EP2035139A1 - Catalyseur de nanometal supporte et son procede de fabrication - Google Patents

Catalyseur de nanometal supporte et son procede de fabrication

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Publication number
EP2035139A1
EP2035139A1 EP07725428A EP07725428A EP2035139A1 EP 2035139 A1 EP2035139 A1 EP 2035139A1 EP 07725428 A EP07725428 A EP 07725428A EP 07725428 A EP07725428 A EP 07725428A EP 2035139 A1 EP2035139 A1 EP 2035139A1
Authority
EP
European Patent Office
Prior art keywords
metal
suspension
catalyst
carrier
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07725428A
Other languages
German (de)
English (en)
Inventor
Götz BURGFELS
Peter RÖGER
Hans-Jörg WÖLK
Richard Fischer
Sybille Ungar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie AG
Original Assignee
Sued Chemie AG
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Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of EP2035139A1 publication Critical patent/EP2035139A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/396—Distribution of the active metal ingredient

Definitions

  • the present invention relates to a supported nanometal catalyst and a process for its preparation.
  • Supported metal catalysts in which relatively small metal particles are deposited on the surface of a solid support are used in particular in synthesis chemical and petrochemical processes.
  • Supported metal catalysts are often made by a multi-step process.
  • the carrier material is impregnated with a metal salt solution of the desired metal.
  • the carrier is then calcined in a third step, wherein the metal is converted by the thermal treatment in an oxide form.
  • the metal oxide is converted into the catalytically active, highly dispersed metal, for example by means of hydrogen, carbon monoxide or wet-chemical reducing agent.
  • the supported metal catalyst is usually stabilized in a fifth step, for example by wet stabilization by means of an oil or by dry stabilization by means of an oxidation (passivation) of the deposited metal particles.
  • the yield of the reduction is usually between 70 and 90%, that is to say that 10% to 30% of the metal deposited on the support is not catalytically activated.
  • WO 2004/045767 discloses a process for the preparation of supported metal catalysts to form an organic complex during the preparation of the catalyst, the after its formation is decomposed, either partially or entirely, before the reduction of the metal to form the catalyst.
  • These catalysts have high metal dispersion values and a uniform distribution of the catalytically active metals on the support. These catalysts are particularly effective in Fischer-Tropsch catalysis and as adsorbents for the removal of organo-sulfur compounds from hydrocarbons.
  • DE 601 01 681 T2 discloses a process for the preparation of a cobalt-based Fischer-Tropsch catalyst in which a support is impregnated with a cobalt salt and the impregnated support is calcined to obtain a calcined material with a corresponding catalytically active cobalt oxide phase becomes.
  • DE 690 10 321 T2 discloses a process for the preparation of catalysts in which a catalytically effective amount of cobalt is distributed on the peripheral outer surface of a porous inorganic oxide support, which catalyst is useful for the conversion of synthesis gas to hydrocarbons.
  • DE 44 43 705 A1 describes a process for the preparation of surfactant-stabilized mono- and bimetallic colloids of metals of Groups VIII and Ib of the Periodic Table, which can be isolated in powder form and are used as precursor compounds for electrocatalysts in fuel cells.
  • DE 197 53 464 A1 discloses palladium clusters of colloidal palladium having an average particle diameter of 0.2 nm to 2 nm, and in which at least 80% of the palladium clusters have a particle diameter which is at most 0.2 nm from the middle Particle diameter deviates.
  • the palladium clusters are preferably stabilized with phosphine ligands.
  • This publication further relates to palladium-containing heterogeneous catalysts comprising supported colloidal palladium.
  • DE 197 45 904 discloses a process for the preparation of metal colloid solutions of platinum, rhodium, rhotenium, iridium or palladium by reacting a corresponding metal compound with a reducing agent. At least one cation exchange polymer is used to stabilize these metal colloid solutions. Sulfonated cation exchange polymers are preferably used. These polymer-stabilized metal colloid solutions are also used as catalysts for fuel cells.
  • Nanometals can be colloidally stabilized in water, but are usually not isolated and soluble in water only in high dilution and thus unsuitable as a catalyst precursor. Also known is the use of hydrophilic P or N donor ligands for water-soluble nanometallic colloids (J.S. Bradley in “Clusters and Colloids” (publisher G. Schmid) VCH, Weinheim 1994).
