WO2000029108A1 - Catalyseur a film mince resistant a l'abrasion et son procede de preparation - Google Patents

Catalyseur a film mince resistant a l'abrasion et son procede de preparation Download PDF

Info

Publication number
WO2000029108A1
WO2000029108A1 PCT/US1999/026508 US9926508W WO0029108A1 WO 2000029108 A1 WO2000029108 A1 WO 2000029108A1 US 9926508 W US9926508 W US 9926508W WO 0029108 A1 WO0029108 A1 WO 0029108A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
coating
substrate
forming polymer
film forming
Prior art date
Application number
PCT/US1999/026508
Other languages
English (en)
Inventor
Yun-Fen Chang
Lawrence L. Murrell
Herbert E. Barner
Original Assignee
Abb Lummus Global Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Abb Lummus Global Inc. filed Critical Abb Lummus Global Inc.
Priority to AU16140/00A priority Critical patent/AU1614000A/en
Priority to JP2000582147A priority patent/JP2002529241A/ja
Priority to EP99958859A priority patent/EP1133358A1/fr
Publication of WO2000029108A1 publication Critical patent/WO2000029108A1/fr

Links

Classifications

    • 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
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • 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
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation

Definitions

  • the present invention relates to solid catalysts and to a method for preparation thereof. Specifically, the invention relates to a method of producing catalysts or catalyst precursors comprising a substrate which is usually catalytically inactive, and a thin film of catalyst or catalyst precursor.
  • solid catalyst comprised of small particles containing catalytically active materials on the surface thereof are desirable for a wide variety of chemical reactions.
  • the production of highly branched hydrocarbons such as trimethylpentane for use as gasoline blending components for octane enhancement traditionally involves alkylation using conventional strong liquid phase catalysts such as hydrofluoric or sulfuric acid.
  • hydrofluoric acid the concern is the possibility of the release of toxic vapors.
  • sulfuric acid there is no acute toxic release problem, but there is the need to truck away and treat the waste acid which involves thermal decomposition and preparation of fresh acid. The transportation of the waste and fresh acid is closely regulated to prevent spills.
  • porous supports can be impregnated with a solution containing a catalyst precursor which fills the pores within the oxide support.
  • This method is often referred to as the dry impregnation method or the incipient wetness method.
  • Impregnation using slurries containing colloidal particles, i.e., a sol using this prior art technique shows that there is substantial penetration of the sol into the substrate.
  • This, as well as the coating techniques themselves, result to varying degrees in a non-uniform coating thickness.
  • prior art preparation methods result in a range of pore diameters and in films of various thicknesses.
  • the pore diameters within the film and the film thicknesses strongly influence the rate of diffusion of the reactants to the active sites in the pores and of the reaction products out of the film. As the core diameters decrease and as the film thicknesses increase, the diffusion of reactants and products will lead to deleterious reaction products which foul the catalyst surface. This concept of catalyst deactivation has been recognized in the published literature. A high flux of reactants and products is necessary to obtain a high number of molecules reacted per unit of time for each active catalyst site and, more importantly, to suppress undesired reaction products which foul the surface. This is partially due to the long residence time within the intricate network of pores resulting in unwanted side reactions in conventional catalyst or in thin film catalysts of uncontrolled film thickness.
  • vinyl pyrollidone acrylic acid; methacrylic acid; hydrophilic esters of acrylic and methacrylic acid, such as esters of polyglycols, glycerol or sugars; alkylene oxide; maleic acid; styrenesulfonic acid; acrylamide and N-substituted acrylamide; vinyl alcohol; or methylvinylether.
  • Dispersible polymers include butyl rubber and carboxylated butyl rubber, polystyrene and polystyrene with divinylbenzene cross-linking agents and these polymers with ethylvinylacetate incorporated to enhance water dispersability. Also, polybutylrubber resin, and styrene butadiene resins, polyphenylsulfide resins, and polyacrylonitrile resins. Other dispersible resins include polymethacrylate resins, etc.
  • the polymer(s) is dissolved and/or dispersed in the liquid portion of the coating composition and, therefore, the polymer is one which is soluble or dispersible in such liquid under the coating conditions.
  • the polymer is also preferably capable of forming a web or complex of filaments in the coating of catalyst element on the substrate.
  • the catalyst comprises a substrate, which is usually catalytically inert (the catalyst substrate is generally an inorganic material), on which is deposited and bonded a thin shell or film of the catalyst element.
  • the catalyst element is also generically inorganic.
  • carbon-based supports can also be used, such as, carbon blacks, graphite, carbon molecular sieves, and inorganic carbides, such as SiC, Si 3 N , iron carbides, tungsten carbides, etc.
  • the thin shell is formed by a deposition process which uses a fluidized bed coating technique which involves repeatedly applying and drying small quantities of a coating composition comprising an aqueous slurry containing the catalyst element, wherein the slurry is in the form of an aqueous colloidal dispersion, or sol, or where the slurry contains very fine, non-colloidal particles preferably mixed with colloidal particles wherein a film forming polymer is dissolved and/or dispersed in the water.
