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WO2010097108A1 - Procédé de préparation de zéolithe hybride ou de matériaux de type zéolithe - Google Patents

Procédé de préparation de zéolithe hybride ou de matériaux de type zéolithe Download PDF

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Publication number
WO2010097108A1
WO2010097108A1 PCT/EP2009/007481 EP2009007481W WO2010097108A1 WO 2010097108 A1 WO2010097108 A1 WO 2010097108A1 EP 2009007481 W EP2009007481 W EP 2009007481W WO 2010097108 A1 WO2010097108 A1 WO 2010097108A1
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zeolite
metal
nanoparticles
process according
hybrid
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Inventor
Karen Thrane HØJHOLT
Kresten Egeblad
Claus Hviid Christensen
Stig Helveg
Anders Bo Laursen
Michael Brorson
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Topsoe AS
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Haldor Topsoe AS
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Priority to PCT/EP2010/001177 priority Critical patent/WO2010097224A2/fr
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    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support
    • B01J2229/66—Synthesis on support on metal supports
    • 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
    • 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
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite

Definitions

  • the invention relates to a process for the preparation of a hybrid zeolite or hybrid zeolite-like material.
  • the invention concerns preparation of hybrid zeolite or zeolite-like material in which metal nanoparticles are encapsulated by the hybrid zeolite or zeolite-like material.
  • Incorporation of metal nanoparticles in host materials can improve the physical properties of the host material in many ways. This is known for host materials such as glasses, where application of metal nanoparticles improves the optical performance necessary for certain optical devices .
  • Materials based on noble metals dispersed on support materials of high surface area are useful in many fields, for instance catalysis. However they are generally not stable at high temperatures due to the increased mobility of the metal particles, and there have been many attempts to prepare such materials that are stable during for instance sintering, which occurs at high temperatures. The reduced stability at high temperature leads to a corresponding reduction in for instance catalytic activity after high temperature treatment.
  • Gold clusters are known to have catalytic properties for reactions such as the water gas shift reaction, CO oxidation and NO reduction and as a result much effort has been devoted to the preparation of zeolites and mesoporous materials incorporated with metal clusters and nanoparticles, with the hope that the microporouos channels in the zeolite crystals limits the migration of gold and the size of the resultant clusters.
  • the preparation of gold clusters or nanoparticles in these materials is not feasible compared to the corresponding silver or copper loaded materials due to, amongst others, the formation of metal (gold) nanoparticles both outside and inside the pores and channels of the zeolite.
  • US patent application no. 20080206562 discloses the preparation of thiol-capped gold nanoparticles which are ligand exchanged, washed, precipitated and dissolved in water to form an aqueous gold nanoparticle solution. This solution is mixed with ethanol and ammonium hydroxide followed by addition of tetraethoxysilane . After stirring and centnrifugation gold-silica core shell colloidal particles are obtained. The mixture is calcined to obtain ligand-free gold nanoparticles in hollow porous spheres of silicate .
  • the product obtained consists of mesoporous silicate particles with each silicate particle encapsulating one metal particle.
  • US patent application no. 20080072705 discloses the preparation of an iron oxide mesostructural matrix.
  • a solution of iron oxide nanoparticles in water is added to a suspension containing zeolitic nanocrystals, then mixed, dried and calcined to obtain iron oxide nanoparticles entrapped in an aluminosilicate matrix with organised mesoporosity .
  • the product obtained consists of a mesoporous amorphous material encapsulating metals or zeolite crystals.
  • Arnal et al. disclose a process for the preparation of high temperature sinter stable catalysts consisting of gold particles encapsulated by a mesoporous ZrO 2 shell. Preparation of these catalysts is complicated, requiring several steps whereby colloidal gold particles are synthesised, covered with a dense silica layer, thereafter covered by a thin layer of zirconia particles and finally silica and loose gold particles are leached out. Sinter stable catalysts are obtained.
  • Mekkawy et al. disclose electrochemical properties of gold catalysts encapsulated within host material NaY zeolite (microporous) or inside a zeolite like structure such as FSM-16 (mesoporous) .
  • the zeolite is first synthesized and partially dehydrated. Subsequent mixing, evacuating and temperature increase leads to vapourisation and migration of AuCl 3 to interact with water molecules in the zeolite pores or channels. This process requires several steps and has the additional disadvantage that the size of the zeolite pores determine the size of the molecules which can migrate into the zeolite.
  • Crystallisation encapsulation allowed the formation of gold nanoparticles having a size exceeding the pore openings of the zeolite crystals, while maintaining the crystal structure as a whole. Gold nanoparticles of 20-50 nm in diameter embedded in the zeolite crystals are seen and it is stated that gold nanoparticles of 40 nm are detected.
  • the procedure proposed by Hashimoto et al. implies that the gold nanoparticles prepared by laser ablation are primarily 40-80 nm in size, which is generally too big for catalysis.
  • a reduction of the particle sizes by an order of magnitude is needed for an efficient use of costly noble metals such as Au in catalytic applications.
  • a reduction of the particle size enhances the tendency for sintering due to the increase in surface free energy.
