CN105107551A - 催化剂制造方法 - Google Patents

催化剂制造方法 Download PDF

Info

Publication number
CN105107551A
CN105107551A CN201510484676.7A CN201510484676A CN105107551A CN 105107551 A CN105107551 A CN 105107551A CN 201510484676 A CN201510484676 A CN 201510484676A CN 105107551 A CN105107551 A CN 105107551A
Authority
CN
China
Prior art keywords
forming unit
metal
monolith
catalyst
powder
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.)
Pending
Application number
CN201510484676.7A
Other languages
English (en)
Inventor
D·R·库普兰德
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.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43037523&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN105107551(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of CN105107551A publication Critical patent/CN105107551A/zh
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9436—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8634—Ammonia
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • 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
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/12—Formation of a green body by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/48—Methods for the preparation of nitrates in general
    • 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
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B43/00—Obtaining mercury
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C22B9/023—By filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/40—Radiation means
    • B22F12/41—Radiation means characterised by the type, e.g. laser or electron beam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/705—Passivation
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Metallurgy (AREA)
  • Plasma & Fusion (AREA)
  • Biomedical Technology (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Acoustics & Sound (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

本发明描述了一种使用叠层法制造催化剂的方法，所述方法包括：(i)形成催化剂或催化剂载体粉末材料层；(ii)根据预定图案使所述层中的所述粉末结合或熔合；(iii)层压层地重复(i)和(ii)以形成成形单元；以及(iv)任选地将催化材料施加至所述成形单元。

