WO1992019574A1 - Composition de catalyseur composite et procede fischer-tropsch utilisant cette composition - Google Patents

Composition de catalyseur composite et procede fischer-tropsch utilisant cette composition Download PDF

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Publication number
WO1992019574A1
WO1992019574A1 PCT/US1992/003601 US9203601W WO9219574A1 WO 1992019574 A1 WO1992019574 A1 WO 1992019574A1 US 9203601 W US9203601 W US 9203601W WO 9219574 A1 WO9219574 A1 WO 9219574A1
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Prior art keywords
catalyst
zeolite
fischer
water
composite
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PCT/US1992/003601
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English (en)
Inventor
Daniel G. Loffler
Paul F. Schubert
Françoise GUTH
Ralph A. Dalla Betta
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Catalytica, Inc.
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Publication of WO1992019574A1 publication Critical patent/WO1992019574A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • 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
    • 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
    • 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
    • B01J2229/64—Synthesis on support in or on refractory materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the eroionite or offretite type, e.g. zeolite T

Definitions

  • This invention is a composite catalyst comprising a water-gas shift catalyst coated by a thin film zeolitic material which, in turn, has a Fischer-Tropsch catalyst deposited on its outer surface.
  • the zeolite has the gatekeeper function of allowing short chain hydrocarbons and steam into the water-gas shift catalyst and allowing the return of the carbon monoxide and hydrogen products back to the Fischer-Tropsch
  • a stream of short chain hydrocarbons e.g., C 1 -C 4 alkanes or alkenes
  • steam is passed to the catalyst composite where it diffuses past the
  • Fischer-Tropsch process permits the synthesis of
  • hydrocarbons ranging from methane to high melting point paraffins, depending on the catalyst and process
  • Cobalt based catalysts for Fischer-Tropsch synthesis have been extensively used during the first half century until the end of World War II. Precipitated
  • Co-ThO 2 -MgO catalysts were the standard used in Germany's fixed bed reactors during the war. Although those catalysts gave the highest yields and longest life, they present some drawbacks. Cobalt is a relatively expensive metal, the methane fraction in the reaction products is rather high, and the metal cannot process carbon
  • the rate-controlling step is variously identified as the
  • the Fischer-Tropsch synthesis proceeds via a polymerization reaction in which the hydrocarbon product grows through the addition of single hydrocarbon monomer units.
  • This growth mechanism implies that the product distribution can be described by the Anderson-Schulz-Flory (ASF) equation for the most probable distribution.
  • ASF Anderson-Schulz-Flory
  • Hydrocarbon product distributions from carbon monoxide-H 2 synthesis including commercial data from the South African Coal, Oil, and Gas Corporation (SASOL) plant, are consistent with ASF polymerization kinetics. Very recent data obtained using sophisticated analytical techniques further support the applicability of ASF polymerization kinetics.
  • C 1 hydrocarbon intermediate for example, methanol, which can be produced from carbon monoxide and H 2 in 100% selectivity
  • methanol which can be produced from carbon monoxide and H 2 in 100% selectivity
  • a typical example of this approach is the synthesis of methanol and its subsequent reaction over ZSM-5 type zeolites, as practiced by Mobil Oil Company, to produce lower olefins or aromatics at very high selectivities.
  • Fischer-Tropsch technology is practiced on a commercial scale by SASOL. This operation uses two types of technology: an older fixed-bed (ARGE) reactor and a newer fluidized-bed (Synthol) unit. These units are differentiated by their catalysts, product distributions, productivity, and required downstream processing. The products of both of these reactors, however, are
  • catalyst composition as a function of active metal promoters, support, surface area, and porosity; temperature; pressure; feed H 2 to carbon monoxide ratio; reactor design; and conversion.
  • the Fischer-Tropsch reaction can be operated at any desired degree of polymerization to achieve the product distribution specified by the ASF polymerization model.
  • Fischer-Tropsch plants will be based on slurry phase reactors. While the technology of hydrocarbon synthesis from synthesis gas in liquid phase (slurry) reactors is relatively old, pre-World War II, the use of slurry reactors for Fischer-Tropsch chemistry is undergoing a renaissance. This is because of certain potential economic advantages, such as integration of the liquid phase Fischer-Tropsch process with the new generation of more efficient coal gasifiers.
