WO2004014798A1 - Aluminosilicates mesopores et micropores a activite catalytique elevee dans des reactions de catalyse acide et leur procede de preparation - Google Patents

Aluminosilicates mesopores et micropores a activite catalytique elevee dans des reactions de catalyse acide et leur procede de preparation Download PDF

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WO2004014798A1
WO2004014798A1 PCT/ES2003/000397 ES0300397W WO2004014798A1 WO 2004014798 A1 WO2004014798 A1 WO 2004014798A1 ES 0300397 W ES0300397 W ES 0300397W WO 2004014798 A1 WO2004014798 A1 WO 2004014798A1
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type material
material according
obtaining
porous aluminosilicate
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Javier AGÚNDEZ RODRÍGUEZ
Isabel DÍAZ CARRETERO
Carlos MÁRQUEZ ÁLVAREZ
Joaquín PÉREZ PARIENTE
Enrique SASTRE DE ANDRÉS
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Consejo Superior de Investigaciones Cientificas CSIC
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction

Definitions

  • This invention relates to materials of the type of microporous and mesoporous alos inosilicates that have a high catalytic activity in acid catalysis reactions, their preparation process and their use as a catalyst for hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation , dimerization and polymerization.
  • Zeolitic materials are widely used as catalysts in the refining and petrochemical industries and in the synthesis of high added value chemical compounds. Its catalytic behavior is due to the presence in these materials of highly acidic active centers, which allow catalyzing a large number of reactions of industrial interest.
  • Both zeolites (crystalline aluminosilicates) and zeolitic materials in general have a crystalline structure in which there are microporous cavities and channels, whose access is limited by openings whose diameter is always less than 2.0 nm, and in most cases it does not exceed 0.8 nm.
  • the size of the cavities and channels present in the structure of zeolites and zeolitic materials is adequate to transform or produce molecules that are small enough, for example, to produce an isomer excluding other possible ones (property known as shape selectivity), it is a Often too small to transform bulky molecules, which cannot access the interior of the microporous system. This represents a severe limitation for the use of zeolites and zeolitic materials in numerous chemical processes of industrial interest.
  • M41S mesoporous materials
  • M41S WO Pat. 91/11390 (1991)
  • These materials are characterized by having a regular distribution of pores whose size, between 2.0 nm and 10.0 nm, is within the mesopore range, therefore, they do not have the limitations of zeolites to process bulky molecules.
  • these materials are amorphous, that is, the inorganic skeleton is made up of a network of SiO 4 and AlO 4 tetrahedra linked in a disorderly way through the oxygen atoms .
  • porous materials that have a regular pore size distribution and an average pore diameter greater than that of zeolites and similar catalytic activity.
  • This invention relates to new materials of the microporous and mesoporous aluminosilicate type with a chemical composition expressed by the following formula (in moles of oxides): Al 2 O 3 : m SiO 2 : n M 2 O where the value of m is included between 2 and 50, preferably between 4 and 10; M represents the Na + or H + cations, and the value of n is between 0.01 and 2, preferably between 0.1 and 1.
  • These materials have a regular distribution of pores whose average diameter is between 1.0 nm and 15 nm. They also have a high catalytic activity in acid catalysis reactions. Their preparation procedure and their use as catalysts of hydrocarbon transformation reactions, such as cracking, isomerization, transalkylation, alkylation, dimerization and polymerization, are described.
  • the present invention refers to the preparation of porous structures that have a lattice formed by the union of SiO 4 and AlO 4 tetrahedra, with a molar ratio of silicon to aluminum between 1 and 100, which have a regular distribution of pores whose average diameter is between 1.0 nm and 15.0 nm, at least one X-ray diffraction peak corresponding to a spacing between 1.5 nm and 20.0 nm, a BET surface area between 300 m 2 / g 1400 m 2 / g, a total pore volume of between 0.2 cm / g and 2.0 cm / g, an acidity determined by the amount of pyridine retained in the sample after heating and vacuuming at 250 ° C of at least 10 "5 ⁇ mol / gsóiido, a catalytic activity in the transformation of m-xylene such that for a contact time value expressed as W / F (gh / mol) between 0.5 and 1 the conversion of -xy
  • the procedure for obtaining the porous materials object of the present invention comprises a two-stage process.
  • a solution A is prepared, called "faujasite zeolite precursor solution". whose main but not only characteristic is that it contains the tetramethylammonium cation.
  • a solution B is prepared whose main but not only characteristic is that it contains a cationic surfactant, which is mixed with solution A.
  • the preparation of this solution comprises treating an aluminum source, such as aluminum hydroxide, with an aqueous solution of tetramethylammonium hydroxide, in which a source of sodium is present, until the dissolution of the aluminum hydroxide is achieved.
