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WO2005039764A1 - Procede de preparation et d'utilisation de granules actives de metaux de base - Google Patents

Procede de preparation et d'utilisation de granules actives de metaux de base Download PDF

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Publication number
WO2005039764A1
WO2005039764A1 PCT/EP2004/011018 EP2004011018W WO2005039764A1 WO 2005039764 A1 WO2005039764 A1 WO 2005039764A1 EP 2004011018 W EP2004011018 W EP 2004011018W WO 2005039764 A1 WO2005039764 A1 WO 2005039764A1
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Prior art keywords
granules
catalyst
grams
minutes
solution
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English (en)
Inventor
Daniel Ostgard
Monika Berweiler
Stefan Röder
Olivier PUISSÉGUR
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Evonik Operations GmbH
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Degussa GmbH
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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
    • 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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • 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
    • B01J37/0063—Granulating
    • 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
    • C07C29/132—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
    • C07C29/143—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 ketones
    • C07C29/145—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 ketones 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
    • 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
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening

Definitions

  • the present invention relates to a method for the production of fixed bed activated base metal catalysts and the use of granulated forms .
  • These granulated forms could either be filled into the reactor as is, or they can be sintered together to form a desired structure.
  • the common forms could include spheres, cylinders, ovals, and other forms as well.
  • the main advantages of these catalysts are their relatively low production costs, low bulk density and high porosity.
  • Activated metal catalysts are known in the field of chemical engineering as Raney-type catalysts . They are used, largely in powder form, for a large number of hydrogenation, dehydrocjenation, 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
  • a further alloying component which is soluble in alkalis Mainly nickel, cobalt, copper, or iron are used as catalyst metals.
  • 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 amount to about ten to one hundred kg per ingot. According to DE 21 59 736 cooling times of up to two hours were obtained. This corresponds to an average rate of cooling of about 0. 2 /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) . The rate of cooling is affected in particular by the particle size and the cooling medium (see Materials Science and Technology edited by R. W. Chan, P. Haasen, E. J. Kramer, Vol. 15, Processing of Metals and Alloys, 1991, VCH-Verlag Weinheim, pages 57 to 110) .
  • a process of this type is used in EP 0 437 788 B 1 in order to prepare a Raney alloy powder.
  • 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.
  • 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 20 and 100 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.
  • 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.
  • 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 known catalysts were stabilized with the appropriate amount of binder.
  • 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 calcined at temperatures below 850°C. As a result of sintering processes in the finely divided binder, this produces solid compounds between the individual particles of the catalysts alloy.
  • rapidly cooled alloys with very fine phase structures can be used to produce formed bodies without metallic binders and such technology may also be applicable to the current invention.
  • An object of the present invention is therefore to provide fixed bed activated base metal catalysts in the form of designed granules which largely avoids the disadvantages of the above known fixed-bed catalysts .
  • Subject of the invention is a method for the preparation of fixed bed activated base material granules consisting via mixing of
  • the precursor alloy is comprised of a catalytic component, a caustic leachable component and optionally one/or more promoters.
  • organic and/or inorganic binders may or may not be necessary to obtain the appropriate catalyst granules.
  • 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 equipment such as Eirich or L ⁇ dige mixers .
  • Such mixers form granules by the use of aggitators in combination with a rotating bottom plate, only a rotating bottom plate where variously oriented baffles may be put in place, or only aggitators.
  • 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.
  • the major advantages of this invention are its low bulk density, its high porosity, its relatively high percentage of activated metal, its relatively low production cost, and the activity these materials exhibit per kilogram of metal as well as the activity the have on a per liter of catalyst basis.
  • Suitable promoters include metallic elements from the groups 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, IB, 2B, 3A, 4A, 5A, the rare earth elements and 6A of the periodic table.
  • the resulting granules of the above mentioned material may be screened to remove the remaining powder and this powder may also be recycled back into granulation process so that the yield of the granules with respect to the alloy powder is very high and commercially viable.
  • the granulation can be started with one type of powder and the type of powder added to the granulation process may be changed as the granules reach a specific size.
  • This change of granulation powder may be performed a number of times and this could be done continuously during the granulation, or the granules may be removed, dried and optionally calcined before they are added again to the granulation apparatus for the addition of new granulation powders .
