WO2012016382A1 - Metal nanocatalyst and preparation method thereof - Google Patents

Metal nanocatalyst and preparation method thereof Download PDF

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Publication number
WO2012016382A1
WO2012016382A1 PCT/CN2010/075736 CN2010075736W WO2012016382A1 WO 2012016382 A1 WO2012016382 A1 WO 2012016382A1 CN 2010075736 W CN2010075736 W CN 2010075736W WO 2012016382 A1 WO2012016382 A1 WO 2012016382A1
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Prior art keywords
nanoparticles
catalyst
carrier
secondary carrier
acid
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PCT/CN2010/075736
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French (fr)
Chinese (zh)
Inventor
李哲修
李正焕
吕运贞
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大连科林爱纳米科技有限公司
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Priority to PCT/CN2010/075736 priority Critical patent/WO2012016382A1/en
Publication of WO2012016382A1 publication Critical patent/WO2012016382A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • 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
    • 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
    • B01J23/44—Palladium
    • 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
    • B01J23/48—Silver or gold
    • 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
    • B01J35/23—
    • B01J35/40—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a catalyst nanoparticle and a method for producing a nanocatalyst using the same.
  • the catalyst is a substance other than the reaction substance in the chemical reaction, and the catalyst itself does not undergo a quantitative or qualitative change before and after the reaction, and can retain the same state as before the reaction, and only a substance which changes in the chemical reaction rate.
  • the field of catalysis was concentrated in the field of chemical engineering. Recently, it has been widely used in automobile exhaust gas purification, pollution prevention such as nitrogen removal in power plants, development of future energy sources such as fuel cells and hydrogen, cooking ovens, stoves, etc. The field, and its needs are growing.
  • Such as electronics, biotechnology, new materials, new energy and other high-tech through the development of a variety of technologies and applications, the catalyst field is currently rated as a core high-tech element.
  • Nanocatalysts are chemically reactive and nano-sized materials. They are constantly researching nanocatalysts in various fields such as energy conversion, photocatalyst, green chemistry, environment, bioimitation technology, and molecular printing technology. In chemical reactions, the reaction rate varies with various conditions such as temperature, pressure, concentration, number of collisions, surface area, and activated energy. For its reaction rate, a catalyst is often used. The role of the nanocatalyst in chemical reactions is to increase the reaction rate while promoting the formation of target reactants in a variety of reactants.
  • the nanocatalyst is generally composed of a catalyst raw material that contributes to the actual reaction and a support capable of supporting the catalyst.
  • the nanocatalyst material In order to increase the chemical reaction rate, the nanocatalyst material must have a large surface area, so that the catalyst material can be uniformly distributed on the carrier. Therefore, it can promote nanocatalysis
  • the agent has a large surface area to form a uniform distribution of the carrier.
  • the carriers frequently used in the field of fine chemistry and petrochemistry are mainly activated carbon and alumina. Of particular importance when selecting a carrier is the ability to select the carrier that is most suitable for each chemical reaction among the various carriers.
  • the main application fields of nano-catalysts using noble metals as catalyst materials and activated carbon as carriers are in the fields of fine chemistry and fuel cells.
  • Most of the precious metal/activated carbon catalysts are manufactured by chemical methods.
  • the chemical method of nanoparticle production has a liquid phase reduction (PL, Precipitation Liquid reduction), PG (Precipitation Gas reduction), Adsorption Liquid reduction (AL, Adsorption Liquid reduction) CAG, Adsorption Gas reduction, etc.
  • precious metal salts are mainly HAuCl 4 , AuCl 3 , KAu(CN) 2 , Organo metallic precursor, H 2 PtCl 6 , Pt(N0 2 ) 2 (N3 ⁇ 4) 2 , PtCl 2 , RuCl 3 , etc.
  • Reducing agents often use LiBH 4 , NaB 3 ⁇ 4 or alcohols that are easily mixed in water.
  • the chemical process of preparing a catalyst requires a complicated process because it is difficult to remove pure nanoparticles by using various additives used in subsequent processes of each process, and it is difficult to control the morphology of the nanoparticles, and by-products occurring after the process will Lead to environmental pollution.
  • a carrier in which two or more kinds of catalysts are attached to one carrier is produced, and an organic compound capable of using two or more kinds of nanomaterials at the same time is obtained.
  • the decomposition temperature of each metal organic compound or its chemical composition has different characteristics, there are extremely few organic chemicals that can be used together for different nano materials.
  • a metal organic chemical is not applicable, a plurality of nanoparticles can be contained, and a multi-skilled catalyst can also be produced.
  • an object of the present invention is to provide a method for producing a nanoparticle catalyst, which can be used for the manufacture of fine chemicals by using a physically produced nanoparticle and attaching a noble metal nanoparticle to an activated carbon carrier. Precious metal nanocatalyst for fuel cells.
  • the present invention provides a process for producing a catalyst for fine chemical or fuel cells, which comprises supporting a catalyst nanoparticle on a support for a catalyst.
  • the catalyst nanoparticles are obtained by depositing a powdery, granular and/or sheet-like primary carrier while depositing a nanomaterial in a vacuum container to obtain nanoparticles.
  • the precious metal raw material of the catalyst nanoparticles includes one or more elements selected from the group consisting of Au, Ag, Pt, Rh, Pd, Ru, Os, Re, and Ir.
  • the composition of the alloy includes one or more elements selected from the group consisting of Au, Ag, Pt, Rh, Pd, Ru, Os, Re, and Ir.
  • the transition metal-based raw material for the catalyst nanoparticles comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, An alloy composed of one or two or more elements of W and Hf.
  • the method comprises: after manufacturing the nanoparticles for the catalyst, to produce a catalyst, using water, distilled water, alcohol, acetone, which can dissolve or disperse the primary carrier containing the nanoparticles for the catalyst, One or a combination of two or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, carbonic acid, boric acid, perchloric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, and ammonia water to produce nanoparticles The solution of the solution.
  • the subsequent process steps include using
  • the solution containing the nanoparticles is stirred by one or a combination of two or more of a stirrer, an ultrasonic oscillating device, and an ultrasonic disperser.
  • the subsequent process step comprising heating the solution containing the nanoparticles.
  • the subsequent process step of producing the catalyst comprises filtering and separating the secondary carrier to which the nanoparticles are adsorbed from the mixed solution.
  • the filter for filtration may include a filter made of one or a combination of paper, polymer material, metal and ceramic material, or the like.
  • the filtering includes utilizing a vacuum or pressurized filtration method.
  • the subsequent process of manufacturing the catalyst includes using a physical method or a chemical method.
  • Pretreatment is carried out on the surface of the secondary carrier.
  • the method of pretreatment of the secondary carrier includes one or a combination of two or more of heat treatment, plasma treatment, ion beam treatment, ozone treatment, acid chemical, and alkaline chemical treatment.
  • the secondary carrier used in the subsequent process step is activated carbon or carbon black or the like.
  • the secondary carrier has a specific surface area of from 50 m 2 /g to 5000 m 2 /g.
  • the secondary carrier has a particle diameter of from 100 nm to 50 mm.
  • the mass of the nanoparticles is from 1 ppm to 80% by mass based on the mass of the catalyst.
  • the method for producing a catalyst nanoparticle and a nanocatalyst provided by the present invention may include the following steps:
  • a primary carrier containing the nanoparticles for the catalyst and a secondary carrier serving as a catalyst carrier are mixed, and the catalyst is subsequently produced by a subsequent process.
  • a method of depositing nanoparticles for catalyst production comprises using a thermal evaporation device, electron beam evaporation (E-beam Evaporation) device, DC Sputtering (DCS) device, RF Sputtering (RFS) device, Middle Frequency (MF) device, Microwave device (Microwave) device, double Dual Magnetron Sputtering device, Ion Beam Sputtering (IBS) device, Molecular Beam Epitaxy (MBE) device, Arc Discharge Process device, Laser ablation (Laser) Ablation) A method of depositing a device and/or an Ion Plating deposition device or the like.
  • deposition is preferably carried out using a direct current sputtering device.
  • the stirring (a stirring method used to produce the catalyst nanoparticles) is carried out by stirring in a vacuum vessel using a stirring device prepared for the purpose of stirring the carrier.
  • the method includes stirring with a horizontal or vertical stirring shaft.
  • a vertical stirring device (Fig. 3) to produce nanoparticles.
  • the raw material of the catalyst comprises Au
  • the above method provided by the present invention is a raw material using a catalyst, a noble metal, namely, Au, Ag, Pt, Rh, Pd, Ru, Os, Re, Ir, or the like, or an alloy composed of two or more elements in its element, metal And other materials, a method for producing nanoparticles for a catalyst.
  • a transfer metal catalyst raw material that is, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, W, and Hf.
  • the above-described production method according to the present invention is a method for producing a nanoparticle for a catalyst by using a transfer metal catalyst raw material, that is, the above various elements or an alloy composed of two or more of the elements.
  • the method comprises: after manufacturing the nanoparticles for the catalyst, in order to produce a catalyst, using a liquid (or chemical) capable of dissolving or dispersing the primary carrier containing the nanoparticles for the catalyst a step of producing a solution containing nanoparticles by one or more combinations, the liquid may be one capable of dissolving or dispersing a nanoparticle-containing one Secondary carrier of water, distilled water, alcohol, acetone, etc.
  • nitric acid ⁇ 0 3 ;>, hydrochloric acid HCl, sulfuric acid 3 ⁇ 4S0 4 , phosphoric acid (3 ⁇ 4P0 4 ), acetic acid (C3 ⁇ 4COOH), carbonic acid (3 ⁇ 4C0 3 ), boric acid (3 ⁇ 4B0 3 ), high Acidic chemicals such as chloric acid (HC10 4 ) or sodium hydroxide (NaOH:), potassium hydroxide (KOH:), calcium hydroxide (Ca(OH) 2 ), barium hydroxide (Ba(OH) 2 ), ammonia ( ⁇ 3 ⁇ 2 0) and other alkaline chemicals or one or more of them.