  • this procedure is not feasible in practise due to the laser ablation .
  • Yet another objective of the invention is to provide a process for the preparation of hybrid zeolite or zeolite- like-nanoparticle materials containing ultra-small metal nanoparticles, in which the nanoparticles are stabilized by being dispersed throughout the crystals of the zeolite or zeolite-like material.
  • the invention therefore relates to a process for the preparation of hybrid zeolite or zeolite-like materials comprising the steps of:
  • the invention also includes the use of the hybrid zeolite or hybrid zeolite-like material prepared according to the process above, as catalytic material for chemical reactions .
  • the process of the invention does not require the use of laser ablation.
  • hybrid zeolite material a conventional microporous zeolite material that has physical and chemical properties which have been modified by encapsulation of nanoparticles within the pore system of the single zeolite crystals.
  • Zeolite materials are known as aluminosilicate molecular sieves and different zeolite structures suitable for application in the process of the invention are ZSM-5, MEL (ZSM-Il), MTW (ZSM-12), Y (faujasite) and BEA (zeolite beta) . Zeolite materials may be dealuminated to modify the properties.
  • hybrid zeolite-like material a conventional microporous zeolite-like material that has physical and chemical properties which have been modified by encapsulation of nanoparticles within the pore system of the single zeolite crystals.
  • zeolite-like materials are non-silicon comprising materials such as aluminium phosphate (AlPO 4 ) molecular sieves, known as AlPO' s.
  • the product of the process of the invention is thus a hybrid zeolite or zeolite-like material with one or more nanoparticles encapsulated within each individual single crystal of the zeolite or the zeolite-like material.
  • the hybrid zeolite or zeolite-like material encapsulates at least two nanoparticles within each individual single crystal of the zeolite or the zeolite-like material.
  • the hybrid zeolite or zeolite-like material encapsulates a plurality of nanoparticles within each individual single crystal of the zeolite or the zeolite-like material.
  • the suspension containing nanoparticles comprising at least one metal is a colloidal solution obtained by dispersing nanoparticles of the at least one metal in a fluid.
  • the colloidal solution is also referred to as a colloid.
  • the suspension containing nanoparticles comprising at least one metal is a colloidal suspension obtained by dispersing nanoparticles of the at least one metal in a fluid.
  • the nanoparticles comprise at least one non-metal and the non-metal may be selected from the group consisting of boron, carbon, nitrogen, oxygen, sulphur, phosphorous and mixtures thereof.
  • the non-metal is selected from the group consisting of carbon, nitrogen, sulphur and mixtures thereof .
  • the nanoparticles comprise at least one metal and the metal is selected from the group consisting of Group IB, HB, IVB, VIIB, VIII and mixtures thereof.
  • the metal is selected from the group consisting of titanium, osmium, iridium, platinum, ruthenium, palladium, rhodium, rhenium, copper, nickel, cobalt, silver, gold, cadmium and mixtures thereof. More preferably, the metal is selected from the group consisting of gold, platinum, cadmium, titanium, copper and mixtures thereof, and most preferably the metal is gold or platinum.
  • the synthesis gel or the synthesis gel precursor of the zeolite or zeolite-like material comprises compounds of elements selected from the group consisting of aluminum, silicon, phosphorous, nitrogen, carbon and mixtures thereof.
  • the aluminum compound of the synthesis gel or the synthesis gel precursor is selected from the group consisting of sodium aluminate (NaAlO 2 ), aluminum isopropoxide (Al [OCH (CH 2 ) 2 ] 3 ) and aluminum nitrate nonahydrate (Al (NO 3 ) 3 -9H 2 O) .
  • the aluminium compound is useful in the preparation of both the hybrid zeolite material and the hybrid zeolite-like material.
  • the silicon compound of the synthesis gel or the synthesis gel precursor is selected from the group consisting of silica, silicates and mixtures thereof.
  • the silicon compound is selected from the group consisting of silica gel, tetraethyl orthosilicate, sodium silicate and mixtures thereof.
  • the silicon compound is useful in the preparation of the hybrid zeolite material.
  • the phosphorous compound is selected from the group consisting of phosphoric acid, phosphate salts and mixtures thereof.
  • phosphate salts is meant salts of phosphates, monohydrogen phosphates and dihydrogen phosphates.
  • the phosphorous compound is useful in the preparation of the hybrid zeolite-like material.
  • the carbon compound of the synthesis gel or the synthesis gel precursor may be combined with the nitrogen compound as a quaternary ammonium compound with four alkyl groups attached to a central nitrogen atom.
  • the alkyl group is selected from the group consisting of ethyl and propyl.
  • the zeolite or zeolite- like synthesis conditions include heating of the mixture from room temperature to a final temperature maximum of 200 0 C and maintaining this final temperature for a predetermined time period. It is important to reach a final temperature maximum of 200 0 C in order to ensure crystallisation of the zeolite or zeolite-like material.
  • the zeolite or zeolite-like synthesis conditions include a predetermined time period of 1-10 days and a final temperature of 100- 220°C.