  • P, N, and S donor ligands undergo metal complex binding with transition metals, which is known to affect the catalytic action of the metals.
  • sulfur is known as a catalyst poison (B. Cornils et al., "Catalysis from AZ", 2 nd ed., Wiley VCH 2003), so that in general hardly any sulfur-containing ligands are used, since in particular with so-called “soft" late transition- talen or cations such.
  • platinum, palladium, gold and silver would result in inactive metal centers that would no longer exhibit catalytic activity.
  • the object of the present invention was therefore to provide a further novel nanometal catalyst in which the metal is present in the form of nanoparticles or in colloidal form, which exhibits good activity and selectivity in the catalytic process.
  • a catalyst which comprises a carrier, on which a first metal in the form of nanoparticles or colloids is applied, wherein the first metal is preferably catalytically active, further comprising a second metal in Form of nanoparticles and wherein the first and the second metal are partially stabilized with S-donor ligands and the second metal has a higher affinity for S-donor ligands than the first metal.
  • higher affinity means according to the invention that the second metal or metal cation both reacts faster with S donor ligands (ie the resulting complex is kinetically preferred) and / or forms a thermodynamically more stable metal S donor ligand complex than the first metal
  • the first metal is preferably selected from the group consisting of vanadium, tungsten, chromium, cobalt, ruthenium, rhodium, nickel, iron, platinum, palladium, iridium, copper and zinc or mixtures thereof. It was surprisingly found that even relatively "soft" metals such as platinum, palladium, iridium and copper can be used according to the invention.
  • mixtures are understood to mean either classical metal alloys or a mixture of two S-donor-stabilized metal suspensions which represent only a physical mixture.
  • metals cobalt, ruthenium, nickel, platinum, palladium and copper, very particularly preferably cobalt, platinum and palladium and ruthenium.
  • This makes it possible to perform a variety of catalytic processes, such as the selective hydrogenation of triple and double bonds, Fischer-Tropsch catalysis, selective oxidation, total oxidation of hydrocarbons, reforming of hydrocarbons.
  • the second metal is selected from silver and gold, or mixtures thereof, as defined above.
  • Silver and gold have a very high affinity for sulfur donor ligands compared to the comparatively "harder” aforementioned "first" metals, such that the sulfur donor ligands preferentially bond to silver and gold.
  • free binding sites on the nanoparticles or nanocolloids of the first catalytically active metal are ready for catalysis.
  • nanoparticles and nanocolloid or colloid are understood to mean according to the invention both individual metal atoms as well as clusters of metal atoms.
  • the sulfur donor ligand is preferably selected from substituted and unsubstituted branched and unbranched alkyl, alkenyl and alkynyl thiols as well as substituted and unsubstituted thiophenes. Particular preference is given to unbranched, linear alkyl thiols, such as, for example, hexanethiol, heptanethiol, octanethiol, decanethiol, dodecanethiol, etc.
  • the weight ratio of the first to the second metal is in a range of 1: 1 to 20: 1, preferably 1: 1 to 7: 1. If the weight ratio is less than 1: 1, there is a great risk that silver and gold will participate in the catalysis and possibly impair the activity or selectivity of the catalysts. At more than a ratio of 20: 1, not enough silver or gold atoms are available, so that the catalytically active metal centers of the first metal remain covered by sulfur donor ligands, so that the activity of the catalyst according to the invention is clearly limited.
  • the metal content (amount of first and second metal) of the catalysts according to the invention is typically from 0.001 to 10% by weight, preferably from 0.01 to 7% by weight, very particularly preferably from 0.03 to 5% by weight and depends on those with these catalysts - reactions to be carried out.
  • the size of the nanoparticles is in the range from 0.5 to 100 nm, preferably 0.5 to 50 nm, very particularly preferably 0.5 to 5 nm, wherein the nanoparticles have a uniform size distribution.
  • the metal surface, ie the catalytically active metal surface of the catalyst is 15 to 40 m 2 per gram and is measured by classical methods such as CO absorption.
  • the dispersion of the nanoparticulate metals is> 40%.
  • "Dispersion" of a supported metal catalyst is understood to mean the ratio of all surface metal atoms of all metal particles of a support to the total number of all metal atoms of the particles.
  • the value of the disperse be relatively high, since in this case relatively many metal atoms are freely accessible for catalytic reaction. This means that for a relatively high dispersion value of a supported metal catalyst, a particular catalytic activity thereof with a relatively small amount of metal used can be achieved.