  • Hydrocarbon synthesis in the slurry reactor is complex from an engineering standpoint due to the
  • H 2 and carbon monoxide leading to a mass transfer coefficient for H 2 that can be 37 times that for carbon monoxide.
  • catalyst surface is of paramount importance permitting this system to operate with low H 2 to carbon monoxide ratio feeds.
  • the presence of the liquid phase may have other beneficial effects. These include temperature control, avoidance of hot spots, and minimization of the Bouduard reaction; solvent washing effects to remove heavy
  • hydrocarbons and/or free carbon hydrocarbons and/or free carbon; and enhancement of the water-gas shift reaction.
  • catalysts prepared from metal salts and cobalt carbonyls deposited on supports such as silica, alumina, and titania have been studied in slurry phase reactors.
  • Promoters such as thoria and zirconia are usually
  • a zeolite Fischer-Tropsch catalyst has three potential advantages.
  • the Fischer-Tropsch function can be highly dispersed in the fresh catalyst, reducing the metal loading needed to attain a specific activity.
  • the zeolite can selectively modify (by acid catalyzed shape selective reactions) the primary Fischer-Tropsch product.
  • a water-gas sift function could be introduced into a molecular sieve based catalyst.
  • CoAPO-34 could be modified by Zn and Cu components as to introduce the water gas shift activity.
  • Our approach is to introduce a water-gas shift function in the catalyst and yet zeolite composite materials with high surface area.
  • These novel materials comprise a conventional porous support lined with a thin layer of zeolite crystallites providing a useful high surface area.
  • the zeolitic layer can support the cobalt metal providing the Fischer-Tropsch function, while serving as a "gatekeeper" for a water-gas shift function located at a catalytic surface beneath it.
  • the molecules participating in the water-gas shift reaction may diffuse through the zeolite layer to catalytic sites on the porous support.
  • the larger hydrocarbon molecules, unable to enter the zeolite pore structure, will react only on the Fischer-Tropsch active sites located on the zeolite surface.
  • this invention is a composite catalyst having an inner water-gas shift catalyst, a thin film of a zeolite coating the water-gas shift catalyst, and a Fischer-Tropsch catalyst dispersed throughout the outer surface of the zeolitic layer. Additionally, the intention involves a process of using the composite upon a hydrocarbon steam stream to produce higher molecular weight hydrocarbons through complementary water-gas and Fischer-Tropsch reactions in the catalyst composite. Preparation of Zeolites
  • zeolite materials are prepared by crystallization from solution.
  • High surface area zeolite coated metals have been prepared by nucleating zeolite crystallites in solution and letting them settle gravitationally onto copper foils (Davis et al, 1990).
  • zeolite crystallization on porous supports such as silica, alumina, zirconia, thoria, or mixtures. These are novel materials because of their structure.
  • the surface of the support is substantially or completely lined by a thin layer of zeolite
  • the key to preparing high surface area zeolites is to obtain small crystallites with a narrow size distribution. Reducing the crystallite size increases the surface to volume ratio. For cube shaped crystals, a tenfold decrease in particle size results in a 100 fold increase in external surface to volume ratio.
  • the zeolite crystallites can be envisaged either as
  • perturbation of the zeolite structure and its electronic field may occur at the zeolite/matrix interface
  • thermogravimetric analysis- differential scanning calorimeter TGA-DSC
  • cobalt Fischer-Tropsch catalysts The major constituents of cobalt Fischer-Tropsch catalysts are cobalt, a second metal (generally Re or Ru, although Pt and Pd may also be used) oxide promoters (ThO 2 , ZrO 2 , Al 2 O 3 , MgO, MnO) and the support. It is likely that the function of the second metal is to lower the reduction temperature of cobalt, presumably by providing a source of spill over hydrogen atoms that facilitates the reduction of the cobalt and prevents the formation of coke. The oxide promoters probably improve the selectivity and lower the deactivation rate of the catalyst.
  • Our materials are molecular sieve based cobalt catalysts. These are basically dual function catalysts where the cobalt metal provides the Fischer-Tropsch function while the molecular sieve modifies the product and protects the water-gas shift function from
  • the acidity of the support has to be carefully controlled to obtain the desired product (long chain paraffins) and low methane selectivity. This can be achieved adding alkali and alkaline earth promoters (i.e Li, Na, K, Ca, Mg or mixtures).