  • the length of time chosen is dependent on the length of time required to ensure crystallisation of the zeolite or zeolite-like material and a final temperature of 220 0 C is suitable for many zeolites or zeolite-like materials, whereby crystallisation is ensured.
  • some zeolite or zeolite-like materials require a higher temperature than 220 0 C and more than 10 days for crystallisation.
  • the solid material containing nanoparticles is an oxide of silicon, aluminium, phosphorous, titanium, galium or mixtures thereof, or the solid material is carbon.
  • the solid material is an oxide of silicon, aluminium, phosphorous or titanium or mixtures thereof.
  • the solid material is silica, alumina, titania or mixtures thereof.
  • the solid material containing nanoparticles comprising at least one metal is obtained by impregnation of the at least one metal on the solid material followed by reduction with a reducing gas.
  • the solid material is impregnated with nanoparticles comprising platinum.
  • a most preferable embodiment of the invention is silica impregnated with platinum.
  • the reducing gas is hydrogen .
  • the solution containing nanoparticles comprising at least one metal is a colloid obtained by reducing a solution of the at least one metal with a reducing agent.
  • the colloid is a salt of the metal and the reducing agent is sodium citrate.
  • the metal is gold.
  • the colloid or the solution containing nanoparticles comprising at least one metal is cooled, mixed with a polymeric compound, optionally centrifuged and thereafter mixed with a synthesis gel for preparing an oxide of silicon, aluminium, phosphorous, titanium, gallium or mixtures thereof, to provide, under synthesis conditions, a solid material containing nanoparticles comprising at least one metal coated with said oxide.
  • a polymeric compound is useful for improving the adhesion between the metal particles and the zeolite or zeolite-like material. Complete adsorption of the polymeric compound on the metal surface is important for adhesion.
  • Polymeric compounds such as polyvinylpyrrolidone can be used.
  • the hybrid zeolite or zeolite-like material prepared by the process of the invention is useful as catalytic material in the water gas shift reaction, alcohol oxidation and CO and NO oxidation reactions.
  • Fig. 1 illustrates the synthetic approach for preparation of hybrid zeolite or zeolite-like materials
  • Figs. 2a and 2b show respectively scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of a hybrid material consisting of Au nanoparticles embedded in silicalite-1 crystals.
  • Fig. 3 shows a tomogram of the hybrid material in figs. 2a and 2b.
  • Fig. 4 shows TEM images of nanocrystals before and after calcination .
  • Fig. 5 shows a TEM image of gold nanoparticles in ZSM-5 zeolite .
  • Fig. 6 shows a TEM image of a single zeolite crystal.
  • Fig. 7 shows a section through the tomogram of the TEM image of Fig. 6.
  • Fig. 8 shows the presence of platinum nanoparticles within the single zeolite crystal.
  • the product of the process of the invention is a hybrid zeolite or zeolite-like material with nanoparticles encapsulated within the individual crystals of the zeolite or the zeolite-like material.
  • the physical and chemical properties of a conventional microporous zeolite or zeolite-like material can be modified by encapsulation of nanoparticles within the pore system of the individual zeolite crystals.
  • the nanoparticles comprise metals having specific chemical properties.
  • the resulting properties of the hybrid zeolite or hybrid zeolite-like material are a combination of the chemical properties of the encapsulated nanoparticles and the molecular sieve properties of the zeolite or zeolite- like material.
  • hybrid material a material which is a combination of a zeolite or a zeolite-like material with a nanoparticle or nanocluster.
  • the process of the invention is advantageous as it is based on synthesis of the zeolite or zeolite-like material around the individual nanoparticles, resulting in hybrid zeolite or zeolite-like material having individual crystals with regular channels whose aperture diameters are in the micropore range of less than 2 nm and simultaneously having encapsulated nanoparticles with desirable chemical properties within the crystal.
  • Carrying out the synthesis of the hybrid zeolite or zeolite-like material simultaneously with encapsulation of the nanoparticles allows prior preparation of the nanoparticles. This is advantageous because nanoparticles having specific desirable qualities such as catalytic properties, can be prepared prior to encapsulation.
  • the zeolite or zeolite-like material having the pore size required for allowing entrance of molecules with a specific size to be catalytically reacted can be chosen.
  • Combining the chosen zeolite or zeolite-like synthesis gel or synthesis gel precursor with the nanoparticles to form a mixture and synthesising hybrid zeolite or zeolite-like material under synthesis conditions for the zeolite or zeolite-like material results in a hybrid zeolite or zeolite-like material that has been tailored to catalyse a specific reaction with some specific reactants.
  • the hybrid zeolite or zeolite-like material obtained is therefore size-selective and at the same time has the catalytic properties required.
  • the hybrid zeolite or zeolite-like material prepared by the process of the invention is thus suitable as catalytic material .
  • nanoparticles comprising at least one metal can be prepared with a size less than 30 nm, thus rendering the nanoparticles particularly suitable for catalysis.
  • the nanoparticle size obtained can be as low as 8 nm.
