generates an ordered network of micropores consisting of channels and cavities whose dimensions are compatible with small organic molecules. Depending on how the framework atoms are arranged, different zeolitic structures can be distinguished (there are currently more than 220 [http://www.izastructure.org/databases]). Each structure therefore has a clean crystal lattice which can be identified by its X-ray diffraction pattern. The applications of zeolites are numerous and relate to fields such as catalysis, adsorption, ion exchange or purification. The use of a zeolite is conditioned by the characteristics of its porous network (dimensions, etc.) and its chemical composition. An aluminosilicic zeolite has a negatively charged framework, because of the charge deficit provided by each aluminum atom relative to silicon, and which therefore requires the presence of easily exchangeable compensation cations (Na +, K +, etc.). When these are replaced, partially or completely, with NH 4 + ammonium cations, it is then possible to calcine the zeolite in order to obtain an acid structure 3031513 2 (the NH 4 + are converted to H + by removal of NH 3). Such materials then find applications in acid catalysis, where their activity and their selectivity will depend on the strength of the acid sites, their density and their location, as well as their accessibility.
    [0003] Among the main zeolites used today are the FAU structural type zeolites, which are used in many industrial processes such as, for example, catalytic cracking of heavy petroleum cuts. These zeolites exist in their natural state: faujasite was first described in 1842 following its discovery in Germany [A. Damour, Annales des Mines 4 (1842) 395], but it was not until more than a century later that it was first obtained in the laboratory. In the synthetic state, two forms are distinguished: zeolite X having a Si / Al ratio of structure between 1 and 1.5 [R.M. Milton, U.S. Patent 2,882,244, 1959] and zeolite Y for which the Si / Al ratio is greater than 1.5 [D.W. Breck, US Patent 3,130,007, 1964].
    [0004] The face-centered cubic structure with 192 TO4 tetrahedra (Fd-3m space group) of faujasite was solved as early as 1958 [G. Bergerhoff, W. H. Baur, W. Nowaki, Neues Jahrb. Ore. Monatsh. 9 (1958) 193] and can be described as an assembly of sodalite cages, consisting of 24 tetrahedra, interconnected by 6-6 building units ("double cycles to 6" or "d6") in symmetry of the type The folejasite mesh parameter a0 can vary between 24.2 and 24.8Å according to the Si / Al framework ratio [DW Breck, EM Flanigen, Molecular Sieves, Society of Chemical Industry, London ( 1968) 47, JR Sohn, SJ DeCanio, JH Lunsford, DJ O'Donnell, Zeolites 6 (1986) 225, H. Fichtner-Schmittler, U. Lohse, G. Engelhardt, V. Patzelova, Cryst, Res Technol 19 (1984)] Within the structure, the arrangement of the tetrahedra gives rise to supercages having a maximum diameter of 11.6 Å and acting as nanoreactors suitable for hydrocarbon cracking and gas adsorption. Moreover, the pore of the faujasite, with a diameter of 7.4 Å for 12 T04 tetrahedrons, allows a good diffusion of the molecules. ules within the porous network [C. Baerlocher, L. B. McCusker, D. H. Oison, Atlas of the Zeolite Framework Type, 6th revised edition, Elsevier (2007)].