  • the molecular sieves may be USY, Si-rich mordenite, offretite, zeolite omega, ZSM-5, silicalite, X, Y and CoAPO-34.
  • the Fischer-Tropsch reaction produces water, hence the catalyst must be stable in the presence of steam.
  • zeolites steam dealumination and structural collapse could occur unless they have a sufficiently high Si/Al ratio.
  • Other suitable Si-rich zeolites include dealuminated materials like USY, Si-rich mordenite, Sirich offretite, zeolite omega, and ZSM-5.
  • Vaporization of Metal Atoms Vaporizing cobalt under low pressure in an organic solvent such as toluene or cyclooctadiene has been used as the first step in the production of small metal clusters in zeolites (Nazar, 1983; Ozin, 1984). The resulting zero valent metal solvent complex is used to impregnate the zeolite. The solvent is then removed at low temperature leaving metal clusters primarily in the zeolite pores. These metal aggregates have been characterized by Mössbauer
  • Microwave Discharge Microwave discharge decomposition has been used to prepare nearly zero valent highly dispersed clusters of cobalt in X and Y zeolites
  • Zeolite catalysts containing a highly dispersed active metal can also be prepared by fixing metal complexes in their void volume.
  • Co-ZSM-5 catalysts have been prepared by impregnation with C 5 H 5 Co(CO) 2 (Shamasi, 1984). Even though a partial ion exchange of Co (II) species for acidic protons occurs, the resulting
  • Cobalt based Fischer-Tropsch catalysts have also been prepared by contacting zeolite NaY with Co(CO) 3 NO and decomposing the encapsulated carbonyl at low temperature in a
  • Methane Selectivity Methane is readily produced on cobalt catalysts under Fischer-Tropsch synthesis
  • the methane fraction obtained on those catalysts is typically larger than predicted by the ASF product distribution curve.
  • Iron based preparations produce less methane but have shorter life than their cobalt based counterparts.
  • the hydrogen transfer activity of the catalyst should be depressed. This may result in increased coke formation and shorter catalyst life.
  • the optimum catalyst should balance methane production and coke formation.
  • the acidity of the zeolite should be moderated through the addition of alkali and alkaline-earth promoters. It is also likely that
  • molecular sieve based catalysts may present a distinct advantage in reducing coke formation through shape selective processes. Thus, it may be possible to reduce the hydrogen transfer activity without severely
  • zeolites e.g. silica or silica/alumina.
  • zeolite e.g. silicalite, ZSM-5, faujasite, X or Y
  • cobalt is deposited on the zeolite surface.
  • a composite high surface area zeolite on a porous support catalyst including a water-gas shift function may be produced as described above.
  • the hydrogen transfer activity on the zeolite layer is adjusted as described above so to minimize the production of methane.
  • the initial pretreatment will be hydrogen activation at reaction temperature.
  • the catalyst synthesis scheme described below is to a particularly desirable catalyst.
  • the scheme produced a cobalt supported on a thin film of silicalite protecting the water-gas shift catalyst which are, in turn, on catalyst microspheres. This is a desirable catalyst form for fluid bed or slurry phase reactors.
  • Spray Drying Commercially available spray dried microspheres may be suitable starting materials for catalyst supports. Modification of this support
  • modifiers is accomplished through impregnation of the catalyst support.
  • Materials can be predeposited in the catalyst support matrix to alter the distribution of the promoters as a function of distance from the particle center.
  • non-aqueous) from the catalyst particle may change the distributions, and is highly affected by the
  • the cobalt should be deposited or selectively moved to the zeolite surface.
  • the porous support supplies some or all of the nutrients needed to form the zeolite structure.
  • the additional nutrients are supplied by solution addition to the support.
  • the support e.g., silica
  • the support is impregnated to incipient wetness with a solution containing sodium silicate, sodium hydroxide, and optionally sodium
  • impregnated support may be dried to limit the water remaining in the pores.
  • the impregnated support is then placed in a vessel, and transferred to a controlled temperature and humidity chamber. Under these conditions
  • zeolite crystallization is initiated. After the desired zeolite level is achieved, the crystallization is terminated.
