WO2005042158A1 - The use of ir, near ir, visible and uv radiation for the preparation of catalysts - Google Patents

The use of ir, near ir, visible and uv radiation for the preparation of catalysts Download PDF

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Publication number
WO2005042158A1
WO2005042158A1 PCT/EP2003/011701 EP0311701W WO2005042158A1 WO 2005042158 A1 WO2005042158 A1 WO 2005042158A1 EP 0311701 W EP0311701 W EP 0311701W WO 2005042158 A1 WO2005042158 A1 WO 2005042158A1
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viii
groups
catalyst
optionally
infrared
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PCT/EP2003/011701
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French (fr)
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Daniel Ostgard
Monika Berweiler
Stefan Röder
Manfred Dannehl
Natalia Hinrichs
Ansgar Oelmann
Steffen Seebald
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Degussa Ag
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Priority to AU2003276139A priority Critical patent/AU2003276139A1/en
Priority to PCT/EP2003/011701 priority patent/WO2005042158A1/en
Priority to PCT/EP2004/011017 priority patent/WO2005039766A1/en
Publication of WO2005042158A1 publication Critical patent/WO2005042158A1/en

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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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • 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
    • B01J25/00—Catalysts of the Raney type
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J35/391—
    • B01J35/394—
    • B01J35/51—
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to the use of infrared, near infrared, visable, microwave and ultraviolet radiation for the preparation and rejuvenation of catalysts as well as their precursors.
  • This could be applied for a broad range of different catalysts such as solid acid, solid base, precious metal powder, precious metal fixed bed, base metal powder, base metal fixed bed, olefin polymerization, Raney- type powder, and Raney-type fixed bed catalysts.
  • This method can also be applied to preparation of supports and/or alloys in which require a heat treatment.
  • the alloys made by the radiation heat treatment of mixed, coated and vaporized/condensed compositions consisting of catalytic metals, caustic leachable metals and/or materials and optionally promoters can be used for the preparation of Raney-Type Catalysts by the removal of most if not all of the leachable material.
  • This method is ideal for the preparation of catalysts, catalyst precursors, and supports that go through a instable phase before they are stabilized through heat treatment.
  • this could be an instable chemical and/or mechanical phase, while for powders the main concern is mostly chemical instability.
  • This method is preferred for formed metals, alloys, metal oxides, oxidic ceramics, nonoxidic ceramics, and active carbons for use in the area of catalysis.
  • This technology could also be used to make formed bodies for other industries, such as the development of lightweight building material and crash adsorbers (e.g., the automobile industry).
  • This technique can be carried out continuously and/or batchwise.
  • the use of reflecting materials on the walls and/or floor of the oven serve to enhance this procedure and if needed, it can be carried out under controlled inert, reducing, oxidizing, hydrating and/or dehydrating gases at normal, high and vacuum types of pressures.
  • controlled inert, reducing, oxidizing, hydrating and/or dehydrating gases at normal, high and vacuum types of pressures.
  • These types of controlled atmospheres can also be applied in the continuous mode.
  • the continuous treatment of catalysts, catalyst precursors and spent catalysts can be carried out in a rotary calciner, in a stationary oven that is being continually fed by conveyence or any other method that allows for the continual feeding of stating material and removal of product.
  • Additional options for the conveyance of material through the radiated zone for the desired treatment include the use of swinging, vibrating, stirred or rotating auger equipment.
  • This radiation treatment can also be used with technologies that involve stationary, continuous or a combination thereof fluidized bed(s) for the placement during heat treatment and/or the transport of the material to be heat treated.
  • One or more of the reactor's walls and/or floor can be optionally transparent to the desired form of radiation, thereby allowing for the separation of the radiation source from the heat treated material and the desired atmosphere.
  • the continuous calcination equipment can also be outfitted with reflecting walls and/or floor for the optimal use of radiation.
  • the radiation source can either be present as a series of panels or a wand type of equipment that can be outfitted into existing ovens or be the intergral part of an oven built especially for this purpose.
  • the IR radiation could either be generated by an electronic or gas/oil source.
  • the IR radiation can be generated via an electronic lamp/ceramic radiation source, a gas heated catalytic/surface radiation source or a gas/oil heated pore burner.
  • the gas/oil IR source has the added benefit of allowing for the immediate burning of waste gases into their oxidized species before they are emmited as exhaust.
  • This process can allow for the rapid transfer of 3000 kW/m 2 radiation energie to the desired reactant for the quick transformation of the above mentioned materials into products, thereby leading to the quicker and more economic manufacture of these products.
  • the use of rapid radiation treatment of materials will also permit the fabrication of commercial product quantities with smaller ovens that can be employed in innovative ways. Since the heat is focused on the reactant material to be converted, the temperature of the process is more readily controlled while the temperature of the reactor itself can be much lower. This means that the reactor will be subjected to less corrosion and stress, leading to less equipment maintenance and far fewer contamination problems with the product.
  • the desired powder inorganic oxide for either fluidized beds or slurry processes can be dried and/or calcined.
  • the temperatures for these processes can range from 20 to 1800°C.
  • the oxide can be treated with additional components (e.g., catalytic metal solutions) prior to Infrared heating via mixing, impregnation or other treatment procedures.
  • This process can be used for the preparation of catalysts and/or supports to be used in olefin polymerization, Fischer Tropsch synthesis, the production of acrolein, acrylnitril and other nitriles as well as acrylic acid, aniline, caprolactam, chlorinated hydrocarbons, cresol, melamin, pyridine, phthalic acid (or rather Phthalic anhydride), vinyacectate, vinylchloride or xylene.
  • These granulated forms could either be filled into the reactor as is, or they can be sintered together to for a desired structure.
  • the common forms could include spheres, foams, cylinders, ovals, hollow spheres, and other forms as well.
  • the main advantages of this process is its relatively low production costs, low bulk density and high porosity.
  • This technology is also suitable for the preparation of fixed bed and powder catalyst supports, where heat treatment is used to modify the material pore and surface structure; burn out modifiers and pore builders; change the oxidation level of the components of the support either via reduction or oxidation; and/or to enhance the impregnation of said support.
  • This impregnation solution can be comprised of either precious metal salts, base metal salts, alkali metal salts, alkaline metal salts, rare earth metal salts, organic compounds of the previously mentioned metals, organic modifiers, inorganic modifiers and/or combinations thereof.
  • the use of these radiations are ideal for "hot" impregnations that can lead to thinner shell impregnations, thereby allowing for the improved control of the impregnated component's penetration into the pore system of the support material.
  • SMSI metal support interactions
  • a special case for this technology involves producing activated metal catalysts which are known in the field of chemical engineering as Raney-type, skeleton, activated base metal, or sponge catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization and hydration reactions of organic compounds.
  • These powdered catalysts are prepared from an alloy of a catalytically-active metal, also referred to herein as a catalyst metal, with a further alloying component which is soluble in alkalis.
  • a catalytically-active metal also referred to herein as a catalyst metal
  • Mainly nickel, cobalt, copper, or iron are used as catalyst metals.
  • Precious metals have also been used as the catalytically active phase in the production of these catalysts.
  • Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
  • Raney alloys are generally prepared by the ingot casting process. In that process a mixture of the catalyst metal and, for example, aluminum are first melted and casted into ingots. Typical alloy batches on a production scale range from about ten to one thousand or more kg per ingot. According to DE2159736, cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0.2 K/s. In contrast to this, rates of 10 2 to 10 6 K/s are achieved in processes where rapid cooling is applied (for example an atomizing process in either inert gases, hydrogen, water or air) . The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. . Chan, P. Haasen, E.
  • the Raney alloy is first finely milled if it has not been produced in the desired powder form during preparation. Then the aluminum is partly (and if need be, totally) removed by extraction with alkalis such as, for example, caustic soda solution to activate the alloy powder. Following extraction of the aluminum, the alloy power has a high specific surface area (BET) , between 10 and 150 m2/g, and is rich in active hydrogen.
  • BET specific surface area
  • the activated catalyst powder is pyrophoric and stored under water or organic solvents or is embedded in organic compounds which are solid at room temperature.
  • the radiation heat treatment of this invention can be used to modify the powder Raney-type alloy prior to activation in order to generate more oxide on the surface, to increase the amount of Al on the surface of the alloy or to improve its leachability.