Description

催化剂制造方法
本申请是基于申请号为201180043238.7、申请日为2011年8月22日、发明名称为“催化剂制造方法”的中国专利申请的分案申请。
本发明涉及通过叠层制造来制造催化剂。
典型地通过对粉末催化金属化合物进行造粒、挤出或成粒，随后煅烧和/或任选的还原阶段，制造非均相催化剂。或者利用催化剂化合物的溶液对通过对催化惰性材料进行造粒或挤出而形成的催化剂载体进行浸渍、干燥，然后经历煅烧和/或还原阶段。造粒、挤出和成粒方法在高效的同时，限制催化剂几何形状和物理性质的变化。
叠层制造(ALM)是顺序放置粉末材料的2-维层并熔合或结合在一起以形成3-维固体物体的技术。已经开发了制作用于航空和医疗用途中的金属和陶瓷部件的技术。
我们已经实现，ALM提供制造具有复杂几何形状和性质的催化剂结构的可能性，这是利用常规成形技术所不能实现的。
因此，本发明提供使用叠层法制造催化剂的方法，所述方法包括：
(i)形成催化剂或催化剂载体粉末材料层；
(ii)根据预定图案使所述层中的所述粉末结合或熔合；
(iii)层压层地重复(i)和(ii)以形成成形单元；以及
(iv)任选地将催化材料施加至所述成形单元。
本发明还提供可通过上述方法得到的催化剂和所述催化剂在催化反应中的用途。
ALM技术提供的主要改进在于催化剂性能和新的设计选项范围，包括更高的几何表面积对体积之比、更低的比重、受控的孔的几何形状、受控的气体/流体流动路径、受控的气体/流体湍流、受控的气体/流体停留时间、强化的填充、受控的热量、受控的热传递、受控的热损失以及更高的转化率和更好的催化选择性。
可使用已知技术将ALM法应用于催化剂设计，所述ALM法也称作层的制造、结构性制造、生成性制造、直接数字制造、自由形式的制作、固体自由形式的制作或随意成型(fabbing)。在所有情况中，通过常规3D设计计算机包能够实施所述ALM法，所述3D设计计算机包使得可将成形单元设计为所谓的“STL文件”，所述“STL文件”是3D形状的简单网眼描述。使用设计软件将STL文件切割成多个二维层，所述二维层是制作工艺的基础。然后，读取二维图案的制作设备以与2D切片相对应的方式顺序层压层地沉积粉末材料。为了成形单元具有结构整体性，在沉积层的同时将粉末材料结合或熔合在一起。重复层的沉积和结合或熔合的工艺，直至产生强壮(robust)的成形单元。未结合或未熔合的粉末易于因例如重力或鼓吹而从成形单元分离。
可获得大量ALM结合和熔合制作技术，显著的是3D印刷和激光烧结技术。然而，可使用任意一种技术。
在激光烧结中，所述工艺包括三个步骤，其中使用刮刀、辊或移动料斗首先将粉末材料的薄层施加到基础板上。对所述层的厚度进行控制。以二维方式施加激光辐射以熔合所述层。例如使用检流计镜根据期望图案对激光位置进行控制。在熔合所述层之后，将在其上放置层的板向下移动一个层的厚度并随后在熔合的层上遮盖新鲜的粉末层。重复所述程序，由此产生三维形式的成形单元。在形成形状之后，简单地通过重力或通过将其吹离，将未熔合的粉末与成形单元分离。
直接激光烧结使用固态纤维激光器在高温下实施所述工艺。这种系统商购得自PhenixSystems，例如如同在WO2005002764中所述的。
替代方法是使用具有聚合涂层的粉末材料或包含粉末材料和聚合粘合剂的组合物。在此情况中，激光用于熔化粘合剂。该技术具有优势，激光功率明显低于熔合方法的激光的功率。聚合涂布技术可商购得自EOSGmbH。
称作光固化快速成型(stereolithography)的其他替代方案使用分散在单体中的粉末，该单体在通过使用UV激光器进行光聚合在层中“固化”以充当粘合剂。所述粉末材料在单体中高达约60体积％。用于实施该工艺的合适设备商购得自Cerampilot。
在这些方法中，但尤其是后者，可对成形单元进行随后的热处理，实施所述热处理以烧掉并除去所有聚合粘合剂和/或改变成形单元的物理化学性质如其强度。
作为激光烧结或光固化快速成型的替代，所述ALM法可以基于将粘合剂印刷在粉末材料上并随后实施或不实施加热。通常，该方法使用多阵列喷墨印刷头将液体粘合剂层喷施在粉末层上以将粒子保持在一起。以与先前相同的方式将载体板向下移动并再次重复所述程序以按上述累积成形单元。在此情况中的层可以为0.02～5.0mm厚。通常应用随后的热处理以除去粘合剂。用于实施该工艺的合适设备可商购得自美国的Z-Corporation。
通过ALM法制造的催化剂成形单元可以为横断面尺寸为1～50mm的微粒或所述成形单元可以为横断面为100～1000mm的诸如蜂巢的独块形式。对于微粒成形单元或独块成形单元，长宽比即长度/宽度可以为0.5～5。
对可使用ALM技术制作的催化剂成形单元的几何形状几乎没有限制。复杂性可以为从骨架框架和晶格或饰边工作结构变化到多特征的且小平面的强壮结构。例如，成形单元可以为在其内含有空隙空间的线-框或骨架框架结构形式且其可具有多个内部增强棒，或成形单元可以为任意形式的蜂巢或固体单元如圆柱体，其可构造有圆顶端、多个叶片和/或通孔。
骨架框架结构是优选的且可包含3个以上的开放面，所述开放面可以为三角形、正方形、五边形或另一个多边形形状。因此，制得的结构可以为四面体、五面体(金字塔形)、六面体(立方体或正方形柱)、七面体、八面体、九面体、十面体、十二面体、二十面体等。还可通过外部棒对骨架架构进行连接以产生2-维或3-维结构。
优选地，成形单元包含一个或多个通孔，其横断面可以为圆形、椭圆形或多边形如三角形、正方形、矩形或六边形。所述通孔可包含平行延伸的两个以上的通孔、或在各种角度下延伸穿过所述成形单元到达成形单元纵轴的不平行的孔。还可使用ALM技术制造弯曲的通孔，这在目前使用常规造粒和挤出技术是不可能实现的。
所述成形单元可以由催化材料制备，或可以由非催化载体材料制备并涂布有催化材料，以提供催化剂。可以以单次或多次施加的方式，将多于一种的催化材料施加于载体上。如果期望，可利用相同或不同催化材料进一步对由催化材料制备的成形单元进行涂覆。
在一个实施方案中，所述粉末材料为催化剂粉末。所述催化剂粉末可包含金属粉末或粉末金属化合物。优选地，所述催化剂粉末包含一种或多种金属或金属化合物，该一种或多种金属或金属化合物含有选自Na、K、Mg、Ca、Ba、Al、Si、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Sn、Sb、La、Hf、W、Re、Ir、Pt、Au、Pb或Ce中的金属。
在催化剂粉末为金属粉末的情况中，优选所述催化剂粉末包含贵金属催化剂粉末，例如任选地与一种或多种过渡金属混合的Pt、Pd、Ir、Ru、Re中的一种或多种。