  • the degree of dispersion of a metal catalyst according to the invention depends on the mean particle diameter of the metal suspension. However, it has to be considered that the loading of the catalyst support with nanoparticulate metal particles can lead to an aggregation of the latter, which leads to a decrease in the degree of dispersion.
  • the metal dispersion of a catalyst according to the invention can be determined, for example, by chemisorption of a catalyst sample. The calculation of the dispersion is based on the total chemisorption of the sample.
  • the support of the catalyst according to the invention preferably contains titanium dioxide, aluminum oxide, zirconium oxide, silicon oxide, zinc oxide, magnesium oxide, aluminum oxide silicon oxide, a SiIi- ziumcarbid, a magnesium silicate or a mixture of two or more thereof.
  • the support is preferably porous and is preferably present as a powder or shaped body.
  • the shaped body can also assume various geometric shapes, such as a honeycomb shape, which is often referred to as a monolith.
  • the monolith is made of either a ceramic or a metal or a metal alloy, the latter being commercially available, for example, from the companies EmiTec and Alantum.
  • the object of the present invention is likewise achieved by a method for producing a metal catalyst according to the invention, which comprises the following steps:
  • a nanoparticulate metal suspension or a nanoparticulate alloy suspension is understood as meaning a suspension which has metal particles or alloy particles with an average particle diameter of ⁇ 100 nm.
  • the metal or alloy nanoparticles can be, for example, single crystals or agglomerated single crystals.
  • supported metal catalysts or supported alloy catalysts can be prepared by a simple three-step process by first loading a support material with a nanoparticulate metal suspension or with a nanoparticulate alloy suspension in which the metal atoms are generally present in the oxidation state 0 , and then the suspending agent is removed.
  • the suspending agent can also be removed, for example, only in part if the supported metal or alloy catalyst is still to be stored or transported and the suspending agent is suitable, the supported
  • Stabilize catalyst (wet stabilization).
  • the suspending agent can for example also be completely removed and the supported catalyst either used directly in a reaction or, for example, for storage or for the transport, be stabilized in a separate step, for example by wet or dry stabilization.
  • Metal catalysts or alloy catalysts can be produced, in which the proportion of catalytically active metal is nearly 100%.
  • the process according to the invention also has the advantage that the process steps of the solid / liquid separation, the oxidation of the metal and the reduction of the metal of the known in the prior art manufacturing process for supported metal or alloy catalysts according to the inventive method by a single process step can be replaced, which includes the removal of the suspending agent.
  • a supported metal or alloy catalyst can be prepared in a simple three-stage process, so that supported metal by means of the inventive method - or alloy catalysts procedurally simpler and thus cheaper to produce sen.
  • the catalyst supports are first impregnated with a metal salt solution of the desired metal.
  • a metal salt solution of the desired metal According to the used Metal salt, that is, the anions used, then arise in the subsequent oxidation step environmentally harmful exhaust gases such as nitrous gases, ammonia or hydrogen halides, which must be intercepted and disposed of.
  • this oxidation step and the use of metal salts are dispensed with, so that according to the process of the invention no polluting exhaust gases are produced which would have to be disposed of cost-intensive.
  • the reduction step customary in parts of the state of the art in which a metal oxide is reduced to the catalytically active metal, for example by means of hydrogen or carbon monoxide, is omitted.
  • reduction enhancers are often used.
  • These reduction improvers which are often noble metals such as, for example, palladium or platinum, are usually applied to the support in the form of their salts together with the metal salt of the desired catalyst metal.
  • the process according to the invention can also dispense with corresponding plants and devices for carrying out these reactions.
  • the avoidance of reduction systems and facilities is advantageous, since these usually have a niscle require high security concept and therefore relatively expensive to purchase and in terms of maintenance and their operating costs.
  • both the oxidation step and the reduction step are carried out at relatively high temperatures.
  • the use of pulverulent carrier materials leads to sintering of the carrier.
  • sintering of the metal precursor or of the metal may occur in the abovementioned reaction steps, which applies analogously to alloys.
  • the high temperatures may cause the metal to be incorporated into the support structure which may, for example, cause deactivation of the metal or formation of undesirable species that catalyze undesired side reactions.