    [0005] An object of the present invention is to provide a method for preparing a structural type Y zeolite Y having nanoscale dimensions. Nanoscale zeolites have a strong interest in catalysis because of their improved diffusion properties: unlike zeolites of micrometric dimensions in which the length of the intracrystalline diffusion paths causes a restriction of the catalytic performances [Y. Tao, H. Kanoh, L. Abrams, K. Kaneko, Chem. Rev. 106 (2006) 896] and progressive deactivation of the catalyst [K. Na, M. Choi, R. Ryoo, Micro. Meso. Mater. 166 (2013) 3], nanoscale zeolites exhibit gains in activity and selectivity [D. Karami, S. Rohani, Petroleum Science and Technology 31 (2013) 1625; Q. Cui, Y. Zhou, Q. Wei, X. Tao, Yu G., Y. Wang, Yang J., Energy & Fuels 26 (2012) 4664]. The present invention makes it possible to obtain a zeolite Y of structural type FAU and whose crystals have dimensions of less than 100 nanometers. An advantage of the preparation method according to the invention is that it makes it possible to obtain such a nanometric Y zeolite of FAU structural type having both a crystal size of less than 100 nm and a high Si / Al ratio and in particular a higher at 2, prepared by the process according to the invention, with a very good crystallinity, compared to conventional methods of the prior art not allowing the production of zeolite Y with a high Si / Al ratio. SUMMARY OF THE INVENTION The subject of the present invention is a method for preparing a nanometric zeolite of structural type FAU having a crystal size of less than 100 nm and an Si / Al ratio greater than 2, preferably greater than 2. , 3, more preferably greater than 2.5 and most preferably greater than 2.6, said method comprising at least the following steps: i) mixing, in an aqueous medium, at least one source A02 of at least one tetravalent element A chosen from among silicon, germanium, titanium alone or as a mixture of at least one source BOb of at least one trivalent element B chosen from aluminum, boron, iron, indium, gallium, alone or as a mixture, of at least one C2,, 0 source of an alkaline or alkaline earth metal C selected from lithium, sodium, potassium, calcium, magnesium alone or in a mixture, said C2 / m0 source of alkali metal or alkaline earth metal C also comprising at least one source of hydroxide ions to obtain a gel, the reaction mixture having the following molar composition: ## STR1 ## being between 1 and 40, preferably between 1 and 20, and very preferably between 15 and 20, w being between 0.1 and 5, preferably between 0.2 and 1.5, x being between 1 and 40, preferably between 1 and 20, y being between 30 and 1000, preferably between 100 and 400, b being between 1 and 3, b being an integer or rational number, m being equal to 1 or 2, ii) the maturation of the gel obtained at the end of step (i) at a temperature between -15 ° C and 60 ° C, preferably 0 ° C and 50 ° C, and very preferably between 20 and 40 ° C, with or without agitation, for a period of time between 1 and 60 days, and preferably between 3 and 30 days, very preferably between 5 and 30 days, and even more preferably between 5 and 30 days, and 20 days, iii) after at least 3 days of curing, the single or repeated addition of at least one A02 source of at least one tetravalent element A chosen from silicon, germanium and titanium, alone or as a mixture in said gel, the molar composition of the gel after the addition is as follows: And most preferably between 20 and 30, w being between 0.1 and 5, preferably between 0.2 and 1.5, - x being between 1 and 40, preferably between 1 and 20, ranging from 200 to 1000, preferably from 200 to 500, where b is an integer or a rational number, m being 1 or 2, iv) the hydrothermal treatment of the gel obtained at the end of step (iii) at a temperature of between 20 ° C. and 200 ° C., preferably between 40 ° C. and 140 ° C., preferably between 50 ° C. C and 100 ° Ct very preferably between 60 and 80 ° C, under autogenous reaction pressure, for a period of between 1 hour and 14 days, preferably between 6 hours and 7 days, preferably between 10 hours and 3 days and Very preferably between 16 hours and 24 hours, to obtain the crystallization of said nanometric zeolite Y of structural type FAU. The present invention therefore makes it possible to obtain a zeolite Y of structural type FAU having both a crystal size of less than 100 nm and an Si / Al ratio of greater than 2 by virtue of the implementation of a ripening step wherein a source of a tetravalent element A selected from silicon, germanium, titanium, alone or in admixture, is added. DESCRIPTION OF THE INVENTION In accordance with the