在催化剂粉末为粉末金属化合物的情况中，优选所述催化剂粉末包含一种或多种过渡金属化合物，包括镧系金属化合物和锕系金属化合物。所述过渡金属化合物可以为金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其混合物。过渡金属氧化物可包含单种或混合的金属氧化物如尖晶石或钙钛矿、或包含两种或更多种过渡金属氧化物的组合物。
所述催化剂粉末可还包含一种或多种粉末惰性材料如氧化铝、氧化硅、氮化硅、碳化硅、碳及其混合物。还可存在诸如堇青石的陶瓷类物质。
或者，所述催化剂粉末可包含沸石。
在替代实施方案中，粉末材料为催化剂载体粉末且所述方法包括将催化剂材料施加在所述成形单元上。催化剂载体粉末包含一种或多种惰性材料如氧化铝、氧化硅、氮化硅、碳化硅、碳及其混合物。还可使用常规的陶瓷类催化剂载体。所述催化剂载体粉末可还包含一种或多种过渡金属化合物，包括镧系金属化合物和锕系金属化合物，所述过渡金属化合物选自金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其混合物。过渡金属化合物可包含单种或混合的金属氧化物或包含两种或更多种过渡金属氧化物的组合物。优选地，所述催化剂载体粉末包含氧化铝、金属-铝酸盐、氧化硅、铝硅酸盐、氧化钛、氧化锆、氧化锌或其混合物。
或者，所述催化剂载体粉末可以为金属粉末如贵金属粉末或非贵金属粉末如铁合金或钢粉末。
或者，催化剂载体粉末可包含沸石。
施加至成形单元的催化材料可包含金属、金属化合物或沸石。
通过金属气相沉积可将催化金属施加至成形单元。或者，可从金属、金属化合物或沸石的溶液或分散液将金属、金属化合物或沸石施加至成形单元。特别合适的用于从溶液中施加的金属化合物为水溶性盐如金属硝酸盐、金属醋酸盐、甲酸盐或草酸盐。
可施加至成形催化剂载体单元的金属或金属化合物优选包含选自Na、K、Mg、Ca、Ba、Al、Si、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Sn、Sb、La、Hf、W、Re、Ir、Pt、Au、Pb或Ce中的一种或多种金属。
所述ALM法使用粉末材料。可将所述材料形成为粉末或使用各种技术如喷雾干燥将所述材料转化成粉末。喷雾干燥的优势在于，可制备不同粉末材料的混合物、施加粘合剂材料或制备自由流动的粉末。
无论通过何种方法制备粉末材料，粉末材料优选具有1～200微米的平均粒径D50。
所述叠层制造方法优选包括3D印刷或激光烧结技术。由此，在一个实施方案中，通过激光对各个层中的粉末进行熔合。在另一个实施方案中，利用粘合剂将各个层中的粉末结合在一起，所述粘合剂可以为无机粘合剂如铝酸钙水泥或有机粘合剂如酚醛树脂聚合物、纤维素、树胶或多糖粘合剂。
在催化剂粉末或粘合剂中可包括烧除性添加剂以控制得到的成形单元的孔隙率。
无论通过何种方法形成成形单元，可期望将其经历随后的加热步骤，可实施所述加热步骤以烧掉有机材料例如粘合剂或孔改性材料，和/或以改进物理化学性质，例如将非氧化金属化合物转化成相应的金属氧化物和/或对粉末材料进行熔合。可在300～1400℃、优选500～1200℃的最高温度下实施该加热步骤。
当成形单元包含一种或多种可还原的金属化合物时，可将成形单元经历还原步骤以将金属化合物转化成相应的金属。这可直接在成形单元上实施而不需要先前的加热步骤，或可在加热步骤之后实施，以将可还原的金属氧化物转化成相应的金属。通过在150～800℃、优选150～600℃的温度下将成形单元暴露在含氢气的气体流股中实现还原。包含还原的金属的催化剂可能是能自燃的，因此期望通过将成形单元受控暴露在含氧气的气体流股下以在所述还原的金属上形成钝化层，将成形单元中的还原的金属钝化。
本发明包括使用ALM方法制备的催化剂。
使用ALM方法制备的催化剂适用于任意催化工艺中，其中在实施催化反应的条件下将反应物混合物与该催化剂成形单元接触。或者，可将该成形单元用于吸附工艺以从工艺流体中催化除去物质，所述工艺流体可以为液体或气体。
催化反应可选自：加氢处理，包括加氢脱硫、氢化；蒸汽转化，包括预转化、催化蒸汽转化、自热转化和二次转化以及用于直接还原铁的转化工艺；催化部分氧化；水煤气变换，包括等温变换、酸变换(sourshift)、低温变换、中间温度变换、中等温度变换和高温变换反应；甲烷化；通过费-托(Fischer-Tropsch)反应合成烃；甲醇的合成；氨的合成；氨的氧化和一氧化二氮的分解反应；或内燃机或发电站废气的选择性氧化或还原反应。
所述ALM法特别适用于制造用于氨的氧化和蒸汽转化的微粒催化剂和用于对源自内燃机或发电站的废气成分进行选择性氧化和还原的独块催化剂。
所述吸附工艺可以为吸附，该吸附选自从污染的气态或液态流体流股中回收硫的化合物或重金属如汞和砷、或从内燃机和发电站的废气中回收微粒物质。特别地，可将所述方法用于制造称作催化烟粒过滤器的蜂巢型独块结构。
参考附图对本发明做进一步说明，其中：
图1描绘了可通过本发明方法得到的线-框催化剂结构；
图2是通过本发明方法制备的激光烧结的氧化铝催化剂载体的图像，所述载体具有图1的十二面体框架结构；且
图3是通过本发明方法制备的烧结的3D印刷的铝硅酸盐催化剂载体的图像，其处于四面体框架的形式。
在图1和2中，对“线-框”催化剂结构进行了描绘，所述催化剂结构包含具有在所述结构中心处连接的十二个内部“棒”的十二个五边形面。使用常规的造粒、挤出或成粒技术不能制造这种结构。
参考如下实例对本发明做进一步说明。
实施例1
将根据图1描绘的线-框氨氧化催化剂与商购获得的造粒的氨氧化催化剂进行了比较。
根据图1的成形单元中的活性面积为约545mm2。所述形状的体积为约135mm3。填充的体积估计为约90mm3。
在此基础上可预测，在相同的操作条件下，通过常规小球数目的15～16％就可提供相同的转化效率。
实施例2
使用PhenixSystemsPX系列激光烧结机械，由氧化铝制备了图2的十二面体框架结构。采用平均尺寸为约10微米的未改性的氧化铝粉末并在激光熔化之前在对各个新粉末层机械压缩的条件下使用约100微米的步长完成了构造。沿着由标准软件驱动的轨迹，使用300W的纤维激光器将氧化铝熔化。刚构造的该部件是易碎的并需要小心地从粉末床中移出、通过在高达约1800℃的温度下的构造后的烧结，可实现增加的强度。
实施例3
使用Z-Corp的3D印刷机和标准商购的结合介质，实现图3的氧化铝-氧化硅四面体形状的“3D-印刷”。使用例行加工条件，在100微米的步长下印刷约30微米中值粒径的粉末。在约8小时时间内使用缓慢升温将制得的原始结构焚烧至约1000℃以将粘合剂烧掉并在不损失整体性的条件下使得组分致密化(收缩)。在完成时，许多制造的3D形状的强度足以承受催化剂涂覆。