  • chloric acid HC10 4
  • sodium hydroxide NaOH:
  • potassium hydroxide KOH:
  • Ca(OH) 2 calcium hydroxide
  • Ba(OH) 2 barium hydroxide
  • ammonia ⁇ 3 ⁇ 2 0
  • the subsequent process steps include using The solution containing the nanoparticles is agitated by one or a combination of one of a blender, an ultrasonic oscillating device (Ultmsomc) and an ultrasonic disperser (Ultrasonic Homogenizer). More preferably, in order to increase the dispersion of the nanoparticles while increasing the solubility of the solution containing the nanoparticles, the subsequent process step comprises heating the solution containing the nanoparticles.
  • a subsequent process step of producing a catalyst includes a primary carrier, a secondary carrier, and a filtration process for separating the catalyst from the catalyst-containing solution, that is, a subsequent process step of manufacturing the catalyst includes
  • the catalyst is separated by filtration from a solution containing the catalyst.
  • the filter used is a filter process using a filter made of paper, metal, polymer, ceramics or the like used for the filtration process or a plane made using such a filter material, a 3 dimensional image, a column image
  • the filter that is, the filter used for filtration, is a filter made of paper, metal, polymer or ceramic material or a flat or columnar filter made of paper, metal, polymer or ceramic material. Filtration filter material, paper, polymer, metal, ceramic, or a filter for filtration composed of two of them.
  • the filtering method includes a filtering method using a reduced pressure or a pressurized method. That is, as a filtration method, a filtration method using a reduced pressure or a pressurized method is included.
  • the subsequent process of manufacturing the catalyst includes using a physical method or a chemical method.
  • Pretreatment is carried out on the surface of the secondary carrier.
  • the method of pretreating the secondary carrier comprises one of heat treatment, plasma treatment, ion beam treatment, ozone treatment, acid chemical or alkaline chemical treatment method or More than one combination.
  • the method may be carried out by using activated carbon as a secondary carrier for producing a catalyst for fine chemicals or a fuel cell.
  • the secondary carrier may be activated carbon having an average surface area in the range of 50 m 2 /g to 5000 m 2 /g or activated carbon having an average particle size in the range of 100 nm to 50 mm.
  • the catalyst is an activated carbon catalyst for a fine chemical active fuel cell having a nanoparticle content of about 80% in 1 ppm.
  • the present invention differs from the conventional nanoparticle physical manufacturing method in that it uses nanoparticle manufacturing equipment, which is specially designed for mass production. Since the nanoparticle production process of the present invention utilizes a conventional vacuum deposition method, it is easy to vaporize a plurality of metals or alloys, and it is possible to uniformly form high-purity nanoparticles on a carrier.
  • the nanomaterial deposition apparatus used in the physical nanoparticle manufacturing apparatus of the present invention has a thermal evaporation (Ether Beam Evaporation) apparatus, an electron beam evaporation (E-beam Evaporation) apparatus, and a DC sputtering (DC Sputtering, DCS).
  • RF Sputtering RFS
  • MBE Molecular Beam Epitaxy
  • Arc Discharge Process Arc Discharge Process device
  • Laser Ablation device Ion Plating deposition device, and the like.
  • a physically post-processed nanoparticle is used to perform a simple post-treatment process, thereby providing a method for producing a catalyst, which may include nanoparticle production, mixing step (mixing engineering), filtration/ Washing step (filtration/washing process) and drying step (drying process).
  • FIG. 1 is a schematic view showing a process for chemically producing nano-catalyst particles using activated carbon
  • FIG. 2 is a schematic view showing a process for manufacturing a nano-catalyst using nanoparticles which are physically manufactured
  • Figure 3 is a schematic view of a nanoparticle manufacturing equipment equipped with a vertical transfer mode mixer
  • Figure 4 is a schematic view showing the size and distribution of nanoparticles of a noble metal activated carbon catalyst produced by the subsequent process of the present invention
  • Fig. 5 is a graph showing a comparison of catalytic reaction effects of a Pd/AC catalyst produced by the present invention. detailed description
  • the present invention relates to a method for producing a catalyst for use in fine chemicals and fuel cells, and provides a method for producing a catalyst by physically producing nanoparticles for a catalyst and using the nanoparticles in a post-treatment step.
  • the nanopowder manufacturing equipment manufactured according to the methods disclosed in the prior patents and documents has low deposition efficiency, uneven agitation of the carrier, uneven nanoparticle size, increased external force of the carrier, and low durability of the device. .
  • the above method is directed to a nanoparticle manufacturing apparatus for carrier agitation, and is mainly designed for research or small-scale production, and thus is not suitable for mass production.
  • the agitating structure of the manufacturing apparatus is a spiral type mounting agitating rotor (303) to more efficiently agitate the carrier (200) up and down.
  • the agitating rotor (303) is coupled to a rotating shaft (302) at a central portion of the agitation group (300), and the rotating shaft (302) is coupled to the motor (301).
  • the motor (301) rotates
  • the agitating rotor (303) rotates, thereby moving the carrier (200) from the vicinity of the wall surface of the agitation group (300) to the lower portion near the center portion of the agitation group (300).
  • the stirring rotor (303) of the stirring device according to the present invention is as shown in Fig.
  • the stirring group (300) is caused by a continuous spiral structure from top to bottom, so that the conventional nanoparticle manufacturing apparatus can be solved.
  • the material and the carrier material loading stage, the vacuum exhaust stage, the nanoparticle manufacturing (stirring/deposition) stage, the vacuum stage are removed, and the stage of the deposited nanoparticle carrier is extracted.
  • a nano material and a carrier material suitable for the application field are selected, a nano material target is mounted on the deposition source (100), and the carrier material is loaded into the mixer.
  • a vacuum evacuation is performed by the low vacuum pump, and when the optimal vacuum degree is reached, the secondary vacuum exhaust is performed by the high vacuum pump.
  • the carrier material in the mixer may be stirred by a stirrer.
  • a deposition step of forming nanoparticles on the support is performed using a physical deposition source.
  • the vacuum in the vacuum group (304) is broken, and the carrier to which the nanopowder has been attached is extracted from the stirring group (300).
  • This stage is the last stage.
  • the deposition stage is controlled by controlling the deposition time to the content of the deposition, and the mass content is controlled at 500 ppm to 5000 ppm.
  • the primary carrier may be in the form of a powder, granule or flake having a solid size of 0.1 ⁇ m to 50 ⁇ .
  • the primary carrier is preferably glucose; and the secondary carrier is preferably activated carbon having an average particle diameter ranging from 50 ⁇ m to 200 ⁇ m.
  • nanoparticle manufacturing process of the present invention is that the structure of the article from the final application
  • the materials used in the carrier are selected for use, thereby achieving simplification of the process, without adding additional additives, and thus being environmentally friendly, and optimally exerting the properties of the nanopowder.
  • a secondary carrier is used to produce a fine chemical catalyst or a fuel cell catalyst.
  • the catalyst manufacturing process of the present invention is to form a nanoparticle after primary carrier, and then mix with a secondary carrier and carry out a subsequent process, so that the chemical or physical properties of the carrier should be considered when selecting the carrier once.
  • the present invention includes a subsequent process step for producing a fine chemical catalyst or a fuel cell catalyst.
  • the subsequent manufacturing process of the catalyst includes a mixing stage, a material heating/stirring stage, a filtration/washing stage, a drying stage, and a charging/packaging stage.
  • the primary carrier, the secondary carrier, the catalytic reaction, etc. the subsequent process steps described above may be omitted, and a new process step may be added.
  • the present invention is described as an example of a process for producing a fine chemical catalyst using activated carbon as a carrier and a catalyst for fuel cell production.
  • nanoparticles and supports suitable for use in fine chemical catalysts or fuel cell catalysts are selected.
  • the nanoparticles are deposited on the primary support in accordance with the nanoparticle fabrication method provided in the present invention.
  • the nanoparticles/primary carrier, distilled water, secondary carrier are mixed.
  • the carrier is not water-soluble, a solution or a chemical capable of dissolving the primary carrier is dissolved to dissolve the primary carrier.
  • the amount of the secondary metal carrier is determined in consideration of the content of the catalyst precious metal material to be produced.
  • the catalyst nanoparticles are moved from the primary carrier to the secondary carrier and adsorbed on the secondary carrier.
  • the step includes mixing and stirring the secondary carrier with the solution containing the nanoparticles.
  • the primary carrier containing the nanoparticles is sufficiently dissolved by distilled water or other suitable solvent, at which time the nanoparticles are separated from the primary carrier.
  • the secondary carrier is mixed and stirred, and the nanoparticles are adsorbed on the surface and pores of the secondary carrier or bonded to the polar functional groups on the surface of the secondary carrier.
  • the solvent in order to dissolve the primary carrier glucose containing the nanoparticles, the solvent may be distilled water in a mixing ratio of 0.5 times to 3.0 times that of the nanoparticle-containing glucose.
  • the solution in which the nanoparticles are mixed is stirred by a solution stirrer.
  • a solution stirrer At the same time, according to the viscosity of the solution, the characteristics of the mixed material, the process of heating the solution can be increased.
  • an ultrasonic oscillating device Ultrasonic
  • an ultrasonic dispersing machine Ultrasonic Homogemzer
  • the catalyst is separated from the solution by a filtration device, dried, and then packaged.
  • a paper filter or a ceramic filter is preferably used.
  • the surface area of the small nanoparticles is larger than that of the large particles, so that a catalytic reaction is likely to occur and the catalytic effect can be increased.
  • the most important influence on the catalytic effect is the size and distribution of nanoparticles.
  • the distribution of the size of the nanoparticles produced according to the present invention is 90% or more of a size of 5 nm or less.
  • the material used in the catalytic reaction is acetophenone, and the type of chemical reaction is a hydrogenation reaction.
  • Acetophenone forms ethylbenzene and phenethyl alcohol under hydrogenation catalytic reaction.
  • phenylethyl alcohol is the main product of this reaction
  • ethylbenzene is a by-product of the reaction.
  • the ordinate shows the conversion of acetophenone to phenylethyl alcohol.
  • the hydrogenation reaction is carried out at normal temperature.
  • a catalyst having a higher content than the fine chemical catalyst is used, and generally 10% to 70% is contained. the amount.
  • Fuel cells require high levels of precious metals, while nanomaterials are expensive, so there is an urgent need for high efficiency fuel cell catalysts. It has been confirmed in the present invention that the high catalytic reaction efficiency can be exhibited in the experimental results of the catalytic reaction for fine chemicals.