  • Raney-type catalytic metal / Al alloys may be slowly cooled or rapidly cooled alloys as described above, and its average particle size may range from ⁇ 1 to 200 ⁇ m or more as required by the desired catalyst properties .
  • the granules may be heated for the removal of the suspending liquid (e.g., water) during granulation so that the granules may proceed directly to calcination and/activation.
  • the suspending liquid may also be left in the granules after granulation and in this case it may be removed by drying before or during calcination.
  • the suspending liquid may be left in the granule so as to facilitate the formation of granule clusters that provide structures that pack looser in a reactor and lead to lower pressure drops in comparison to other fixed bed geometries.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either s ⁇ wly_cooled g _rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof .
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consl ' st of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder in an Eirich mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters .
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder in a L ⁇ dige mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be_ either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters .
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and Iva.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof .
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder in a L ⁇ dige mixer to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters .
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled_via redesign contact.,—_ quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.
  • the catalytic component can consist Ni, Co, Cu, Fe or combinations therof that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof .
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • This granulation process, the choice of the possible binders, the drying procedure and the calcination procedure are performed in such a way that the granules form foam-type structures with high macroporosity.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters.
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, b, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the catalyst can be promoted by the addition of salts of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the catalyst.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and optionally one or more promoters .
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements and the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the precursor alloy can be either slowly cooled or rapidly cooled via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and one or more promoters.
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the catalyst can be promoted by the addition of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the alloy before caustic activation.
  • the preparation of fixed bed activated base metal granules can be made via the mixing of the precursor alloy powder with optionally an organic binder and optionally an inorganic binder to form granules that are dried, calcined for stabilization purposes and then activated in a caustic solution.
  • the catalyst can be promoted by the addition of salts of one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa to the catalyst.
  • the precursor alloy can be either slowly cooled or rapidly cooled 'via contact, quenching, spraying in or spraying with a variety of mediums such as, but not limited to, inert gases and water.
  • the precursor alloy can be comprised of a catalytic component, a caustic leachable component and one or more promoters .
  • the catalytic component can consist of one or more metals from groups VIII and lb of the periodic chart of elements that are optionally promoted with one or more elements from the periodic groups la, Ila, Ilia, IVb, Vb, Vlb, Vllb, lb, lib, Ilia and IVa.
  • the caustic leachable component can consist of Al, Si, Zn or mixtures therof.
  • the catalyst can be promoted via both the addition of one or more promoters to the alloy before activation and the addition of salts of one or more promoters to the catalyst afer caustic activation.
  • the fixed bed granules of catalyst precursors are formed by the addition of one or more Raney-type alloy (s) to a mixture of an organic binder (e.g., polyvinyl alcohol), water, optionally an inorganic binder (e.g., Ni, Co, Fe, Cu or other metal powders), optionally promoters, and optionally pore builders followed by the aggitation of this mixture for the formation of granules.
  • the aggitation of this mixture into granules can be performed by placing the powder between two plates where one rotates differently than the other or by mixing this powder with aggitators, a rotating bottom plate with and without baffles and/or with both the a ⁇ itator and p forementioned rotating bottom plate together.
  • Plate granulators Eirich mixers und L ⁇ dige mixers are examples of such equipment that may be used in this granulation process .
  • These resulting granules are then calcined to the desired temperature (e.g. from 100 to 1200°C) , activated with an alkali leaching solution (e.g. an aqueous caustic solution), and washed with basic (e.g., caustic) and/or pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst.
  • an alkali leaching solution e.g. an aqueous caustic solution
  • basic e.g., caustic
  • pH neutral aqueous solutions for the production of this fixed bed activated base metal catalyst.
  • the choice of an organic binder, the types of other components, the ratio of the various components and the treatment of the resulting granules may be done so that the final fixed body foams up and create a metallic foam structure that has a high porosity and lower bulk density. This higher porosity can lead to a more complete leaching process and it leads to a catalyst with a higher activity for catalytic chemical reactions .