  • Hao et al. Lei, Hao; Song, Zhen; Bao, Xinhe; Mu, Xuhong; Zong, Baoning; Min, Enze, "XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy" Surf. Interface Anal. (2001), 32(1), 210-213.) pretreating the alloy with hydrogen caused a distinct phase transfer resulting in the formation of more of the Ni 2 Al 3 phase.
  • the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores.
  • metallic Al in the hydrogen- pretreated alloy appeared to be leached more easily and thus the aluminum species remaining on the catalyst surface is aluminum oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface.
  • this heat treatment was performed by conventional methods that may result in lower product throughput and inhomogeneity of the treatment.
  • This can also be applied to the air oxidation of the alloy prior to activation, where the resulting alloy contains A1 2 0 3 which can have a positive influence for some reactions.
  • the above mentioned radiation treatment can also be used to manufacture the alloy itself in the presence of inert, oxidizing or reducing gases to obtain the desired effects.
  • Powdered catalysts have the disadvantage that they can be used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed.
  • coarse particulate Raney alloys i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution.
  • Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
  • Patent application EP 0 648 534 Bl describes shaped, activated Raney metal fixed-bed catalysts and their preparation. To avoid the disadvantages described above, e.g., poor mechanical stability resulting from activating the outer layer of the particle, these catalysts were stabilized with the appropriate amount of binder. These catalysts were prepared by forming a homogeneous mixture of at least one catalyst alloy powder, pore builders, and a binder. The catalyst alloys each contain at least one catalytically active catalytic metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components can be used as binders. The use of binder material in an amount of 0. 5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation.
  • the freshly prepared items which are obtained are normally calcined at temperatures below 900°C.
  • this produces solid compounds that function as inert bridges between the individual alloy particles of the catalysts.
  • These compounds in contrast to catalyst alloys, are non-extractable or only extractable to a small extent so that a mechanically stable structure is obtained even after activation.
  • the added binder has the disadvantage that it is substantially catalytically inactive and thus when used wrongly, it can reduce the number of active centers in the activated layer.
  • the absolutely essential use of a binder means that only restricted range of amounts of pore producers can be used without endangering the stregnth of the shaped item. For this reason, the bulk density of these catalysts cannot be reduced to a value of less than 1. 9 kg per liter without incurring loss of strength. This leads to a considerable economic disadvantage when using these catalysts in industrial processes.
  • the high bulk density leads to a high investment per reactor bed, which is, however partly compensated for by the high activity and long-term stability of these catalysts. In certain cases, the high bulk density of the catalyst also requires a mechanically reinforced reactor structure .
  • Patent EP 984831 describes the use of rapidly quenched alloys for the production of fixed bed Raney-type catalysts of higher porosity and lower bulk density that don't need binders in order to form the preferred stablized formed catalytic bodies used in fixed bed reactions. This is accomplished by sintering the smaller phases of the rapidly quenched alloy together between various particles, thereby connecting them and resulting in higher mechanical stability without the use of binders.
  • This technology has been further advanced by the development of activated hollow spheres (US Patents 6437186, 6486366 and 6437180 as well as European patent 1068900) .
  • the activated hollow spheres have the advantages of improved mass transfer properties, lower costs, higher selectivities and improved activities per unit of reactor volume.
  • the activated hollow spheres can be produced by spraying stryrene balls with an alloy slurry, drying the coated spheres, calcining them (for the removal of styrofoam and to increase their mechanincal stability) and activating them in a aqueous caustic solution.
  • the hollow spheres can also be produce by the coating of an evaporable carrier (e.g., polyethylene, various waxes and others) via different methods with the desired mixture of an alloy and/or metal together with organic and/or inorganic binders followed by the appropriate heat treatment to remove the carrier.
  • an evaporable carrier e.g., polyethylene, various waxes and others
  • the hollow alloy spheres remaining after removal of the carrier are then activated with an aqueous caustic solution.
  • These granules are formed by mixing the desired alloy powder (s) with organic and/or inorganic binders and water in such a way that the particles agglomerate into granules .
  • These granules can be made by mixing the above mentioned mixture between two parallel plates (plate granulator) , or in any other suitable pieces of high energy mixers (e.g., Eirich or Lodige mixers). After mixing, the granules are dried, calcined, activated in caustic, and washed.
  • the organic binder can be chosen such that it expands orlusterfoams up" during either mixing, drying or calcination thereby producing a metallic foam structure that exhibits a high porosity while maintaining its mechanical strength.
  • Fixed bed activated metal catalysts can also be extruded to the desired length, dried, calcined, activated and washed as described for the other catalysts mentioned in this patent..As with the other catalyst forms, these catalyst can also be calzined and heat treated with the radiation technology (e.g., IR) mentioned here.
  • Another type of catalyst can result from the surface treament of a catalytic metal body (e.g., group VIII and lb metals and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa) with one or more caustic leachable materials such as Zn, Al and Si.
  • a catalytic metal body e.g., group VIII and lb metals and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib
  • the catalytic metal can be in the form of tubes, sheets, monoliths, beads, pellets, rings, hollow spheres, trilobes, powders, miniliths, distillation column packing material, and other solid materials.
  • the leachable component can be deposited via vaporization, chemical bond formation, precipitation and other suitable methods.
  • the surface treated material can then be heat treated via the above mentioned radiation method where the outer layer forms a Raney-type alloy that can be activated with caustic solutions to produce highly porous and active catalysts that may be optionally promoted after activation with metals from groups la, Ila, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa.
  • the fixed bed activated base metal (Raney-type) takes, its production will involve a heat treatment after making the formed body and before its activation.
  • This heat treatment is used to burn out any pore builders that may be present, as well as, sinter any binder for the increased fnechanical stability of the formed body before its activation.
  • this heat treatment will also sinter the very small phases together and form new ones.
  • Sintering induced phase reconstruction can either take place inside the particle or between the various particles. When it occurs between 2 or more particles, then the newly formed sintered phases will act as stabilizers between the particles of the catalyst and increase its mechanical stability.
  • the activated hollow spheres are a special case where the stabilization of the metallic layer before or during the removal of the evaporable carrier (e.g., styrene) can be important to catalyst stability. If the outer shells of the raw alloy coated evaporable carrier (e.g., styrofoam) are initially stabilized by localized radiation induced sintering (such as infrared radiation or the other radiations mentioned above) before the evaporable carrier (e.g., styrofoam) is removed, then the overall yield of the catalysts production will be increased and the finished product will exhibit higher mechanical stability, selectivity, and activity at very low bulk densities.
  • the evaporable carrier e.g., styrene
  • An object of the present invention is therefore to provide improved heat treated catalysts (such as olefin polymerization catalysts as well as base and/or precious metal powder or fixed bed catalysts in the form of designed granules, tablets and activated hollow spheres) which improves process efficiency and largely avoids a loss of catalyst yield while producing more stable catalysts that display higher reaction activities and selectivities in the hydrogenation of nitrile, nitro, alkene, alkyne, and carbonyl groups.
  • improved heat treated catalysts such as olefin polymerization catalysts as well as base and/or precious metal powder or fixed bed catalysts in the form of designed granules, tablets and activated hollow spheres
  • Example 1 The production of activated hollow spheres.
  • the activated Metalyst ® hollow spheres were produced according to the patent literature (-German Patents 19933450.1, 10065029.5, 10101646.8, 10065031.7 and 10101647.6) by first spraying an aqueous polyvinyl alcohol containing suspension of the base metal-Al alloy and optionally a binder (e.g., Ni powder) onto a fluidized bed of styrofoam balls.
  • This spraying can be performed in 1 or 2 steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals.
  • the catalysts produced here were made by coating the styrofoam balls twice with the above mention alloy suspension.
  • the coated styrofoam spheres were first dried and then calcined in a standard oven to burn out the styrofoam.
  • the hollow spheres of alloy were then activated in a 20 wt.% caustic solution over 1.5 hours at 80°C.
  • the activated catalyst was then stored under a mildly caustic aqueous solution (pH ⁇ 10.5) until use. Since the hollow spheres were preactivated, activation in the reactor before testing was not necessary.
  • the crush strengths of the activated hollow spheres ranged from 20 to 200 N.
  • the catalysts la, lb and lc were made according to this procedure.
  • Example 2 The production of activated hollow spheres with infrared calcination according to the invention.
  • the activated Metalyst ® hollow spheres were produced according to the patent literature (German Patents 19933450.1, 10065029.5, 10101646.8, 10065031.7 and 10101647.6) by first spraying an aqueous polyvinyl alcohol containing suspension of the base metal-Al alloy and optionally a binder (e.g., Ni powder) onto a fluidized bed of styrofoam balls.