  • the catalyst for a fuel cell can be produced by the method of the present invention, and a catalyst having higher efficiency can be produced, the amount of precious metal of the catalyst for a fuel cell can be reduced, and the price competitiveness of the catalytic product can be ensured.

Abstract

A metal nanocatalyst and its preparation method are disclosed. The method comprises the following steps: depositing the nanometer metal on a primary support in a vacuum vessel with a stirring device to obtain nanoparticles; dissolving or dispersing the nanoparticles with a primary support in solvents; adsorbing the nanoparticles on the secondary support. The catalyst can be used in many fields, such as the field of fine chemicals or fuel cell.

Description

金属纳米催化剂及制造方法  Metal nanocatalyst and manufacturing method
技术领域 Technical field
本发明涉及一种催化剂用纳米粒子的制造方法及利用其方法的纳米催 化剂制造方法。  The present invention relates to a method for producing a catalyst nanoparticle and a method for producing a nanocatalyst using the same.
背景技术 Background technique
催化剂是在化学反应中作为反应物质以外的物质， 在反应前后催化剂 本身不会发生量或质上的变化， 能保留与反应前同样的状态， 只对化学反 应速度产生变化的一种物质。 初期的催化领域都集中在化学工程领域中， 但最近， 能广泛的应用到汽车尾气净化， 发电厂的脱氮等公害防止， 燃料 电池， 氢气等未来能源的开发， 做料理用烤箱， 炉灶等领域， 并且其需要 日益增长。 如电子、 生物技术、 新材料、 新能源等多种高新技术， 通过多 种技术开发及应用上的不断发展， 目前催化剂领域也被评为核心高新技术 要素。  The catalyst is a substance other than the reaction substance in the chemical reaction, and the catalyst itself does not undergo a quantitative or qualitative change before and after the reaction, and can retain the same state as before the reaction, and only a substance which changes in the chemical reaction rate. In the early days, the field of catalysis was concentrated in the field of chemical engineering. Recently, it has been widely used in automobile exhaust gas purification, pollution prevention such as nitrogen removal in power plants, development of future energy sources such as fuel cells and hydrogen, cooking ovens, stoves, etc. The field, and its needs are growing. Such as electronics, biotechnology, new materials, new energy and other high-tech, through the development of a variety of technologies and applications, the catalyst field is currently rated as a core high-tech element.
纳米催化剂领域被认定为能解决由高度产业化而造成的能源枯竭及由 以往的化学燃料利用而导致的环境污染等问题的下一代技术。 纳米催化剂 是具有化学反应活性， 有纳米大小的物质， 在能源转换、 光催化剂、 绿色 化学、 环境、 生体模仿技术、 分子印刷技术等多种领域上不断进行对纳米 催化剂的研究。 在化学反应上， 反应速度是随着温度、 压力、 浓度、 冲突 次数、 表面积、 活性化能源等多种条件的变化而变， 为其反应速度， 经常 使用催化剂。 在化学反应中纳米催化剂的作用是增加反应速度的同时在多 种反应物中促进目标反应物的形成。  In the field of nanocatalysts, it is recognized as a next-generation technology that can solve problems such as energy depletion caused by highly industrialization and environmental pollution caused by the use of conventional chemical fuels. Nanocatalysts are chemically reactive and nano-sized materials. They are constantly researching nanocatalysts in various fields such as energy conversion, photocatalyst, green chemistry, environment, bioimitation technology, and molecular printing technology. In chemical reactions, the reaction rate varies with various conditions such as temperature, pressure, concentration, number of collisions, surface area, and activated energy. For its reaction rate, a catalyst is often used. The role of the nanocatalyst in chemical reactions is to increase the reaction rate while promoting the formation of target reactants in a variety of reactants.
纳米催化剂一般由为实际反应贡献的催化剂原材料和能够支持催化剂 的载体构成。 为增加化学反应速度， 纳米催化剂材料必须具备较大的表面 积， 从而使催化剂材料能够均匀分布在载体上。 因此， 能够促进纳米催化 剂具备较大的表面积形成均匀分布的就是载体。 精细化学领域及石油化学 领域中经常使用的载体主要有活性炭和氧化铝等。 在选定载体时最重要的 是在多种载体中能够选定最适合于各个化学反应的载体。 The nanocatalyst is generally composed of a catalyst raw material that contributes to the actual reaction and a support capable of supporting the catalyst. In order to increase the chemical reaction rate, the nanocatalyst material must have a large surface area, so that the catalyst material can be uniformly distributed on the carrier. Therefore, it can promote nanocatalysis The agent has a large surface area to form a uniform distribution of the carrier. The carriers frequently used in the field of fine chemistry and petrochemistry are mainly activated carbon and alumina. Of particular importance when selecting a carrier is the ability to select the carrier that is most suitable for each chemical reaction among the various carriers.
以贵金属为催化剂材料， 以活性炭为载体的纳米催化剂的主要应用领 域都有精细化学领域及燃料电池领域等。 贵金属 /活性炭催化剂的制造大部 分都是用化学方法来制造。 如图 1 所示， 化学方法的纳米粒子制造都有沉 淀液相还原（PL , Precipitation Liquid reduction)、 沉淀气相还原（PG， Precipitation Gas reduction) 吸附液相还原 (AL， Adsorption Liquid reduction) 吸附气相还原 CAG， Adsorption Gas reduction) 等，贵金属盐主要是 HAuCl4、 AuCl3、 KAu(CN)2、 Organo metallic precursor、 H2PtCl6、 Pt(N02)2(N¾)2、 PtCl2、 RuCl3等。 还原剂经常使用 LiBH4、 NaB¾或容易混合在水中的酒精类。 用 化学方法制造催化剂需要经过复杂的工艺， 因为在每一个工艺的后续工艺 中使用的多种添加剂， 所以很难取出纯纳米粒子， 很难控制纳米粒子的形 态， 而且工艺后发生的副产物会导致环境污染。 The main application fields of nano-catalysts using noble metals as catalyst materials and activated carbon as carriers are in the fields of fine chemistry and fuel cells. Most of the precious metal/activated carbon catalysts are manufactured by chemical methods. As shown in Fig. 1, the chemical method of nanoparticle production has a liquid phase reduction (PL, Precipitation Liquid reduction), PG (Precipitation Gas reduction), Adsorption Liquid reduction (AL, Adsorption Liquid reduction) CAG, Adsorption Gas reduction, etc., precious metal salts are mainly HAuCl 4 , AuCl 3 , KAu(CN) 2 , Organo metallic precursor, H 2 PtCl 6 , Pt(N0 2 ) 2 (N3⁄4) 2 , PtCl 2 , RuCl 3 , etc. . Reducing agents often use LiBH 4 , NaB 3⁄4 or alcohols that are easily mixed in water. The chemical process of preparing a catalyst requires a complicated process because it is difficult to remove pure nanoparticles by using various additives used in subsequent processes of each process, and it is difficult to control the morphology of the nanoparticles, and by-products occurring after the process will Lead to environmental pollution.
利用以往的纳米粒子化学制造方法时， 要制造出在一个载体上附着两 种以上催化剂的载体， 得有能同时使用两种以上纳米材料的有机化合物。 但是因为各个金属有机化合物的分解温度或其化学组成具有不同的特性， 所以能共同使用于不同纳米材料的有机化学物极其少。 用物理方式制造纳 米催化剂时， 由于不适用金属有机化学物， 因此可以包含多种纳米粒子， 并且也可以制造出多技能的催化剂。 用化学方法制造催化剂的工艺中， 会 残留一些盐酸离子、 硝酸离子、 有机金属化学物的分解物等多种不纯物的 载体， 所以还需要洗洁工艺。 如此， 纳米粒子的化学制造方法存在着复杂， 工艺中
Figure imgf000004_0001
高价化学试剂污染， 无法制造纳米合金等缺 陷， 要解决此问题， 需要物理方式的纳米粒子制造方法。 利用物理方式的 纳米催化剂制造方式， 既可制造高纯度， 高效率纳米催化剂， 可减少纳米 材料的使用量， 也可制造出亲环境的纳米催化剂等。 发明内容 In the conventional nanoparticle chemical production method, a carrier in which two or more kinds of catalysts are attached to one carrier is produced, and an organic compound capable of using two or more kinds of nanomaterials at the same time is obtained. However, since the decomposition temperature of each metal organic compound or its chemical composition has different characteristics, there are extremely few organic chemicals that can be used together for different nano materials. When the nanocatalyst is physically produced, since a metal organic chemical is not applicable, a plurality of nanoparticles can be contained, and a multi-skilled catalyst can also be produced. In the process of chemically producing a catalyst, a carrier of various impurities such as hydrochloric acid ions, nitrate ions, and decomposition products of an organic metal chemical remains, so a cleaning process is also required. Thus, the chemical manufacturing method of nanoparticles is complicated, in the process.
Figure imgf000004_0001
High-priced chemical reagents are contaminated, and defects such as nano-alloys cannot be produced. To solve this problem, a physical method of manufacturing nanoparticles is required. The use of a physical nanocatalyst manufacturing method can produce high-purity, high-efficiency nanocatalysts, reduce the amount of nanomaterials used, and produce environmentally friendly nanocatalysts. Summary of the invention
为解决上述技术问题， 本发明的目的在于提供一种纳米粒子催化剂的 制造方法， 利用以物理方式制造出的纳米粒子， 把贵金属纳米粒子附着在 活性炭载体上的方法， 可用于制造精细化学用及燃料电池用贵金属纳米催 化剂。  In order to solve the above technical problems, an object of the present invention is to provide a method for producing a nanoparticle catalyst, which can be used for the manufacture of fine chemicals by using a physically produced nanoparticle and attaching a noble metal nanoparticle to an activated carbon carrier. Precious metal nanocatalyst for fuel cells.
为达到上述目的， 本发明提供了一种精细化学或燃料电池用催化剂的 制造方法， 该方法是在催化剂用载体上负载催化剂用纳米粒子。  In order to achieve the above object, the present invention provides a process for producing a catalyst for fine chemical or fuel cells, which comprises supporting a catalyst nanoparticle on a support for a catalyst.
