EP2512654A1 - Préparation de catalyseur palladium-or - Google Patents

Préparation de catalyseur palladium-or

Info

Publication number
EP2512654A1
EP2512654A1 EP10779908A EP10779908A EP2512654A1 EP 2512654 A1 EP2512654 A1 EP 2512654A1 EP 10779908 A EP10779908 A EP 10779908A EP 10779908 A EP10779908 A EP 10779908A EP 2512654 A1 EP2512654 A1 EP 2512654A1
Authority
EP
European Patent Office
Prior art keywords
extrudate
palladium
cellulose
titania
produce
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.)
Ceased
Application number
EP10779908A
Other languages
German (de)
English (en)
Inventor
Daniel Travis Shay
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.)
Lyondell Chemical Technology LP
Original Assignee
Lyondell Chemical Technology LP
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
Priority claimed from US12/653,563 external-priority patent/US8329611B2/en
Priority claimed from US12/653,592 external-priority patent/US8273682B2/en
Application filed by Lyondell Chemical Technology LP filed Critical Lyondell Chemical Technology LP
Publication of EP2512654A1 publication Critical patent/EP2512654A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • 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
    • B01J23/52—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
    • 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
    • B01J21/063—Titanium; 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
    • B01J23/38—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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—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
    • 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
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C04B24/383—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/28—Polysaccharides or derivatives thereof
    • C04B26/285—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00129—Extrudable mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6021—Extrusion moulding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C04B2235/721—Carbon content

Definitions

  • the invention relates to a method of preparing a palladium-gold catalyst containing a titania extrudate.
  • Palladium-gold catalysts are useful in the oxidation of ethylene or propylene in the presence of acetic acid to produce vinyl acetate or allyl acetate. Acetoxylation is commonly conducted in the vapor phase using a supported palladium-gold catalyst. Palladium-gold catalysts containing titania carriers are known (U.S. Pat. No. 6,022,823; U.S. Pat. Appl. Pub. Nos. 2008/0146721 and 2008/0281 122; copending application serial number 1 1/801 ,935 filed May 1 1 , 2007). Acetoxylation is preferably conducted in a fixed-bed reactor.
  • titania is produced as a fine powder. To prepare catalysts suitable for fixed-bed reactions, it is necessary to form titania powder into particles, such as spheres, tablets, extrudates, and the like. Despite many efforts in developing methods for producing titania extrudates in the past, many are not suitable for commercial production because of their poor processibility. Therefore, there is a continued need to develop new processes for making titania extrudates that can be used as carriers for palladium-gold catalysts (see, e.g., co-pending application Docket No. 01-2767A [serial number has not yet been assigned] filed on December 16, 2009).
  • the invention is a method for preparing a palladium-gold catalyst.
  • the method comprises (a) mixing titania, a carboxyalkyl cellulose, and a hydroxyalkyl cellulose to form a dough; (b) extruding the dough to produce an extrudate; (c) calcining the extrudate to produce a calcined extrudate; (d) impregnating the calcined extrudate with a palladium compound and a gold compound to produce an impregnated extrudate; and (e) calcining the impregnated extrudate to produce the palladium-gold catalyst.
  • the invention also includes a process for producing vinyl
  • I acetate comprising reacting ethylene, oxygen, and acetic acid in the presence of a palladium-gold catalyst.
  • the invention is a method for preparing a palladium-gold catalyst containing a titania carrier.
  • the method comprises mixing titania, a carboxyalkyi cellulose, and a hydroxyalkyl cellulose to form a dough.
  • Suitable titanias can be rutile, anatase, brookite, or a mixture of them.
  • the titania is an anatase.
  • Titanias may be produced by the chloride process, the sulfate process, the hydrothermal process, or the flame hydrolysis of titanium tetrachloride.
  • suitable titanias include TiONA® DT-51 , DT-52, DT-51 D, DT-40, and DT-20 of Millennium Inorganic Chemicals.
  • the functional properties of carboxyalkyi celluloses depend on the degree of substitution of the cellulose structure (i.e., how many of the hydroxy! groups are substituted), as well as the chain length of the cellulose backbone and the degree of clustering of the substituents.
  • the average number of substituted hydroxyl groups per glucose unit in cellulose derivatives is referred to as the degree of substitution (DS).