  • the nanoparticles encapsulated in an oxide have a size of 8-15 nm before encapsulation in the zeolite or zeolite-like material.
  • the hybrid zeolite or zeolite-like material obtained by the process of the invention has the advantage of being more stable towards sintering than for instance hybrid zeolite or zeolite-like materials prepared by impregnation of precursor compounds on already prepared zeolite or zeolite-like materials. Impregnation of already prepared zeolite or zeolite-like materials with nanoparticles leads to deposition of nanoparticles on the surface of the zeolite or zeolite-like material, and these nanoparticles are more exposed to sintering than nanoparticles located inside the micropores of the zeolite or zeolite-like material.
  • Zeolite materials are known as aluminosilicate molecular sieves and different zeolite structures suitable for application in the process of the invention are ZSM-5, MEL (ZSM-Il), MTW (ZSM-12), Y (faujasite) and BEA (zeolite beta) . Zeolite materials may be dealuminated to modify the properties .
  • a solution comprising at least one metal can be prepared, and subsequently optionally the metal can be encapsulated by an oxide of for example silicon (SiO 2 ) forming a nanoparticle of a metal particle or a nanocluster surrounded by the oxide of silicon (metal/SiO 2 nanoparticle) .
  • SiO 2 oxide of for example silicon
  • a zeolite or zeolite-like material can be synthesized around the metal/SiO 2 nanoparticle with the SiO 2 participating in the synthesis of the hybrid zeolite or zeolite-like material.
  • the presence of aluminium in the synthesis gel or the synthesis gel precursor leads to the formation of a hybrid zeolite material based on aluminium and silicon, while the absence of aluminium in the synthesis gel or the synthesis gel precursor leads to the formation of a hybrid zeolite material based on silicon only, for instance silicalite.
  • the synthetic approach can comprise the following : 1.
  • the oxide of silicon can be replaced by an oxide of aluminium, phosphorous, titanium, gallium, or mixtures thereof, including mixtures with oxides of silicon.
  • the solution containing nanoparticles comprising at least one metal is mixed directly with the synthesis gel or synthesis gel precursor of the zeolite or zeolite-like material
  • the synthetic approach can comprise the following:
  • a solution comprising at least one metal can be prepared, and subsequently impregnated on a solid material to provide a solid material containing nanoparticles comprising at least one metal. Subsequently a zeolite or zeolite-like material can be synthesized around the solid material.
  • hydrothermal conditions an autogenous pressure of steam at a temperature of max. 200°C. Furthermore often a template for controlling which type of zeolite is crystallised is added.
  • hydrothermal conditions are required for preparation of the hybrid zeolite or zeolite- like material in combination with a maximum temperature of 200 0 C or 220°C, depending on which zeolite or zeolite-like material is to be prepared.
  • the synthesis of the zeolite or zeolite-like material requires a synthesis gel which can include an organic template that assists in determining the zeolite or zeolitet-like material to be obtained.
  • the organic template is typically a quartenary ammonium salt such as tetrapropyl ammonium bromide (TPA-Br) and tetrapropyl ammonium hydroxide (TPAOH) .
  • the synthesis gel or the synthesis gel precursor of the zeolite or zeolite-like material is mixed in an autoclave with the solution or suspension or solid material containing nanoparticles comprising at least one metal, to form a mixture that is converted under zeolite or zeolite- like synthesis conditions to hybrid zeolite or zeolite- material encapsulating nanoparticles comprising at least one metal.
  • the zeolite or zeolite-like synthesis conditions are autoclaving under hydrothermal conditions at a maximum temperature of 200°C or 220°C, depending on which zeolite or zeolite-like material is to be prepared, during which the zeolite or zeolite-like material crystallises. Finally the obtained product is dried and calcined, for instance at 550 0 C for removal of the template.
  • the obtained product a zeolite or zeolite-like material, is crystalline and microporous.
  • Fig. 1 illustrates an example of the synthetic approach of the process of the invention.
  • a metal nanoparticle colloid with suitable anchoring points for generation of a silica shell is prepared.
  • This is followed by encapsulation of the particles in an amorphous silica matrix.
  • the silica-nanoparticle precursor is subjected to hydrothermal conditions in order for zeolite crystallization to take place.
  • Example 1 Preparation of Au encapsulated in silicalite-1
  • a material consisting of approximately 1 nm sized Au nanoparticles embedded in silicalite-1 crystals is prepared. X-ray diffraction reveals that the material contains exclusively Au as well as MFI structured material.
  • Figs. 2a and 2b show scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of the hybrid material consisting of Au nanoparticles embedded in silicalite-1 crystals.
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • the mosaic TEM image (Fig. 2b) reveals an overall uniform contrast extending over the entire crystal superimposed by areas of darker and brighter contrast.
  • the varying contrast is attributed to varying mass-thickness contrast and so that the darker areas correspond to Au particles and the brighter areas correspond to voids in the crystal.
  • Gold particles imaged in plane view in the crystal are ca . 1 nm whereas those imaged in profile view at the crystal edges are significantly larger as well as more agglomerated.