  • an aluminum source such as aluminum hydroxide
  • an aqueous solution of tetramethylammonium hydroxide in which a source of sodium is present, until the dissolution of the aluminum hydroxide is achieved.
  • a source of sodium are sodium hydroxide and various soluble sodium salts, such as sodium chloride, sodium sulfate, or sodium nitrate.
  • the aluminum hydroxide used in the invention can be advantageously prepared by precipitating it from a solution of a soluble aluminum salt, such as aluminum sulfate or aluminum nitrate, by mixing it with a solution of a base, such as ammonium hydroxide.
  • a soluble aluminum salt such as aluminum sulfate or aluminum nitrate
  • metallic aluminum can be dissolved in the tetramethylammonium hydroxide solution.
  • the value of y is between 0.2 and 10, preferably between 0.5 and 5.
  • the value of z is between 0.001 and 0.2, preferably between 0.01 and 0.1.
  • the treatment of said hydroxide with the basic solution containing tetramethylammonium and a sodium source is carried out at a temperature between 10 ° C and 100 ° C, preferably between 20 ° C and 60 ° C, for a time between 5 minutes and 5 hours, preferably between 10 minutes and 1 hour.
  • the objective of this treatment is to achieve the complete dissolution of the aluminum hydroxide.
  • the resulting solution is mixed with a silicon source, non-limiting examples of which are colloidal silica, precipitated silica, pyrogenic silica, or silicon alkoxides, such as tetramethoxysilane and tetraethoxysilane.
  • a silicon source non-limiting examples of which are colloidal silica, precipitated silica, pyrogenic silica, or silicon alkoxides, such as tetramethoxysilane and tetraethoxysilane.
  • the silicon source can be reacted with a portion of the tetramethylammonium hydroxide solution used in the preparation.
  • colloidal silica is used as the silicon source, it can optionally be treated with a cation exchange resin in order to decrease the content of alkaline cations, preferably sodium, that it contains.
  • the value of x is between 2 and 10, preferably between 3 and 5.
  • solution A can contain one or more alcohols (ROH) that have a number of carbon atoms between 1 and 6, can be linear or branched , and preferably methanol, ethanol, or mixtures of both.
  • ROH alcohols
  • the value of v is between 0 and 200, preferably between 0 and 50.
  • the value of w (moles of water for each mole of Al 2 O 3 of the gel) is between 50 and 5000, preferably between 200 and 1000.
  • solution A is prepared, it is aged at a temperature between 4 ° C and 150 ° C, preferably between 60 ° C and 110 ° C, for a period of time between 10 minutes and 7 days, preferably between 1 hour and 48 hours. It is characteristic of the present invention that the aging of solution A is carried out under conditions of temperature and time such that the formation of faujasite crystals at the end of aging is not detected. For this reason, solution A is referred to in the present invention as "faujasite precursor solution”.
  • Solution B is prepared by dissolving one or more cationic surfactants in water, an organic solvent, or a mixture of both.
  • Non-restrictive examples of this cationic surfactant They are hexadecyltrimethylammonium, dimethyldidodecylammonium, and benzyltrimethylammonium.
  • Solution B to which the invention refers may contain one or more of the surfactants described, and its proportion by weight with respect to the solvent is between 2 and 50%, preferably between 10% and 30%.
  • the preferred solvent to prepare solution B is water, but optionally an alcohol or mixture of two or more alcohols, or a mixture of alcohols with water can be used.
  • the alcohols used can contain a number of carbon atoms between 1 and 6, preferably methanol or ethanol.
  • solution B can contain tetramethylammonium and optionally also sodium, in a proportion not exceeding 90% of the tetramethylammonium and 90% of the sodium contained together in solutions A and B.
  • the molar ratio between the silica in solution A and the cationic surfactant in solution B is between 0.1 and 15, preferably between 0.5 and 5.
  • Solution B can contain a proportion of the total solvent used in the preparation comprised between 1% and 95%, preferably between 10% and 50%.
  • the gel resulting from the mixture of solutions A and B is heated to a temperature between 20 ° C and 200 ° C, preferably between 100 ° C and 180 ° C, for a period of time between 30 minutes and 7 days, preferably between 1 hour and 48 hours.
  • the solid product obtained after this heating step is filtered, washed with deionized water and dried.
  • the product thus obtained is heated in air at temperatures between 400 ° C and 800 ° C, preferably between 500 ° C and 700 ° C, in order to eliminate the organic matter it contains.
  • the calcination can be carried out in an atmosphere of an inert gas, such as nitrogen, optionally followed by a calcination in air.
  • the calcined material obtained by the procedure described in the present invention is characterized by having a chemical composition expressed by the following formula (in moles of oxides):