Claims (16)

1.用于内燃机废气的组分的选择性氧化或还原的催化剂整体或粒状成形单元，所述催化剂整体或粒状成形单元能够通过包括叠层法的方法获得，所述方法包括以下步骤：
(i)形成粉末状催化材料或粉末状催化剂载体材料的层；
(ii)根据预定图案使所述层中的所述粉末状催化材料或粉末状催化剂载体材料结合或熔合；
(iii)层压层地重复(i)和(ii)以形成整料或颗粒；以及
(iv)在所述整料或颗粒由粉末状催化剂载体材料形成时，将催化材料施加至所述催化剂载体材料，
其中所述粉末状催化材料或者在步骤(iv)中施加至所述整体或粒状的催化剂载体材料的所述催化材料包含一种或多种选自以下的金属或者含有选自以下的金属的金属化合物：Na、K、Mg、Ca、Ba、Al、Si、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Sn、Sb、La、Hf、W、Re、Ir、Pt、Au、Pb或Ce。
2.根据权利要求1所述的催化剂整体或粒状成形单元，其中所述粉末状催化材料包含贵金属催化剂粉末，所述贵金属催化剂粉末包含Pt、Pd、Ir、Ru或Re中的一种或多种。
3.根据权利要求1或2所述的催化剂整体或粒状成形单元，其中所述粉末状催化材料包含选自金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其混合物中的过渡金属化合物。
4.根据前述权利要求中任一项所述的催化剂整体或粒状成形单元，其中所述粉末状催化材料包含一种或多种惰性材料。
5.根据权利要求4所述的催化剂整体或粒状成形单元，其中所述一种或多种惰性材料选自氧化铝、二氧化硅、氮化硅、碳化硅、碳及其混合物。
6.根据权利要求1所述的催化剂整体或粒状成形单元，其中所述粉末状催化材料包含沸石。
7.根据权利要求1所述的催化剂整体或粒状成形单元，其中所述催化剂载体材料包含一种或多种惰性材料，所述惰性材料选自氧化铝、金属-铝酸盐、二氧化硅、铝硅酸盐、氮化硅、碳化硅、二氧化钛、碳、氧化锆、氧化锌及其任意两种或更多种的混合物。
8.根据权利要求7所述的催化剂整体或粒状成形单元，其中所述催化剂载体材料包含一种或多种过渡金属化合物，所述过渡金属化合物选自一种或多种金属氧化物、金属氢氧化物、金属碳酸盐、金属碱式碳酸盐或其任意两种或更多种的混合物。
9.根据权利要求1所述的催化剂整体或粒状成形单元，其中所述催化剂载体粉末包含沸石。
10.根据权利要求7、8或9所述的催化剂整体或粒状成形单元，其中在步骤(iv)中施加至所述催化剂成形单元的催化材料包含金属、金属化合物或沸石。
11.根据前述权利要求中任一项所述的催化剂整体或粒状成形单元，其中所述粉末状催化材料或粉末状催化剂载体材料具有1～200微米的平均颗粒尺寸D50。
12.根据前述权利要求中任一项所述的催化剂整体或粒状成形单元，其中该成形单元是蜂窝体整料。
13.制备根据前述权利要求中任一项所述的催化剂整体或粒状成形单元的方法，其中所述叠层法包括3D印刷、光固化快速成型或激光烧结技术。
14.根据权利要求13所述的方法，其中利用粘合剂将各个层中的粉末结合在一起。
15.根据权利要求13或14所述的方法，其中将所述整体或粒状成形单元经历加热步骤。
16.根据权利要求1-12中任一项所述的催化剂整体或粒状成形单元的用途，用于催化内燃机或发电站废气的选择性氧化或还原反应。
CN201510484676.7A 2010-09-08 2011-08-22 催化剂制造方法 Pending CN105107551A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB1014950.8 2010-09-08
GBGB1014950.8A GB201014950D0 (en) 2010-09-08 2010-09-08 Catalyst manufacturing method
CN201180043238.7A CN103118782B (zh) 2010-09-08 2011-08-22 催化剂制造方法