  • Concerning the Au particles in the crystal it is not possible from the mosaic TEM image shown in Fig. 2b to determine whether the particles are located on the crystal surfaces oriented perpendicular to the electron beam or inside the zeolite crystal because the TEM image represents a two-dimensional projection of the specimen.
  • the reconstructed tomogram shows all the characteristic features observed in the TEM images except the smallest gold particles which are a result of the blurring effect caused by the weighted back projection algorithm.
  • TEM images of nanocrystals acquired before and after calcination in air at 550 0 C for 3 h were recorded.
  • the majority of the Au particles are generally 1 nm (Fig. 4a) .
  • the particles imaged in profile view at the edges of particle obtain a larger size and more round (Fig. 4b), whereas the majority of the particles imaged in plane view in the crystal remain unaltered in size, indicating that the Au particles embedded within the zeolite crystals have an enhanced stability towards sintering despite the smaller Au particles size.
  • the present synthesis approach yields a hybrid Au-silicalite-1 material with an enhanced sintering stability of the metal nanoparticles .
  • the enhanced stabilization of the Au nanoparticles is further corroborated by a series of in situ transmission electron microscopy images (Fig. 4c) obtained during exposure of the hybrid material to an oxygen atmosphere at temperatures from 25 0 C to 500 0 C.
  • the sample area contains Au particles of different sizes (Fig. 4c-e) .
  • Fig. 4c-e the larger Au particles that sinter, while the smallest particles are stable. This is regarded as unexpected since the sintering rate of nanoparticles usually scales inversely with their size.
  • the in situ observation is fully consistent with the finding that particle embedment improves the stability towards sintering.
  • Hybrid Au-silicalite-1 material prepared according to the process of the invention has been shown to consist of 1 nm sized Au embedded in the silicalite-1 crystals.3- dimensional TEM tomography shows that some Au particles are embedded within and some are on the external surface of the zeolite crystals. Moreover, calcination experiments by both ex situ and in situ TEM indicate that the nanoparticles embedded in the zeolite crystals are highly stable towards sintering, whereas the particles located at the outer surface of the zeolite tend to sinter under similar conditions .
  • Example 2 Preparation of Au encapsulated in zeolite Step 1: Preparation of Au encapsulated in SiO 2
  • Catalyst preparation Millipore water (212.5 inL, 18.2 MWcm_2 ) was vigorously stirred under reflux and a HAuC14 solution (25 mL, 2.54 K 10_3m; Alfa-Aesar, 99.99%) was added. The resultant solution was stirred until boiling point was reached again. Then, a sodium citrate solution (12.5 mL, 10 mgmL_l ; citric acid trisodium salt dehydrate, 99% purity from ACROS Organics) was added and the system was refluxed for 30 min. Finally, the resultant colloid was cooled to room temperature.
  • Step 2 Synthesis of Au encapsulated in zeolite
  • Step 1 Preparation of Pt impregnated on SiO 2 :
  • 0,256g NaOH is dissolved in 14,34g TPAOH (40 wt%) and impregnated on the Pt/SiO 2 compound. The mixture is dried over night at room temperature (25 0 C) .
  • the mixture is then transferred into a Teflon beaker inside an autoclave along with approximately 20ml water outside the beaker.
  • the autoclave is then heated in a furnace using the following heating program: room temperature -> 18O 0 C and the final temperature is maintained for 5 days. Then cooling to room temperature (25 0 C) .
  • the solid product is collected by filtration, washed with 1 1 of deionized water and dried for 12 hours at 110 0 C. Finally, the product is calcined at 550 0 C for 5 hours.
  • Example 4 TEM analysis of Au particles in ZSM-5
  • a sample containing gold particles in ZSM-5 zeolite prepared according to Example 2 was tested by TEM analysis to determine whether the gold particles were located on the surface of the zeolite crystals or whether they were encapsulated by ZSM-5.
  • Sample preparation A sample was crushed and distributed in ethanol using ultrasound. A drop of the suspension was placed on a transmission electron microscopy (TEM) grid (Cu med lacey C) .
  • TEM transmission electron microscopy
  • CM200 was used for the TEM photograph, while bright-field electron tomography was used elsewhere. Electron tomography was carried out on a single zeolite crystal with TEM depiction over tilt-angles from - 75 to 75° med 1° step. Reconstruction of the tomogram was made with Avizo.
  • Fig. 5 shows a TEM image of gold nanoparticles in ZSM-5 zeolite.
  • the gold nanoparticles shown in profile on the borders of the zeolite indicate that some gold nanoparticles are present on the surface of the zeolite crystals.
  • a single zeolite crystal is studied using tomography in order to determine whether gold nanoparticles also are located within the zeolite crystal.
  • Fig. 6 shows a TEM image of the single zeolite crystal and fig. 7 shows a section through the corresponding tomogram. Figs. 6 and 7 both show the presence of gold nanoparticles within the single zeolite crystal.
  • Fig. 7 clearly shows three gold nanoparticles in the sample with two gold nanoparticles at the periphery of the sample and one gold nanoparticle of approximately 25 nm encapsulated centrally within the sample.