invention, at least one source A02 of at least one tetravalent element A is incorporated in step (i) of the preparation process. According to the invention, A is chosen from silicon, germanium, titanium and the mixture of at least two of these tetravalent elements and very preferably A is silicon. The source (s) of the said tetravalent element (s) may be any compound comprising element A and capable of releasing this element in aqueous solution in reactive form. Element A is incorporated into the mixture in an oxidized form A02 or in any other form. When A is titanium, Ti (EtO) 4 is advantageously used as a source of titanium. When A is germanium, amorphous GeO 2 is advantageously used as the source of germanium. In the preferred case where A is silicon, the silicon source may be any of the sources commonly used for the synthesis of zeolites, for example silica powder, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS). Among the powdered silicas, it is possible to use precipitated silicas, especially those obtained by precipitation from an alkali metal silicate solution, pyrogenic silicas, for example "CAB-O-SIL" and silica gels. Colloidal silicas having different particle sizes, for example, having a mean equivalent diameter of between 10 and 15 nm or between 40 and 50 nm, such as those sold under registered trademarks such as "LUDOX", may be used. Preferably, the silicon source is LUDOX. According to the invention, at least one source C2,, 0 of an alkali metal or alkaline earth metal C is incorporated in step (i) of the preparation process. According to the invention, C is one or more alkali metal (s) and / or alkaline earth metal (s) preferably selected from lithium, sodium, potassium, calcium, magnesium, and the like. at least two of these metals, and most preferably C is sodium. The source (s) C2 / 0 of said alkali or alkaline earth metal C may be any compound comprising element C and capable of releasing this element in solution. aqueous reactive form. According to the invention, said C2 / 0 source of alkali metal or alkaline earth metal C can also release at least one source of hydroxide ions in aqueous solution. Preferably, the source C2,, 0 of an alkali metal or alkaline earth metal C also comprising at least one source of hydroxide ions is chosen from lithium hydroxide, sodium hydroxide and potassium hydroxide. , calcium hydroxide and magnesium hydroxide, alone or in admixture. According to the invention, at least one source BOb of at least one trivalent element B is added in step (i) of mixing the preparation process. According to the invention, said trivalent element B is chosen from aluminum, boron, iron, indium, gallium or the mixture of at least two of these trivalent elements and very preferably B is aluminum. The source (s) of said trivalent element (s) B may be any compound comprising element B and capable of releasing this element in aqueous solution in reactive form. Element B may be incorporated into the mixture in an oxidized form BOb with 1b 3 (b being an integer or a rational number) or in any other form. In the preferred case where B is aluminum, the aluminum source is preferably sodium aluminate or an aluminum salt, for example chloride, nitrate, hydroxide or sulphate, an alkoxide aluminum or alumina itself, preferably in hydrated or hydratable form, such as, for example, colloidal alumina, pseudoboehmite, gamma-alumina or alpha or beta trihydrate. It is also possible to use mixtures of the sources mentioned above. According to the invention, the different sources are added in step (i) of mixing so that the reaction mixture has the following composition 113 molar: v A02: w BOb: x C2 / mO: y H20 v being between 1 and 40, preferably between 1 and 20 and very preferably between 15 and 20, w being between 0.1 and 5, preferably between 0.2 and 1.5, 15 x being between 1 and 20. 40, preferably between 1 and 20, y being between 30 and 1000, preferably between 100 and 400, b being between 1 and 3, b being an integer or rational number, m being equal to 1 or 2, where A, B and C have the same definition as above, namely A is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, very preferably A is silicon, where B is one or more trivalent element (s) chosen from the group formed by the elements the following: aluminum, iron, boron, indium and gallium, most preferably B is aluminum, where C is one or more alkali and / or alkaline earth metal (s) chosen from lithium, sodium, potassium, calcium, magnesium and the mixture of at least two of these metals, very preferably C is sodium. Preferably, said mixing step (i) is carried out in the absence of organic structuring agent.