  • the bulk density of the resulting fixed bed catalyst is very important for highly active catalysts. While the standard fixed bed activated base metal catalysts have bulk densities ranging from 2.4 to 1.8 kg/1, bulk densities similar to other fixed bed applications such as 1.0 to 1.8 kg/1 are highly desirable to keep the cost to fill a commercial reactor at a minimum.
  • the ratio by weight of catalyst metal to extractable alloying component in the catalyst alloy is, as is conventional with Raney alloys, in the range from 20:80 to 80:20.
  • Catalysts according to the invention may also be doped with other metals in order to have a positive effect on the catalytic properties of the invention.
  • the purpose of this type of doping is, for example, to improve the activity, selectivity, and lifetime of the catalyst in a specific reaction. Doping metals are frequently also called promoters.
  • the doping or promoting of Raney catalyst is _ described for example in U.S. patent _4,153_, 578 and DE-AS 21 01 856 in DE-OS 21 00 373 and in the DE-AS 2053799.
  • any known metal alloys with extractable elements such as aluminum zinc and Silicon maybe used for the present invention.
  • Suitable promoters are transition elements in groups of 3B to 7B and 8 and group IB of the Periodic Table of Elements and also the rare-earth metals. The other elements mentioned previously in this document are also considered to be suitable promoters. They are also used in an amount of up to 20 wt% or more, with respect of the total weight of catalyst. Chromium, manganese, iron, cobalt, vanadium, tantalum, titanium, tungsten, rhenium, platinum, palladium, ruthenium, nickle, copper, silver, gold, and/or molybdenum and metals from platinum group are preferably used as promoters.
  • the promoting elements could be added as alloying constituents in the catalyst alloy or they could be added to the catalyst after activation.
  • promoters may be added as binders, they may be present as separate alloy powders with extractable elements and/or, they may be added to the catalyst after calcination and before activation. Optimum adjustment of the catalyst properties to the particular catalyst process is thus possible.
  • the Raney-type catalyst precursors resulting from calcination are also very important with regard the economic viability of invention. They are not pyrophoric and can be handled and transported without difficulty. Activation can be performed by the user shortly before use. Storage under water or organic solvents or embedding in organic compounds is not required for the catalyst precursors.
  • a further subject of the invention is the use of the catalyst prepared by the method according to the invention for the transformation of organic compounds, preferred the use of the catalyst according to the invention for the hydrogenation of organic compounds .
  • the catalysts made according to the method of the invention can be used.
  • Another part of this invention is the use of these activated metal granules for catalytic chemical reactions such as the hydrogenation, isomerization, hydration, reductive amination, reductive alklyation, dehydration, oxidation and dehydrogenation of organic compounds .
  • These catalysts are preferred for the continuous hydrogenation of organic, compounds such as nitro compounds, nitriles, imines , carbonyl compounds , alkenes , alkynes and aromatic compounds . These moeities may have already existed in the reactant(s) or they may have been incorporated into the reactant(s) just prior or during the reaction. These reactants may be sugars, nitriles, dinitriles, nitro compound, dinitro compounds and multifunctional compounds. These catalysts may also be used for the removal of some groups, such as, halides and sulfur containing compounds (e.g., thiols) via their hydrogenolysis .
  • Example 1 Activated Ni / Al granules from a casted Ni / Al alloy (1 st Ni catalyst version)
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour .
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 2 Activated Ni / Al granules from a casted Ni / Al alloy (2 nd Ni catalyst version)
  • the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 ml of a 5.7-wt% aqueous polyvinyl alcohol solution was added.
  • the remaining powder and the undersized granules could be then recycled to the next batch.
  • the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C_before_being_ ramped to 775°C over 9_0_ minutes followed by a 120 minute soak at 775°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 3 Activated Ni / Al granules from a casted Ni / Al alloy (3 rd Ni catalyst version)
  • the bottom plate was adjusted to the rotation rate of 86 rpm for the addition of 10 grams of a 5.7-wt% aqueous polyvinyl alcohol solution and at 30 minutes 10 more grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added as the bottom plate rotation was readjusted to 43 rpm for the duration of the preparation. From the 30 to 40 minute time interval the mixer was also heated with hot air to 120°C as 20 grams of a 5.7-wt% aqueous polyvinyl alcohol solution were added.