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201180043238.7A Division CN103118782B (zh) 2010-09-08 2011-08-22 催化剂制造方法

Publications (1)

Publication Number Publication Date
CN105107551A true CN105107551A (zh) 2015-12-02

Family

ID=43037523

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201510611136.0A Pending CN105195235A (zh) 2010-09-08 2011-08-22 催化剂制造方法
CN201180043238.7A Active CN103118782B (zh) 2010-09-08 2011-08-22 催化剂制造方法
CN201510484676.7A Pending CN105107551A (zh) 2010-09-08 2011-08-22 催化剂制造方法

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CN201510611136.0A Pending CN105195235A (zh) 2010-09-08 2011-08-22 催化剂制造方法
CN201180043238.7A Active CN103118782B (zh) 2010-09-08 2011-08-22 催化剂制造方法

Country Status (9)

Country Link
US (4) US9278338B2 (zh)
EP (2) EP2613879B2 (zh)
JP (2) JP2013537847A (zh)
CN (3) CN105195235A (zh)
AU (1) AU2011300512B2 (zh)
BR (1) BR112013004969A2 (zh)
GB (1) GB201014950D0 (zh)
RU (1) RU2598381C2 (zh)
WO (1) WO2012032325A1 (zh)

Families Citing this family (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201014950D0 (en) * 2010-09-08 2010-10-20 Johnson Matthey Plc Catalyst manufacturing method
FR2978682B1 (fr) * 2011-06-01 2016-01-01 Sicat Llc Procede catalytique pour la conversion d'un gaz de synthese en hydrocarbures
EP2716363A1 (en) * 2012-10-04 2014-04-09 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Optimized catalyst shape for steam methane reforming processes
CN103055934B (zh) * 2013-01-02 2015-03-04 北京化工大学 一种分解一氧化二氮的双金属负载分子筛催化剂的制备方法
US10189017B2 (en) 2013-01-25 2019-01-29 Yara International Asa Honeycomb monolith structure
CN103111322A (zh) * 2013-02-03 2013-05-22 北京化工大学 一种n2o分解用整体蜂窝状分子筛催化剂制备方法
GB2512355B (en) * 2013-03-27 2016-06-01 Warwick Tim Infused additive manufactured objects
DE102013205510A1 (de) 2013-03-27 2014-10-02 Matthias Fockele SLM-Filtersystem
FR3006606B1 (fr) * 2013-06-11 2015-07-03 Tech Avancees Et Membranes Industrielles Procede de fabrication de membranes de filtration par technique additive et membranes obtenues
RU2684908C2 (ru) * 2013-07-31 2019-04-16 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Катализатор разложения закиси азота
WO2015140250A1 (en) * 2014-03-21 2015-09-24 Shell Internationale Research Maatschappij B.V. Catalyst
CN105312074B (zh) * 2014-08-01 2017-11-24 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105289720B (zh) * 2014-08-01 2018-03-20 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105312078B (zh) * 2014-08-01 2017-11-28 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105312084B (zh) * 2014-08-01 2017-12-22 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105289682B (zh) * 2014-08-01 2017-12-22 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105289705B (zh) * 2014-08-01 2018-03-20 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105289706B (zh) * 2014-08-01 2018-03-20 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
FR3024664B1 (fr) * 2014-08-11 2020-05-08 Technologies Avancees Et Membranes Industrielles Nouvelles geometries d'elements tubulaires multicanaux de separation par flux tangentiel integrant des promoteurs de turbulences et procede de fabrication
FR3024665B1 (fr) * 2014-08-11 2020-05-08 Technologies Avancees Et Membranes Industrielles Element de separation par flux tangentiel integrant des obstacles a la circulation et procede de fabrication
FR3024663B1 (fr) * 2014-08-11 2020-05-08 Technologies Avancees Et Membranes Industrielles Nouvelles geometries d'elements tubulaires monocanaux de separation par flux tangentiel integrant des promoteurs de turbulences et procede de fabrication
CN105435832B (zh) * 2014-09-17 2018-07-31 中国石油化工股份有限公司 一种加氢处理催化剂及其应用
AU2015347232B2 (en) 2014-11-11 2018-02-01 Exxonmobil Upstream Research Company High capacity structures and monoliths via paste imprinting
TWI534131B (zh) 2014-11-27 2016-05-21 財團法人工業技術研究院 氫化４，４’－二胺基二苯甲烷的觸媒與方法
EP3233276A1 (en) * 2014-12-19 2017-10-25 Johnson Matthey Public Limited Company Catalyst manufacturing method
CN105854917B (zh) * 2015-01-22 2017-08-22 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105854929B (zh) * 2015-01-22 2017-09-29 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
CN105854930B (zh) * 2015-01-22 2017-08-22 中国石油化工股份有限公司 一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法
JP6304099B2 (ja) * 2015-03-27 2018-04-04 トヨタ自動車株式会社 排ガス浄化触媒及びその製造方法
GB201506325D0 (en) * 2015-04-14 2015-05-27 Johnson Matthey Plc Shaped catalyst particle
RU2722157C1 (ru) 2015-07-22 2020-05-27 Басф Корпорейшн Катализаторы с высокой геометрической площадью поверхности для получения винилацетатного мономера
JP6488216B2 (ja) * 2015-09-11 2019-03-20 日本碍子株式会社 ハニカム構造体の製造方法、ハニカム構造体の製造装置及びハニカム構造体
KR20180083911A (ko) 2015-11-16 2018-07-23 엑손모빌 업스트림 리서치 캄파니 흡착재 및 이산화탄소의 흡착 방법
JP6885611B2 (ja) 2015-12-18 2021-06-16 ユニバーシティ オブ カンタベリー 分離媒体
DE102016000435A1 (de) * 2016-01-18 2017-07-20 Audi Ag Substanz zum Herstellen eines Bauteils
CN108883358B (zh) 2016-03-18 2021-06-08 埃克森美孚上游研究公司 用于与其相关的变吸附工艺的装置和系统
NO341465B1 (en) 2016-05-03 2017-11-20 Sintef Tto As Method for manufacturing a porous foam support, and porous foam supports for catalytic reactors, adsorption processes and energy storage
RU2702545C1 (ru) 2016-05-31 2019-10-08 Эксонмобил Апстрим Рисерч Компани Устройство и система для осуществления процессов циклической адсорбции
EP3463620A1 (en) 2016-05-31 2019-04-10 ExxonMobil Upstream Research Company Apparatus and system for swing adsorption processes
CN106247159B (zh) * 2016-08-02 2019-01-18 西安铂力特增材技术股份有限公司 一种用于金属3d打印的镂空单元体和具有该单元体的零件
CN106311109A (zh) * 2016-08-26 2017-01-11 江苏大学 一种嵌入式中空磁性印迹光催化纳米反应器及其制备方法