  • the removal of the suspending agent can be carried out at relatively low temperatures, so that it leads neither to a sintering of the support material nor to the incorporation of metal in the support structure.
  • the inventive method has the further advantage that it can be produced by means of this supported metal or alloy catalysts having a relatively high loading of catalytically active metal, and it may be necessary in some cases, the process of the invention, apart from the stabilization step, perform several times to reach high loads. At the same time, the process according to the invention leads to a homogeneous distribution of the metal or the alloy on the support with simultaneously high dispersion of the metal particles.
  • supported metal or alloy catalysts can also be prepared on which several different metals or alloys are deposited.
  • the inventive method can be performed several times, wherein in a first implementation of a first metal and a second implementation of a second metal is applied to the carrier.
  • Supported metal catalysts are often not shipped in the form in which the support material is already loaded with the catalytically active metal in its reduced form. Rather, the catalyst manufacturers often offer carriers laden with the corresponding metal salts or metal oxides, which have to be oxidized and reduced or reduced by the user himself.
  • the supported metal or alloy catalysts prepared according to the process of the invention can be handled and stored relatively simply, for example under protective gas, so that the production of supported catalysts loaded with active metal or with active alloy is transferred to the catalyst manufacturer by means of the process according to the invention can.
  • the method according to the invention also has the advantage that no binders are required for the deposition of the nanoparticulate metal or alloy particles.
  • the contacting of the carrier with the nanoparticulate metal suspension or with the nanoparticulate alloy suspension takes place by spraying the metal suspension or the alloy suspension onto the carrier.
  • the substantially uniform occupancy with Metallg. Alloy suspension of the carrier forms the basis for the production of supported metal or alloy catalysts. with as homogeneous and highly dispersed metal or alloy occupation as possible.
  • the spraying of the metal or alloy suspension preferably takes place under a protective gas atmosphere.
  • nitrogen or noble gases for example helium, neon, argon or krypton, are suitable as protective gas, depending on the metal or alloy.
  • step a) of the method according to the invention then comprises the following steps:
  • step 4) continuously passing the mixture from step 3) through the catalyst support.
  • the contacting of the support with the nanoparticulate metal suspension or with the nanoparticulate alloy suspension may be effected by immersing the support in the metal suspension or in the alloy suspension according to a further preferred embodiment of the method according to the invention.
  • the catalyst support is immersed in the nanoparticulate metal or alloy suspension, freed of metal or alloy suspension which does not adhere to the support surface, and then subjected to step b) of the process according to the invention.
  • the immersion as well as the process steps associated with the immersion takes place under a protective gas atmosphere in order to prevent an undesired reaction of the metal or alloy nanoparticles with constituents of the air.
  • a protective gas for example, the noble gases helium, neon, argon and krypton and, depending on the metal used or the alloy used, nitrogen can also be used.
  • the contacting of the carrier with the nanoparticulate metal suspension or with the nanoparticulate alloy suspension takes place by means of the pore filling method. In this case, the carrier is brought into contact with an amount of suspension whose volume corresponds to the pore volume of the carrier used. The carrier stays behind The load of the suspension externally dry and thus free-flowing.
  • the support is introduced into the nanoparticulate metal suspension or into the nanoparticulate alloy suspension with a predetermined amount of nanoparticulate metal or nanoparticulate alloy and the suspension agent then according to step b) of the method according to the invention Will get removed. This ensures that the carrier can be loaded with the desired amount of metal or alloy in a single process run.
  • the carrier which is in powder form, for example, is first suspended in the nanoparticulate metal or alloy suspension.
  • the suspending agent is removed, for example, under vacuum by means of a rotary evaporator.
  • this method alternative according to the invention is also carried out under a protective gas atmosphere, in particular in order to prevent oxidation of the metal or alloy nanoparticles by the atmospheric oxygen.
  • Nanoparticulate metal or alloy dispersions are often unstable at high temperatures, since the increased particle movement can lead to a collision and correspondingly to an aggregation of the corresponding nanoparticles.
  • removal of the suspending agent takes place under reduced pressure, preferably under a protective gas atmosphere.
  • the removal of the suspending agent below a temperature of 120 0 C preferably below a temperature of 100 0 C, preferably below a temperature of 90 0 C, more preferably below a temperature of 80 0 C, more preferably below a temperature of 70 0 C, more preferably below a temperature of 60 0 C and most preferably below a temperature of 50 0 C.