  • the remaining powder and the undersized granules could be then recycled to the next batch.
  • the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 750°C over 90 minutes followed by a 120 minute soak at 750°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour. Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 4 Activated Ni / Al granules from a casted Ni / Al alloy (4 th Ni catalyst version)
  • Example 5 Activated Ni / Al granules from a casted Ni / Al alloy (5 th Ni catalyst version)
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 6 Activated Co / Al granules from a casted Co / Al alloy (1 st Co catalyst version)
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 7 LiOH doped activated Co / Al granules from a casted Co / Al alloy
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water. Before use, the catalyst was treated for 3 hours in a 10%LiOH solution followed by being washed with water.
  • Example 8 Activated Cu / Al granules from a casted Cu / Al alloy (1 st Cu catalyst version)
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 9 Pt doped activated Cu / Al granules from a casted Cu / Al alloy
  • Example 10 Fe doped activated Cu / Al granules from a casted Cu / Al alloy
  • the 2 to 4 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 800°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • the washed catalyst was then treated in a circulating aqueous solution containing Iron(III) chloride, whose pH value was adjusted up.
  • the doped catalyst was then washed and the final iron content of the catalyst was 1.0%Fe.
  • Example 11 Activated Ni / Al granules from a rapidly quenched N 2 sprayed Ni / Al alloy (6 th Ni catalyst version)
  • Example 12 Activated Ni / Al granules from a rapidly quenched N 2 sprayed Ni / Al alloy (7 th Ni catalyst version)
  • Example 13 Activated Cu / Al granules from a rapidly quenched water sprayed Cu / Al alloy (2 nd Cu catalyst version)
  • the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 240 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 240 minutes followed by a 120 minute soak at 900°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water .
  • Example 14 Zn doped activated Cu / Al granules from a rapidly quenched water sprayed Cu / Zn / Al alloy
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 15 Cr doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
  • Example 16 Cr and Li doped activated Co / Al granules from a rapidly quenched water sprayed Co / Cr / Al alloy
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water. Before use, the catalyst was treated for 4 hours in a 10%LiOH solution followed by being washed with water.
  • Example 17 Mo doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Mo / Al alloy (1 st Mo doped Ni catalyst version)
  • the undersized material was placed back into the mixer for 15 minutes of additional mixing followed by sieving out the granules larger than 2.24 mm for a second harvest.
  • the undersized material was placed in the mixer for a third time for continued agitation as 10 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution were given to it.
  • This third mixing period lasted for 10 minutes and at the end all of the granules larger than 2.24 mm were sieved out for a third harvest.
  • the first, second and third harvests from this process were then mixed for the further preparation of this catalyst.
  • Example 18 Activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Al alloy (8 th Ni catalyst version)
  • the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to 400°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 900°C over 120 minutes followed by a 180 minute soak at 900°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 0°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 19 Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (1 st Cr doped Ni catalyst version)
  • Example 20 Cr doped activated Ni / Al granules from a rapidly quenched nitrogen sprayed Ni / Cr / Al alloy (2 nd Cr doped Ni catalyst version)
  • the > 2.24 mm granules were treated in air while ramping the temperature from 25°C to • 00°C over 60 minutes followed by a 120 minute soak at 400°C before being ramped to 800°C over 90 minutes followed by a 120 minute soak at 800°C.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 riour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 21 Cr and Fe doped activated Ni / Al granules from a. rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
  • Example 22 Activated Ni / Al granules from a rapidly cooled water sprayed Ni / Al alloy (9 th Ni catalyst version)
  • Example 23 Mo doped activated Ni / Al granules from a x-apidly cooled water sprayed Ni / Al alloy (2 nd Mo doped Ni catalyst version)
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • This catalyst was doped with a sodium molybdate solution and after this post activation doping, the molybdenum content of the catalyst was 0.3%.
  • the procedure can also be carried out with other Mo containing compounds such as ammonium heptamolybdate .