  • This spraying can be performed in 1 or 2 steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals.
  • the catalysts produced here were made by coating the styrofoam balls twice with the above mention alloy suspension.
  • the coated styrofoam spheres were first dried and then calcined in an infrared oven that stabilized the metallic outer shell either during or before the styrofoam was burnt out.
  • the hollow spheres of alloy were then activated in a 20 wt.% caustic solution over 1.5 hours at 80°C.
  • the activated catalyst was then stored under a mildly caustic aqueous solution (pH ⁇ 10.5) until use. Since the hollow spheres were preactivated, activation in the reactor before testing was not necessary.
  • the crush strengths of the activated hollow spheres ranged from 20 to 200 N.
  • the catalysts 2a, 2b, 2c and 2d were made according to this procedure.
  • Example 3 The production of activated tablets.
  • Example 4 The production of activated tablets with infrared calcination according to the invention.
  • Example 5 The production of activated granules.
  • the activated base metal granules were made by agglomerating particles of the desired alloys along with polyvinyl alcohol and water in a high energy mixer (e.g., a L ⁇ diger mixer) , drying them, calcining the dried granules in a normal oven, activating them in a caustic solution (as mentioned in example 1 above) and washing the activated product.
  • Catalyst 5 in table 1 was produced according to this procedure.
  • Example 6 The production of activated granules with infrared calcination according to the invention.
  • the activated base metal granules were made by agglomerating particles of the desired alloys along with polyvinyl alcohol and water in a high energy mixer (e.g., a L ⁇ diger mixer) , drying them, calcining the dried granules in an infrared oven, activating them in a caustic solution (as mentioned in example 1 above) and washing the activated product.
  • Catalyst 6 in table 1 was produced according to this procedure.
  • Example 7 The production of activated extrudates .
  • Cobalt extrudates were made according to the patent literature () by extruding a mixture containing a 50 wt.%Co / 50 wt.%Al alloy and polymethylene copolymers at 190°C and a throughput of 10 kg/h with a double wave extruder. To decompose the polymethylene copolomers the extruded forms were then heated in a normal oven to 120°C followed by continual heating to 280°C within 90 minutes. Afterwards the temperature was ramped up to 800°C over 125 minutes and kept at this temperature for 140 minutes.
  • Example 8 The production of activated extrudates granules with infrared calcination according to the invention.
  • Cobalt extrudates were made according to the patent literature () by extruding a mixture containing a 50 wt.%Co / 50 wt.%Al alloy and polymethylene copolymers at 190°C and a throughput of 10 kg/h with a double wave extruder. To decompose the polymethylene copolomers the extruded forms were then heated in an oven to 120°C followed by continual heating to 280°C within 90 minutes. Afterwards the extrudates were calcined in an infrared oven as described in table 1.
  • X HS is the abbreviation for hollow spheres
  • Adiponitrile ADN
  • HMD hexamethylenediamine
  • ACN aminocapronitrile
  • Example 9 Drying of a precious metal powder catalyst
  • a commercially available wet precious metal powder catalyst from Degussa was treated by IR radiation.
  • the wet catalyst with an initial moisture content of 50-65 wt-% was dried in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalyst powders with moisture contents less than 10 wt.-% (see table 6) .
  • the resulting dried catalysts were characterised using a standard activity test procedure (see application example 5) .
  • Example 10 Reduction of a precious metal powder catalyst
  • a commercially available oxidic catalyst from Degussa was treated by IR radiation.
  • the catalyst was reduced in an infrared oven under a hydrogen gas atmosphere at various temperatures, initial moisture contents and residence times to yield dried and reduced catalyst powders with moisture contents less than 2 wt.-% (see table 7).
  • the resulting dried and reduced catalysts were characterised using a standard activity test procedure (see application example 5).
  • Example 11 Calcination of a precious metal powder catalyst
  • a commercially available catalyst from Degussa was treated by IR radiation.
  • the catalyst precursor was calcined in an infrared oven under an inert gas atmosphere at various temperatures, initial moisture contents and residence times to yield dry catalyst powders with moisture contents less than 2 wt.-% (see table 8).
  • the resulting calcined catalysts were characterised using a standard activity test procedure (see application example 5) .
  • Table 8 Data from the IR calcination of a precious metal powder catalyst.
  • the catalytic activities of the precious metal powder catalysts prepared by infrared treatment were determined by the hydrogenation of cinnamic acid.
  • the hydrogenation test reaction was carried out in a stirred tank reactor at 25°C and ambient pressure under a continuous flow of hydrogen in an ethanolic cinnamic acid solution.
  • the hydrogenation activity of the catalyst was determined by the hydrogen consumption during the reaction (see table 9) . Relative activities were compared using catalyst 10a as reference.
  • Table 9 The cinnamic acid hydrogenation data.
  • Example 12 Drying of a precious metal fixed bed catalyst
  • a catalyst was prepared according to literature-known methods by the incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation.
  • the wet catalyst precursor was dried in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%.
  • the resulting dried catalysts were characterised by CO chemisorption (see table 10) .
  • Table 10 Data from the IR drying of a precious metal fixed bed catalyst.
  • a catalyst was prepared according to literature-known methods by incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation.
  • the catalyst was reduced in an infrared oven under a hydrogen gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%.
  • the resulting dried and reduced catalysts were characterised by CO chemisorption (see table 11) .
  • Table 11 Data from the IR reduction of a precious metal fixed bed catalyst.
  • a catalyst was prepared according to literature-known methods by incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation.
  • the catalyst was calcined in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%.
  • the resulting calcined catalysts were characterised by CO chemisorption (see table 12) .
  • Table 12 Data from the IR calcination of a precious metal fixed bed catalyst
  • Aerocat ® 50 grams were distributed over a sample sheet that was placed under a gas infrared radiation source. Aerocat ® consists of spray-formed granules made of a pyrogenic silica called Aerosil ® 380 from the company Degussa AG. The Aerocat ® granules have an average particle size (D 50 ) of ⁇ 45 ⁇ m and have a residual moisture content of 45% that needs to be carefully reduced.
  • the sample sheet covers an area of 40 cm X 40 cm and it contains protrusions that have a 15cm X 15 cm footprint and protrude 15cm out.
  • the Aerocat ® sample was distribute evenly over the tops of these protrusions and the distance between the sample and the infrared radiation source was 200 mm.
  • the infrared radiation source was of the type "AK4" from the company GoGas. Aerocat ® and it is capable of operating at 950 °C.
  • the temperature of the Aerocat sample was ⁇ 200 °C due to the formation of water vapor which also leads to its autofluidization without changes in the particle size distribution.
  • the moisture of Aerocat ® was reduced from 45% to 22.5% water over the first 45 seconds of infrared drying and after 60 seconds the final moisture was found to be 10% water.

Abstract

The preparation of activated hollow bodies (e.g., spheres) with an organic (e.g., polyvinyl alcohol) and optionally inorganic binder (e.g., Ni or Co powders) containing suspension of the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and Ib and mixtures thereof optionally promoted with metals from groups Ia, IIa, IIIb, IVb, Vb, VIb, VIIb, VIII, Ib, IIb, IIIa and IVa with one or more caustic leachable materials such as Zn, Al and Si. The alloy suspension is initially sprayed onto a fluidized bed of evaporable carrier (e.g., styrofoam). This spraying can be performed in 1 or more steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals. After impregnation, the coated evaporable carrier (e.g., styrofoam) is optionally dried and then calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation. The hollow bodies of alloy are then activated in a caustic solution.

Description

THE USE OF IR, NEAR IR, VISIBLE AND UV RADIATION FOR THE PREPARATION OF CATALYSTS
Introduction and Background
The present invention relates to the use of infrared, near infrared, visable, microwave and ultraviolet radiation for the preparation and rejuvenation of catalysts as well as their precursors. This could be applied for a broad range of different catalysts such as solid acid, solid base, precious metal powder, precious metal fixed bed, base metal powder, base metal fixed bed, olefin polymerization, Raney- type powder, and Raney-type fixed bed catalysts. This method can also be applied to preparation of supports and/or alloys in which require a heat treatment. The alloys made by the radiation heat treatment of mixed, coated and vaporized/condensed compositions consisting of catalytic metals, caustic leachable metals and/or materials and optionally promoters can be used for the preparation of Raney-Type Catalysts by the removal of most if not all of the leachable material. In essence, this procedure is suitable for the chemical and/or physical transformation of materials via near infrared and infrared (wavelength = 750 nm to 500 μm) , visible (wavelength = 380 nm to 750 nm) , ultraviolet (wavelength = 172 nm to 380 nm) and microwave radiation to obtain treatment temperatures ranging from slightly above room temperature to 2800°C for the production of powders and formed bodies for catalysts and their precursors as well as the production of formed bodies to be used in the construction of fillers, crash buffers, sensors and lightweight materials .