  • n 0.01 and 2 preferably between 0.1 and 1.9.
  • porous material obtained according to the procedure described in the present invention is distinguished by having the following characteristics:
  • the material described in the invention can be used in a wide variety of hydrocarbon transformation reactions, among which catalytic cracking, isomerization, hydroisomerization, hydrocracking, alkylation, dimerization and polymerization can be mentioned as examples, among which it is worth mentioning how Non-limiting example of w-xylene conversion.
  • Figure 1 X-ray diffractogram of the calcined sample obtained according to the procedure described in Example 1. The box that appears inside the figure includes the diffractogram in the region of values of 2 ⁇ between 4 ° and 40 ° .
  • Figure 2. Nuclear Magnetic Resonance Spectrum of 27 A1 with Magic Angle Rotation of the calcined sample obtained according to the procedure described in Example 1.
  • Example 1 illustrate the invention without, however, constituting a limitation of the invention.
  • a solution A is prepared with the following composition: Al 2 O 3 : 1.53 (TMA) 2 O: 0.088 Na 2 O: 3.62 SiO 2 : 246 H 2 O
  • a solution of 53.20 g of aluminum sulfate in 135 g of milliQ water is prepared.
  • Al (OH) 3 is precipitated by adding 60.01 g of H 4 OH (30%) to the solution, filtered and washed with deionized water.
  • 89.64 g of TMAOH (25% by weight aqueous solution) 142.42 g of milliQ water and 15.08 g of NaOH are placed in a polypropylene (PP) bottle. It is stirred for 15 minutes and then Al (OH) 3 is added . Stir until the hydroxide is completely dissolved, which occurs in 20 minutes.
  • the dry solid product is calcined at a temperature of 550 ° C under N 2 flow for 1 hr, followed by air at the same temperature for 6 hr.
  • the BET surface of the sample is 692 m 2 / g, its volume of pore of 0.37 cm 3 / g and its average pore diameter of 2.0 nm.
  • the chemical composition of the solid (by weight) is: 73.7% SiO 2 , 25.3% Al 2 O 3 and 1.0% Na 2 O.
  • Figure 2 shows the rotating nuclear magnetic resonance spectrum.
  • the signal at 1 ppm is characteristic of aluminum atoms that are in an extrareticular octahedral environment, while the signal at 55 ppm indicates the presence of tetrahedral aluminum, that is, belonging to the inorganic skeleton of the material.
  • the signal at 27 ppm can be attributed to pentacoordinated aluminum or to aluminum in strongly distorted tetrahedral coordination.
  • the concentration of pyridine that remains adsorbed determined from the band at 1545 cm "1 corresponding to the pyridinium ion is 2, lxl O "5 ⁇ mol / g Só .i do -
  • this sample produces a reagent conversion of 21%.
  • a solution A is prepared with the following composition:
  • the X-ray diffraction diagram of the calcined solid shows a strong peak at a spacing value of 2.5 nm; a BET area of 687 m 2 / g; a pore volume of 0.37 cm 3 / g and an average pore diameter of 2.2 nm.
  • the chemical composition of the solid by weight is 74.2% SiO 2 , 24.8% Al 2 O 3 and 1.0% Na 2 O.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention se rapporte à de nouveaux matériaux de type aluminosilicates micropores et mésopores présentant une composition chimique exprimée par la formule suivante (en moles d'oxydes): Al2O3 : m SiO2 : n M2O où la valeur de m est comprise entre 2 et 50, de préférence entre 4 et 10; où M représente les cations Na+ o H+, et où la valeur de n est comprise entre 0,01 et 2, de préférence entre 0,1 et 1. Ces matériaux possèdent une distribution régulière de pores dont le diamètre moyen est compris entre 1,0 nm et 15 nm. Ces matériaux présentent également une activité catalytique élevée dans des réactions de catalyse acide. L'invention concerne le procédé de préparation et d'utilisation en tant que catalyseurs de réactions de transformation d'hydrocarbures, tels que le craquage, l'isomérisation, la transalquilation, l'alquilation, la dimérisation et la polymérisation.<>
PCT/ES2003/000397 2002-08-01 2003-07-31 Aluminosilicates mesopores et micropores a activite catalytique elevee dans des reactions de catalyse acide et leur procede de preparation Ceased WO2004014798A1 (fr)

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ES200201821A ES2201915B1 (es) 2002-08-01 2002-08-01 Aluminosilicatos mesoporosos y microporosos con elevada actividad catalitica en reacciones de catalisis acida y su procedimiento de preparacion.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7678955B2 (en) 2005-10-13 2010-03-16 Exxonmobil Chemical Patents Inc Porous composite materials having micro and meso/macroporosity
CN101003380B (zh) * 2006-01-19 2010-05-12 中国石油化工股份有限公司 一种多级孔道zsm-5沸石的合成方法
CN107519933A (zh) * 2016-06-21 2017-12-29 中国石油天然气股份有限公司 Y/eu‑1/sba‑15/asa/mof复合材料及其制备方法
EP3184873A4 (fr) * 2014-10-20 2018-01-24 LG Chem, Ltd. Matériau de partie centrale pour matériau d'isolation à vide ayant un aluminosilicate poreux et matériau d'isolation à vide le comportant
US20250161916A1 (en) * 2023-11-20 2025-05-22 Saudi Arabian Oil Company Amorphous silica-alumina and methods of preparing

Citations (3)

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Publication number Priority date Publication date Assignee Title
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