  • Example 24 Activated Ni / Al granules from a rapidly cooled ,water sprayed Ni / Al alloy (10 th Ni catalyst version)
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 25 Mo doped activated Ni / Al granules from a rapidly cooled nitrogen sprayed Ni / Mo / Al alloy (3 rd Mo doped Ni catalyst version)
  • 60%Al rapidly cooled nitrogen sprayed alloy were mixed together with 150 grams of Ni powder and 35 grams of polyvinyl alcohol for 2 minutes while the bottom plate rotated at 43 rpm and the agitator spun at 1506 rpm. This -was followed by the careful addition of 100 grams of an aqueous 5.7-wt.% polyvinyl alcohol solution while the mixture continued to mix. After mixing for 50 minutes 20 grams of the 5.7-wt% aqueous polyvinyl alcohol solution were added. At 60 minutes of mixing 20 more grams of a 5.7- wt% aqueous polyvinyl alcohol solution were added and at 140 minutes of mixing the process was stopped and the granules above 2.24 mm were screened out.
  • the granules were then cooled, packed into a basket that was lowered into a stirring 20-wt.% NaOH aqueous solution at 90°C and activated in this fashion for 1 hour.
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • Example 26 Pd, Cr and Fe doped activated Ni / Al granules from a rapidly cooled water sprayed Ni / Cr / Fe / Al alloy
  • Another option for this activation would be to circulate the 90°C 20-wt.% NaOH aqueous solution through a fixed bed of the catalyst for 1 hour.
  • the catalyst was initially washed with a caustic solution and this was followed by washing with water.
  • This catalyst was then doped with a palladium nitrate solution that previously had its pH to 6 with sodium carbonate adjusted.
  • the end Pd content of the catalyst was 0.2%.
  • Comparative Example 1 Shell activated Ni / Al tablets from a rapidly cooled water sprayed Ni / Al alloy
  • Table 1 The acetone hydrogenation data.
  • the trickle phase hydrogenation of glucose was carried out over an activated base metal catalyst in a tube reactor in the presence of hydrogen with a 40% aqueous glucose solution at 140°C and 50 bar.
  • the data from this test are displayed in table 2.
  • Table 2 The glucose hydrogenation data A. The catalyst's bulk density. B. The percentage of glucose conversion during the reaction. C. The mmoles of glucose reacted per gram of catalyst per hour. D. The mmoles of glucose reacted per ml of catalyst per hour.
  • A The catalyst's bulk density.
  • B The percent hexamethylendiamine selectivity.
  • C The percent aminocapronitrile selectivity.
  • D The percentage of adiponitrile conversion during the reaction.
  • E The mmoles of adiponitrile reacted per gram of catalyst per hour.
  • F The mmoles of adiponitrile reacted per ml of catalyst per hour.
  • Application Example 5 The hydrogenation of adiponitrile via method 2
  • A The catalyst ' s bulk density.
  • B The percent hexamethylendiamine selectivity.
  • C The percent aminocapronitrile selectivity.
  • D The percentage of adiponitrile conversion during the reaction.
  • E The mmoles of adiponitrile reacted per gram of catalyst per hour .
  • F The mmoles of adiponitrile reacted per ml of catalyst per hour .
  • A The catalyst's bulk density.
  • B The percent hexamethylendiamine selectivity.
  • C The percent aminocapronitrile selectivity.
  • D The percentage of adiponitrile conversion during the reaction.
  • E The mmoles of adiponitrile reacted per gram of catalyst per hour.
  • F The mmoles of adiponitrile reacted per ml of catalyst per hour.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de granulés de métaux de base activés en lit fixe par mélange de la poudre d'alliage précurseur au moyen éventuellement d'un liant organique et éventuellement d'un liant inorganique afin que soient formés des granulés qui sont séchés, calcinés à des fins de stabilisation puis activés dans une solution caustique. L'alliage précurseur peut être refroidi lentement ou rapidement par contact, trempe, vaporisation dans ou au moyen d'une variété de milieux entre autres, gaz inertes et eau. L'alliage précurseur comprend également un composant catalytique, un composant lixiviable caustique et éventuellement un ou plusieurs promoteurs. Le composant catalytique peut comprendre un ou plusieurs métaux du groupe VIII et Ib de la classification périodique des éléments qui sont également renforcés par un ou plusieurs éléments des groupes périodiques Ia, IIa, IIIa, IVb, Vb, VIb, VIIb, Ib, IIb, IIIa et IVa. Le composant lixiviable caustique comprend les éléments suivants : Al, Si, Zn ou des mélanges de ceux-ci. Les granulés peuvent être utilisés pour l'hydrogénation de composés organiques.