  • the metal or alloy nanoparticles do not have a high affinity for the support material and can therefore be poorly immobilized on the support, it may be provided that after removal of the suspending agent, the nanoparticles on the support by means of a separate Process step to be fixed.
  • the step of removing the suspending agent b) is followed by a stabilizing or fixing step c), by means of which the metal Particles or alloy particles are fixed to the carrier, preferably under a protective gas atmosphere.
  • the aforementioned fixing step c) can be carried out in various ways and ways, for example by the use of binders.
  • the fixing step c) is carried out by heating the loaded with the metal particles or alloy particles carrier to a temperature of 120 0 C to 700 0 C, preferably under an inert gas atmosphere to an undesirable reaction of Prevent metal particles or alloy particles with components of the air.
  • the fixing step c) by heating the loaded with the metal particles or alloy particles carrier to a temperature of 300 0 C to 650 0 C, preferably to a temperature of 350 0 C to 600 0 C, preferably to a temperature of 400 0 C to 550 0 C and particularly preferably to a temperature of 45O 0 C to 500 0 C.
  • the catalyst is stabilized and, if appropriate, packaged airtight, wherein a protective gas atmosphere exists within the packaging. This prevents the metal or alloy nanoparticles from reacting with constituents of the air, which could lead to a deactivation of the catalyst.
  • the step of removing the suspending agent b) is followed by the fixing or stabilizing step d), which ensures the storage of the Particles or alloy particles loaded carrier under a protective gas atmosphere includes.
  • the metal or alloy nanoparticles can be applied to the support homogeneously and in high dispersion, in particular, if the suspending agent is water or an organic solvent is preferably an aromatic solvent, preferably toluene, benzene, etc. Another preferred embodiment of the process according to the invention is therefore the suspending agent water or an organic solvent, preferably toluene.
  • the suspending agent may also contain, as further components, the S donor ligands as stabilizers which counteract aggregation of the nanoparticles.
  • the carrier used in the method according to the invention may be a porous or a non-porous carrier.
  • Porous carriers are characterized in particular by a large surface which is formed almost exclusively by the inner walls of the pores.
  • the carrier is a porous carrier.
  • the support is formed of a titanium dioxide, an alumina, a zirconia, a silica, a zinc oxide, a magnesia, an alumina-silica, a silicon carbide, a magnesium silicate, or a mixture of two or more of the foregoing.
  • oxides, carbides or silicates may be used in mixed forms, but especially in the form of defined compounds, preferably in the form of TiO 2 , Al 2 O 3 , preferably alpha-, gamma-, delta- or theta-Al 2 O.
  • the type or nature of the carrier material to be used generally depends on the metal or alloy which is to be fixed on the carrier.
  • amorphous porous supports are preferred, preferably those having a high proportion of mesopores and / or macropores, in the context of the present invention by the terms macropores and mesopores being understood as meaning those pores which are larger in diameter than 50 nm or a diameter of 1 to 50 nm.
  • the support may be a crystalline support, preferably a molecular sieve material, such as a zeolite or a zeolite-like material.
  • molecular sieves are silicates, aluminosilicates, aluminophosphates, silicoaluminophosphates, metalloaluminophosphates or metalloaluminophosphosilicates.
  • molecular sieve material is used as the catalyst support depends on the one hand on the metal or alloy particles to be deposited on the support, and on the other hand on the application in which the supported metal or alloy catalyst produced according to the method of the invention is to be used. Examples of such applications are separations, catalytic applications as well as combinations of catalytic application and separation.
  • molecular sieves which correspond to one of the following structural types: AFI, AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, OFF, TON and MFI.
  • AFI, AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, OFF, TON and MFI Although some of the abovementioned materials are not genuine zeolites, they are frequently referred to as such in the literature and should also be included in the context of the present invention under the term zeolite.
  • molecular sieve materials which are prepared using amphiphilic compounds. Preferred examples of such materials are described in US 5,250,282, and are incorporated by reference into the present invention. Examples of amphiphilic compounds are further given in Winsor, Chemical Reviews, 68 (1), 1968. Further suitable molecular sieve materials of this type which are preferred according to the invention are also described in "Review of Ordered Mesoporous Materials” U. Ciesla and F. Schuth, Microporous and Mesoporous Materials, 27, (1999), 131-49 and are incorporated herein by reference Invention included.
  • the catalyst support is a powder, a shaped body or a monolith.