在本发明提供的上述方法中， 优选地， 所述催化剂用纳米粒子是在真 空容器内沉积纳米材料的同时搅拌粉末状、 颗粒状和 /或片状的一次载体进 行沉积， 得到纳米粒子。  In the above method provided by the present invention, preferably, the catalyst nanoparticles are obtained by depositing a powdery, granular and/or sheet-like primary carrier while depositing a nanomaterial in a vacuum container to obtain nanoparticles.
在本发明提供的上述方法中， 优选地， 所述催化剂用纳米粒子的贵金 属原材料包括 Au、 Ag、 Pt、 Rh、 Pd、 Ru、 Os、 Re和 Ir等中的一种或两种 以上的元素组成的合金。  In the above method provided by the present invention, preferably, the precious metal raw material of the catalyst nanoparticles includes one or more elements selected from the group consisting of Au, Ag, Pt, Rh, Pd, Ru, Os, Re, and Ir. The composition of the alloy.
在本发明提供的上述方法中， 优选地， 所述催化剂用纳米粒子的过渡 金属类原材料包含 Ti、 V、 Cr、 Mn、 Fe、 Co、 Ni、 Cu、 Zn、 Y、 Zr、 Nb、 Mo、 W和 Hf等中的一种或两种以上的元素组成的合金。  In the above method provided by the present invention, preferably, the transition metal-based raw material for the catalyst nanoparticles comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, An alloy composed of one or two or more elements of W and Hf.
在本发明提供的上述方法中， 优选地， 该方法包括： 制造催化剂用纳 米粒子后， 为制造出催化剂， 利用能溶解或分散含有催化剂用纳米粒子的 一次载体的水、 蒸馏水、 酒精、 丙酮、 硝酸、 盐酸、 硫酸、 磷酸、 醋酸、 碳酸、 硼酸、 高氯酸、 氢氧化钠、 氢氧化钾、 氢氧化钙、 氢氧化钡和氨水 等中的一种或两种以上的组合制造含有纳米粒子的溶液的歩骤。  In the above method provided by the present invention, preferably, the method comprises: after manufacturing the nanoparticles for the catalyst, to produce a catalyst, using water, distilled water, alcohol, acetone, which can dissolve or disperse the primary carrier containing the nanoparticles for the catalyst, One or a combination of two or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, carbonic acid, boric acid, perchloric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, and ammonia water to produce nanoparticles The solution of the solution.
在本发明提供的上述方法中， 优选地， 作为为制造催化剂的后续工艺 歩骤， 以提高纳米粒子的分散度， 使纳米粒子吸附在二次载体上为目的， 所述后续工艺歩骤包括使用搅拌机、 超声震荡装置和超声分散机等中的一 种或两种以上的组合对含有纳米粒子的溶液进行搅拌。  In the above method provided by the present invention, preferably, as a subsequent process step for manufacturing a catalyst, in order to increase the dispersion degree of the nanoparticles and adsorb the nanoparticles on the secondary carrier, the subsequent process steps include using The solution containing the nanoparticles is stirred by one or a combination of two or more of a stirrer, an ultrasonic oscillating device, and an ultrasonic disperser.
在本发明提供的上述方法中， 优选地， 为增加纳米粒子分散度的同时 增加含有纳米粒子的溶液溶解度， 所述后续工艺歩骤包括对含有纳米粒子 的溶液进行加热。 In the above method provided by the present invention, preferably, in order to increase the dispersion degree of the nanoparticles Increasing the solubility of the solution containing the nanoparticles, the subsequent process step comprising heating the solution containing the nanoparticles.
在本发明提供的上述方法中， 优选地， 制造催化剂的后续工艺歩骤包 括将吸附了纳米粒子的二次载体从混合溶液中过滤分离。 其中， 所述过滤 用过滤器可以包括纸、 高分子材料、 金属和陶瓷材料等中的一种或两种以 上的组合制成的过滤器。 所述过滤包括利用减压或加压式的过滤方法。  In the above method provided by the present invention, preferably, the subsequent process step of producing the catalyst comprises filtering and separating the secondary carrier to which the nanoparticles are adsorbed from the mixed solution. Wherein, the filter for filtration may include a filter made of one or a combination of paper, polymer material, metal and ceramic material, or the like. The filtering includes utilizing a vacuum or pressurized filtration method.
在本发明提供的上述方法中， 优选地， 以增加二次载体与纳米催化剂 粒子之间的吸附力或分布均一的纳米粒子为目的， 制造催化剂的后续工艺 歩骤包括利用物理方法或化学方法在二次载体的表面上进行前处理。 其中， 所述二次载体的前处理的方法包括热处理、 等离子处理、 离子束处理、 臭 氧处理、 酸性化学药品和碱性化学药品处理方法等中的一种或两种以上的 组合。  In the above method provided by the present invention, preferably, for the purpose of increasing the adsorption or uniform distribution of nanoparticles between the secondary carrier and the nanocatalyst particles, the subsequent process of manufacturing the catalyst includes using a physical method or a chemical method. Pretreatment is carried out on the surface of the secondary carrier. Here, the method of pretreatment of the secondary carrier includes one or a combination of two or more of heat treatment, plasma treatment, ion beam treatment, ozone treatment, acid chemical, and alkaline chemical treatment.
在本发明提供的上述方法中， 优选地， 后续工艺歩骤中使用的二次载 体是活性炭或炭黑等。 其中， 所述二次载体的比表面积在 50m2/g 到 5000m2/g。 所述二次载体的粒径在 lOOnm到 50mm。 In the above method provided by the present invention, preferably, the secondary carrier used in the subsequent process step is activated carbon or carbon black or the like. Wherein the secondary carrier has a specific surface area of from 50 m 2 /g to 5000 m 2 /g. The secondary carrier has a particle diameter of from 100 nm to 50 mm.
在本发明提供的上述方法中， 优选地， 以催化剂的质量计， 在所述催 化剂中， 纳米粒子的质量含量为 lppm到 80%。  In the above method provided by the present invention, preferably, the mass of the nanoparticles is from 1 ppm to 80% by mass based on the mass of the catalyst.
本发明提供的催化剂用纳米粒子及纳米催化剂的制造方法， 可以包括 以下歩骤：  The method for producing a catalyst nanoparticle and a nanocatalyst provided by the present invention may include the following steps:
在真空容器内沉积纳米材料的同时搅拌粉末状 (powder：)、颗粒状 (pellet) 和 /或片状 (chip)的一次载体；  Stirring a powder (powder:), pellet and/or chip primary carrier while depositing the nanomaterial in a vacuum vessel;
制造催化剂用纳米粒子后， 混合含有催化剂用纳米粒子的一次载体和 用作催化剂载体的二次载体， 利用后续工艺歩骤制造催化剂。  After the nanoparticles for the catalyst are produced, a primary carrier containing the nanoparticles for the catalyst and a secondary carrier serving as a catalyst carrier are mixed, and the catalyst is subsequently produced by a subsequent process.
本发明提供的上述制造方法是采用物理方法的， 包含沉积源的催化剂 用纳米粒子制造方法。 在上述制造方法中， 优选地， 制造催化剂用纳米粒 子的沉积方法包括利用热蒸发 （Thermal Evaporation) 装置、 电子束蒸发 (E-beam Evaporation) 装置、 直流溅射 （DC Sputtering, DCS ) 装置、 射 频溅射 （RF Sputtering, RFS ) 装置、 中频溅射 （Middle Frequency, MF) 装置、微波溅射（Microwave)装置、双磁控溅射（Dual Magnetron Sputtering) 装置、离子束溅射（Ion Beam Sputtering, IBS )装置、分子束外延（Molecular Beam Epitaxy, MBE) 装置、 电弧放电 （Arc Discharge Process) 装置、 激 光烧蚀（Laser Ablation)装置和 /或离子镀（Ion Plating)沉积装置等进行沉 积的方法。 本发明中优选利用直流溅射装置进行沉积。 The above-described production method provided by the present invention is a method for producing a catalyst nanoparticle comprising a deposition source by a physical method. In the above manufacturing method, preferably, a method of depositing nanoparticles for catalyst production comprises using a thermal evaporation device, electron beam evaporation (E-beam Evaporation) device, DC Sputtering (DCS) device, RF Sputtering (RFS) device, Middle Frequency (MF) device, Microwave device (Microwave) device, double Dual Magnetron Sputtering device, Ion Beam Sputtering (IBS) device, Molecular Beam Epitaxy (MBE) device, Arc Discharge Process device, Laser ablation (Laser) Ablation) A method of depositing a device and/or an Ion Plating deposition device or the like. In the present invention, deposition is preferably carried out using a direct current sputtering device.
在本发明提供的上述方法中， 优选地， 所述搅拌 （为制造出催化剂用 纳米粒子而使用的搅拌方法） 是在真空容器内， 采用以载体的搅拌为目的 而制作的搅拌装置进行搅拌的方式， 包括利用水平或垂直搅拌轴进行搅拌。 本发明中优选采用垂直搅拌的装置 （如图 3 ) 制造纳米粒子。  In the above method provided by the present invention, preferably, the stirring (a stirring method used to produce the catalyst nanoparticles) is carried out by stirring in a vacuum vessel using a stirring device prepared for the purpose of stirring the carrier. The method includes stirring with a horizontal or vertical stirring shaft. In the present invention, it is preferred to use a vertical stirring device (Fig. 3) to produce nanoparticles.
在本发明提供的上述方法中， 优选地， 所述催化剂的原材料包括 Au、 In the above method provided by the present invention, preferably, the raw material of the catalyst comprises Au,
Ag、 Pt、 Rh、 Pd、 Ru、 Os、 Re和 Ir等中的一种， 或者由其中的两种以上 的元素组成的合金。 本发明提供的上述方法是利用催化剂的原材料一一贵 金属类即 Au、 Ag、 Pt、 Rh、 Pd、 Ru、 Os、 Re、 Ir等或在其元素中由两个 以上元素组成的合金， 金属类等材料， 制造催化剂用纳米粒子的方法。 One of Ag, Pt, Rh, Pd, Ru, Os, Re, and Ir, or an alloy composed of two or more of them. The above method provided by the present invention is a raw material using a catalyst, a noble metal, namely, Au, Ag, Pt, Rh, Pd, Ru, Os, Re, Ir, or the like, or an alloy composed of two or more elements in its element, metal And other materials, a method for producing nanoparticles for a catalyst.