  • DS degree of substitution
  • a carboxymethyl celluloses is used.
  • Preferred carboxymethyl celluloses have a degree of substitution of 0.5 to 0.9 (D. B. Braun and M. R. Rosen, Rheoloav Modifiers Handbook: Practical Use and Applications (2000) William Andrew Publishing, pp. 109-131 ).
  • Carboxymethyl celluloses are known as extrusion aids (U.S. Pat. Nos. 5,884,138 and 6,709,570; U.S. Pat. Appl. Pub. No. 2008/0146721 ).
  • Carboxyalkyl cellulose, R H, alkyl
  • the method also uses a hydroxyalkyl cellulose.
  • a hydroxyalkyl cellulose is a derivative of cellulose in which some of the hydroxyl groups in the repeating glucose units are hydroxyalkylated. Some of the hydroxyl groups in a hydroxyalkyl cellulose may also be alkylated.
  • the hydroxyalkyl group is selected from the group consisting of 2- hydroxyethyl, 2-hydroxypropyl, and mixtures thereof. More preferably the hydroxyalkyl cellulose is alkylated. Most preferably, the hydroxyalkyl cellulose is selected from the group consisting of methyl 2-hydroxyethyl cellulose, methyl 2- hydroxypropyl cellulose, and mixtures thereof. Preferably, the degree of methyl substitution is from 1 to 2, more preferably from 1.5 to 1.8; and the 2-hydroxyethyl or 2-hydroxypropyl molar substitution is from 0.1 to 0.3.
  • METHOCELTM K4M cellulose derivative a product of Dow Chemical Company and having a methyl substitution of 1.4 and a hydroxypropyl molar substitution of 0.21 , is preferably used.
  • Hydroxyalkyi celluloses are known as extrusion aids (U.S. Pat. Nos. 5,884,138, 6,316,383, and 6,709,570).
  • the weight ratio of the carboxyalkyi cellulose to the titania is preferably from
  • the weight ratio of the hydroxyalkyi cellulose to the titania is preferably from 0.1 :100 to 2.5:100, more preferably from 0.2:100 to 2:100, most preferably from 0.5:100 to 1 :100.
  • the weight ratio of the carboxyalkyi cellulose to the hydroxyalkyi cellulose is preferably from 5:1 to 1 :2, more preferably from 3:1 to 1 :1.
  • the method comprises mixing titania, the carboxyalkyi cellulose, and the hydroxyalkyi cellulose to form a dough.
  • a solvent may be used. Suitable solvents include water, alcohols, ethers, esters, amides, aromatic compounds, halogenated compounds, and the like, and mixtures thereof. Preferred solvents are water and alcohols.
  • a titania sol may be used as a source of the titania.
  • a titania sol is a colloidal suspension of titania particles in a liquid.
  • a titania sol can be prepared by hydrolyzing a titania precursor. Suitable titania precursors include titanium salts, titanium halides, titanium alkoxides, titanium oxyhalides, and the like.
  • the method comprises extruding the dough to produce an extrudate by an operation called extrusion.
  • Extrusion is a process in which a dough is pushed through a die or an orifice to create long objects of a fixed cross-section. Extrusion is commonly used to process plastics or food, and to form adsorbents, catalysts, or catalyst carriers. Any conventional extruder may be used. A suitable screw-type extruder is described in "Particle Size Enlargement," Handbook of Powder Technology, vol. 1 (1980) pp. 112-22.
  • the carboxyalkyi cellulose and the hydroxyalkyi cellulose are used as extrusion aids.
  • An extrusion aid helps the mixing, mulling, and extruding operation and may improve the mechanical and/or physical properties of the extrudate such as crushing strength, surface area, pore size, or pore volume.
  • the extrudate comprising titania, the carboxyalkyi cellulose and the hydroxyalkyi cellulose has a smooth outer surface. They do not tend to stick to each other while being formed, dried, and calcined, which is suitable for large scale production.
  • extrusion aids may be used to form the dough.
  • suitable extrusion aids include alkyl amines, carboxylic acids, alkyl ammonium compounds, amino alcohols, starch, polyacrylates, polymethacrylates, poly( vinyl alcohol)s, poly(vinylpyrrolidone)s, po!y(amino acid)s, polyethers, poly(tetrahydrofuran)s, metal carboxylates, and the like, and mixtures thereof.