  • Preferred shaped bodies are, for example, spheres, rings, cylinders, perforated cylinders, trilobes or cones, and a preferred monolith is, for example, a honeycomb body.
  • the metal or alloy nanoparticles deposited on the carrier are as small as possible, since a very high degree of dispersion is thereby achieved.
  • the ratio of the number of metal atoms which form the surface of the nanoparticles to the total number of metal atoms on a support is understood as the degree of dispersion.
  • the mean particle diameter of the nanoparticulate metal or alloy suspension to be used also depends on the later use of the catalyst, the nature of the catalyst support and the pore distribution of the support material.
  • the particles of the nanoparticulate metal or alloy suspension have an average particle diameter of 0.5 to 100 nm, preferably 1 to 50 nm, preferably 1 to 25 nm, more preferably 1 to 20 nm more preferably 1 to 15 nm and more preferably 1 to 10 nm.
  • the particles of the nanoparticulate metal or alloy suspension have an average particle diameter of 1 to 9 nm, preferably 1 to 8 nm, preferably 1 to 7 nm and more preferably one of 1 to 6 nm, and more preferably 1 to 5 nm.
  • supported metal catalysts or supported alloy catalysts of all metals or alloys can be produced.
  • a prerequisite is that a nanoparticulate metal or alloy suspension can be produced from the metal or from the alloy.
  • Metals preferred according to the invention are, for example, metals of group 5 (group Va, Vb), for example vanadium; the group 6 (group VIa, VIb), such as chromium, molybdenum and tungsten; Group 7 (Group VIIa, VIIb) such as manganese and rhenium; Group 8, 9 and 10 (Group VIII, Villa) such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.
  • Particularly preferred alloys according to the invention are alloys of one of the abovementioned metals.
  • the nanoparticulate metal suspension is therefore a suspension of the metal cobalt or ruthenium.
  • the cobalt or ruthenium nanoparticles preferably have an average diameter of 8 to 20 nm.
  • the dispersion of the cobalt or the ruthenium particles is preferably from 0.5 to 20%, preferably from 1 to 15% and particularly preferably from 1 to 10%.
  • Cobalt and ruthenium exhibit a very high catalytic activity in addition to iron in the so-called Fischer-Tropsch synthesis, in which hydrocarbons are synthesized from a mixture of carbon monoxide and hydrogen. Accordingly, the inventive method is particularly suitable for the production of so-called Fischer-Tropsch catalysts.
  • Titanium dioxide both in the anatase and rutile modification or mixed forms thereof
  • silicon dioxide silicon dioxide-Al 2 O 3
  • alumina in the modifications alpha-, gamma-, delta- or theta-Al 2
  • Carriers based on gamma-Al 2 O 3 are particularly preferred.
  • titania / zirconia based supports may be preferred.
  • titanium dioxide is initially chloride-free and then impregnated with a zirconia precursor such as ZrO (NO 3 ) 2 ⁇ 4 H 2 O, dried and calcined to form a ZrO 2 / TiO 2 support .
  • the carrier comprises up to 50% by weight of zirconium dioxide, preferably up to 35% by weight, more preferably up to 20% by weight, more preferably up to 10% by weight and most preferably 0.1 to 5 % By weight zirconium dioxide based on the total weight of the carrier.
  • metals such as rhenium, zirconium, hafnium, cerium and uranium can be added to the cobalt to improve the activity and regenerability of a supported cobalt catalyst with respect to Fischer-Tropsch synthesis.
  • Corresponding supported metal catalysts with a carrier, on which, for example, both cobalt and rhenium nanoparticles are deposited, can likewise be prepared by means of the process according to the invention. In this case, for example, it is possible to proceed in such a way that the process according to the invention is carried out with a nanoparticulate metal suspension which contains both cobalt and rhenium nanoparticles.
  • the support can first be loaded with cobalt nanoparticles.
  • the resulting supported cobalt catalyst is then subjected again to the process according to the invention, in which case a nanoparticulate rhenium suspension is used as the metal suspension.
  • supported nickel catalysts prepared by the process according to the invention also have a very homogeneous and highly dispersed distribution of the metal nanoparticles.
  • the nanoparticulate metal suspension is a suspension of the metal nickel.
  • Supported nickel catalysts can be used in particular in the desulfurization of gases or liquids.