在本发明提供的上述方法中， 优选地， 利用转移金属类催化剂原材料 即 Ti、 V、 Cr、 Mn、 Fe、 Co、 Ni、 Cu、 Zn、 Y、 Zr、 Nb、 Mo、 W和 Hf等 中的一种， 或由其中两种以上的元素组成的合金， 制造催化剂用纳米粒子 的方法。 本发明提供的上述制造方法是： 利用转移金属类催化剂原材料即 上述各种元素或由其中两个以上元素而组成的合金， 制造催化剂用纳米粒 子的方法。  In the above method provided by the present invention, it is preferable to use a transfer metal catalyst raw material, that is, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, W, and Hf. A method of producing nanoparticles for a catalyst, or an alloy composed of two or more of them. The above-described production method according to the present invention is a method for producing a nanoparticle for a catalyst by using a transfer metal catalyst raw material, that is, the above various elements or an alloy composed of two or more of the elements.
在本发明提供的上述方法中， 优选地， 该方法包括： 制造催化剂用纳 米粒子后， 为制造出催化剂， 利用能溶解或分散含有催化剂用纳米粒子的 一次载体的液体 （或者说化学药品） 中的一种或一种以上的组合制造含有 纳米粒子的溶液的歩骤， 上述液体可以是能溶解或分散含有纳米粒子的一 次载体的水、 蒸馏水、 酒精、 丙酮等溶液或硝酸 (ΗΝ03;>、 盐酸HCl 硫酸 ¾S04、 磷酸 (¾P04)、 醋酸 (C¾COOH)、 碳酸 (¾C03)、 硼酸 (¾B03)、 高 氯酸 (HC104)等酸性化学药品或氢氧化钠 (NaOH：)、 氢氧化钾 (KOH：)、 氢氧化 钙 (Ca(OH)2)、氢氧化钡 (Ba(OH)2)、氨水 (ΝΗ3·Η20)等碱性化学药品或含其中 一个以上的化学药品。 In the above method provided by the present invention, preferably, the method comprises: after manufacturing the nanoparticles for the catalyst, in order to produce a catalyst, using a liquid (or chemical) capable of dissolving or dispersing the primary carrier containing the nanoparticles for the catalyst a step of producing a solution containing nanoparticles by one or more combinations, the liquid may be one capable of dissolving or dispersing a nanoparticle-containing one Secondary carrier of water, distilled water, alcohol, acetone, etc. or nitric acid (ΗΝ0 3 ;>, hydrochloric acid HCl, sulfuric acid 3⁄4S0 4 , phosphoric acid (3⁄4P0 4 ), acetic acid (C3⁄4COOH), carbonic acid (3⁄4C0 3 ), boric acid (3⁄4B0 3 ), high Acidic chemicals such as chloric acid (HC10 4 ) or sodium hydroxide (NaOH:), potassium hydroxide (KOH:), calcium hydroxide (Ca(OH) 2 ), barium hydroxide (Ba(OH) 2 ), ammonia (碱性3 ·Η 2 0) and other alkaline chemicals or one or more of them.
在本发明提供的上述方法中， 优选地， 作为为制造催化剂的后续工艺 歩骤， 以提高纳米粒子的分散度， 使纳米粒子吸附在二次载体上为目的， 所述后续工艺歩骤包括使用搅拌机、 超声震荡装置 （Ultmsomc) 和超声分 散机（Ultrasonic Homogenizer)中的一种或一种以上的组合对含有纳米粒子 的溶液进行搅拌。 更优选地， 为增加纳米粒子分散度的同时增加含有纳米 粒子的溶液溶解度， 后续工艺歩骤包括对含有纳米粒子的溶液进行加热。  In the above method provided by the present invention, preferably, as a subsequent process step for manufacturing a catalyst, in order to increase the dispersion degree of the nanoparticles and adsorb the nanoparticles on the secondary carrier, the subsequent process steps include using The solution containing the nanoparticles is agitated by one or a combination of one of a blender, an ultrasonic oscillating device (Ultmsomc) and an ultrasonic disperser (Ultrasonic Homogenizer). More preferably, in order to increase the dispersion of the nanoparticles while increasing the solubility of the solution containing the nanoparticles, the subsequent process step comprises heating the solution containing the nanoparticles.
在本发明提供的上述方法中， 优选地， 制造催化剂的后续工艺歩骤， 包括一次载体， 二次载体及从含有催化剂的溶液中分离催化剂的过滤工艺， 即制造催化剂的后续工艺歩骤包括将催化剂从含有催化剂的溶液中过滤分 离。 其中， 所采用的过滤器是利用被用于过滤过程的用纸， 金属， 高分子， 陶瓷等材料制作的过滤器的过滤工艺或利用此类过滤材料而制作的平面， 3 次元形象， 柱状形象的过滤器， 即用于过滤的过滤器是用纸、 金属、 高分 子或陶瓷材料制作的过滤器或利用纸、 金属、 高分子或陶瓷材料制作的平 面状、 或者柱状的过滤器。 过滤用过滤器材料， 纸、 高分子、 金属、 陶瓷、 或由其中两项组合而构成的过滤用过滤器。  In the above method provided by the present invention, preferably, a subsequent process step of producing a catalyst includes a primary carrier, a secondary carrier, and a filtration process for separating the catalyst from the catalyst-containing solution, that is, a subsequent process step of manufacturing the catalyst includes The catalyst is separated by filtration from a solution containing the catalyst. Among them, the filter used is a filter process using a filter made of paper, metal, polymer, ceramics or the like used for the filtration process or a plane made using such a filter material, a 3 dimensional image, a column image The filter, that is, the filter used for filtration, is a filter made of paper, metal, polymer or ceramic material or a flat or columnar filter made of paper, metal, polymer or ceramic material. Filtration filter material, paper, polymer, metal, ceramic, or a filter for filtration composed of two of them.
在本发明提供的上述方法中， 优选地， 所述过滤方式包括利用减压或 加压方式的过滤方法。 即作为一种过滤方式， 包括利用减压或加压方式的 过滤方法。  In the above method provided by the present invention, preferably, the filtering method includes a filtering method using a reduced pressure or a pressurized method. That is, as a filtration method, a filtration method using a reduced pressure or a pressurized method is included.
在本发明提供的上述方法中， 优选地， 以增加二次载体与纳米催化剂 粒子之间的吸附力或分布均一的纳米粒子为目的， 制造催化剂的后续工艺 歩骤包括利用物理方法或化学方法在二次载体的表面上进行前处理。 在本发明提供的上述方法中， 优选地， 所述二次载体的前处理的方法 包括热处理、 等离子处理、 离子束处理、 臭氧处理、 酸性化学药品或碱性 化学药品处理方法中的一种或一种以上的组合。 In the above method provided by the present invention, preferably, for the purpose of increasing the adsorption or uniform distribution of nanoparticles between the secondary carrier and the nanocatalyst particles, the subsequent process of manufacturing the catalyst includes using a physical method or a chemical method. Pretreatment is carried out on the surface of the secondary carrier. In the above method provided by the present invention, preferably, the method of pretreating the secondary carrier comprises one of heat treatment, plasma treatment, ion beam treatment, ozone treatment, acid chemical or alkaline chemical treatment method or More than one combination.
在本发明提供的上述方法中， 优选地， 该方法可以以活性炭为二次载 体， 用于制造精细化学用或燃料电池用催化剂。  In the above method provided by the present invention, preferably, the method may be carried out by using activated carbon as a secondary carrier for producing a catalyst for fine chemicals or a fuel cell.
在本发明提供的上述方法中， 优选地， 所述二次载体可以为平均表面 积在 50m2/g到 5000m2/g范围内的活性炭或平均粒子大小在 lOOnm到 50mm 范围内的活性炭。 In the above method provided by the present invention, preferably, the secondary carrier may be activated carbon having an average surface area in the range of 50 m 2 /g to 5000 m 2 /g or activated carbon having an average particle size in the range of 100 nm to 50 mm.
在本发明提供的上述方法中， 优选地， 所述催化剂是在 lppm中纳米粒 子的含量为 80%左右的精细化学用活燃料电池用活性炭催化剂。  In the above method provided by the present invention, preferably, the catalyst is an activated carbon catalyst for a fine chemical active fuel cell having a nanoparticle content of about 80% in 1 ppm.
本发明与以往的纳米粒子物理制造方式不同， 是使用纳米粒子制造设 备， 此设备是为实现大量生产而特殊设计的。 因为本发明的纳米粒子制造 工艺是利用以往的真空沉积方法， 所以容易实现多种金属或合金的蒸汽化， 能够在载体上均一的形成高纯度纳米粒子。 本发明中的被使用在物理的纳 米粒子制造装置中的纳米材料沉积装置（ΙΟΟ)有利用热蒸发 Thermal Evaporation)装置， 电子束蒸发 (E-beam Evaporation)装置， 直流溅射 (DC Sputtering, DCS)装置，射频溅射（RF Sputtering, RFS)装置， Middle Frequency (MF)方式的溅射装置，微波（Microwave)方式的溅射装置， Dual Magnetron Sputtering装置， 离子束溅射 （Ion Beam Sputtering, IBS) 装置， 分子束外 延（Molecular Beam Epitaxy, MBE)装置， 电弧放电 (Arc Discharge Process) 装置， 激光烧蚀（Laser Ablation)装置， 离子镀（Ion Plating)沉积装置等。 如图 2所示， 本发明中， 使用以物理方式制造的纳米粒子遂行简单的后处 理工艺， 从而提供制造催化剂的方法， 该方法可以包括纳米粒子制造、 混 合歩骤 （混合工程）、 过滤 /洗涤歩骤 （过滤 /洗涤工程） 和干燥歩骤 （干燥 工程）。 附图说明 The present invention differs from the conventional nanoparticle physical manufacturing method in that it uses nanoparticle manufacturing equipment, which is specially designed for mass production. Since the nanoparticle production process of the present invention utilizes a conventional vacuum deposition method, it is easy to vaporize a plurality of metals or alloys, and it is possible to uniformly form high-purity nanoparticles on a carrier. The nanomaterial deposition apparatus used in the physical nanoparticle manufacturing apparatus of the present invention has a thermal evaporation (Ether Beam Evaporation) apparatus, an electron beam evaporation (E-beam Evaporation) apparatus, and a DC sputtering (DC Sputtering, DCS). Device, RF Sputtering (RFS) device, Middle Frequency (MF) sputtering device, Microwave sputtering device, Dual Magnetron Sputtering device, Ion Beam Sputtering, IBS The device, Molecular Beam Epitaxy (MBE) device, Arc Discharge Process device, Laser Ablation device, Ion Plating deposition device, and the like. As shown in FIG. 2, in the present invention, a physically post-processed nanoparticle is used to perform a simple post-treatment process, thereby providing a method for producing a catalyst, which may include nanoparticle production, mixing step (mixing engineering), filtration/ Washing step (filtration/washing process) and drying step (drying process). DRAWINGS
图 1是利用活性炭、 以化学方式制造纳米催化剂粒子工艺的示意图； 图 2是利用以物理方式制造出的纳米粒子的纳米催化剂制造工艺的示 意图；  1 is a schematic view showing a process for chemically producing nano-catalyst particles using activated carbon; and FIG. 2 is a schematic view showing a process for manufacturing a nano-catalyst using nanoparticles which are physically manufactured;
图 3是安装垂直移送方式搅拌机的纳米粒子制造装备示意图；  Figure 3 is a schematic view of a nanoparticle manufacturing equipment equipped with a vertical transfer mode mixer;
图 4是利用本发明中的后续工艺制造的贵金属活性炭催化剂的纳米粒 子大小及分布度示意图；  Figure 4 is a schematic view showing the size and distribution of nanoparticles of a noble metal activated carbon catalyst produced by the subsequent process of the present invention;
图 5是利用本发明制造的 Pd/AC催化剂的催化反应效果比较图。 具体实施方式  Fig. 5 is a graph showing a comparison of catalytic reaction effects of a Pd/AC catalyst produced by the present invention. detailed description
以下通过具体实施例详细说明本发明的具体实施方案和所带来的有益 效果， 旨在帮助阅读者更好地理解本发明的精神实质， 但不能理解为对本 发明的实施范围的任何限定。  The specific embodiments of the present invention and the beneficial effects thereof are described in detail below by way of specific examples, which are intended to provide a better understanding of the spirit of the invention, but are not to be construed as limiting the scope of the invention.