  • Incremental layers of one or more catalysts mixed throughout the thin film, or formed as separate layers of different catalysts within the film are deposited and dried to form the final thin shell which has a highly uniform thickness which is usually less than 250 microns, and more preferably less than 100 microns.
  • the catalyst material can be a part of the shell forming material, or can be added to the formed shell, or can be formed by subsequent reaction with the formed shell.
  • the catalyst particles formed by the present invention may be used for a wide variety of chemical reactions including the alkylation reactions previously discussed.
  • Figures 2 and 3 are graphical representations of the effect of using PVP for coating under shear conditions; and Figure 4 is a graphical representation of the effect of using OPADRY,
  • the substrate onto which the thin film of catalyst element is coated is preferably a catalytically inactive material, with a thin shell formed on the substrate being comprised of the catalyst element.
  • the substrate is preferably in paniculate form and usually comprises alpha alumina particles but may be formed from particles or microspheres of transitional alumina, silica, zeolites, zirconia, titania, clay minerals, silicon carbide or their mixtures.
  • the substrate may also be formed from non-porous materials such as hollow spheres of inorganic materials, such as silica or alumina, metal, clay minerals, silicon carbide, silicon nitride, or carbon-based materials such as graphite.
  • catalytically inert means inert with respect to the particular reaction in which the catalyst is being used even though the substrate may have catalytic activity with respect to some other reaction.
  • the substrate is preferably a particle, the present invention is not limited to a substrate in the form of a particle.
  • the present invention is not limited to any particular type, or brand, of fluidized bed coaters or coating processes, one type that has been found to be particularly useful and is given by way of example only, is known as Wurster coaters or the Wurster process named after one of the original inventors, Dale E. Wurster.
  • Wurster coaters or the Wurster process named after one of the original inventors, Dale E. Wurster.
  • U.S. Patent 3,196,827 and some of the later patents relating to this coating technique such as U.S. Patents 5,236,503 and 5,437,889, all of which are incorporated herein by reference.
  • the nozzle is located such that the travel distance of the liquid or suspension droplet from the nozzle is minimized.
  • the coated particles are lifted on the air stream which dries the coating as the particles are carried upward. Because the system uses large volumes of air, it has a large drying capacity. Also, because the particles are separated from each other as they are carried on the air stream and coated, it is possible to coat a wide range of particle sizes including very small core particles (less than 50 microns) while at the same time controlling and minimizing agglomeration.
  • the preferred system comprises a conically shaped product container with an open ended cylindrical inner partition.
  • An air distribution plate is located at the lower end of the production container to distribute the fluidization air between the inner and outer partitions. The majority of the air is channeled through the inner partition leaving sufficient air flow to suspend particles in the outer partition. Particles are drawn into the inner partition by the pressure differential created by the difference in air velocities between the two partitions. The particles are carried through the inner partition and into the expansion chamber. As gravity overcomes the force of the fluidizing air, the particles fall back into the outer partition where they are suspended in a slowly, downwardly moving bed.
  • the coating composition of the present invention is added via a pneumatically atomized nozzle located at the center of the air distributor plate.
  • a product container section opens upwardly into an expansion chamber and downwardly into a lower plenum chamber through a generally horizontally disposed air distribution plate having openings formed therethrough for the upward air flow from said lower plenum chamber into said product container section.
  • the product container section includes a substantially cylindrical partition spaced above the air distribution plate for dividing the product container section into an inner up-bed area and an outer down-bed area.
  • An upwardly discharging spray nozzle is mounted substantially centrally within the cylindrical partition.
  • the rotor coater (or spin disk coater) is used in a wide range of operations. Ideal for agglomeration, coating or granulating of any kind of powder.
  • the rotor insert combines short processing times with consistent uniformity of product.
  • inlet air is introduced into the coater from the side wall to form an air curtain, a fluidizing motion is created along the wall of the rotor coater. This, on one hand provides the force to suspend the solid particles from falling through the slit and at the same time creates a mechanism to roll the particles over.
  • the combination of centrifugal force generated by the spinning rotor, rotation speed, gravity and slit air create a rope-action, or whirling that helps the product to mix quickly and evenly into the cyclic movement of the rotor bed.
  • the particle stream and its degree of fluidization are controlled by rotor speed, air volume and the air velocity at the rotor slit gap.