  • supported metal or alloy catalysts can be produced which have a certain area per gram of metal. The metal or alloy surface can vary within a very wide range.
  • the total metal surface area of the supported metal or alloy catalyst is from 0.01 to 60 m 2 / g metal, preferably from 10 to 55 m 2 / g, preferably from 12 to 50 m 2 / g, more preferably from 14 to 45 m 2 / g, and most preferably from 15 to 40 m 2 / g.
  • supported metal or alloy catalysts are produced therewith whose metal or alloy particles have a dispersion of 1 to 10%, preferably one of more than 20%, more preferably one of more than 30%. , preferably one of more than 35%, more preferably one of more than 40%, more preferably one of more than 45%, and most preferably one of more than 50%.
  • the present invention further relates to the use of a nanoparticulate metal suspension or a nanoparticulate alloy suspension for producing a supported metal catalyst or alloy catalyst.
  • nanoparticulate metal or alloy dispersions used in the process according to the invention are commercially available and can be used either directly or after a corresponding adjustment of the metal or alloy particle concentration in the process according to the invention.
  • the present invention will be explained in more detail by way of non-limiting exemplary embodiments.
  • Example 1 Preparation of a palladium-supported catalyst
  • a solution containing 2.25% by weight of palladium nanoparticles (stabilized with dodecanethiol, Pd content 26.8%, particle size 1.2 nm, available from Nanosolutions GmbH in Hamburg, Germany) is prepared in toluene.
  • An alumina-coated support was impregnated with the solution by immersion at room temperature.
  • the ⁇ -Al 2 O 3 coating had a BET value of 16 m 2 / g and a pore volume of 225m 3 / g.
  • the pore radius of 95% of the pores was greater than 40 nm.
  • the coating consisted of Ot-Al 2 O 3 with 5% ZrO 2 on an aluminum support with channels (Linde AG, Kunststoff, Germany). Subsequently, the impregnated support was dried for one hour at 120 0 C and then annealed at 350 0 C for three hours.
  • the catalyst had 0.2 g / m 2 palladium.
  • An alumina carrier ( ⁇ -Al 2 O 3 tablets, 4x4 mm, BET 15 m 2 / g, pore radius: 97% of pores> 40 nm, pore volume 226 m 3 / g) was impregnated with palladium chloride and silver nitrate by spraying, followed by one hour Dried 120 0 C and annealed at 350 0 C for three hours.
  • the activity at 20 0 C was chosen.
  • Example 2 36 0, 97 20, 3
  • the best results were obtained with the silver-doped catalyst of Example 2 according to the invention.
  • an increase in the activity, ie the conversion of 20% was achieved.
  • catalysts of the invention are z.
  • Pd, Pt, Pu, Rh singly in combination with Ag or Au for the total oxidation of hydrocarbons, Ni or Rh in combination with Ag and Au for the reforming of hydrocarbons.

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

Abstract

La présente invention concerne un catalyseur supporté, comportant un support, sur lequel est appliqué un premier métal, qui est catalytiquement actif, sous formes de nanoparticules, comportant en outre un second métal sous forme de nanoparticules et les nanoparticules du premier et du second métal étant en partie stabilisées avec des ligands donneurs S et le second métal comprenant une affinité par rapport aux ligands donneurs S supérieure à celle du premier métal.
EP07725428A 2006-05-30 2007-05-22 Catalyseur de nanometal supporte et son procede de fabrication Withdrawn EP2035139A1 (fr)

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DE102006025148A DE102006025148A1 (de) 2006-05-30 2006-05-30 Verfahren zur Herstellung eines geträgerten Metallkatalysators
PCT/EP2007/004528 WO2007137736A1 (fr) 2006-05-30 2007-05-22 catalyseur de nanométal supporté et son procédé de fabrication

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CN111410171B (zh) * 2020-03-31 2021-03-02 中国华能集团清洁能源技术研究院有限公司 一种煤气化合成气脱汞剂及其制备方法
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RU2783193C1 (ru) * 2021-12-29 2022-11-09 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Катализатор, модифицированный хитозаном, для селективного гидрирования пиридина и его производных и процесс гидрирования пиридина и его производных с использованием катализатора, модифицированного хитозаном

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DE102006025148A1 (de) 2007-12-06
ZA200810659B (en) 2009-11-25
WO2007137736A1 (fr) 2007-12-06

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