本发明是关于被用于精细化学及燃料电池用的催化剂制造方法， 提供 用物理方法制造催化剂用纳米粒子， 在后处理歩骤中利用此纳米粒子， 制 造催化剂的制造方法。  The present invention relates to a method for producing a catalyst for use in fine chemicals and fuel cells, and provides a method for producing a catalyst by physically producing nanoparticles for a catalyst and using the nanoparticles in a post-treatment step.
用物理方法在粉末状 (powder：)、 颗粒状 (pellet：)、 片状 (chip)等载体上形 成纳米粒子的方法是在以下专利或文献中已被多次记载。  The method of physically forming nanoparticles on a powder (powder:), pellet (pellet), chip or the like is described in the following patents or literature.
[1] High dispersion platinum catalyst by RF sputtering, J. Catal. 83 (1983), p. 477；  [1] High dispersion platinum catalyst by RF sputtering, J. Catal. 83 (1983), p. 477;
[2] High-dispersion d.c. sputtered platinum-titania powder catalyst active in ethane hydrogenolysis, J. Phys. Chem. 93 (1989), p. 1510;  [2] High-dispersion d.c. sputtered platinum-titania powder catalyst active in ethane hydrogenolysis, J. Phys. Chem. 93 (1989), p. 1510;
[3] Nanoparticles of gold on γ-Α1203 produced by dc magnetron sputtering. J. Catal. 231 (2005), p.151；  [3] Nanoparticles of gold on γ-Α1203 produced by dc magnetron sputtering. J. Catal. 231 (2005), p.151;
[4] Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide, J. Catal. 115 (1989), p. 301 ;  [4] Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide, J. Catal. 115 (1989), p. 301;
[5] A technique for sputter coating of ceramic reinforcement particles, Surf. Coat. Technol. 91 (1997), p. 64; [5] A technique for sputter coating of ceramic enhance particles, Surf. Coat. Technol. 91 (1997), p. 64;
[6] Catalysis by Gold, Catal. Rev.-Sci. Eng. 41 (1999), p. 319；  [6] Catalysis by Gold, Catal. Rev.-Sci. Eng. 41 (1999), p. 319;
[7] Gold: a relatively new catalyst, Catal. Today 72 (2002), p. 5;  [7] Gold: a relatively new catalyst, Catal. Today 72 (2002), p. 5;
[8] Surface treatment of aluminum oxide and tungsten carbide powders by ion beam sputter deposition, Surf. Coat. Technol. 163-164 (2003), p. 281；  [8] Surface treatment of aluminum oxide and tungsten carbide powders by ion beam sputter deposition, Surf. Coat. Technol. 163-164 (2003), p. 281;
[9] Gold as a Novel Catalyst in the 21st Century: Preparation, Working Mechanisms and Applications, Gold Bull. 37 (2004), p. 27；  [9] Gold as a Novel Catalyst in the 21st Century: Preparation, Working Mechanisms and Applications, Gold Bull. 37 (2004), p. 27;
[10] Oxidation of CO on Gold Supported Catalysts Prepared by Laser Vaporization: Direct Evidence of Support Contribution, J. Am. Chem. Soc. 126 (2004), p. 1199；  [10] Oxidation of CO on Gold Supported Catalysts Prepared by Laser Vaporization: Direct Evidence of Support Contribution, J. Am. Chem. Soc. 126 (2004), p. 1199;
[11] 公开号为 GB1537839的英国专利申请；  [11] British Patent Application No. GB1537839;
[12] PCT 专利申请 No.US031265(2004);  [12] PCT Patent Application No. US031265 (2004);
[13] 韩国专利申请 No.KR100586270;  [13] Korean Patent Application No. KR100586270;
[14] 美国专利申请 No.US0095189(2005); [14] US Patent Application No. US0095189 (2005) ;
[15] 韩国专利申请 No.KRlO-2005-0101112;  [15] Korean Patent Application No. KRlO-2005-0101112;
[16] 美国专利申请 No.US6984404(2006)。  [16] U.S. Patent Application No. US6984404 (2006).
照着在先的专利及文献中提示的方法制造的纳米粉末制造装备存在着 沉积效率低， 载体的搅拌不均匀， 纳米粒子大小不均匀， 载体所受的外力 增加， 设备的耐久性低等缺陷。 上述的方法是针对载体搅拌方式的纳米粒 子制造设备的， 主要是为研究用或少量生产用而设计， 因此不适于产业大 量生产。  The nanopowder manufacturing equipment manufactured according to the methods disclosed in the prior patents and documents has low deposition efficiency, uneven agitation of the carrier, uneven nanoparticle size, increased external force of the carrier, and low durability of the device. . The above method is directed to a nanoparticle manufacturing apparatus for carrier agitation, and is mainly designed for research or small-scale production, and thus is not suitable for mass production.
载体粒子接近微米或使用像活性炭等比重非常低的载体时， 在搅拌过 程中载体散射的现象非常严重。 并且搅拌载体材料时， 转子被曝光到沉积 领域， 在转子上沉积纳米粒子， 从而降低沉积效率。 同时在现有专利或文 献中报告的纳米制造设备存在着就是耐久性低， 载体搅拌不均匀， 大量生 产的局限性等很多缺陷。 本发明中， 为解决上述缺陷， 利用了垂直移动方 式纳米粒子制造设备， 该设备的构造如图 3所示。 依照本发明的纳米粒子 制造装置的搅拌结构是以螺线型安装搅拌转子 （303 )， 从而更有效地上下 搅拌载体（200)。搅拌转子（303 )与搅拌组（300)中心部位的旋转轴（302) 连接， 旋转轴 （302 ) 与电机 （301 ) 连接。 随着电机 （301 ) 的转动， 搅拌 转子 （303 ) 旋转， 从而使载体 （200) 从搅拌组 （300 ) 的壁面附近移动到 搅拌组 （300 ) 的中心部附近的下部。 依照本发明的搅拌装置的搅拌转子 (303 ) 如图 3 所示， 搅拌组 （300 ) 的从上到下是以连续的螺线型结构而 造成， 因此能解决以往的纳米粒子制造用装置普遍存在的耐久性低， 载体 的搅拌不均匀， 载体的粉碎， 载体的过渡飞散等搅拌方式缺陷， 同时可以 本发明中的纳米粒子制造设备的工艺是由纳米材料及载体材料的选 定， 装纳米材料及， 载体材料装入阶段， 真空排气阶段， 纳米粒子制造（搅 拌 /沉积） 阶段， 撤销真空阶段， 抽取已沉积纳米粒子的载体的阶段构成。 为制造纳米粒子， 首先要选定适合于应用领域的纳米材料和载体材料， 在 沉积源 (100)上安装纳米材料靶材， 再把载体材料装入到搅拌机里。 真空排 气阶段中， 在大气压状态上， 利用低真空泵实行一次真空排气， 达到最佳 真空度时再利用高真空泵实行二次真空排气。 在做真空排气时， 为有效地 除去载体材料所含有的空气或载体材料之间存在的空气， 可利用搅拌机， 搅拌搅拌机里的载体材料。 真空排气歩骤结束后， 利用物理方式的沉积源， 进行在支持体上形成纳米粒子的沉积歩骤。 纳米粒子制造歩骤结束之后， 破毁真空组 (304)内的真空， 从搅拌组 (300)里抽取已附着纳米粉末的载体， 这阶段是属于最后一个阶段。 在本发明中， 沉积阶段用控制沉积时间达到 沉积的含量控制， 其质量含量控制在 500ppm-5000ppm。 When the carrier particles are close to micrometers or when a carrier having a very low specific gravity such as activated carbon is used, the scattering of the carrier during the stirring process is very serious. And when the carrier material is agitated, the rotor is exposed to the deposition field, and nanoparticles are deposited on the rotor, thereby reducing deposition efficiency. At the same time, nano-fabrication equipment reported in existing patents or literatures has many defects such as low durability, uneven carrier agitation, and limitations of mass production. In the present invention, in order to solve the above drawbacks, a vertical movement type nanoparticle manufacturing apparatus is utilized, and the structure of the apparatus is as shown in FIG. Nanoparticles in accordance with the invention The agitating structure of the manufacturing apparatus is a spiral type mounting agitating rotor (303) to more efficiently agitate the carrier (200) up and down. The agitating rotor (303) is coupled to a rotating shaft (302) at a central portion of the agitation group (300), and the rotating shaft (302) is coupled to the motor (301). As the motor (301) rotates, the agitating rotor (303) rotates, thereby moving the carrier (200) from the vicinity of the wall surface of the agitation group (300) to the lower portion near the center portion of the agitation group (300). The stirring rotor (303) of the stirring device according to the present invention is as shown in Fig. 3, and the stirring group (300) is caused by a continuous spiral structure from top to bottom, so that the conventional nanoparticle manufacturing apparatus can be solved. There are low durability, uneven agitation of the carrier, pulverization of the carrier, transitional scattering of the carrier, and the like, and the process of the nanoparticle manufacturing device of the present invention is selected from the nano material and the carrier material, and the nanometer is loaded. The material and the carrier material loading stage, the vacuum exhaust stage, the nanoparticle manufacturing (stirring/deposition) stage, the vacuum stage are removed, and the stage of the deposited nanoparticle carrier is extracted. In order to manufacture the nanoparticles, first, a nano material and a carrier material suitable for the application field are selected, a nano material target is mounted on the deposition source (100), and the carrier material is loaded into the mixer. In the vacuum exhaust stage, in the atmospheric pressure state, a vacuum evacuation is performed by the low vacuum pump, and when the optimal vacuum degree is reached, the secondary vacuum exhaust is performed by the high vacuum pump. In order to effectively remove air present between the air contained in the carrier material or the carrier material during vacuum evacuation, the carrier material in the mixer may be stirred by a stirrer. After the vacuum evacuation is completed, a deposition step of forming nanoparticles on the support is performed using a physical deposition source. After the end of the nanoparticle production process, the vacuum in the vacuum group (304) is broken, and the carrier to which the nanopowder has been attached is extracted from the stirring group (300). This stage is the last stage. In the present invention, the deposition stage is controlled by controlling the deposition time to the content of the deposition, and the mass content is controlled at 500 ppm to 5000 ppm.