  • Example 5 TEM analysis of Pt particles in ZSM-5 A sample containing platinum particles in ZSM-5 zeolite prepared according to Example 3 was analysed by TEM analysis using the procedure described in Example 3 to determine whether the platinum particles were located on the surface of the zeolite crystals or whether they were encapsulated by zeolite ZSM-5.
  • Fig. 8 shows the presence of platinum nanoparticles within the single zeolite crystal.
  • Example 6 Preparation of Au encapsulated in zeolite Step 1: gold colloid synthesis
  • HAuCl 4 -3H 2 O 0.404 g HAuCl 4 -3H 2 O are dissolved in 20.0 ml deionised water in an Erlenmeyer flask. Simultaneous 60.0 ml 0.2 M NaOH are mixed with 900 ml deionised water in an Erlenmeyer flask. Both solutions are magnetically stirred vigorously lOmin. Then 20 ml 0.203 M tetrakishydroxymethylphosphonium chloride solution and stirred another 2 min before adding the gold solution. After 30 min' s vigorous stirring the colloidal solution has reacted.
  • Step 2 silica covering of gold colloid and crystallisation to Silicalite-1
  • 260 ml of the Au colloid (prepared in step 1) is stirred vigorously in an Erlenmeyer flask on a heating plate then 69.4 ml 1 mM 3-mercaptopropyltrimethoxysilane is added. After stirring 30 min 503 ml diluted water glass (0.16 wt% SiO 2 ) is added and stirred at 500 rpm for 24 h. Next the solution is dropwise added 1.10 L 99 % ethanol under continuous stirring. 1.00 ml 25 % NH 4 OH is added. Finally 0.270 ml 98 % tetraethoxysilane is added 3 times a day until the total amount of silica has been added (9.82 ml) .
  • the solution is left stirring 16 h and the colloidal particles settled out by adding NaCl to make an over saturated solution.
  • the colloid After 16 h the colloid has precipitated and is recovered by filtration and washed in 2 L water.
  • the product is dried at 120 0 C for 16h.
  • 89.7 ml deionised water, 23.0 g 99 % ethanol, 0.110 g NaOH, and 2.91 g 40% tetrapropylammoniumhydroxide are magnetically stirred 10 min at 600 rpm.
  • 0.755 g Au in silica are added and stirred 10 min.
  • the suspension is transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 100 0 C for 72 h.
  • the solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product is dried at 120 0 C for 16h.
  • the sample is calcined at 550 0 C for 3 h to remove the template molecules.
  • Example 7 Preparation of Au encapsulated in zeolite
  • Step 1 gold nanocluster colloid synthesis
  • 0.062 g HAuCl 4 -3H 2 O is dissolved in 4.4 mL THF in a round- bottomed flask, and cooled to 0 0 C. After 30 min. 0.156 ml of 3-mercaptopropyltrimethoxysilane is added. Next the stirring is reduced around 60 rpm. After 24 h the stirring is increased anew to 1200 rpm after which 60 mg NaBH 4 dissolved freshly in 1.5 ml ice-cold deionised water is quickly added. After 3 h of reaction time, the ice bath is removed and the solution allowed to heat to room temperature. After 60 h the precipitates (by-products) are removed by filtration over a cellulose filter. The solution is diluted to the final 10 g by adding THF.
  • Step 2 silica covering of gold nanocluster colloid and crystallisation to Silicalite-1 20.0 ml of the gold colloid produced in step 1 is diluted to 420 ml by THF under vigorous stirring on a heating plate then 4.20 ml 25% NH 4 OH are added. Next 0.312 ml 98% tetraethoxysilane are added 3 times a day until the total amount of silica has been added (11.9 ml) . After the last addition the solution is left stirring 16 h and the colloidal particles settled out by gravitation.
  • the colloid After 16 h the colloid has precipitated and is recovered by filtration and washed in 2 L water. The product is dried at 120 0 C for 16h.
  • 240 ml deionised water, 61.4 g 99 % ethanol, 0.294 g NaOH, and 7.77 g 40 % tetrapropylammoniumhydroxide are magnetically stirred in an Erlenmeyer flask for 10 min at 600 rpm.
  • 2.02 g Au in silica are added and stirred 10 min.
  • the suspension is transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 100 °C for 240 h.
  • the solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product is dried at 120 0 C for 16h.
  • the sample is calcined at 550 0 C for 3 h to remove the template molecules.
  • Step 1 Pt colloid synthesis
  • Step 2 Pt colloid in silica and crystallisation to Silicalite-1
  • step 1 75.0 ml of the platinum colloid produced in step 1 is diluted to 431 ml by THF under vigorous stirring on a heating plate, then 0.200 ml 25% NH 4 OH are added. Next 0.279 ml TEOS are added 3 times a day until the total amount of silica has been added (12.6ml) . After the last addition the solution is left stirring 16 h the colloid is diluted by 300 ml deionised water and washed in n-heptane by two phase extraction. The solid product is recovered by evaporation at 120 0 C for 16h.