  • Preferred poly(alkylene oxide)s are poly(ethylene oxide)s, poly( ropylene oxide)s, or copolymers of ethylene oxide and propylene oxide.
  • Organic extrusion aids are usually removed by calcination.
  • the extrudate is optionally dried after it is formed.
  • the drying operation removes at least a portion of the solvents from the extrudate.
  • the drying operation may be performed at 30 to 200°C at atmospheric pressure or under vacuum.
  • the drying may occur in air or an inert atmosphere. Sometimes, it is preferable to raise the drying temperature slowly so the extrudate will not be cracked or weakened.
  • the method comprises calcining the extrudate to produce a calcined extrudate.
  • the calcination is carried out in an oxygen-containing gas to burn off the organic materials (e.g., residual solvent and extrusion aids) contained in the extrudate.
  • the calcination may be carried out at 400 to 1000°C, more preferably from 450 to 800°C, most preferably from 650 to 750°C.
  • a calcined extrudate after the calcination contains less than 0.5 wt% carbon. Preferably, it contains less than 0.1 wt% carbon.
  • the method comprises impregnating the calcined extrudate with a palladium compound and a gold compound to produce an impregnated extrudate.
  • Suitable palladium compounds include palladium chloride, sodium chloropalladate, palladium nitrate, palladium sulfate, the like, and mixtures thereof.
  • Suitable gold compounds include auric chloride, tetrachloroauric acid, sodium tetrachloroaurate, the like, and mixtures thereof.
  • the impregnated extrudate may comprise from 0.1 wt% to 3 wt% of palladium and from 0.1 wt% to 3 wt% of gold and has a weight ratio of palladium to gold within the range of 5:1 to 1 :3. More preferably, the impregnated extrudate comprises 0.5 wt% to 1.5 wt% of palladium and 0.25 wt% to 0.75 wt% of gold.
  • a fixing agent may preferably be added to the extrudate while it is being impregnated. Fixing agents help to bind the palladium compound and the gold compound to the extrudate. Suitable fixing agents include alkali metal, alkaline earth metal, or ammonium compounds, for example, their hydroxides, carbonates, bicarbonates, metasilicates, and the like, and mixtures thereof.
  • the impregnation method can be used to produce the impregnated extrudate.
  • the calcined extrudate may be simultaneously or successively impregnated with the palladium compound, the gold compound, and optionally a fixing agent.
  • it is impregnated with aqueous solutions although other impregnating solvents may be used.
  • the impregnated extrudate is preferably washed with water or other solvents to remove any halide (e.g., chloride) from the extrudate.
  • halide e.g., chloride
  • the method optionally comprises drying the impregnated extrudate.
  • the impregnated extrudate can be dried at 50 to 150°C at atmospheric pressure or under vacuum, primarily to remove at least a portion of the solvents.
  • the drying may occur in air or an inert gas at atmospheric pressure or under vaccum. Sometimes, it is important to raise the drying temperature slowly to prevent the extrudate from losing its mechanical strength.
  • the method comprises calcining the impregnated extrudate, preferably after it is dried first, to produce the palladium-gold catalyst.
  • the calcination of the impregnated extrudate occurs at an elevated temperature in a non-reducing atmosphere.
  • the calcination of the impregnated extrudate is carried out at a temperature of 150 to 600°C.
  • Suitable non-reducing gases used for the calcination include inert or oxidizing gases such as helium, nitrogen, argon, neon, oxygen, air, carbon dioxide, the like, and mixtures thereof.
  • the calcination is carried out in an atmosphere of nitrogen, oxygen, or air, or mixtures thereof.
  • the palladium-gold catalyst obtained from the calcination step is preferably chemically reduced to generate a reduced palladium-gold catalyst.
  • the reduction is usually performed by contacting the palladium-gold catalyst with a reducing agent.
  • Suitable reducing agents include hydrogen, carbon monoxide, hydrocarbons, olefins, aldehydes, alcohols, hydrazine, the like, and mixtures thereof. Hydrogen, ethylene, propylene, alkaline hydrazine and alkaline formaldehyde are preferred reducing agents and ethylene and hydrogen are particularly preferred.
  • Temperatures employed for the reduction can range from 20 to 700°C.