一次载体可采用粉末状、 颗粒状或片状的平均大小为 0.1μπι-50πιπι 的 固体。 在本发明中， 一次载体优选采用葡萄糖； 二次载体优选采用平均粒 径为 50μπι-200μπι范围的活性炭。  The primary carrier may be in the form of a powder, granule or flake having a solid size of 0.1 μm to 50 πιπι. In the present invention, the primary carrier is preferably glucose; and the secondary carrier is preferably activated carbon having an average particle diameter ranging from 50 μm to 200 μm.
本发明中的纳米粒子制造工艺的另一个优点是， 从最终应用制品的构 成材料中挑选被用来载体的材料使用， 从而实现工艺的单纯化， 不添加附 加添加物， 因此是亲环境的， 并且能最佳发挥纳米粉末本有的特性。 根据 上述方法， 在一次载体上形成纳米粒子后， 为制造出精细化学用催化剂或 燃料电池用催化剂使用二次载体。 本发明的催化剂制造工艺是在一次载体 上形成纳米粒子后， 与二次载体相混合并进行后续工艺歩骤， 因此选定一 次载体时要考虑载体的化学特性或物理特性。 Another advantage of the nanoparticle manufacturing process of the present invention is that the structure of the article from the final application The materials used in the carrier are selected for use, thereby achieving simplification of the process, without adding additional additives, and thus being environmentally friendly, and optimally exerting the properties of the nanopowder. According to the above method, after the nanoparticles are formed on the primary carrier, a secondary carrier is used to produce a fine chemical catalyst or a fuel cell catalyst. The catalyst manufacturing process of the present invention is to form a nanoparticle after primary carrier, and then mix with a secondary carrier and carry out a subsequent process, so that the chemical or physical properties of the carrier should be considered when selecting the carrier once.
本发明包括为制造精细化学用催化剂或燃料电池用催化剂的后续工艺 歩骤。 催化剂后续制造工艺包括混合阶段， 材料加热 /搅拌阶段， 过滤 /洗涤 阶段， 干燥阶段， 收取 /包装阶段。 根据纳米粒子， 一次载体， 二次载体， 催化反应等种类可省略上述的后续工艺歩骤， 也可追加新的工艺歩骤。 本 发明是把活性炭用作载体的精细化学用催化剂制造及燃料电池用催化剂制 造的后续工艺为例作说明。  The present invention includes a subsequent process step for producing a fine chemical catalyst or a fuel cell catalyst. The subsequent manufacturing process of the catalyst includes a mixing stage, a material heating/stirring stage, a filtration/washing stage, a drying stage, and a charging/packaging stage. Depending on the type of the nanoparticles, the primary carrier, the secondary carrier, the catalytic reaction, etc., the subsequent process steps described above may be omitted, and a new process step may be added. The present invention is described as an example of a process for producing a fine chemical catalyst using activated carbon as a carrier and a catalyst for fuel cell production.
进入材料混合阶段之前， 先选定好适用于精细化学用催化剂或燃料电 池用催化剂领域的纳米粒子及载体。 选定纳米材料和载体材料后， 根据本 发明中提供的纳米粒子制造方法在一次载体上沉积纳米粒子。 在后处理歩 骤的混合阶段， 混合纳米粒子 /一次载体， 蒸馏水， 二次载体。 一次载体不 具有水溶性时混合能溶解一次载体的溶液或化学药品溶解一次载体。 测量 一次载体所含的纳米粒子量后， 考虑要制造的催化剂贵金属材料的含量， 决定二次载体的量。 在本发明中， 在一次载体上形成催化剂用纳米粒子后， 使催化剂用纳米粒子从一次载体移动到二次载体并吸附在二次载体上。 该 歩骤包括使二次载体与含有纳米粒子的溶液相混合并搅拌。 利用蒸馏水或 其他适当的溶剂充分溶解含纳米粒子的一次载体， 此时纳米粒子与一次载 体分离。 投入二次载体混合搅拌， 此时纳米粒子吸附在二次载体的表面及 孔隙当中或与二次载体表面的极性官能团进行结合。 本发明中， 为溶解含 纳米粒子的一次载体葡萄糖， 溶剂可以采用蒸馏水， 混合比例为含纳米粒 子葡萄糖的 0.5倍 -3.0倍。 利用溶液搅拌机搅拌混有纳米粒子的溶液。 同时， 可根据溶液的粘度， 混合材料的特性， 可增加加热溶液的工艺歩骤在搅拌工艺歩骤中， 为纳米 粒子的均匀分散，可利用超声震荡装置（Ultrasonic) ,超声分散机（Ultrasonic Homogemzer)等装置进行后续工艺歩骤。完成一定时间的搅拌工艺歩骤后， 利用过滤装置， 从溶液中分离催化剂， 干燥后再包装。 本发明中， 优选采 用纸过滤器或陶瓷过滤器。 Prior to entering the material mixing stage, nanoparticles and supports suitable for use in fine chemical catalysts or fuel cell catalysts are selected. After the nanomaterial and the support material are selected, the nanoparticles are deposited on the primary support in accordance with the nanoparticle fabrication method provided in the present invention. In the mixing stage of the post-treatment step, the nanoparticles/primary carrier, distilled water, secondary carrier are mixed. When the carrier is not water-soluble, a solution or a chemical capable of dissolving the primary carrier is dissolved to dissolve the primary carrier. After measuring the amount of the nanoparticles contained in the carrier once, the amount of the secondary metal carrier is determined in consideration of the content of the catalyst precious metal material to be produced. In the present invention, after the catalyst nanoparticles are formed on the primary carrier, the catalyst nanoparticles are moved from the primary carrier to the secondary carrier and adsorbed on the secondary carrier. The step includes mixing and stirring the secondary carrier with the solution containing the nanoparticles. The primary carrier containing the nanoparticles is sufficiently dissolved by distilled water or other suitable solvent, at which time the nanoparticles are separated from the primary carrier. The secondary carrier is mixed and stirred, and the nanoparticles are adsorbed on the surface and pores of the secondary carrier or bonded to the polar functional groups on the surface of the secondary carrier. In the present invention, in order to dissolve the primary carrier glucose containing the nanoparticles, the solvent may be distilled water in a mixing ratio of 0.5 times to 3.0 times that of the nanoparticle-containing glucose. The solution in which the nanoparticles are mixed is stirred by a solution stirrer. At the same time, according to the viscosity of the solution, the characteristics of the mixed material, the process of heating the solution can be increased. In the stirring process step, for the uniform dispersion of the nanoparticles, an ultrasonic oscillating device (Ultrasonic) and an ultrasonic dispersing machine (Ultrasonic Homogemzer) can be used. And other devices perform subsequent process steps. After completion of the stirring process for a certain period of time, the catalyst is separated from the solution by a filtration device, dried, and then packaged. In the present invention, a paper filter or a ceramic filter is preferably used.