This method is ideal for the preparation of catalysts, catalyst precursors, and supports that go through a instable phase before they are stabilized through heat treatment. For formed materials, this could be an instable chemical and/or mechanical phase, while for powders the main concern is mostly chemical instability. This method is preferred for formed metals, alloys, metal oxides, oxidic ceramics, nonoxidic ceramics, and active carbons for use in the area of catalysis. This technology could also be used to make formed bodies for other industries, such as the development of lightweight building material and crash adsorbers (e.g., the automobile industry).
This technique can be carried out continuously and/or batchwise. In the batch process, the use of reflecting materials on the walls and/or floor of the oven serve to enhance this procedure and if needed, it can be carried out under controlled inert, reducing, oxidizing, hydrating and/or dehydrating gases at normal, high and vacuum types of pressures. These types of controlled atmospheres can also be applied in the continuous mode. The continuous treatment of catalysts, catalyst precursors and spent catalysts can be carried out in a rotary calciner, in a stationary oven that is being continually fed by conveyence or any other method that allows for the continual feeding of stating material and removal of product. Additional options for the conveyance of material through the radiated zone for the desired treatment include the use of swinging, vibrating, stirred or rotating auger equipment. This radiation treatment can also be used with technologies that involve stationary, continuous or a combination thereof fluidized bed(s) for the placement during heat treatment and/or the transport of the material to be heat treated. One or more of the reactor's walls and/or floor can be optionally transparent to the desired form of radiation, thereby allowing for the separation of the radiation source from the heat treated material and the desired atmosphere. The continuous calcination equipment can also be outfitted with reflecting walls and/or floor for the optimal use of radiation. The radiation source can either be present as a series of panels or a wand type of equipment that can be outfitted into existing ovens or be the intergral part of an oven built especially for this purpose. Specifically, the IR radiation could either be generated by an electronic or gas/oil source. The IR radiation can be generated via an electronic lamp/ceramic radiation source, a gas heated catalytic/surface radiation source or a gas/oil heated pore burner. The gas/oil IR source has the added benefit of allowing for the immediate burning of waste gases into their oxidized species before they are emmited as exhaust. This process can allow for the rapid transfer of 3000 kW/m2 radiation energie to the desired reactant for the quick transformation of the above mentioned materials into products, thereby leading to the quicker and more economic manufacture of these products. The use of rapid radiation treatment of materials will also permit the fabrication of commercial product quantities with smaller ovens that can be employed in innovative ways. Since the heat is focused on the reactant material to be converted, the temperature of the process is more readily controlled while the temperature of the reactor itself can be much lower. This means that the reactor will be subjected to less corrosion and stress, leading to less equipment maintenance and far fewer contamination problems with the product.
In the realm of olefin polymerization catalysts, the desired powder inorganic oxide for either fluidized beds or slurry processes can be dried and/or calcined. The temperatures for these processes can range from 20 to 1800°C. The oxide can be treated with additional components (e.g., catalytic metal solutions) prior to Infrared heating via mixing, impregnation or other treatment procedures. This process can be used for the preparation of catalysts and/or supports to be used in olefin polymerization, Fischer Tropsch synthesis, the production of acrolein, acrylnitril and other nitriles as well as acrylic acid, aniline, caprolactam, chlorinated hydrocarbons, cresol, melamin, pyridine, phthalic acid (or rather Phthalic anhydride), vinyacectate, vinylchloride or xylene.
These granulated forms could either be filled into the reactor as is, or they can be sintered together to for a desired structure. The common forms could include spheres, foams, cylinders, ovals, hollow spheres, and other forms as well. The main advantages of this process is its relatively low production costs, low bulk density and high porosity.
This technology is also suitable for the preparation of fixed bed and powder catalyst supports, where heat treatment is used to modify the material pore and surface structure; burn out modifiers and pore builders; change the oxidation level of the components of the support either via reduction or oxidation; and/or to enhance the impregnation of said support. This impregnation solution can be comprised of either precious metal salts, base metal salts, alkali metal salts, alkaline metal salts, rare earth metal salts, organic compounds of the previously mentioned metals, organic modifiers, inorganic modifiers and/or combinations thereof. The use of these radiations are ideal for "hot" impregnations that can lead to thinner shell impregnations, thereby allowing for the improved control of the impregnated component's penetration into the pore system of the support material.
In the manufacture of base, mixed base/precious and precious metal powder and fixed bed catalysts, these radiations can be utilized for improved impregnation, fixing of the metal salts to the support, reduction and/or oxidation of the various components present on the catalyst during its preparation. This can also lead to the improved promotion of the catalyst system and strong metal support interactions (SMSI) . In the case of SMSI, the support is reduced by the metal and becomes a part of the catalytic surface, thereby generating a different type of active site that could enhance catalyst selectivity, stability and activity.
A special case for this technology involves producing activated metal catalysts which are known in the field of chemical engineering as Raney-type, skeleton, activated base metal, or sponge catalysts. They are used, largely in powder form, for a large number of hydrogenation, dehydrogenation, isomerization and hydration reactions of organic compounds. These powdered catalysts are prepared from an alloy of a catalytically-active metal, also referred to herein as a catalyst metal, with a further alloying component which is soluble in alkalis. Mainly nickel, cobalt, copper, or iron are used as catalyst metals. Precious metals have also been used as the catalytically active phase in the production of these catalysts. Aluminum is generally used as the alloying component which is soluble in alkalis, but other components may also be used, in particular zinc and silicon or mixtures of these with aluminum.
These so-called Raney alloys are generally prepared by the ingot casting process. In that process a mixture of the catalyst metal and, for example, aluminum are first melted and casted into ingots. Typical alloy batches on a production scale range from about ten to one thousand or more kg per ingot. According to DE2159736, cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0.2 K/s. In contrast to this, rates of 102 to 106 K/s are achieved in processes where rapid cooling is applied (for example an atomizing process in either inert gases, hydrogen, water or air) . The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. . Chan, P. Haasen, E. J. Kramer, Vol. 15, Processing of Metals and Alloys, 1991, VCH-Verlag Weinheim, pages 57 to HO) . A process of this type is used in EP0437788B1 in order to prepare a Raney alloy powder. In that process the molten alloy at a temperature of 50 to 500°C above its melting point is atomized and cooled using water and/or a gas.
To prepare a catalyst, the Raney alloy is first finely milled if it has not been produced in the desired powder form during preparation. Then the aluminum is partly (and if need be, totally) removed by extraction with alkalis such as, for example, caustic soda solution to activate the alloy powder. Following extraction of the aluminum, the alloy power has a high specific surface area (BET) , between 10 and 150 m2/g, and is rich in active hydrogen. The activated catalyst powder is pyrophoric and stored under water or organic solvents or is embedded in organic compounds which are solid at room temperature. The radiation heat treatment of this invention can be used to modify the powder Raney-type alloy prior to activation in order to generate more oxide on the surface, to increase the amount of Al on the surface of the alloy or to improve its leachability. According to Hao et al. (Lei, Hao; Song, Zhen; Bao, Xinhe; Mu, Xuhong; Zong, Baoning; Min, Enze, "XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy" Surf. Interface Anal. (2001), 32(1), 210-213.) pretreating the alloy with hydrogen caused a distinct phase transfer resulting in the formation of more of the Ni2Al3 phase. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen- pretreated alloy appeared to be leached more easily and thus the aluminum species remaining on the catalyst surface is aluminum oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. In the literature, this heat treatment was performed by conventional methods that may result in lower product throughput and inhomogeneity of the treatment. Hence using the radiation technologies mentioned here for catalyst heating during hydrogen treatment will improve the quality of the product and the speed in which it can be produced. This can also be applied to the air oxidation of the alloy prior to activation, where the resulting alloy contains A1203 which can have a positive influence for some reactions. The above mentioned radiation treatment can also be used to manufacture the alloy itself in the presence of inert, oxidizing or reducing gases to obtain the desired effects.