US10434458B2 (en) 2016-08-31 2019-10-08 Exxonmobil Upstream Research Company Apparatus and system for swing adsorption processes related thereto
SG11201900842QA (en) 2016-09-01 2019-03-28 Exxonmobil Upstream Res Co Swing adsorption processes for removing water using 3a zeolite structures
NL2017453B1 (en) * 2016-09-13 2018-03-20 Stichting Energieonderzoek Centrum Nederland Method for additive manufacturing of a 3D structure
EP3512619A1 (en) 2016-09-13 2019-07-24 Stichting Energieonderzoek Centrum Nederland Method for additive manufacturing of a 3d structure
US10537883B2 (en) 2016-10-07 2020-01-21 King Fahd University Of Petroleum And Minerals Method for producing a hydrodesulfurization catalyst
CN106541129B (zh) * 2016-11-08 2019-05-14 西安铂力特增材技术股份有限公司 一种颗粒增强金属基复合材料的制备方法
AU2017379684B2 (en) * 2016-12-21 2020-03-12 Exxonmobil Upstream Research Company Self-supporting structures having active materials
EP3558490B1 (en) 2016-12-21 2022-06-29 ExxonMobil Upstream Research Company Self-supporting structures having foam-geometry structure and active materials
CN106694884B (zh) * 2016-12-29 2020-02-21 西安铂力特增材技术股份有限公司 一种具有梯度功能性的镂空点阵夹层及其制造方法
WO2018213111A1 (en) * 2017-05-17 2018-11-22 Exxonmobil Research And Engineering Company A method of preparing an activated catalytic metal component
CN107115763B (zh) * 2017-05-25 2020-11-13 广西壮族自治区环境保护科学研究院 一种吸收vocs材料的制备方法
WO2019008232A1 (en) 2017-07-05 2019-01-10 Weeefiner Oy POROUS BODY, MANUFACTURING METHOD THEREOF AND USE THEREOF FOR COLLECTING SUBSTANCE FROM SOURCE MATERIAL
EP3466648A1 (de) 2017-10-09 2019-04-10 Basf Se Verfahren zur herstellung von katalysatorformkörpern durch mikroextrusion
WO2019147516A1 (en) 2018-01-24 2019-08-01 Exxonmobil Upstream Research Company Apparatus and system for temperature swing adsorption
CN108115136B (zh) * 2018-02-01 2019-07-09 东北大学 一种k417g高温合金粉末及其制备方法和使用方法
US11413567B2 (en) 2018-02-28 2022-08-16 Exxonmobil Upstream Research Company Apparatus and system for swing adsorption processes
WO2019177614A1 (en) 2018-03-15 2019-09-19 Hewlett-Packard Development Company, L.P. Composition
RU2706222C2 (ru) * 2018-04-09 2019-11-15 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) Способ получения композитных каркасных материалов (варианты)
JP7035780B2 (ja) * 2018-05-08 2022-03-15 トヨタ自動車株式会社 触媒構造体
EP3574993A1 (en) 2018-05-29 2019-12-04 Basf Se Method for producing transition alumina catalyst monoliths
EP3613505A1 (de) 2018-08-24 2020-02-26 Basf Se Verfahren zur mikroextrusion von formkörpern durch mehrere mikroextrusionsdüsen
AT16307U3 (de) * 2018-11-19 2019-12-15 Plansee Se Additiv gefertigtes Refraktärmetallbauteil, additives Fertigungsverfahren und Pulver
FI20186003A1 (en) * 2018-11-26 2020-05-27 Weeefiner Oy Porous piece, process for its preparation and its use for catalysis
RU2715184C1 (ru) * 2018-11-30 2020-02-25 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) Способ получения сорбентов
US11318410B2 (en) 2018-12-21 2022-05-03 Exxonmobil Upstream Research Company Flow modulation systems, apparatus, and methods for cyclical swing adsorption
RU2734425C2 (ru) * 2019-03-21 2020-10-16 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Способ получения каталитических материалов методом 3D-печати
KR102216179B1 (ko) * 2019-04-22 2021-02-16 한국화학연구원 촉매구조체 제조용 3d 프린팅 잉크 조성물 및 이를 이용한 촉매구조체의 제조방법
WO2020222932A1 (en) 2019-04-30 2020-11-05 Exxonmobil Upstream Research Company Rapid cycle adsorbent bed
CN110142060B (zh) * 2019-06-13 2022-06-28 国家能源投资集团有限责任公司 碳化硅/氮化硅载体及其制备方法、费托合成催化剂及其制备方法和应用
US20200398456A1 (en) * 2019-06-24 2020-12-24 The Curators Of The University Of Missouri Additively-manufactured structure for reactionary processes
GB201909269D0 (en) * 2019-06-27 2019-08-14 Johnson Matthey Plc Layered sorbent structures
US11655910B2 (en) 2019-10-07 2023-05-23 ExxonMobil Technology and Engineering Company Adsorption processes and systems utilizing step lift control of hydraulically actuated poppet valves
WO2021076594A1 (en) 2019-10-16 2021-04-22 Exxonmobil Upstream Research Company Dehydration processes utilizing cationic zeolite rho
EP3812154B1 (de) 2019-10-21 2023-05-17 Heraeus Deutschland GmbH & Co. KG Verfahren zur herstellung eines katalysatorsystems für gasreaktionen
CN110901046B (zh) * 2019-12-10 2021-03-30 厦门大学 一种基于3d打印技术的仿生结构整体型催化剂的制备方法
CN111266123B (zh) * 2019-12-31 2023-03-10 南京环福新材料科技有限公司 一种净化用多功能催化剂及其制备方法和应用
RU2730485C1 (ru) * 2020-01-30 2020-08-24 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) Способ получения пористого каталитически активного материала
WO2021212110A1 (en) 2020-04-17 2021-10-21 Eagle Engineered Solutions, Inc. Powder spreading apparatus and system
DE102020112372A1 (de) 2020-05-07 2021-11-11 Clariant International Ltd Verfahren zur herstellung von katalysatoren mit 3d-drucktechnik
CN112519283B (zh) * 2020-11-21 2022-12-06 西安热工研究院有限公司 一种熔融沉积成型3d打印脱汞袋笼及其制备方法
GB202019905D0 (en) 2020-12-16 2021-01-27 Johnson Matthey Plc Carbon dioxide sorbent
WO2023122170A1 (en) * 2021-12-21 2023-06-29 Firehawk Aerospace, Inc. Catalytic decomposition reactors
DE102022203604A1 (de) 2022-04-11 2023-10-12 Siemens Energy Global GmbH & Co. KG Pulver, keramische Wand, Reaktionskammer sowie Verfahren
CN115957751A (zh) * 2022-09-08 2023-04-14 厦门大学 一种基于激光烧结制备多孔反应载体板的方法及其应用
CN115414933B (zh) * 2022-09-30 2024-01-30 重庆市生态环境科学研究院 一种贵金属负载型催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552663A (zh) * 2003-12-19 2004-12-08 上海交通大学 液相强化烧结制备金属陶瓷增强的碳复合材料的方法
CN101524647A (zh) * 2007-10-19 2009-09-09 北京化工大学 用于甲烷氧化偶联制低碳烃的金属基整体式催化剂及其制备方法
US20100222209A1 (en) * 2007-10-08 2010-09-02 Basf Se Use of shaped bodies having catalytic properties as reactor internals