  • Slit air controls the peripheral airflow during the process, assisting the spiraling motion of the bed while simultaneously drying the product.
  • the slit air gap is adjustable by moving the air gap ring closer to or farther away from the rotor plate. As centrifugal force moves the product into the spray zone, the particles are coated by a peripherally mounted spray gun.
  • the range of core particle sizes for the catalyst of the present invention can range from 5 microns (0.005 mm) up to 20,000 microns (20 mm) with the preferred range being 0.03 mm up to 4.0 mm.
  • the operating conditions for the fluidized bed coating process would be adjusted accordingly to maintain the desired fluidizing conditions coupled with the control of the drying conditions. It is also possible to carry out the coating process using a fluid bed coating technique which relies on mechanical means to produce the fluidization within the coating chamber.
  • the preferred material for producing the shell or film on the catalyst particles is an alumina colloidal dispersion or sol.
  • the catalyst element in the coating composition may be used in the form of a sol or in the form of a liquid dispersion of small, non-colloidal particles preferably mixed with colloidal particles which serve as the binder.
  • the suspended coating particles may be alumina particles from 2 millimicrons (2 nanometers) up to 10 or more micron size particles.
  • the coating slurry may even contain milled particles of up to 100 microns diameter but preferably less than 10 microns.
  • the coating material is a sol of a transitional alumina precursor, such as boehmite or pseudoboehmite formed with an average particle size of 2 - 100 nm (2 - 100 millimicrons).
  • a transitional alumina precursor such as boehmite or pseudoboehmite formed with an average particle size of 2 - 100 nm (2 - 100 millimicrons).
  • Another typical coating material is a slurry containing milled commercially available transitional alumina with an average particle size of about 4 microns, and containing 10-90% by weight colloidal alumina particles in the slurry on a water free basis.
  • the slurry contains a separate binder phase which may actually be a quantity of alumina sol, or a binder created in situ by adding acetic or other acids to the transitional alumina slurry prior to milling of the alumina to reduce the particle size.
  • a separate binder phase which may actually be a quantity of alumina sol, or a binder created in situ by adding acetic or other acids to the transitional alumina slurry prior to milling of the alumina to reduce the particle size.
  • the term slurry includes sols as well as liquid dispersions of fine, non- colloidal size particles.
  • an object of the invention is to produce a thin coating as well as a uniformly thick, homogeneous coating.
  • the use of the fluidized bed coating process such as the Wurster process produces the uniform and homogeneous coating, and is capable of producing the desired thin coatings by merely controlling the duration of the coating cycle.
  • the desired coating thickness may vary depending upon the particular catalyst being produced, but the preferred range of thicknesses is between about 0.1 microns and 100 microns. In a preferred embodiment the film thickness is at least 10 microns.
  • the atomized spray of the slurry produces very fine droplets, perhaps on the order of 20-30 microns.
  • each pass of the support or substrate particles through the atomized spray of coating composition only a small percentage of the surface of the core particle is coated, perhaps only 2 or 3%.
  • the successive passes of the particles through the atomized spray and the drying of the coating between each pass produces the film.
  • Determination of the BET (Brunauer, Emmett and Teller) surface area of samples removed at different times demonstrates that there is a uniform rate of deposition of the slurry onto the core particles and that there is a continual build-up of the layers of the shell.
  • this precursor is treated in air, or in an inert gas atmosphere, or in a mixture of the two gases, in each case with or without steam, to convert the boehmite or pseudoboehmite phase in the thin film to a transitional alumina phase.
  • Temperatures of 200-1100°C can be employed to give the desired combination of physical and chemical characteristics in the transitional alumina film.
  • the gas atmosphere may contain the steam at different amounts to control the conversion process to the most desirable surface area and pore size within the film according to known techniques.
  • the film can be converted to a solid acid catalyst by a wide number of techniques that are well known to those skilled in the art.
  • U.S. Patents 2,999,074 Block
  • 4,433,191 Esleasar
  • 4,347,399 Ring
  • 4,179,581 Melchel
  • the film can be converted to an acid catalyst by halogenating or sulfating.
  • the transitional alumina films which have been formed can be reacted in the gas phase with such reactive chlorine containing species as carbon tetrachloride, chloroform, sulfonylchloride, hydrogen/hydrogen chloride mixtures, chlorine gas with/without added oxygen, etc.
  • reactive chlorine containing species as carbon tetrachloride, chloroform, sulfonylchloride, hydrogen/hydrogen chloride mixtures, chlorine gas with/without added oxygen, etc.
  • the time of treatment, the flow rate of the gas, and the temperature of treatment for a given film thickness are all variables which are known to effect the amount of retention of chlorine within the film and directly impact on the acidity of the film.
  • treatment can be carried out with fluorine containing gases such as carbon tetrafluoride, boron trifluoride, hydrogen fluoride, etc.
  • Solids that can be vaporized/sublimed onto the alumina film can also be used to prepare solid acids by deposition of the solid within the thin film.