    [0006] Step (i) of the process according to the invention consists in preparing an aqueous reaction mixture called gel and containing at least one source A02 of at least one tetravalent element A, at least one source BOb of at least one element trivalent B, B being preferably aluminum, at least one C2, 0 source of an alkali or alkaline earth metal C, C being preferably sodium. The amounts of said reagents are adjusted so as to confer on this gel a composition allowing its crystallization into a nanometric Y zeolite of structural type FAU. It may be advantageous to add seeds to the reaction mixture during said step (i) of the process of the invention in order to reduce the time required for formation of FAU structural nanometer zeolite Y crystals and / or total crystallization time. Said seeds also promote the formation of said zeolite Y structural type FAU at the expense of impurities. Such seeds comprise crystalline solids, preferably zeolite crystals of structural type FAU. The crystalline seeds are generally added in a proportion of between 0.01 and 10% of the mass of the source of the element A, preferably oxide A02, used in the reaction mixture. Step (ii) of the process according to the invention consists in carrying out a maturation of the gel obtained at the end of step (i) of mixing. Said ripening step can be carried out with or without agitation, in static condition. In the case where said step 20 is carried out with stirring, it is preferably carried out with magnetic or mechanical stirring, with a stirring speed of between 0 and 1000 rpm. Said ripening stage advantageously operates at a temperature of between -15 ° C. and 60 ° C., preferably between 0 ° C. and 50 ° C., and very preferably between 20 ° and 40 ° C. for a period of time between 1 and 50 ° C. 60 days, and preferably between 3 and 30 days, very preferably between 5 and 30 days, and even more preferably between 5 and 20 days. According to step (iii) of the process according to the invention, after at least 3 days of curing at least one source A02 of at least one tetravalent element A chosen from silicon, germanium and titanium, alone or as a mixture , is added to the gel 3031513 9 obtained at the end of step (i) of mixing. The addition may advantageously be carried out during or after step (ii) of maturing. In the case where the addition is carried out during the ripening step (ii), the addition is preferably carried out after at least 5 days of ripening.
    [0007] The addition may be repeated one or more times, with the same or different amount. Said repeated additions may be spaced apart for a period of between 5 minutes and 3 days, and preferably between 12 and 24 hours. A has the same definition as above, namely A is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, and very preferably A is silicon. The source (s) of the said tetravalent element (s) may be any compound comprising element A and capable of releasing this element in aqueous solution in reactive form. Element A may be incorporated into the mixture in an oxidized form A02 or in any other form. Preferably, the tetravalent element A added in the step (iii) of curing the process according to the invention may be identical to or different from the tetravalent element A added in step (i) of mixing and preferably identical . In the preferred case where A is silicon, the silicon source may be any of said sources commonly used for zeolite synthesis and described in step (i) of mixing.
    [0008] At the end of the addition according to step (iii), the molar composition of the gel is as follows: ## STR3 ## where: ## STR2 ## where V is between 5 and 50, preferably between 10 and 35 and very preferably between 20 and 30, w being between 0.1 and 5, preferably between 0.2 and 1.5, x being between 1 and 40, preferably between 1 and 20, there being between 200 and 1000, preferably between 200 and 500, wherein b is an integer or rational, m being 1 or 2. According to step (iv) of the process according to the invention, the gel obtained at the end of step (iii) of adding a source of at least one tetravalent element A is subjected to a treatment. hydrothermal, carried out at a temperature between 20 ° C and 200 ° C, preferably between 40 ° C and 140 ° C, preferably between 50 ° C and 100 ° C, and very preferably between 60 and 80 ° C, under pressbn of re autogenous action, for a period of between 1 hour and 14 days, preferably between 6 hours and 7 days, preferably between 10 hours and 3 days and very preferably between 16 hours and 24 hours to obtain the crystallization of said zeolite Y nanometric structural type FAU. The gel is advantageously placed under hydrothermal conditions under an autogenous reaction pressure, possibly by adding gas, for example nitrogen. Step (iv) of the preparation process according to the invention is carried out under static conditions or with stirring. At the end of the reaction, when said nanometric Y zeolite of structural type FAU is formed following the implementation of said step (iv) of the preparation process of the invention, the solid phase formed of nanoscale Y zeolite FAU structural type is advantageously filtered, washed and dried. Drying is preferably carried out at a temperature of from 20 ° C to 150 ° C, preferably from 70 ° C to 120 ° C, for a period of time between 5 and 20 hours. The nanometric Y zeolite of structural type FAU, dried, 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 a nanometric Y zeolite of pure FAU structural type, in the absence of any other crystalline or amorphous phase. Said nanometric zeolite of FAU structural type, obtained at the end of step (iv) and optionally dried, is called synthetic crude zeolite. At the end of the drying step, said synthetic crude zeolite optionally undergoes at least one calcination step and at least one ion exchange step. For these steps, all the conventional methods known to those skilled in the art can be used.