Powdered catalysts have the disadvantage that they can be used only in a batch process and, after the catalytic reaction, have to be separated from the reaction medium by costly sedimentation and/or filtration. Therefore a variety of processes for preparing moulded items which lead to activated metal fixed-bed catalysts after extraction of the aluminum have been disclosed. Thus, for example, coarse particulate Raney alloys, i.e., Raney alloys which have only been coarsely milled, are obtainable and these can be activated by a treatment with caustic soda solution.
Extraction and activation then occurs only in a surface layer the thickness of which can be adjusted by the conditions used during extraction.
Substantial disadvantages of catalysts prepared by these prior methods are their poor mechanical stability of the activated outer layer, their low level of porosity, and their relatively very low percentage of activated metal .
Since only the outer layer of these catalysts are catalytically active, abrasion leads to rapid deactivation and renewed activation of the deeper lying layers of alloy with caustic soda solution only leads, at best, to partial reactivation.
Patent application EP 0 648 534 Bl describes shaped, activated Raney metal fixed-bed catalysts and their preparation. To avoid the disadvantages described above, e.g., poor mechanical stability resulting from activating the outer layer of the particle, these catalysts were stabilized with the appropriate amount of binder. These catalysts were prepared by forming a homogeneous mixture of at least one catalyst alloy powder, pore builders, and a binder. The catalyst alloys each contain at least one catalytically active catalytic metal and an extractable alloying component. The pure catalyst metals or mixtures thereof which do not contain extractable components can be used as binders. The use of binder material in an amount of 0. 5 to 20 weight percent with respect to the catalyst alloy, is essential in order to achieve sufficient mechanical stability after activation. After shaping the catalyst alloy and the binder with conventional shaping aids and pore producers, the freshly prepared items which are obtained are normally calcined at temperatures below 900°C. As a result of sintering processes with the finely divided binder, this produces solid compounds that function as inert bridges between the individual alloy particles of the catalysts. These compounds, in contrast to catalyst alloys, are non-extractable or only extractable to a small extent so that a mechanically stable structure is obtained even after activation. However, the added binder has the disadvantage that it is substantially catalytically inactive and thus when used wrongly, it can reduce the number of active centers in the activated layer. In addition, the absolutely essential use of a binder means that only restricted range of amounts of pore producers can be used without endangering the stregnth of the shaped item. For this reason, the bulk density of these catalysts cannot be reduced to a value of less than 1. 9 kg per liter without incurring loss of strength. This leads to a considerable economic disadvantage when using these catalysts in industrial processes. In particular when using more expensive catalysts alloys, for example cobalt alloys, the high bulk density leads to a high investment per reactor bed, which is, however partly compensated for by the high activity and long-term stability of these catalysts. In certain cases, the high bulk density of the catalyst also requires a mechanically reinforced reactor structure .
Patent EP 984831 describes the use of rapidly quenched alloys for the production of fixed bed Raney-type catalysts of higher porosity and lower bulk density that don't need binders in order to form the preferred stablized formed catalytic bodies used in fixed bed reactions. This is accomplished by sintering the smaller phases of the rapidly quenched alloy together between various particles, thereby connecting them and resulting in higher mechanical stability without the use of binders. This technology has been further advanced by the development of activated hollow spheres (US Patents 6437186, 6486366 and 6437180 as well as european patent 1068900) . The activated hollow spheres have the advantages of improved mass transfer properties, lower costs, higher selectivities and improved activities per unit of reactor volume. The activated hollow spheres can be produced by spraying stryrene balls with an alloy slurry, drying the coated spheres, calcining them (for the removal of styrofoam and to increase their mechanincal stability) and activating them in a aqueous caustic solution. The hollow spheres can also be produce by the coating of an evaporable carrier (e.g., polyethylene, various waxes and others) via different methods with the desired mixture of an alloy and/or metal together with organic and/or inorganic binders followed by the appropriate heat treatment to remove the carrier. In the case of activated hollow spheres, the hollow alloy spheres remaining after removal of the carrier are then activated with an aqueous caustic solution. Of course this technology can be applied to a wide range of hollow bodied objects and not only spheres. Another technology involves the production of alloy granules via their agglomeration in appropriately equipped mixers under the right conditions . The advantages of the granules is that they too exhibit high activities and selectivities at satisfactory bulk densities while being easy to produce. The activated base metal granules were made by agglomerating particles of the desired alloys along with organic and/or inorganic binders, calcining these granules, and activating them in caustic solution in order to make them catalytically active. Depending on the conditions of catalyst preparation and the catalyst alloys being used, the use of both organic and inorganic binders may not be necessary. These granules are formed by mixing the desired alloy powder (s) with organic and/or inorganic binders and water in such a way that the particles agglomerate into granules . These granules can be made by mixing the above mentioned mixture between two parallel plates (plate granulator) , or in any other suitable pieces of high energy mixers (e.g., Eirich or Lodige mixers). After mixing, the granules are dried, calcined, activated in caustic, and washed. The organic binder can be chosen such that it expands or „foams up" during either mixing, drying or calcination thereby producing a metallic foam structure that exhibits a high porosity while maintaining its mechanical strength. It is also possible to make metallic foams that are not in the shape of a granule by this method. The major advantages of these granules are their low bulk density, high porosity, relatively high percentage of activated metal, relatively low production cost, and the activity these materials exhibit per kilogram of metal as well as the activity they have on a per liter of catalyst basis.
Fixed bed activated metal catalysts can also be extruded to the desired length, dried, calcined, activated and washed as described for the other catalysts mentioned in this patent..As with the other catalyst forms, these catalyst can also be calzined and heat treated with the radiation technology (e.g., IR) mentioned here. Another type of catalyst can result from the surface treament of a catalytic metal body (e.g., group VIII and lb metals and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa) with one or more caustic leachable materials such as Zn, Al and Si. The catalytic metal can be in the form of tubes, sheets, monoliths, beads, pellets, rings, hollow spheres, trilobes, powders, miniliths, distillation column packing material, and other solid materials. The leachable component can be deposited via vaporization, chemical bond formation, precipitation and other suitable methods. The surface treated material can then be heat treated via the above mentioned radiation method where the outer layer forms a Raney-type alloy that can be activated with caustic solutions to produce highly porous and active catalysts that may be optionally promoted after activation with metals from groups la, Ila, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa.
Regardless of the form the fixed bed activated base metal (Raney-type) takes, its production will involve a heat treatment after making the formed body and before its activation. This heat treatment is used to burn out any pore builders that may be present, as well as, sinter any binder for the increased fnechanical stability of the formed body before its activation. In the case of the rapidly cooled alloys, this heat treatment will also sinter the very small phases together and form new ones. Sintering induced phase reconstruction can either take place inside the particle or between the various particles. When it occurs between 2 or more particles, then the newly formed sintered phases will act as stabilizers between the particles of the catalyst and increase its mechanical stability. The activated hollow spheres are a special case where the stabilization of the metallic layer before or during the removal of the evaporable carrier (e.g., styrene) can be important to catalyst stability. If the outer shells of the raw alloy coated evaporable carrier (e.g., styrofoam) are initially stabilized by localized radiation induced sintering (such as infrared radiation or the other radiations mentioned above) before the evaporable carrier (e.g., styrofoam) is removed, then the overall yield of the catalysts production will be increased and the finished product will exhibit higher mechanical stability, selectivity, and activity at very low bulk densities.
An object of the present invention is therefore to provide improved heat treated catalysts (such as olefin polymerization catalysts as well as base and/or precious metal powder or fixed bed catalysts in the form of designed granules, tablets and activated hollow spheres) which improves process efficiency and largely avoids a loss of catalyst yield while producing more stable catalysts that display higher reaction activities and selectivities in the hydrogenation of nitrile, nitro, alkene, alkyne, and carbonyl groups.
Example 1. The production of activated hollow spheres.
The activated Metalyst® hollow spheres were produced according to the patent literature (-German Patents 19933450.1, 10065029.5, 10101646.8, 10065031.7 and 10101647.6) by first spraying an aqueous polyvinyl alcohol containing suspension of the base metal-Al alloy and optionally a binder (e.g., Ni powder) onto a fluidized bed of styrofoam balls. This spraying can be performed in 1 or 2 steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals. The catalysts produced here were made by coating the styrofoam balls twice with the above mention alloy suspension. After impregnation, the coated styrofoam spheres were first dried and then calcined in a standard oven to burn out the styrofoam. The hollow spheres of alloy were then activated in a 20 wt.% caustic solution over 1.5 hours at 80°C. The activated catalyst was then stored under a mildly caustic aqueous solution (pH ~10.5) until use. Since the hollow spheres were preactivated, activation in the reactor before testing was not necessary. The crush strengths of the activated hollow spheres ranged from 20 to 200 N. The catalysts la, lb and lc were made according to this procedure.