  • the solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product is dried at 120 0 C for
  • Step 1 Pd colloid synthesis
  • the colloid is prepared by dissolving 0.324 g Pd 2 (dibenzylidieneacetone) 3 in 150 ml THF and transferring this to an evacuated Schlenk flask fitted with a Schlenk funnel. The flask is evacuated and one bar CO atmosphere is applied. After reacting 20 min under vigorous stirring the flask is evacuated and a nitrogen atmosphere is introduced. 0.034 ml 95 % 3-mercaptopropyltrimethoxysilane is degassed in the funnel by nitrogen flow, then added and allowed to react for 16 h.
  • Step 2 Pd colloid in silica and crystallisation to Silicalite-1
  • step 1 75.0 ml of the palladium colloid produced in step 1 is diluted to 431 ml by THF under vigorous stirring on a heating plate, then 0.200 ml 25% NH 4 OH are added. Next 0.279 ml TEOS are added 3 times a day until the total amount of silica has been added (12.6ml) . After the last addition the solution is left stirring 16 h the colloid is diluted by 300 ml deionised water and washed in n-heptane by two phase extraction. The solid product is recovered by evaporation at 120 0 C for 16h.
  • 89.7 ml deionised water, 23.0 g 99 % ethanol, 0.110 g NaOH, and 2.91 g 40 % tetrapropylammoniumhydroxide are magnetically stirred in an Erlenmeyer flask for 10 min at 600 rpm. 0.755 g Pd in silica are added and stirred 10 min.
  • the suspension is transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 100 0 C for 240 h.
  • the solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product is dried at 120 0 C for 16h.
  • the sample is calcined at 550 0 C for 3 h to remove the template molecules.
  • Example 10 Preparation of rutile TiO 2 encapsulated in zeolite
  • Step 1 Rutile TiO 2 colloid synthesis
  • Step 2 Rutile TiO 2 in ZSM-5 (zeolite hybrid material)
  • the solid product is recovered and washed in deionised water by filtration on a cellulose filter.
  • the product a zeolite hybrid material, is dried at 120 0 C for 16h.
  • the sample is calcined at 550 0 C for 3 h to remove the template molecules.
  • Example 11 Preparation of anatase TiO 2 encapsulated in zeolite
  • Step 1 anatase TiO 2 colloid synthesis
  • TiOSO 4 solution 413 ml 15 % TiOSO 4 solution is added dropwise to 14.53 ml 90 % Lactic acid in 330 ml deionised water under stirring. The final mixture is heated to 70 0 C for 5 days. The solid product is recovered by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times. The product is dried at 120 0 C for 16h.
  • Step 2 anatase TiO 2 in ZSM-5 (zeolite hybrid material)
  • the solid product is recovered and washed in deionised water by filtration on a cellulose filter.
  • the product a zeolite hybrid material, is dried at 120 °C for 16h.
  • the sample is calcined at 550 0 C for 3 h to remove the template molecules.
  • Example 12 Preparation of CdS encapsulated in zeolite Step 1: synthesis of CdS covered in silica colloid 92.O g Triton XlOO (polyoxyethylene ( 10 ) octylphenyl ether) is mixed with 48.1g 1-butanol, and 212g cyclohexane to make a clear emulsifier solution. A H of this is mixed with 0.678g Cd(NO 3 ) 2 - 4H 2 O in 11.0 g deionised water to make a clear emulsion.
  • Triton XlOO polyoxyethylene ( 10 ) octylphenyl ether
  • Another H of the emulsifier solution is mixed with 0.341 ml 40-48 % (NH 4 ) 2 S solution in 11.0 g deionised water to make a clear yellow solution.
  • the Cd emulsion is degassed in a Schlenk funnel fitted on an evacuated Schlenk flask by sparking the solution with nitrogen for 5 min.
  • the Cd emulsion is stirred at 900 rpm while the sulphide emulsion is degassed in the funnel.
  • the two emulsions are mixed under nitrogen for 2 h.
  • the rest of the emulsifier solution is mixed with 22.0 g 25 % NH 4 OH to make a clear solution which is degassed prior to adding it to the CdS emulsion.
  • 0.315 ml 98 % tetraethoxysilane are added and stirred 72 h.
  • 1.07 ml tetraethoxysilane are added and stirred 24 h, this is repeated 4 times.
  • 54.57 ml tetraethoxysilane are then added and stirred 24 h.
  • the emulsion is ruptured by adding 200 ml acetone and leaving the solid to precipitate for 16 h.
  • the solid is recovered by filtration and washed in 1 L 1:1 water/ethanol mixture, then 0.5 L water.
  • the solid is dried overnight at room temperature under Al-foil.
  • Step 2 template free synthesis of CdS in ZSM-5 (zeolite hybrid material)
  • 0.261 g NaOH, 1.00 g CdS in silica produced in step 1, and 11.75 ml deionised water are mixed 10 min on a heating plate at 500 rpm.