    [0009] The calcination of the nanoscale Y zeolite of synthetic FAU structural type obtained by the process of the invention is preferably carried out at a temperature between 500 and 700 ° C and for a period of between 5 and 15 hours. The preparation process according to the invention makes it possible to obtain a Y zeolite having a crystal size of less than 100 nm, preferably less than 60 nm and preferably less than 50 nm, and a Si / Al ratio greater than 2, preferably greater than 2.3, more preferably greater than 2.5, and most preferably greater than 2.6. The size of the crystals of the zeolite obtained is measured on one or more transmission electron micrographs; it is the maximum size observed on the snapshots. As a general rule, the cation (s) C of the nanometric Y zeolite of FAU structural type obtained by the process of the invention may be replaced by one or more cation (s) of metals, and in particular those of groups IA, IB, IIA, IIB, IIIA, IIIB (including rare earths), VIII (including noble metals), as well as lead, tin and bismuth by ion exchange step. Said ion exchange step is carried out by means of any water-soluble salts containing the appropriate cation. It is also advantageous to obtain the hydrogen form of the nanometric zeolite Y of structural type FAU obtained by the preparation method 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 ammonium chloride, sulphate or nitrate . Said ion-exchange step may advantageously be carried out by suspending said FAU structural-type nano-zeolite Y in one or more times with the ion exchange solution 3031513. Said zeolite can be calcined before or after the ion exchange step, or between two ion exchange steps. The calcination of said zeolite after the ion exchange step (s) makes it possible to obtain the acid form thereof. Said acid form of the nanoscale zeolite may advantageously be used for catalysis applications. The structure of said material is identified by X-ray diffractometry, in the diffraction angle range 26 = 5 ° at 40 ° ± 0.02 °, in reflection geometry. The X-ray source is a copper anticathode supplied at a voltage of 40 kV and an intensity of 40 mA, and providing a Cu-Kal monochromatic radiation (λ = 1.5406 Å). Said zeolite Y of structural type FAU obtained by the process according to the invention advantageously has an X-ray diffraction pattern including at least the lines listed in the table corresponding to the X-ray diffraction pattern of the zeolite below: Inter-reticular distance (At) Intensity (%) 14.11 F 8.68 f 7.40 f 5.63 m 4.72 f 4.35 mf 3.87 f 3.75 FF 3.44 ff 3.29 F 3.01 mf 2.89 m 2.85 FF 2.75 mf 2.62 f 2.37 f 2.18 f 2.09 ff 15 FF = very strong; F = strong; m = average; mf = weak medium; f = weak; The relative intensity 1/10 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 pattern: ff <15; 15f <30; 30rnf <50; 50m <65; 65F <85; FF85. The zeolite obtained by the process of the invention can be used after ion exchange as an acidic solid for catalysis, that is to say as a catalyst 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 may be combined with an inorganic matrix, which may be inert or catalytically active, and to a metallic phase. The inorganic matrix can be present simply as a binder to hold small particles of the zeolite together in the various known forms of catalysts (extrudates, pellets, beads, powders), or can be added as a diluent to impose the degree of conversion in a process that would progress if not at a rate too fast leading to a clogging of the catalyst as a result of a significant formation of coke. Typical inorganic matrices include support materials for catalysts such as silica, various forms of alumina, magnesia, zirconia, oxides of titanium, boron, zirconium, aluminum phosphates, titanium , kaolin clays, bentonites, montmorillonites, sepiolite, attapulgite, fuller's earth, synthetic porous materials such as SiO2-Al2O3, SiO2-ZrO2, SiO2-Th02, SiO2-BeO, SiO2-TiO2 or any combination thereof 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 method of the invention may also be associated with at least one other zeolite and act as the main active phase or additive. The metal phase is introduced on the zeolite alone, the inorganic matrix alone or the inorganic-zeolite matrix assembly by ion exchange or impregnation with cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca , Sr, 3031513 14 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 of elements. The metals can be introduced either all in the same way, or by different techniques, at any time of 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 different metals. The catalytic compositions comprising the nanometric zeolite Y of structural type FAU prepared according to the process of the invention are generally suitable for carrying out the main hydrocarbon conversion processes and the synthesis reactions of organic compounds such as ethers. Any shaping method known to those skilled in the art is suitable for the catalyst comprising zeolite Y nanometric structural type FAU. For example, pelletization or extrusion or bead formation may be used. The shaping of the catalyst containing the zeolite prepared by the process of the invention and at least partly in acid form is generally such that the catalyst is preferably in the form of extrudates or beads for use.