  • Examples would be aluminum trichloride, antimony pentafluoride, and hydrogen baron tetrafluoride.
  • these thin films it is known that there may be a continuous addition of the chloride or fluoride-containing compounds during the reaction to maintain the activity of the solid acid catalyst in such applications as paraffin and olefin isomerization, aromatics alkylation, and gasoline alkylation.
  • the chlorination or fluorination can be carried out by treatment in a solvent containing reactive chlorination species such as alkyl aluminum chloride, sulfonyl chloride, etc.
  • a solvent containing reactive chlorination species such as alkyl aluminum chloride, sulfonyl chloride, etc.
  • post treatment at different temperatures between 100 - 900°C may be beneficial in a variety of gas atmospheres including hydrogen, hydrogen chloride, or their mixture, air or mixtures of air diluted with an inert gas such as nitrogen, or treatment in an inert gas such a nitrogen or helium, the duration of treatment of the catalyst, the temperature of treatment, and the flow rate of the treatment gas may be used to control the acidity of these catalysts for different applications.
  • Another example of the present invention involves the conversion of the alumina thin films to nickel catalysts which are particularly useful for hydrogenation. Many hydrogenation reactions are very fast reactions which benefit from having small catalyst particles.
  • the process of the present invention for forming thin film catalyst particles is one approach to having effectively small catalyst particles. The benefits are a lower catalyst inventory for a given reactor volume and lower rates of catalyst deactivation due to fouling of the catalyst surface.
  • Nickel catalysts on an alumina support formed by prior art processes are currently used commercially such as in catalytic distillation.
  • the dispersion of the nickel is a key to the effective utilization of the nickel content since the dispersion directly relates to the amount of nickel surface area available for catalysis. Also, the dispersion is directly related to the size of the nickel metal particles whose exterior surface is available for catalytic function in hydrogenation. For a nickel catalyst with a dispersion of 30%, the nickel particles are about 2 nm in diameter. Information on the nickel metal dispersion allows a comparison of the effectiveness of the nickel catalysts prepared according to the present invention and the effectiveness of commercial nickel catalysts that do not possess the thin film of the present invention.
  • nickel metal dispersions are approximately 30% for nickel/alumina catalysts similar in surface area to those produced by the present invention for nickel loadings of 14 to 18 wt. percent based on the weight of the thin film.
  • U.S. Patent 4,073,750 which also discloses the use of nickel metal precursors and the conversion to the nickel metal which can also be used in the present invention.
  • the substrate or support is coated with a thin film or coating of a catalyst element by the use of a fluidized bed coating technique
  • the present invention insofar as it is directed to the use of a coating composition which includes a polymer is not limited to such a fluidized bed coating technique even though such coating composition provides particular advantages when used with a fluidized coating technique.
  • the coating composition of the present invention may be employed for coating a catalyst element on a support by coating techniques such as dip coating or conventional impregnation.
  • the coating composition of the invention is particularly advantageous wherein the method of coating applies a shear force to the coating during application of the catalyst or catalyst precursor to the substrate.
  • a thin film of a catalyst element is coated onto a porous substrate without essential penetration of the catalyst element into the pores of the porous support.
  • the catalyst element dispersed in a liquid is applied to the porous substrate as a spray or droplets under conditions such that the liquid is rapidly evaporated after application to the substrate.
  • application of the coating composition to the substrate with rapid evaporation of the liquid may be effected in a fluidized bed coating apparatus or in a rotor coater, as hereinabove described.
  • the coating composition may or may not include a film forming polymer and preferably includes a film forming polymer.
  • the aluminum sol [Condea 23N4-20 sol] used has a solid content of 20 weight percent as alumina. To obtain diluted sol, the 20 weight percent sol was added to the required amount of distilled water drop-wise while under constant stirring.
  • the polymer is a polyvinyl pyrollidone (Povidone K-90 from BASF) dissolved in distilled water to make a 1% solution .
  • 1% Povidone solution and 20% Condea sol were mixed in equal amount to give 10% sol and 0.5% Povidone.
  • Coating Dip coating was used to soak the alumina plates in sols. After removal from the coating, excess sol was removed by shaking and the plates were dried under ambient conditions. However, in order to simulate fluid bed coating conditions, an air knifing technique was used to apply high pressure air ( ⁇ 80psi) to newly formed fluid film on alumina plate surface to blow away excess sol and dry the coating.
  • Figure 1 summarizes the results for dip coating of alumina plates with a number of different sols.
  • Figures 2 and 3 summarize the results for multiple coating with air knifing at approximately 60-80 psi of alumina plates with a number of different sols.
  • the coating sol contained 10% Condea 23N4-20 and 150ppm of sodium nitrate and 0.05-1% of polymer additives.