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS521920B2 (zh) * 1973-11-12 1977-01-18
US5204055A (en) * 1989-12-08 1993-04-20 Massachusetts Institute Of Technology Three-dimensional printing techniques
AU5588194A (en) * 1993-10-27 1995-05-22 Scientific Dimensions Usa, Inc. Open cell foam structures, catalysts supported thereby and method of producing the same
GB9405934D0 (en) * 1994-03-25 1994-05-11 Johnson Matthey Plc Coated article
IT1282267B1 (it) * 1995-03-14 1998-03-16 Montecatini Tecnologie Srl Catalizzatori e supporti per catalizzatori ottenuti per pastigliatura
US6130182A (en) * 1997-07-25 2000-10-10 International Business Machines Corporation Dielectric catalyst structures
US6193832B1 (en) * 1997-07-25 2001-02-27 International Business Machines Corporation Method of making dielectric catalyst structures
CA2304339C (en) † 1997-09-26 2007-04-03 Massachusetts Institute Of Technology Metal and ceramic containing parts produced from powder using binders derived from salt
DE10223796C1 (de) * 2002-05-29 2003-07-10 Univ Clausthal Tech Aus Elementen zusammengesetzte Struktur und Verfahren zu seiner Herstellung
UA82110C2 (uk) 2003-06-13 2008-03-11 Яра Интернешнл Аса Спосіб одержання каталізаторів на підкладці
FR2856614B1 (fr) 2003-06-30 2006-08-11 Phenix Systems Dispositif de realisation de couches minces de poudre notamment a hautes temperatures lors d'un procede base sur l'action d'un laser sur de la matiere
DE10357951A1 (de) * 2003-12-11 2005-07-07 Emitec Gesellschaft Für Emissionstechnologie Mbh Wabenkörper mit mindestens einem platzsparenden Messfühler, sowie entsprechende Lambdasonde
TW201236755A (en) † 2003-12-19 2012-09-16 Celanese Int Corp Halide free precursors for catalysts
GB0405015D0 (en) * 2004-03-05 2004-04-07 Johnson Matthey Plc Method of loading a monolith with catalyst and/or washcoat
WO2006009453A1 (en) 2004-07-19 2006-01-26 Yara International Asa Catalyst packing, a structured fixed bed reactor and use
JP2007014936A (ja) * 2005-01-07 2007-01-25 Kri Inc 微小構造体の製造方法およびマイクロリアクター
US7393511B2 (en) † 2005-02-16 2008-07-01 Basf Catalysts Llc Ammonia oxidation catalyst for the coal fired utilities
GB0715164D0 (en) * 2007-08-06 2007-09-12 Airbus Uk Ltd Method and apparatus for manufacturing a composite material
GB2457651A (en) * 2008-01-23 2009-08-26 Johnson Matthey Plc Catalysed wall-flow filter
DE102008030186A1 (de) 2008-06-26 2009-12-31 Siemens Aktiengesellschaft Verfahren zum Erzeugen eines Bauteils durch selektives Laserschmelzen sowie hierfür geeignete Prozesskammer
EP2150035A1 (en) † 2008-07-28 2010-02-03 Alcatel, Lucent Method for communicating, a related system for communicating and a related transforming part
GB0816703D0 (en) * 2008-09-12 2008-10-22 Johnson Matthey Plc Shaped heterogeneous catalysts
GB0816705D0 (en) 2008-09-12 2008-10-22 Johnson Matthey Plc Shaped heterogeneous catalysts
GB201014950D0 (en) * 2010-09-08 2010-10-20 Johnson Matthey Plc Catalyst manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552663A (zh) * 2003-12-19 2004-12-08 上海交通大学 液相强化烧结制备金属陶瓷增强的碳复合材料的方法
US20100222209A1 (en) * 2007-10-08 2010-09-02 Basf Se Use of shaped bodies having catalytic properties as reactor internals
CN101524647A (zh) * 2007-10-19 2009-09-09 北京化工大学 用于甲烷氧化偶联制低碳烃的金属基整体式催化剂及其制备方法