    [0010] DESCRIPTION OF THE FIGURES FIGS. 1 and 2 show the X-ray diffraction patterns of the FAU-type nanoscale Y zeolites synthesized in Examples 1 and 2, in the diffraction angle range 26 = 5 ° to 40 °.
    [0011] EXAMPLES The invention is illustrated by the following examples, which in no way present a limiting character. EXAMPLE 1 Preparation of a Nanometric Zeolite X of Structural Type FAU and a Si / Algal Molar Ratio of 1.4 According to a Process Not in Accordance with the Invention A nanometric X zeolite of FAU structural type containing the elements Si and Al, with a molar ratio Si / Al equal to 1.4, is synthesized according to a method of preparation known to those skilled in the art. Typically, the aluminum source (sodium aluminate, Strem Chemicals, 99%) and the mineralizing agent (sodium hydroxide, 113 Fluka, 99%) are dissolved in deionized water with stirring. The source of silicon (Ludox AS-40, 40%, Sigma Aldrich) is then added dropwise, in order to obtain a reaction mixture whose molar composition is 15.2 SiO 2: 1 Al 2 O 3: 17 Na 2 O: 360 H2O. The reaction mixture is stirred vigorously for 17 days at room temperature. The product is then filtered and washed before drying in an oven overnight at 100 ° C. No silicon or other tetravalent sauce is added during the ripening step. The X-ray diffraction pattern of the material shown in FIG. 1 is indexable in the cubic system of the FAU structural type zeolite. Analysis of the X-ray diffractogram gives a molar Si / Al ratio of 1.4 according to the Fichtner-Schmittler equation. These characteristics correspond to a zeolite X of structural type FAU. The size of the crystals of the zeolite obtained, measured on 8 transmission electron micrographs, is between 15 and 50 nm.
    [0012] EXAMPLE 2 Preparation of the Nanometric Y Zeolite of Structural Type FAU and of the Si / Algal Mole Ratio of 2.7 According to a Process According to the Invention A nanometric Y zeolite of FAU structural type containing the elements Si and Al, with a Si / Al molar ratio equal to 2.7, is synthesized according to a preparation method 3031513 16 described in Example 1 with respect to step (i). ) mixture. Typically, the source of aluminum (sodium aluminate, Strem Chemicals, 99%) and the mineralizing agent (sodium hydroxide, Fluka, 99%) are dissolved in deionized water with stirring. The silicon source (Ludox AS-40, 40%, Sigma Aldrich) is then added dropwise, in order to obtain a reaction mixture whose molar composition is 15.2 SiO 2: 1 Al 2 O 3: 17 Na 2 O: 360 H2O. The gel thus formed is placed under strong stirring at room temperature. After 7 days of maturing, a source of silicon (Ludox AS-40, 40%, Sigma Aldrich) is added dropwise. The operation is repeated the next day and the day after tomorrow. After the 3 silicon source additions, the gel thus formed has the following composition: SiO 2: Al 2 O 3: 18.4 Na 2 O: 480 H 2 O. The reaction mixture is stirred vigorously for a further 4 days at room temperature and is transferred to a polypropylene bottle. This flask is placed in an oven at 60 ° C. for 24 hours under autogenous pressing and without the addition of gas. After cooling the flask to room temperature, the product is filtered and washed, before being oven-dried overnight at 100 ° C. The X-ray diffraction pattern of the material shown in FIG. 2 is indexable in the cubic system of zeolite of structural type FAU. Analysis of the X-ray diffractogram gives a Si / Al molar ratio of 2.7 according to the Fichtner-Schmittler equation. These characteristics also correspond to a zeolite Y of structural type FAU. The size of the crystals of the zeolite obtained, measured on 8 transmission electron micrographs, is between 15 and 50 nm.