Landscapes

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

Abstract

Un film mince d'un catalyseur est appliqué sur un substrat à l'aide d'une composition de revêtement contenant un polymère filmogène afin de réduire la fissuration du revêtement pendant le processus de revêtement, le résultat étant un produit en film mince résistant à l'abrasion. La pyrrolidone polyvinylique et la méthylcellulose hydropropyle sont utilisés comme polymères filmogènes dans les exemples.
PCT/US1999/026508 1998-11-12 1999-11-11 Catalyseur a film mince resistant a l'abrasion et son procede de preparation WO2000029108A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU16140/00A AU1614000A (en) 1998-11-12 1999-11-11 Attrition resistant thin film catalyst and method of preparation
JP2000582147A JP2002529241A (ja) 1998-11-12 1999-11-11 摩滅耐性薄膜触媒とその調製方法
EP99958859A EP1133358A1 (fr) 1998-11-12 1999-11-11 Catalyseur a film mince resistant a l'abrasion et son procede de preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19074598A 1998-11-12 1998-11-12
US09/190,745 1998-11-12

Publications (1)

Publication Number Publication Date
WO2000029108A1 true WO2000029108A1 (fr) 2000-05-25

Family

ID=22702597

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/026508 WO2000029108A1 (fr) 1998-11-12 1999-11-11 Catalyseur a film mince resistant a l'abrasion et son procede de preparation

Country Status (4)