  • 0.217 g Al 2 (SO 4 ) 3 • 8H 2 O are dissolved in
  • Step 1 synthesis of Cu covered in silica colloid
  • Triton XlOO 200 g Triton XlOO is mixed with 50.0 g 1-pentanol, and 1937 g cyclohexane to make a clear emulsifier solution.
  • Half of this is mixed with 0.825 g CuCl 2 -2H 2 O in 21.75 ml deionised water and stirred until clear emulsion is obtained.
  • the other half of the emulsifier solution is mixed with 0.332 g NaBH 4 solution in 21.75 ml deionised water to make a clear solution.
  • the NaBH 4 emulsion is degassed in a Schlenk funnel fitted on an evacuated Schlenk flask by sparking the solution with nitrogen for 5 min.
  • the NaBH 4 emulsion is stirred at 900 rpm while the Cu emulsion is degassed in the funnel.
  • the two emulsions are mixed under nitrogen for 2 h.
  • the solution is added 51.33 ml 98 % tetraethoxysilane and stirred 24h.
  • 4 ml 0.2 M NaOH are added next after which the solution is heated to 50 °C over night.
  • 100 ml 0.2 M NaOH are added to secure condensation of the silica after 3 h the emulsion is ruptured by adding 1 L acetone. After another 3 h the solid may be recovered by filtration on a cellulose filter. Drying this product at 120 °C overnight yields a CuO 2 product.
  • Step 2 crystallisation of Cu in silica to Silicalite-1 89.7 ml deionised water, 23.0 g 99 % ethanol, 0.11 g NaOH, and 2.91 g 40 % tetrapropylammoniumhydroxide are magnetically stirred in an Erlenmeyer flask for 10 min at 600 rpm. 0.755 g Cu in silica produced in step 1 are added and stirred 10 min. The suspension is transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 100 0 C for 240 h. The solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times. The product is dried at 120 0 C for 16h. The sample is calcined at 550 0 C for 3 h to remove the template molecules and reduce any malachite to copper oxide.
  • Example 14 Preparation of Cu encapsulated in zeolite Step 1: As example 13, step 1.
  • Step 2 template free synthesis of Cu in ZSM-5
  • 0.261 g NaOH, 1.00 g Cu in silica (step 1), and 11.75 ml deionised water are mixed 10 min on a heating plate at 500 rpm.
  • 0.217 g Al 2 (SO 4 ) 3 • 8H 2 O are dissolved in 11.75 ml deionised water.
  • the aluminium source is added to the Cu suspension produced in step 1 and stirred another 10 min.
  • the suspension is then transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 180 0 C for 5 days.
  • the solid product is recovered centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product is dried at 120 0 C for 16h.
  • Example 15 Preparation of Co/Pt alloy encapsulated in zeolite
  • Step 1 synthesis of solid Co/Pt alloy in silica 200 mL of 12.9 mM NaBH 4 and 0.409 mM citric acid in deionised water is degassed in a Schlenk funnel under nitrogen prior to introduction into an evacuated Schlenk flask. This solution is stirred under nitrogen at 600 rpm. Next 52.5 ⁇ L of 0.8 M CoCl 2 in deionised water and 45 ⁇ L 0.4 M H ⁇ PtCl ⁇ also in deionised water are degassed in a Schlenk funnel and simultaneously added to the Schlenk flask.
  • Step 2 crystallisation of Co/Pt alloy in silica to silicalite-1
  • 29.7 ml deionised water, 7.62 g 99 % ethanol, 0.0364 g NaOH, and 0.964 g 40 % tetrapropylammoniumhydroxide are magnetically stirred in an Erlenmeyer flask for 10 min at 600 rpm. 0.250 g Co-Pt-alloy in silica are added and stirred 10 min.
  • the suspension is transferred to a 150 ml Teflon lined autoclave, sealed, and heated to 100 0 C for 240 h.
  • the solid product is recovered and washed in deionised water by centrifugation at 9000 rpm for 12 min this cycle is repeated 5 times.
  • the product, zeolite hybrid material is dried at 120 0 C for 16h.
  • the sample is calcined at 550 °C for 3 h to remove the template molecules .

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Abstract

La présente invention concerne un procédé de préparation de zéolithe hybride ou de matériaux de type zéolithe, comportant les étapes consistant à utiliser une solution ou une suspension ou un matériau solide contenant des nanoparticules comprenant au moins un métal, à utiliser un gel de synthèse ou un précurseur d'un gel de synthèse d'une zéolithe ou d'un matériau de type zéolithe, à mélanger le gel de synthèse ou le précurseur du gel de synthèse de la zéolithe ou du matériau de type zéolithe avec la solution ou la suspension ou le matériau solide contenant les nanoparticules comprenant au moins un métal pour obtenir un mélange, à convertir le mélange, dans des conditions permettant la synthèse de zéolithe ou de matériaux de type zéolithe, en zéolithe hybride ou en un matériau de type zéolithe encapsulant des nanoparticules comprenant au moins un métal.
PCT/EP2009/007481 2009-02-27 2009-10-19 Procédé de préparation de zéolithe hybride ou de matériaux de type zéolithe Ceased WO2010097108A1 (fr)

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