    [0013] Example 3: not in accordance with the invention According to a process not in accordance with the invention, a gel of the same composition as that described in Example 3 is prepared after the first three additions of silicon source: SiO 2: Al 2 O 3: 18, 4 Na2O: 480 H2O. This gel is stirred vigorously at room temperature for 13 days, corresponding to the total ripening time of the gel prepared in Example 3. The reaction mixture is then transferred to a polypropylene vial. This bottle is placed in an oven at 60 ° C for 24 hires under autogenous pressure and without addition of gas. After cooling the flask to room temperature, the product is filtered and washed, before being dried in an oven overnight at 100 ° C.
    [0014] The X-ray diffraction pattern of the material shown in Figure 4 shows that no crystallized product was formed at the end of the crystallization step at 60 ° C. The preparation method described in this example does not therefore make it possible to obtain a nanometric zeolite of structural type FAU. 10
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A process for the preparation of a nanometric Y zeolite of FAU structural type having a crystal size of less than 100 nm and an Si / Al ratio greater than 2, said method comprising at least the following steps: i) mixing, in an aqueous medium, at least one source A02 of at least one tetravalent element A chosen from silicon, germanium, titanium alone or as a mixture of at least one source BOb of at least one trivalent element B chosen from aluminum , boron, iron, indium, gallium, alone or as a mixture, of at least one C2 / m0 source of an alkali or alkaline earth metal C selected from lithium, sodium, potassium, calcium, magnesium alone or in admixture, said C2 / mO source of alkali metal or alkaline earth metal C also comprising at least one source of hydroxide ions to obtain a gel, the reaction mixture having the following molar composition: v A02: w BOb: x C2 / mO: y H20 - v being between 1 and 40, - w esta n between 0.1 and 5, x being between 1 and 40, y being between 30 and 1000, b being between 1 and 3, b being an integer or rational number, m being equal to 1 or 2, ii) maturing of the gel obtained at the end of step (i) at a temperature of between -15 ° C. and 60 ° C., with or without stirring, for a period of between 1 and 60 days, iii ) after at least 3 days of ripening, the single or repeated addition of at least one source A02 of at least one tetravalent element A chosen from silicon, germanium, titanium, alone or as a mixture, in said gel, the molar composition of the gel at the end of the addition being as follows: ## EQU1 ## where v is between 5 and 50, w being between 0.1 and Wherein x is from 1 to 40, where y is an integer or a rational number; m is 1 or 2; hydrothermal gel obtained at the end of step (iii) at a temperature of between 20 ° C. and 200 ° C., under presion of an autogenous reaction, for a period of between 1 hour and 14 days, in order to obtain the crystallization of said nanometric Y zeolite of structural type FAU.
    [0002]
    The method of claim 1 wherein A is silicon.