PCT/EP2004/011018 2003-10-22 2004-10-02 Procede de preparation et d'utilisation de granules actives de metaux de base Ceased WO2005039764A1 (fr)

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EP3300798A1 (fr) * 2016-09-30 2018-04-04 Evonik Degussa GmbH Lit fixe de catalyseur comprenant de la mousse métallique
US11260375B2 (en) 2016-09-30 2022-03-01 Evonik Operations Gmbh Process and catalyst for preparing 1,4-butanediol
US11401224B2 (en) 2018-02-14 2022-08-02 Evonik Operations Gmbh Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes
US11819832B2 (en) 2019-09-25 2023-11-21 Evonik Operations Gmbh Catalytic reactor

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EP2486976A1 (fr) 2005-09-08 2012-08-15 Evonik Degussa GmbH Fabrication et utilisation de catalyseurs à base de métaux activés et supportés pour des transformations organiques
TWI787215B (zh) 2016-11-22 2022-12-21 美商Ｗ Ｒ 康格雷氏公司 降低損耗的催化劑及其製造方法

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US6262307B1 (en) * 1997-05-26 2001-07-17 Degussa-Huls Aktiengesellschaft Shaped, activated metal, fixed-bed catalyst
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US10125089B2 (en) 2015-01-30 2018-11-13 Evonik Degussa Gmbh Process for preparing 3 aminomethyl-3,5,5-trimethylcyclohexylamine
WO2016120235A1 (fr) * 2015-01-30 2016-08-04 Evonik Degussa Gmbh Procédé de production de 3-aminométhyl-3,5,5-triméthylcyclohexylamine
CN107428673A (zh) * 2015-01-30 2017-12-01 赢创德固赛有限公司 制备3‑氨基甲基‑3,5,5‑三甲基环己胺的方法
CN107428673B (zh) * 2015-01-30 2021-05-07 赢创运营有限公司 制备3-氨基甲基-3,5,5-三甲基环己胺的方法
EP3050870A1 (fr) * 2015-01-30 2016-08-03 Evonik Degussa GmbH Procédé de fabrication de 3-aminométhyl-3,5,5-triméthylcyclohexylamine
JP2019530572A (ja) * 2016-09-30 2019-10-24 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ 金属発泡体を含む固定触媒床
CN109789389A (zh) * 2016-09-30 2019-05-21 赢创德固赛有限公司 包含金属泡沫体的固定催化床
KR20190055831A (ko) * 2016-09-30 2019-05-23 에보닉 데구사 게엠베하 금속 발포체를 포함하는 고정 촉매 층
WO2018060245A1 (fr) * 2016-09-30 2018-04-05 Evonik Degussa Gmbh Lit de catalyseur fixe comprenant des corps en mousse métallique
EP3300798A1 (fr) * 2016-09-30 2018-04-04 Evonik Degussa GmbH Lit fixe de catalyseur comprenant de la mousse métallique
US11090637B2 (en) * 2016-09-30 2021-08-17 Evonik Operations Gmbh Fixed catalyst bed comprising metal foam bodies
US11260375B2 (en) 2016-09-30 2022-03-01 Evonik Operations Gmbh Process and catalyst for preparing 1,4-butanediol
KR102444992B1 (ko) 2016-09-30 2022-09-19 에보닉 오퍼레이션스 게엠베하 금속 발포체를 포함하는 고정 촉매 층
TWI782921B (zh) * 2016-09-30 2022-11-11 德商贏創運營有限公司 含有金屬發泡體之固定式觸媒床
JP7479149B2 (ja) 2016-09-30 2024-05-08 エボニック オペレーションズ ゲーエムベーハー 金属発泡体を含む固定触媒床
US11401224B2 (en) 2018-02-14 2022-08-02 Evonik Operations Gmbh Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes
US11819832B2 (en) 2019-09-25 2023-11-21 Evonik Operations Gmbh Catalytic reactor

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