Also Published As

Publication number Publication date
US9272264B2 (en) 2016-03-01
EP2752244A1 (en) 2014-07-09
JP2017029981A (ja) 2017-02-09
US20130230721A1 (en) 2013-09-05
CN103118782B (zh) 2015-11-25
BR112013004969A2 (pt) 2016-08-16
JP6389490B2 (ja) 2018-09-12
EP2613879B2 (en) 2024-02-14
US9839907B2 (en) 2017-12-12
GB201014950D0 (en) 2010-10-20
RU2013115444A (ru) 2014-10-20
US20150360207A1 (en) 2015-12-17
JP2013537847A (ja) 2013-10-07
RU2016134735A (ru) 2018-12-11
RU2598381C2 (ru) 2016-09-27
AU2011300512B2 (en) 2017-02-02
EP2752244B1 (en) 2021-01-27
US20160136634A1 (en) 2016-05-19
AU2011300512A1 (en) 2013-05-02
CN105195235A (zh) 2015-12-30
WO2012032325A1 (en) 2012-03-15
US9278338B2 (en) 2016-03-08
EP2613879A1 (en) 2013-07-17
RU2016134735A3 (zh) 2019-12-04
US20170189897A1 (en) 2017-07-06
EP2613879B1 (en) 2021-01-27
CN103118782A (zh) 2013-05-22

Similar Documents

Publication Publication Date Title
CN103118782B (zh) 催化剂制造方法
US10843174B2 (en) Catalyst manufacturing method
RU2701190C2 (ru) Частица катализатора определенной формы
EP3721997B1 (en) Process for producing a catalyst
CN110023054A (zh) 制造催化剂整料的方法
JP2017537786A5 (zh)
RU2774626C2 (ru) Способ изготовления катализатора

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20151202

RJ01 Rejection of invention patent application after publication