Country Link
EP (1) EP1133358A1 (fr)
JP (1) JP2002529241A (fr)
AU (1) AU1614000A (fr)
WO (1) WO2000029108A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002007882A1 (fr) * 2000-07-24 2002-01-31 Shell Internationale Research Maatschappij B.V. Catalyseur metallique en coquille et son precurseur, procede de preparation dudit catalyseur et dudit precurseur et utilisation dudit catalyseur
WO2004038092A2 (fr) * 2002-10-22 2004-05-06 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Systemes et procedes d'obtention de polysulfures
WO2010119226A1 (fr) * 2009-04-16 2010-10-21 Saint-Gobain Centre De Recherches Et D'etudes Europeen Substrat de catalyseur en nid d'abeilles et son procédé d'obtention
WO2011050953A3 (fr) * 2009-10-30 2012-02-09 Süd-Chemie AG Procédé de fabrication d'un matériau composite
WO2012110780A1 (fr) * 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac
US20180056261A1 (en) * 2016-08-30 2018-03-01 Allergan, Inc. Method of manufacturing coated beads
US10252254B2 (en) * 2013-03-22 2019-04-09 Clariant International Ltd. Removable protective coating for the receipt of a dust free catalyst
RU2687749C2 (ru) * 2014-07-03 2019-05-16 Эрека С.А Способ ограничения саморазогрева активированных катализаторов
US11078085B2 (en) 2016-05-26 2021-08-03 Allergan, Inc. Production of rounded salt particles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5533341B2 (ja) * 2010-06-28 2014-06-25 三菱レイヨン株式会社 コーティングされたメタクリル酸合成用固体触媒の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2134413A (en) * 1983-01-10 1984-08-15 Atomic Energy Authority Uk Coating process
US4521618A (en) * 1981-06-26 1985-06-04 Degussa Aktiengesellschaft Process for preparing acrylic or methacrylic acid
WO1995013874A1 (fr) * 1993-11-16 1995-05-26 Basf Aktiengesellschaft Catalyseurs separables magnetiquement
WO1998014274A1 (fr) * 1996-10-04 1998-04-09 Abb Lummus Global Inc. Catalyseur et son procede de preparation
JPH10337478A (ja) * 1997-06-09 1998-12-22 Sumitomo Metal Ind Ltd 酸化チタン光触媒用ゾル、光触媒多機能部材の製造方法および使用方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4521618A (en) * 1981-06-26 1985-06-04 Degussa Aktiengesellschaft Process for preparing acrylic or methacrylic acid
GB2134413A (en) * 1983-01-10 1984-08-15 Atomic Energy Authority Uk Coating process
WO1995013874A1 (fr) * 1993-11-16 1995-05-26 Basf Aktiengesellschaft Catalyseurs separables magnetiquement
WO1998014274A1 (fr) * 1996-10-04 1998-04-09 Abb Lummus Global Inc. Catalyseur et son procede de preparation
JPH10337478A (ja) * 1997-06-09 1998-12-22 Sumitomo Metal Ind Ltd 酸化チタン光触媒用ゾル、光触媒多機能部材の製造方法および使用方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 03 31 March 1999 (1999-03-31) *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002007882A1 (fr) * 2000-07-24 2002-01-31 Shell Internationale Research Maatschappij B.V. Catalyseur metallique en coquille et son precurseur, procede de preparation dudit catalyseur et dudit precurseur et utilisation dudit catalyseur
AU2001281976B2 (en) * 2000-07-24 2004-09-09 Shell Internationale Research Maatschappij B.V. A shell metal catalyst and a precursor thereof, a process for their preparation and the use of the catalyst
US7087191B2 (en) 2000-07-24 2006-08-08 Shell Oil Company Shell metal catalyst and a precursor thereof, a process for their preparation and the use of the catalyst
WO2004038092A2 (fr) * 2002-10-22 2004-05-06 L'air Liquide - Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Systemes et procedes d'obtention de polysulfures
WO2004038092A3 (fr) * 2002-10-22 2004-07-22 Air Liquide Systemes et procedes d'obtention de polysulfures
WO2010119226A1 (fr) * 2009-04-16 2010-10-21 Saint-Gobain Centre De Recherches Et D'etudes Europeen Substrat de catalyseur en nid d'abeilles et son procédé d'obtention
US9327272B2 (en) 2009-10-30 2016-05-03 Clariant International Ltd. Method for producing a composite material
WO2011050953A3 (fr) * 2009-10-30 2012-02-09 Süd-Chemie AG Procédé de fabrication d'un matériau composite
WO2012110780A1 (fr) * 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac
US10252254B2 (en) * 2013-03-22 2019-04-09 Clariant International Ltd. Removable protective coating for the receipt of a dust free catalyst
RU2687749C2 (ru) * 2014-07-03 2019-05-16 Эрека С.А Способ ограничения саморазогрева активированных катализаторов
US11078085B2 (en) 2016-05-26 2021-08-03 Allergan, Inc. Production of rounded salt particles
US20180056261A1 (en) * 2016-08-30 2018-03-01 Allergan, Inc. Method of manufacturing coated beads
WO2018045103A1 (fr) * 2016-08-30 2018-03-08 Allergan, Inc. Procédé de fabrication de billes enrobées
AU2017318572B2 (en) * 2016-08-30 2020-06-25 Allergan, Inc. Method of manufacturing coated beads
AU2017318572C1 (en) * 2016-08-30 2021-01-07 Allergan, Inc. Method of manufacturing coated beads