    [0003]
    3. Method according to one of claims 1 or 2 wherein B is aluminum.
    [0004]
    4. Method according to one of claims 1 to 3 wherein C is sodium. 15
    [0005]
    5. Method according to one of claims 1 to 4 wherein the reaction mixture of step (i) mixture has the following molar composition: v A02. w BOb. x C2 / m0: y H20 - v being between 15 and 20, w being between 0.2 and 1.5, where x is between 1 and 20 and y is between 100 and 400; 1 and 3, b being an integer or rational number - m being equal to 1 or 2, where A, B and C have the same definition as above. 25
    [0006]
    6. Method according to one of claims 1 to 5 wherein sprouts comprising zeolite crystals of structural type FAU are added during step (i) of mixing. 3031513 20
    [0007]
    7. Method according to one of claims 1 to 6 wherein the tetravalent element A added in step (iii) of curing the process according to the invention may be identical to or different from the tetravalent element A added in the step (i) of mixing. 5
    [0008]
    8. Method according to one of claims 1 to 7 wherein the single or repeated addition of at least one source of at least one tetravalent element A is carried out during step (ii) curing.
    [0009]
    The method of claim 8 wherein the single or repeated addition of at least one source of at least one tetravalent element A is performed after at least 5 days of cure.
    [0010]
    10. Method according to one of claims 1 to 9 wherein the single or repeated addition of at least one source of at least one tetravalent element A is performed after step (ii) curing.
    [0011]
    11. A method according to one of claims 1 to 10 wherein the molar composition of the gel after the addition to step (iii), is the following: v A02: w BOb: x C2 / mO wherein y H2O - v is between 20 and 30, w being between 0.2 and 1.5 - x being between 1 and 20 - y being between 200 and 500 - b being between 1 and 3, b being an integer or rational number - m being equal to 1 or 2, where A, B and C have the same definition as above.
    [0012]
    12. Method according to one of claims 1 to 11 wherein the nanoscale Y zeolite structural type FAU formed at the end of step (iv) is filtered, washed and then dried at a temperature between 20 ° C and 150 ° C. 3031513 21
    [0013]
    13. The method of claim 12 wherein said zeolite obtained at the end of the drying step undergoes at least one calcination step and at least one ion exchange step.
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    同族专利:
    公开号 | 公开日
    WO2016110534A1|2016-07-14|
    US20180009670A1|2018-01-11|
    US10370256B2|2019-08-06|
    FR3031513B1|2017-02-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3690823A|1969-04-16|1972-09-12|Union Oil Co|Manufacture of silica-rich zeolites|
    CN101767799A|2008-12-31|2010-07-07|中国石油化工股份有限公司|Method for synthesizing high-silicon small grain NaY molecular sieve|
    CN104118885A|2013-04-23|2014-10-29|中国石油天然气股份有限公司|Synthetic method for NaY zeolite with high silica-alumina ratio|
    US2882244A|1953-12-24|1959-04-14|Union Carbide Corp|Molecular sieve adsorbents|
    US3130007A|1961-05-12|1964-04-21|Union Carbide Corp|Crystalline zeolite y|FR3056575B1|2016-09-23|2018-10-19|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A NANOMETRIC Y ZEOLITE|
    FR3066706B1|2017-05-24|2019-06-21|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A NANOMETRIC Y ZEOLITE IN PROTONED FORM|
    CN109305686B|2017-07-28|2020-10-13|中国石油天然气股份有限公司|Preparation method of Y-type molecular sieve|
    CN111825104A|2019-04-18|2020-10-27|中国科学院大连化学物理研究所|Method for preparing high-silicon Y molecular sieve by seed crystal method|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1550149A|FR3031513B1|2015-01-08|2015-01-08|PROCESS FOR THE PREPARATION OF A NANOMETRIC Y ZEOLITE|FR1550149A| FR3031513B1|2015-01-08|2015-01-08|PROCESS FOR THE PREPARATION OF A NANOMETRIC Y ZEOLITE|
    PCT/EP2016/050201| WO2016110534A1|2015-01-08|2016-01-07|Method for preparing a nanometric zeolite y|
    US15/542,273| US10370256B2|2015-01-08|2016-01-07|Method for preparing a nanometric zeolite Y|
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