Example 2. The production of activated hollow spheres with infrared calcination according to the invention.
The activated Metalyst® hollow spheres were produced according to the patent literature (German Patents 19933450.1, 10065029.5, 10101646.8, 10065031.7 and 10101647.6) by first spraying an aqueous polyvinyl alcohol containing suspension of the base metal-Al alloy and optionally a binder (e.g., Ni powder) onto a fluidized bed of styrofoam balls. This spraying can be performed in 1 or 2 steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals. The catalysts produced here were made by coating the styrofoam balls twice with the above mention alloy suspension. After impregnation, the coated styrofoam spheres were first dried and then calcined in an infrared oven that stabilized the metallic outer shell either during or before the styrofoam was burnt out. The hollow spheres of alloy were then activated in a 20 wt.% caustic solution over 1.5 hours at 80°C. The activated catalyst was then stored under a mildly caustic aqueous solution (pH ~10.5) until use. Since the hollow spheres were preactivated, activation in the reactor before testing was not necessary. The crush strengths of the activated hollow spheres ranged from 20 to 200 N. The catalysts 2a, 2b, 2c and 2d were made according to this procedure.
Example 3. The production of activated tablets.
In accordance with the literature (US Patents 5536694 and 6262307) the preparation of the shell activated Metalyst® tablets started with a homogeneous mixture of the desired alloy and shaping aids that was tableted, calcined in a normal oven, activated in caustic solution (as described in example 1 above) , washed, and stored under a mildly caustic aqueous solution (pH ~10.5) until use. Since Metalyst® tablets are preactivated, activation in the reactor before testing was not necessary. The crush strength of Metalyst® tablets is approximately 300 N, thus eliminating catalyst attrition during reactor loading and the reaction itself. The catalyst 3 in table 1 was produced according to this procedure.
Example 4. The production of activated tablets with infrared calcination according to the invention.
In accordance with the literature (US Patents' 5536694 and 6262307) the preparation of the shell activated Metalyst® tablets started with a homogeneous mixture of the desired alloy and shaping aids that was tableted, calcined in an infrared oven, activated in caustic solution (as described in example 1 above) , washed, and stored under a mildly caustic aqueous solution (pH ~10.5) until use. Since Metalyst® tablets are preactivated, activation in the reactor before testing was not necessary. The crush strength of Metalyst® tablets is approximately 300 N, thus eliminating catalyst attrition during reactor loading and the reaction itself. The catalysts 4a, 4b, 4c and 4d in table 1 were produced according to this procedure.
Example 5. The production of activated granules.
The activated base metal granules were made by agglomerating particles of the desired alloys along with polyvinyl alcohol and water in a high energy mixer (e.g., a Lδdiger mixer) , drying them, calcining the dried granules in a normal oven, activating them in a caustic solution (as mentioned in example 1 above) and washing the activated product. Catalyst 5 in table 1 was produced according to this procedure.
Example 6. The production of activated granules with infrared calcination according to the invention.
The activated base metal granules were made by agglomerating particles of the desired alloys along with polyvinyl alcohol and water in a high energy mixer (e.g., a Lδdiger mixer) , drying them, calcining the dried granules in an infrared oven, activating them in a caustic solution (as mentioned in example 1 above) and washing the activated product. Catalyst 6 in table 1 was produced according to this procedure.
Example 7. The production of activated extrudates .
Cobalt extrudates were made according to the patent literature () by extruding a mixture containing a 50 wt.%Co / 50 wt.%Al alloy and polymethylene copolymers at 190°C and a throughput of 10 kg/h with a double wave extruder. To decompose the polymethylene copolomers the extruded forms were then heated in a normal oven to 120°C followed by continual heating to 280°C within 90 minutes. Afterwards the temperature was ramped up to 800°C over 125 minutes and kept at this temperature for 140 minutes. The extrudates were then cooled, activated in a 20% caustic solution at 80°C over 120 minutes, washed, and stored under a mildly caustic aqueous solution (pH ~10.5) until use. Catalyst 7 in table 1 was produced according to this procedure.
Example 8. The production of activated extrudates granules with infrared calcination according to the invention.
Cobalt extrudates were made according to the patent literature () by extruding a mixture containing a 50 wt.%Co / 50 wt.%Al alloy and polymethylene copolymers at 190°C and a throughput of 10 kg/h with a double wave extruder. To decompose the polymethylene copolomers the extruded forms were then heated in an oven to 120°C followed by continual heating to 280°C within 90 minutes. Afterwards the extrudates were calcined in an infrared oven as described in table 1. The extrudates were then cooled, activated in a 20% caustic solution at 80°C over 120 minutes, washed, and stored under a mildly caustic aqueous solution (pH ~10.5) until use. Catalyst 8 in table 1 was produced according to this procedure.
Table 1 The activated base metal catalysts of this patent.
Figure imgf000018_0001
XHS is the abbreviation for hollow spheres
Application Example 1: The Hydrogenation of adiponitrile
The trickle phase hydrogenation of a 20 wt.% adiponitrile in methanol solution at 65 bar and 113°C was carried out with 3 mm activated tablets, hollow spheres, granules or extrudates at the LHSV (liquid hourly space velocity) value 1.0 h-1. Adiponitrile conversion and selectivities were determined by GC. The Adiponitrile hydrogenation data is displayed in table 2.
Table 2 Adiponitrile hydrogenation data.
Figure imgf000019_0001
together.
The abbreviations are => Adiponitrile (ADN) , hexamethylenediamine (HMD) and aminocapronitrile (ACN)
Application Example 2 : The Hydrogenation of dinitrotoluene
The trickle phase hydrogenation of a 4 wt.% dinitrotoluene in methanol solution at 60 bar and 81°C was carried out with 3 mm activated hollow spheres at the LHSV (liquid hourly space velocity) values of 0.76, 1.5, 2.5 and 3.3 h" 1. Dinitrotoluene conversion and selectivities were determined by GC. The dinitrotoluene hydrogenation data is displayed in table 3.
Table 3 Dinitrotoluene (DNT) hydrogenation data.
Figure imgf000019_0002
1. TDA => toluenediamine Application Example 3: The Hydrogenation of 1,4-butynediol
The trickle phase hydrogenation of a 50 wt.% 1,4-butynediol in water solution that was pH adjusted to 7 with NaHC03 at 60 bar and 135°C was carried out with 3 mm activated tablets and hollow spheres at the WHSV (weight hourly space velocity) values of 0.8 and 1.6 h-1. 1, 4-Butynediol conversion and selectivities were determined by GC. The 1,4-butynediol hydrogenation data is displayed in table 4.
Table 4. The 1,4-butynediol (BYD) hydrogenation data.
Figure imgf000020_0001
The selectivity of 2-butene-l, 4-diol (BeD)
Application Example 4: The Hydrogenation of glucose
The trickle phase hydrogenation of a 40 wt.% glucose in water solution at 50 or 65 bar and 110 or 140°C was carried out with 3 mm activated tablets at the WHSV (weight hourly space velocity) values ranging from 0.07 to 1.08 h"1. Glucose conversion and selectivities were determined by HPLC. The glucose hydrogenation data is displayed in table 5. Table 5 Glucose hydrogenation data
Figure imgf000021_0001
Example 9: Drying of a precious metal powder catalyst
A commercially available wet precious metal powder catalyst from Degussa was treated by IR radiation. The wet catalyst with an initial moisture content of 50-65 wt-% was dried in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalyst powders with moisture contents less than 10 wt.-% (see table 6) . The resulting dried catalysts were characterised using a standard activity test procedure (see application example 5) .
Table 6: Data from the IR drying of a precious metal powder catalyst
Figure imgf000021_0002
Example 10: Reduction of a precious metal powder catalyst
A commercially available oxidic catalyst from Degussa was treated by IR radiation. The catalyst was reduced in an infrared oven under a hydrogen gas atmosphere at various temperatures, initial moisture contents and residence times to yield dried and reduced catalyst powders with moisture contents less than 2 wt.-% (see table 7). The resulting dried and reduced catalysts were characterised using a standard activity test procedure (see application example 5).