  • the zeolite is immersed in the nutrient containing solution, and zeolite crystallization is initiated in the slurry. After a brief time, the slurry is filtered, and the support particles with zeolite nuclei may be further dried to limit the water remaining in the pores. This material is placed in an open vessel, and transferred to a controlled temperature and humidity chamber. Under these
  • a solution is prepared which has the correct levels of sodium silicate, sodium hydroxide, and optionally sodium aluminate and
  • Crystallization is started under hydrothermal conditions and proceeds until zeolite nuclei are present in the solution.
  • the support is then impregnated with this zeolite seeding solution.
  • the impregnated support is then placed in a vessel, and transferred to a controlled temperature and humidity chamber. Under these conditions
  • Standard methods for in situ zeolite growth require heated, stirred crystallization reactors which are known equipment. Key crystallization parameters are those which are typically encountered for zeolite
  • synthesis and include time, temperature, nutrient concentrations, template selection, etc.
  • Drying and Calcining are standard procedures in the processing of the catalyst. Various moving bed or moving belt driers and calciners may also be used for production of the catalyst. Catalyst Reduction. The cobalt must be reduced for use in the reactor. This can be carried out by several methods. It may be performed in the catalyst preparation facility, and then the catalyst transported to the reactor. At the reactor, the transporting
  • container may be attached to reactor in a manner
  • the reduced catalyst is then added to the reactor. Reduction of the catalyst at the reactor site probably more desirable because it would greatly reduce the possibility that a portion of the cobalt was oxidized during storage or transport. This would be accomplished by having a pretreatment chamber connected to the reactor. The catalyst is added to the pretreatment chamber, reduced, and then dropped directly into the reactor without exposure to air. Key elements for the reduction include time, temperature, flow rate, and the concentration of reducing gases.
  • the composite produced as specified above is used in a stream containing water and short chain hydrocarbons at a temperature, pressure, catalyst to feed ratio (and the like) as suitable to produce higher molecular hydrocarbons than those fed to the catalyst composite.
  • zeolites could be prepared using vapor phase synthetic techniques similar to those used in Example 1. For each experiment, two grams of silica were used and were impregnated with 2 cc of a solution consisting of one part tetrapropylammonium bromide (TPAB) powder
  • the vapor pressure depression was obtained by placing appropriate NaCl solutions (1.5 to 5.0 M) in the TEFLON autoclave liner instead of the distilled water of Example 1. After synthesis, the samples were washed by stirring the pellets in 300 ml of distilled water, and then filtering them as in Example 1. The samples were analyzed using X-ray and using thermogravimetric
  • TGA-DSC analysis-differential scanning calorimetry
  • crystallinity by XRD is 0%
  • crystallinity by TGA-DSC are materials of this invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention décrit un catalyseur composite comprenant un catalyseur de transformation eau-gaz revêtu d'une couche mince de matière zéolitique, sur la surface extérieure de laquelle est déposé un catalyseur Fischer-Tropsch. La zéolite a pour fonction de céder des hydrocarbures à chaîne courte et de la vapeur au cataalyseur de transformation eau-gaz et de permettre la restitution des produits de monoxyde de carbone et d'hydrogène au catalyseur Fischer-Tropsch sur sa surface extérieure. Le procédé utilisant ce catalyseur composite fait appel aux caractéristiques complémentaires des diverses parties du catalyseur. Un courant d'hydrocarbures à chaîne courte (par exemple alcanes ou alcènes C1-C4) et de vapeur est transmis au catalyseur composite où il se diffuse jusqu'au catalyseur de transformation eau-gaz en passant par le catalyseur Fischer-Tropsch et en traversant la couche zéolitique. Au niveau de cette surface, l'hydrocarbure à chaîne courte réagit avec l'eau pour donner du monoxyde de carbone et de l'hydrogène. Ces produits se diffusent ensuite en retour jusqu'à la surface où ils réagissent sur le catalyseur Fischer-Tropsch pour donner des oligomères d'hydrocarbure.
PCT/US1992/003601 1991-05-01 1992-05-01 Composition de catalyseur composite et procede fischer-tropsch utilisant cette composition WO1992019574A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US69420091A 1991-05-01 1991-05-01
US694,200 1991-05-01
US72499491A 1991-07-01 1991-07-01
US724,994 1991-07-01
US75119891A 1991-08-29 1991-08-29
US751,198 1991-08-29
US79173791A 1991-11-08 1991-11-08
US791,737 1991-11-08

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672388A (en) * 1994-07-08 1997-09-30 Exxon Research & Engineering Company Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition
NL1003778C2 (nl) * 1996-08-09 1998-02-12 Univ Delft Tech Werkwijze ter vervaardiging van een composiet-katalysator.