Also Published As

Publication number Publication date
AU1614000A (en) 2000-06-05
JP2002529241A (ja) 2002-09-10
EP1133358A1 (fr) 2001-09-19

Similar Documents

Publication Publication Date Title
US5935889A (en) Catalyst and method of preparation
EP0123293B1 (fr) Procédé pour préparer des supports superficiellement poreux pour chromatographie et catalyseurs
KR100872810B1 (ko) 리튬 알루미네이트 층상 촉매 및 이 촉매를 이용하는선택적 산화 방법
RU2283179C2 (ru) Неорганические микросферические частицы с повышенным сопротивлением истиранию, способ их приготовления, материал катализатора на основе микрочастиц и его использование
WO2000029108A1 (fr) Catalyseur a film mince resistant a l'abrasion et son procede de preparation
RU2268773C2 (ru) Катализатор для гидродехлорирования четыреххлористого углерода в хлороформ, способ получения катализатора и способ гидродехлорирования водородом четыреххлористого углерода в хлороформ
JPH10509762A (ja) 担持された触媒系を製造する方法及びその方法から製造された触媒系
FR2512004A1 (fr) Composition d'alumine pour le revetement d'un support de catalyseur, son procede de fabrication et le support de catalyseur obtenu
US4902666A (en) Process for the manufacture of spheroidal bodies by selective agglomeration
US20220387984A1 (en) Support and ft synthesis catalyst, and preparation methods therefor and applications thereof
JPH05309254A (ja) 単分散微小球状粒子の製造方法
US4737478A (en) Process for the manufacture of spheroidal bodies by selective agglomeration
US4599321A (en) Process for the manufacture of spherical bodies by selective agglomeration
US20120016170A1 (en) Process for preparing a core-layer material having good mechanical strength
US11596925B2 (en) Aerosol processing method for controlled coating of surface species to generate catalysts
US11344874B2 (en) Methods for reacting chemical streams with catalysts comprising silica, alumina, and tungsten
Regenhardt et al. Monolithic stirrer reactor: The selective lactose oxidation in liquid phase over Au/Al2O3 nanostructured catalysts
Chen et al. Immobilization of CNFs on the surface and inside of the modified activated carbon
Ran et al. Liquid–gas boundary catalysis by using gold/polystyrene-coated hollow titania
US2641583A (en) Process for producing silica gel spheres in oil
JP3118244B2 (ja) 表面含浸分散コバルト金属触媒の製造法
CA1276069C (fr) Methode de fabrication de corps spheriques par agglomeration selective
Tyerman Sputtered catalysts
Zhao et al. Porous noble metal/ceramic catalytic membranes prepared by modification of the surface of sol particles

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 2000 16140

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 582147

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 1999958859

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999958859

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999958859

Country of ref document: EP