Table 7 : Data from the IR reduction of a precious metal powder catalyst
Figure imgf000022_0001
Example 11: Calcination of a precious metal powder catalyst
A commercially available catalyst from Degussa was treated by IR radiation. The catalyst precursor was calcined in an infrared oven under an inert gas atmosphere at various temperatures, initial moisture contents and residence times to yield dry catalyst powders with moisture contents less than 2 wt.-% (see table 8). The resulting calcined catalysts were characterised using a standard activity test procedure (see application example 5) . Table 8 : Data from the IR calcination of a precious metal powder catalyst.
Figure imgf000023_0001
Application Example 5: Hydrogenation of cinnamic acid
The catalytic activities of the precious metal powder catalysts prepared by infrared treatment were determined by the hydrogenation of cinnamic acid. The hydrogenation test reaction was carried out in a stirred tank reactor at 25°C and ambient pressure under a continuous flow of hydrogen in an ethanolic cinnamic acid solution. The hydrogenation activity of the catalyst was determined by the hydrogen consumption during the reaction (see table 9) . Relative activities were compared using catalyst 10a as reference. Table 9: The cinnamic acid hydrogenation data.
Figure imgf000024_0001
Example 12 : Drying of a precious metal fixed bed catalyst
A catalyst was prepared according to literature-known methods by the incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation. The wet catalyst precursor was dried in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%. The resulting dried catalysts were characterised by CO chemisorption (see table 10) . Table 10: Data from the IR drying of a precious metal fixed bed catalyst.
Figure imgf000025_0001
Example 13 Reduction of a precious metal fixed bed catalyst
A catalyst was prepared according to literature-known methods by incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation. The catalyst was reduced in an infrared oven under a hydrogen gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%. The resulting dried and reduced catalysts were characterised by CO chemisorption (see table 11) . Table 11: Data from the IR reduction of a precious metal fixed bed catalyst.
Figure imgf000026_0001
Example 14 Calcination of a precious metal fixed bed catalyst
A catalyst was prepared according to literature-known methods by incipient-wetness impregnation of a formed activated carbon support with a precious metal salt solution and then treated by IR radiation. The catalyst was calcined in an infrared oven under an inert gas atmosphere at various temperatures and residence times to yield dry catalysts with moisture contents less than 2 wt.-%. The resulting calcined catalysts were characterised by CO chemisorption (see table 12) . Table 12: Data from the IR calcination of a precious metal fixed bed catalyst
Figure imgf000027_0001
Example 15: The drying of Aerocat
50 grams of Aerocat® were distributed over a sample sheet that was placed under a gas infrared radiation source. Aerocat® consists of spray-formed granules made of a pyrogenic silica called Aerosil® 380 from the company Degussa AG. The Aerocat® granules have an average particle size (D50) of ~45 μm and have a residual moisture content of 45% that needs to be carefully reduced. The sample sheet covers an area of 40 cm X 40 cm and it contains protrusions that have a 15cm X 15 cm footprint and protrude 15cm out. The Aerocat® sample was distribute evenly over the tops of these protrusions and the distance between the sample and the infrared radiation source was 200 mm. The infrared radiation source was of the type "AK4" from the company GoGas. Aerocat® and it is capable of operating at 950 °C. During drying, the temperature of the Aerocat sample was < 200 °C due to the formation of water vapor which also leads to its autofluidization without changes in the particle size distribution. The moisture of Aerocat® was reduced from 45% to 22.5% water over the first 45 seconds of infrared drying and after 60 seconds the final moisture was found to be 10% water. The use of infrared radiation for the effective drying of Aerocat under mild conditions have lead to desired moisture content without attrition and the loss of fine particle properties. Hence, this method is also suitable for other olefin poly erizaton catalyst supports, powder catalyst supports and fixed bed catalyst supports. Due to the high temperature capabilities of the radiation source, one could also use this techology for the high temperature calcination of catalyst fixed bed and powder supports.

Claims

Claims
1. The preparation of activated hollow bodies (e.g., spheres) with an organic (e.g., polyvinyl alcohol) and optionally inorganic binder (e.g., Ni or Co powders) containing suspension of the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The alloy suspension is initially sprayed onto a fluidized bed of evaporable carrier (e.g., styrofoam). This spraying can be performed in 1 or more steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals. After impregnation, the coated evaporable carrier (e.g., styrofoam) is optionally dried and then calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation. The hollow bodies of alloy are then activated in a caustic solution.
2. The preparation of activated hollow spheres with an organic (e.g., polyvinyl alcohol) and optionally inorganic binder (e.g., Ni or Co powders) containing suspension of the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The alloy suspension is initially sprayed onto a fluidized bed of styrofoam balls. This spraying can be performed in 1 or more steps depending on the need to either produce a thicker shell or to produce a catalyst with a designed layering of different alloys and/or metals. After impregnation, the coated styrofoam spheres are optionally dried and then calcined in an infrared oven or any other equipment capable of treating this material with infrared radiation. The hollow spheres of alloy are then activated in a caustic solution.
3. The preparation of activated hollow spheres with an organic (e.g., polyvinyl alcohol) and optionally inorganic binder (e.g., Ni or Co powders) containing suspension of the desired Raney-type alloy comprised of a Ni, Al and optionally one or more promoters from groups IVb, Vb, Vlb,Vllb, VIII and lb. The alloy suspension is initially sprayed onto a fluidized bed of styrofoam balls. This spraying can be performed in 1 or more steps depending on the need to either produce a thicker shell or to pro-duce a catalyst with a designed layering of different alloys and/or metals. After impregnation, the coated styrofoam spheres are optionally dried and then calcined in an infrared oven or any other equipment capable of treating this material with infrared radiation. The hollow spheres of alloy are then activated in a caustic solution.
4. The preparation of activated hollow spheres with an organic (e.g., polyvinyl alcohol) and optionally inorganic binder (e.g., Ni or Co powders) containing suspension of the desired Raney-type alloy comprised of a Co, Al and optionally one or more promoters from groups IVb, Vb, Vlb,Vllb, VIII and lb. The alloy suspension is initially sprayed onto a fluidized bed of styrofoam balls . This spraying can be performed in 1 or more steps depending on the need to either produce a thicker shell or to pro-duce a catalyst with a designed layering of different alloys and/or metals. After impregnation, the coated styrofoam spheres are optionally dried and then calcined in an infrared oven. The hollow spheres of alloy are then activated in a caustic solution.
5. The preparation of hollow bodies with optionally an organic (e.g., polyvinyl alcohol) and/or inorganic binder (e.g., Ni or Co powders). The hollow bodies contain the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as
Zn, Al and Si. The preparation of the activated hollow bodies involve drying and/or calcination steps in equipment capable of treating the material with infrared, near infrared, visable, microwave and/or ultraviolet radiation. The hollow alloy bodies are then activated in a caustic solution to form the catalyst.
6. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of organic compounds .
7. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of carbonyl groups.
8. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of nitro groups.
9. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of nitrile groups.
10. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of alkyene, alkyne and aromatic groups .
11. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of adiponitrile.
12. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of dinitrotoluene.
13. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of 2-butyne-l, 4- diol.
14. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of aldoses and ketoses.
15. The use of a catalyst fabricated according to claims 1, 2, 3, 4 or 5 for the hydrogenation of monosacharides and disacharides from their respective ketoses and/or aldoses to the corresponding sugar alcohols.
16. Shell activated Raney-type metal tablets prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are tableted; calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation; activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
17. Shell activated Raney-type metal tablets prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are tableted, calcined equipment capable of treating the material with infrared radiation, activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
18. Activated Raney-type metal extrudates prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are extruded; calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation; activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
19. Activated Raney-type metal extrudates prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are extruded, calcined in equipment capable of treating the material with infrared radiation, activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
20. Activated Raney-type metal granules prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are granulated; calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation; activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
21. Activated Raney-type metal granules prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are granulated, calcined in equipment capable of treating the material with infrared radiation, activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
22. Activated Raney-type metal formed bodies prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are formed; calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation; activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
3. Activated Raney-type metal formed bodies prepared from a homogeneous mixture of the desired alloy comprised of a catalytic metal, a caustic leachable metal, and optionally one or more promoters mixed together with shaping aids that are formed, calcined in equipment capable of treating the material with infrared radiation, activated in caustic solution and washed. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si.
24. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in an oxidizing gas in equipment outfitted with infrared, near infrared, visable, microwave and ultraviolet radiation.
25. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in a reducing gas in equipment outfitted with infrared, near infrared, visable, microwave and ultraviolet radiation.
26. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in an inert gas in equipment outfitted with infrared, near infrared, visable, microwave and ultraviolet radiation.
27. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in an oxidizing gas in equipment outfitted with infrared radiation.
28. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in a reducing gas in equipment outfitted with infrared radiation.
29. The preparation of fixed bed Raney-type catalysts as described in claims 1, 2, 3, 4, 5, 16, 17, 18, 19, 20, 21, 22, or 23 where the catalyst is heat treated in an inert gas in equipment outfitted with infrared radiation.
30. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The powder is optionally dried and then calcined in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation. The Raney-type powder is then activated in a caustic solution.
31. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The powder is optionally dried and then treated with a hydrogen containing gas in an oven capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation. The Raney-type powder is then activated in a caustic solution.
32. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The powder is optionally dried and then treated with an inert gas in an oven capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation. The Raney-type powder is then activated in a caustic solution.
33. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters . The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The powder is optionally dried and then calcined in an oven capable of treating the material with infrared radiation. The Raney-type powder is then activated in a caustic solution.
34. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and. Si. The powder is optionally dried and then treated with a hydrogen containing gas in an oven capable of treating the material with infrared radiation. The Raney-type powder is then activated in a caustic solution.
35. The preparation of Raney-type powder catalysts from the desired Raney-type alloy comprised of a catalytic metal, a caustic leachable metal and optionally one or more promoters. The catalytic metal can be from groups VIII and lb and mixtures thereof optionally promoted with metals from groups la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa with one or more caustic leachable materials such as Zn, Al and Si. The powder is optionally dried and then treated with an inert gas in an oven capable of treating the material with infrared radiation. The Raney-type powder is then activated in a caustic solution.
36. The use of a catalyst fabricated according to claims
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,
30, 31, 32, 33, 34 or 35 for the hydrogenation of organic compounds.
37. he use of a catalyst fabricated according to claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of carbonyl. groups.
38. The use of a catalyst fabricated according to claims
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,
30, 31, 32, 33, 34 or 35 for the hydrogenation of nitro groups.
39. The use of a catalyst fabricated according to claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,
30, 31, 32, 33, 34 or 35 for the hydrogenation of nitrile groups.
40. The use of a catalyst fabricated according to claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of alkyene, alkyne and aromatic groups.
41. The use of a catalyst fabricated according to claims
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of adiponitrile.
42. The use of a catalyst fabricated according to claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of dinitrotoluene .
43. The use of a catalyst fabricated according to claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of 2- butyne-1, 4-diol.
44. The use of a catalyst fabricated according to claims claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of aldoses and ketoses.
45. The use of a catalyst fabricated according to claims claims 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 for the hydrogenation of monosacharides and disacharides from their respective ketoses and/or aldoses to the corresponding sugar alcohols.
46. The preparation of supported precious metal powder catalysts that involved a drying step performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
47. The preparation of supported precious metal powder catalysts that involved a reduction step in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
48. The preparation of supported precious metal powder catalysts that involved a reduction and at the same time a drying step in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
49. The preparation of supported precious metal powder catalysts that involved a calcining step performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and Iva groups of the periodic chart.
50. The preparation of supported precious metal powder catalysts that involved a reduction step and introduction of the strong metal support interaction in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
51. The preparation of supported precious metal powder catalysts that involved a drying step performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
52. The preparation of supported precious metal powder catalysts that involved a reduction step in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
53. The preparation of supported precious metal powder catalysts that involved a reduction and at the same time a drying step in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart .
54. The preparation of supported precious metal powder catalysts that involved a calcining step performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart .
55. The preparation of supported precious metal powder catalysts that involved a reduction step and introduction of the strong metal support interaction in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
56. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a drying step performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
57. he preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction step in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and Iva groups of the periodic chart.
58. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction and at the same time a drying step in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and Iva groups of the periodic chart.
59. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a clacining step performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and Iva groups of the periodic chart.
60. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction step and introduction of the strong metal support interaction in a reducing medium performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIIB, VIII and IB groups that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and Iva groups of the periodic chart.
61. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a drying step performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
62. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction step in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, Vllb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
63. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction and at the same time a drying step in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, VHb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
64. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a calcining step performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, VHb, VIII, lb, Hb, Ilia and IVa groups of the periodic chart.
65. The preparation of supported precious metal fixed bed catalysts in the form of tablets, extrudates, trilobes, hollow spheres and other formed shapes that involved a reduction step and introduction of the strong metal support interaction in a reducing medium performed in equipment capable of treating the catalyst with infrared radiation. The catalysts can consist of zirconia, magnesia, carbon, silica, barium sulfate, calcium carbonate, carbon black, titania, alumina and supports consisting of physical or chemical mixtures thereof impregnated with one or more metals of the VIII group that are optionally promoted with one or more elements from the la, Ha, Illb, IVb, Vb, Vlb, VHb, VIII, lb, lib, Ilia and IVa groups of the periodic chart.
66. The preparation of catalytic materials that involve a drying, reduction, and/or calcination step of either a powder or a fixed bed form performed in equipment capable of treating the catalyst with infrared, near infrared, visable, microwave and ultraviolet radiation.
67. The preparation of catalytic materials that involve a drying, reduction, and/or calcination step of either a powder or a fixed bed form performed in equipment capable of treating the catalyst with infrared radiation.
68. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of organic compounds.
69. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of carbonyl groups .
70. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of nitro groups.
71. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of nitrile groups.
72. The use of a catalyst fabricated according to claims
46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of alkyene, alkyne and aromatic groups.
73. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of adiponitrile.
74. The use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of dinitrotoluene.
75. he use of a catalyst fabricated according to claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of 2-butyne-l,4-diol.
76. The use of a catalyst fabricated according to claims claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of aldoses and ketoses.
77. The use of a catalyst fabricated according to claims claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of monosacharides and disacharides from their respective ketoses and/or aldoses to the corresponding sugar alcohols.
78. The use of a catalyst fabricated according to claims claims 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 for the hydrogenation of cinnamic acid.
79. The preparation of hollow bodies with optionally an organic (e.g., polyvinyl alcohol) and/or inorganic binder (e.g., Ni or Co powders). The hollow bodies are comprised of mostly metal and/or ceramic components. The preparation of the hollow bodies involve drying and/or calcination steps in equipment capable of treating the material with infrared, near infrared, visable, microwave and/or ultraviolet radiation.
80. The preparation of hollow bodies with optionally an organic (e.g., polyvinyl alcohol) and/or inorganic binder (e.g., Ni or Co powders). The hollow bodies are comprised of mostly metal and/or ceramic components. The preparation of the hollow bodies involve drying and/or calcination steps in equipment capable of treating the material with infrared radiation.
81. The drying of olefin polymerization supports in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation.
82. The drying of olefin polymerization supports in equipment capable of treating the material with infrared radiation.
83. The drying of alumina, silica, titania, zirconia, carbon, calcium carbonate, magnesia, barium sulfate, hydrotalcite, zeolites, mixed metal oxides and mixtures therof to be used as powder catalyst supports in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation.
84. The drying of alumina, silica, titania, zirconia, carbon, calcium carbonate, magnesia, barium sulfate, hydrotalcite, zeolites, mixed metal oxides and mixtures therof to be used as powder catalyst supports in equipment capable of treating the material with infrared radiation.
85. The drying of alumina, silica, titania, zirconia, carbon, calcium carbonate, magnesia, barium sulfate, hydrotalcite, zeolites, mixed metal oxides and mixtures therof to be used as fixed bed catalyst supports in equipment capable of treating the material with infrared, near infrared, visable, microwave and ultraviolet radiation.
86. The drying of alumina, silica, titania, zirconia, carbon, calcium carbonate, magnesia, barium sulfate, hydrotalcite, zeolites, mixed metal oxides and mixtures therof to be used as fixed bed catalyst supports in equipment capable of treating the material with infrared radiation.
PCT/EP2003/011701 2003-10-22 2003-10-22 The use of ir, near ir, visible and uv radiation for the preparation of catalysts WO2005042158A1 (en)

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