一般情况下， 小纳米粒子的表面积比大粒子的表面积更大， 所以易发 生催化反应， 能增大催化效果。 催化制品中， 对催化效果起最大影响的是 纳米粒子的大小及分布， 要制造高效率催化剂， 最关键是制造大小均匀的 小纳米粒子。如图 4 所示，根据本发明制造出的纳米粒子大小的分布是 5nm 以下大小的占 90%以上。 利用根据本发明制造出的钯纳米粒子， 通过后续 工艺制造出的催化剂的催化反应结果如图 5所示。 催化反应中被使用的材 料是苯乙酮 （acetophenone) , 化学反应的种类是加氢反应。 苯乙酮在加氢 催化反应下生成乙苯 (ethylbenzene) 禾 Π 苯乙醇 （phenethyl alcohol) , 其中 苯乙醇是此反应的主要产物， 乙苯是反应的副产物。 图 5中纵坐标（Yield) 显示苯乙酮转换成苯乙醇的转换率。 本发明中， 加氢反应是在常温下进行。 在催化反应结果中能看出， 反应两个小时后， 5%Pd/AC 商用制品 ( 5wt%Pd/AC— commercial 1 ) 的主反应效果是 99%， 而根据本发明制造出 的 2%Pd/AC催化剂 （2wt%Pd/AC— iNano) 的主反应效果是 87.5%。 制造 3 个 5%Pd/AC 催化剂样品 （5wt%Pd/ACl— iNano、 5wt%Pd/AC2_iNano 和 5wt%Pd/AC3_iNano)后对各个样品进行催化反应试验， 结果一小时十分钟 的催化反应后，它们的主反应效果的平均值是 97.6%。根据本发明制造出的 催化剂比商用制品呈现更高的主反应效果， 其主要原因是， 根据本发明制 造出的纳米粒子比商用制品的纳米粒子更小更均一。 精细化学用催化剂时， 制造的催化用纳米粒子的含量一般低于 10%以下， 燃料电池用催化剂时， 使用比精细化学用催化剂的含量较高的催化剂， 一般使用 10%-70%以内含 量。 燃料电池需要含量较高的贵金属， 而纳米材料费用较高， 因此迫切需 要高效率燃料电池催化剂的制造。 本发明中已确认， 精细化学用催化反应 实验结果中能体现高催化反应效率。 以此类推， 用本发明中的方法制造燃 料电池用催化剂， 能制造成更高效率的催化剂， 能减少燃料电池用催化剂 的贵金属量， 确保催化制品的价格竞争力。 In general, the surface area of the small nanoparticles is larger than that of the large particles, so that a catalytic reaction is likely to occur and the catalytic effect can be increased. In catalytic products, the most important influence on the catalytic effect is the size and distribution of nanoparticles. To produce high-efficiency catalysts, the most important thing is to make small nanoparticles with uniform size. As shown in Fig. 4, the distribution of the size of the nanoparticles produced according to the present invention is 90% or more of a size of 5 nm or less. The catalytic reaction results of the catalyst produced by the subsequent process using the palladium nanoparticles produced according to the present invention are shown in FIG. The material used in the catalytic reaction is acetophenone, and the type of chemical reaction is a hydrogenation reaction. Acetophenone forms ethylbenzene and phenethyl alcohol under hydrogenation catalytic reaction. Among them, phenylethyl alcohol is the main product of this reaction, and ethylbenzene is a by-product of the reaction. In Figure 5, the ordinate shows the conversion of acetophenone to phenylethyl alcohol. In the present invention, the hydrogenation reaction is carried out at normal temperature. As can be seen from the results of the catalytic reaction, after two hours of reaction, the main reaction effect of the 5% Pd/AC commercial product (5 wt% Pd/AC-commercial 1) was 99%, while the 2% Pd produced according to the present invention. The main reaction effect of the /AC catalyst (2 wt% Pd/AC-iNano) was 87.5%. After preparing three 5% Pd/AC catalyst samples (5 wt% Pd/ACl-iNano, 5 wt% Pd/AC2_iNano, and 5 wt% Pd/AC3_iNano), each sample was subjected to a catalytic reaction test, and after one hour and ten minutes of catalytic reaction, The average of their main response effects was 97.6%. Catalysts made in accordance with the present invention exhibit higher primary reaction effects than commercial articles, with the primary reason that nanoparticles made in accordance with the present invention are smaller and more uniform than nanoparticles of commercial articles. In the case of a fine chemical catalyst, the content of the catalytic nanoparticles produced is generally less than 10%. In the case of a fuel cell catalyst, a catalyst having a higher content than the fine chemical catalyst is used, and generally 10% to 70% is contained. the amount. Fuel cells require high levels of precious metals, while nanomaterials are expensive, so there is an urgent need for high efficiency fuel cell catalysts. It has been confirmed in the present invention that the high catalytic reaction efficiency can be exhibited in the experimental results of the catalytic reaction for fine chemicals. By analogy, the catalyst for a fuel cell can be produced by the method of the present invention, and a catalyst having higher efficiency can be produced, the amount of precious metal of the catalyst for a fuel cell can be reduced, and the price competitiveness of the catalytic product can be ensured.

Claims

权利要求书 Claim
1、 一种精细化学或燃料电池用催化剂的制造方法， 该方法是在催 化剂用载体上负载催化剂用纳米粒子。 A method for producing a fine chemical or fuel cell catalyst, which comprises supporting a catalyst nanoparticle on a catalyst carrier.
2、 如权利要求 1所述的方法， 其中， 所述催化剂用纳米粒子是在 真空容器内沉积纳米材料的同时搅拌粉末状、 颗粒状和 /或片状的一次 载体进行沉积， 得到纳米粒子。  The method according to claim 1, wherein the catalyst nanoparticles are a powdery, granular and/or sheet-like primary carrier which is deposited while depositing a nanomaterial in a vacuum vessel to obtain nanoparticles.
3、 如权利要求 1所述的方法， 其中， 所述催化剂用纳米粒子的贵 金属原材料包括 Au、 Ag、 Pt、 Rh、 Pd、 Ru、 Os、 Re和 Ir中的一种或 两种以上的元素组成的合金。  The method according to claim 1, wherein the precious metal raw material of the catalyst nanoparticles includes one or more elements of Au, Ag, Pt, Rh, Pd, Ru, Os, Re, and Ir. The composition of the alloy.
4、 如权利要求 1所述的方法， 其中， 所述催化剂用纳米粒子的过 渡金属类原材料包含 Ti、 V、 Cr、 Mn、 Fe、 Co、 Ni、 Cu、 Zn、 Y、 Zr、 Nb、 Mo、 W和 Hf中的一种或两种以上的元素组成的合金。  4. The method according to claim 1, wherein the transition metal-based raw material for the catalyst nanoparticles comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo An alloy composed of one or two or more elements of W and Hf.
5、 如权利要求 1所述的方法， 其中， 该方法包括： 制造催化剂用 纳米粒子后， 为制造出催化剂， 利用能溶解或分散含有催化剂用纳米 粒子的一次载体的水、 蒸馏水、 酒精、 丙酮、 硝酸、 盐酸、 硫酸、 磷 酸、 醋酸、 碳酸、 硼酸、 高氯酸、 氢氧化钠、 氢氧化钾、 氢氧化钙、 氢氧化钡和氨水中的一种或两种以上的组合制造含有纳米粒子的溶液 的歩骤。  5. The method according to claim 1, wherein the method comprises: after manufacturing the nanoparticles for the catalyst, to produce a catalyst, using water, distilled water, alcohol, acetone capable of dissolving or dispersing the primary carrier containing the nanoparticles for the catalyst And one or a combination of two or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, carbonic acid, boric acid, perchloric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and ammonia in the production of nanoparticles The solution of the solution.
6、 如权利要求 5所述的方法， 其中， 作为为制造催化剂的后续工 艺歩骤， 以提高纳米粒子的分散度， 使纳米粒子吸附在二次载体上为 目的， 所述后续工艺歩骤包括使用搅拌机、 超声震荡装置和超声分散 机中的一种或两种以上的组合对含有纳米粒子的溶液进行搅拌。  6. The method according to claim 5, wherein, as a subsequent process step for manufacturing a catalyst, in order to increase the dispersion degree of the nanoparticles and adsorb the nanoparticles on the secondary carrier, the subsequent process steps include The solution containing the nanoparticles is stirred using one or a combination of two or more of a stirrer, an ultrasonic oscillating device, and an ultrasonic disperser.
7、 如权利要求 5所述的方法， 其中， 为增加纳米粒子分散度的同 时增加含有纳米粒子的溶液溶解度， 所述后续工艺歩骤包括对含有纳 米粒子的溶液进行加热。 7. The method according to claim 5, wherein, in order to increase the dispersion degree of the nanoparticles while increasing the solubility of the solution containing the nanoparticles, the subsequent process step comprises heating the solution containing the nanoparticles.
8、 如权利要求 1所述的方法， 其中， 制造催化剂的后续工艺歩骤 包括将吸附了纳米粒子的二次载体从混合溶液中过滤分离。 8. The method according to claim 1, wherein the subsequent process of manufacturing the catalyst comprises filtering and separating the secondary carrier to which the nanoparticles are adsorbed from the mixed solution.
9、 如权利要求 8所述的方法， 其中， 所述过滤用过滤器包括纸、 高分子材料、 金属和陶瓷材料中的一种或两种以上的组合制成的过滤 器  9. The method according to claim 8, wherein the filter for filtration comprises a filter made of one or a combination of two or more of paper, polymer material, metal and ceramic material.
10、 如权利要求 8所述的方法， 其中， 所述过滤包括利用减压或 加压式的过滤方法。  10. The method of claim 8, wherein the filtering comprises utilizing a reduced pressure or pressurized filtration method.
11、 如权利要求 6所述的方法， 其中， 以增加二次载体与纳米催 化剂粒子之间的吸附力或分布均一的纳米粒子为目的， 制造催化剂的 后续工艺歩骤包括利用物理方法或化学方法在二次载体的表面上进行 前处理。  11. The method according to claim 6, wherein the subsequent process of manufacturing the catalyst comprises the use of a physical method or a chemical method for the purpose of increasing the adsorption or uniform distribution of the nanoparticles between the secondary carrier and the nanocatalyst particles. Pretreatment is carried out on the surface of the secondary carrier.
12、 如权利要求 11所述的方法， 其中， 所述二次载体的前处理的 方法包括热处理、 等离子处理、 离子束处理、 臭氧处理、 酸性化学药 品和碱性化学药品处理方法中的一种或两种以上的组合。  12. The method according to claim 11, wherein the method of pretreatment of the secondary carrier comprises one of heat treatment, plasma treatment, ion beam treatment, ozone treatment, acid chemical, and alkaline chemical treatment method. Or a combination of two or more.
13、 如权利要求 1 所述的方法， 其中， 后续工艺歩骤中使用的二 次载体是活性炭或炭黑。  13. The method of claim 1 wherein the secondary carrier used in the subsequent process step is activated carbon or carbon black.
14、 如权利要求 13所述的方法， 其中， 所述二次载体的比表面积 在 50m 到 5000m  14. The method according to claim 13, wherein the secondary carrier has a specific surface area of 50 m to 5000 m
15、 如权利要求 13或 14所述的方法， 其中， 所述二次载体的粒 径在 lOOnm到 50mm。  The method according to claim 13 or 14, wherein the secondary carrier has a particle diameter of from 100 nm to 50 mm.
16、 如权利要求 1 所述的方法， 其中， 以催化剂的质量计， 在所 述催化剂中， 纳米粒子的质量含量为 lppm到 80%。  The method according to claim 1, wherein the nanoparticles have a mass content of from 1 ppm to 80% by mass based on the mass of the catalyst.
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