US5824617A (en) * 1994-07-08 1998-10-20 Exxon Research & Engineering Company Low alkaline inverted in-situ crystallized zeolite membrane
US5871650A (en) * 1994-07-08 1999-02-16 Exxon Research And Engineering Company Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer
WO2004058632A2 (fr) * 2002-12-20 2004-07-15 Honda Giken Kogyo Kabushiki Kaisha Formulations de catalyseur a base de platine alcalin/alcalino-terreux pour production d'hydrogene
WO2015080611A1 (fr) 2013-11-26 2015-06-04 Infra XTL Technology Limited Catalyseur pour diriger la production d'huile synthétique riche en isoparaffines et procédé de préparation du catalyseur
WO2017162575A1 (fr) * 2016-03-24 2017-09-28 Friedrich-Alexander-Universität Erlangen-Nürnberg Fabrication d'un matériau composite à base de zéolithe avec une porosité hiérarchique
US11229898B2 (en) 2015-12-29 2022-01-25 Friedrich-Alexander-Universität Erlangen-Nürnberg Nanometer-size zeolitic particles and method for the production thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468815A (en) * 1967-09-11 1969-09-23 Texaco Inc Extended zeolitic structures
US4579830A (en) * 1984-06-27 1986-04-01 Union Carbide Corporation Enhanced catalyst for converting synthesis gas to liquid motor fuels

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468815A (en) * 1967-09-11 1969-09-23 Texaco Inc Extended zeolitic structures
US4579830A (en) * 1984-06-27 1986-04-01 Union Carbide Corporation Enhanced catalyst for converting synthesis gas to liquid motor fuels

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672388A (en) * 1994-07-08 1997-09-30 Exxon Research & Engineering Company Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition
US5824617A (en) * 1994-07-08 1998-10-20 Exxon Research & Engineering Company Low alkaline inverted in-situ crystallized zeolite membrane
US5849980A (en) * 1994-07-08 1998-12-15 Exxon Research And Engineering Company Low alkaline inverted in-situ crystallized zeolite membrane
US5871650A (en) * 1994-07-08 1999-02-16 Exxon Research And Engineering Company Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer
NL1003778C2 (nl) * 1996-08-09 1998-02-12 Univ Delft Tech Werkwijze ter vervaardiging van een composiet-katalysator.
WO1998006495A1 (fr) * 1996-08-09 1998-02-19 Technische Universiteit Delft Procede de preparation d'un catalyseur composite
WO2004058632A2 (fr) * 2002-12-20 2004-07-15 Honda Giken Kogyo Kabushiki Kaisha Formulations de catalyseur a base de platine alcalin/alcalino-terreux pour production d'hydrogene
WO2004058632A3 (fr) * 2002-12-20 2004-12-29 Honda Motor Co Ltd Formulations de catalyseur a base de platine alcalin/alcalino-terreux pour production d'hydrogene
US7744849B2 (en) 2002-12-20 2010-06-29 Honda Giken Kogyo Kabushiki Kaisha Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation
WO2015080611A1 (fr) 2013-11-26 2015-06-04 Infra XTL Technology Limited Catalyseur pour diriger la production d'huile synthétique riche en isoparaffines et procédé de préparation du catalyseur
US11229898B2 (en) 2015-12-29 2022-01-25 Friedrich-Alexander-Universität Erlangen-Nürnberg Nanometer-size zeolitic particles and method for the production thereof
WO2017162575A1 (fr) * 2016-03-24 2017-09-28 Friedrich-Alexander-Universität Erlangen-Nürnberg Fabrication d'un matériau composite à base de zéolithe avec une porosité hiérarchique
CN109475858A (zh) * 2016-03-24 2019-03-15 埃朗根-纽伦堡弗里德里希-亚历山大大学 基于沸石的具有层级式孔隙度的复合材料的制造
JP2019509968A (ja) * 2016-03-24 2019-04-11 フリードリヒ−アレクサンダー−ウニヴェルシテート エアランゲン−ニュルンベルク 階層的多孔性を有するゼオライトベースの複合材料の製造

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