  • hydrogen is the reducing agent
  • a gas mixture containing hydrogen and another gas such as argon, helium, nitrogen, or the like, is usually used.
  • the reduction temperature with hydrogen is preferably in the range of 300 to 700°C, more preferably in the range of 450 to 550°C.
  • the pailadium-gold catalyst prepared according to the invention can be used for the acetoxylation of an olefin, such as ethylene or propylene, to produce an acetoxylated olefin such as vinyl acetate or allyl acetate.
  • a promoted palladium-gold catalyst which can be produced by adding an activator to the reduced palladium-gold catalyst, is used in the acetoxylation reaction.
  • An activator is an alkali or alkaline earth metal compound, examples of which are hydroxides, acetates, nitrates, carbonates, and bicarbonates of potassium, sodium, cesium, magnesium, barium, and the like. Potassium salts are preferred activators.
  • the activator content may be in the range of 0 to 15 wt%, preferably 1.5 to 10 wt% of the catalyst.
  • the invention also include a process for preparing vinyl acetate, comprising reacting a feed comprising ethylene, oxygen, and acetic acid in the presence of the palladium-gold catalyst, preferably in the presence of the reduced palladium-gold catalyst, more preferably in the presence of the promoted palladium-gold catalyst.
  • the feed typically comprise 20 to 70 mol% ethylene, 2 to 8 mol% oxygen, and 2 to 20 mol% acetic acid.
  • the feed may comprise a diluent.
  • suitable diluents inciude propane, nitrogen, helium, argon, carbon dioxide, the like, and mixtures thereof.
  • the reaction is generally performed at a temperature in the range of 100 to 250°C, preferably 125 to 200°C and under a pressure of 15 to 500 psig.
  • the dough produced is placed in the hopper of a Bonnot 2-inch extruder (The Bonnot Company) equipped with a die face of 25 holes with a diameter of 1/8 inch.
  • the extrusion is performed at a rate of approximately 0.25 kg/mi n.
  • the extrudates produced have smooth outer surface and there is minimal sticking each other occuring. Almost no feathering is observed.
  • the extrudates are piled 1 inch deep on a collection tray and dried in air at
  • the calcination temperature is raised from room temperature to 500°C at a rate of 2°C/min, held at 500°C for 2 h, raised from 500°C to 700°C at a rate of 10°C/min, held at 700°C for 3 h, then lowered to room temperature.
  • the crush strength of the calcined titania extrudate is measured with a Chatillon crush strength analyzer (Model DPP 50). The force necessary for failure in 25 measurements is averaged to give the reported value.
  • Bulk density is measured by placing 40 g of the calcined extrudates in a 100-mL graduated cylinder ( ⁇ nominal outer diameter). The graduated cylinder is tapped until the apparent volume no longer changes, and then this value is divided into the mass to calculate the bulk density.
  • Void age is determined by adding the pellets to 50 mL water in a second graduated cylinder and then tapping until all voids are filled. The resulting water level is subtracted from the total volume of the water and the pellets taken separately to determine the void volume occupied by water.
  • Total pore volume is determined by pouring the mixture through a sieve basket, shaking to remove excess water and then weighing the wet extrudates. The increase in mass over the initial 40 g of extrudates divided by the density of water is taken as the measure of the pore volume.
  • Example 2 The procedure of Example 1 is repeated with the formulation shown in Table 1. The extrudates are droopy as they exit the die face of the extruder and tend to stick to each other as they lay on the collection tray. COMPARATIVE EXAMPLE 3
  • Example 1 The procedure of Example 1 is repeated with the formulation shown in Table 1.
  • the extrudates are droopy as they exit the die face of the extruder and tend to stick to each other as they lay on the collection tray.
  • Example 2 The procedure of Example 1 is repeated, except that the formulation is as follows: DT-51 (2000 g), TAMOLTM 1124 dispersant (a hydrophilic polyelectrolyte copolymer from The Dow Chemical Company, 32.6 g), METHOCELTM K4M cellulose derivative (54.6 g), lactic acid (6 g), water (950 g), aqueous ammonium hydroxide (14.8 M, 70 g).
  • TAMOLTM 1124 dispersant a hydrophilic polyelectrolyte copolymer from The Dow Chemical Company, 32.6 g
  • METHOCELTM K4M cellulose derivative 54.6 g
  • lactic acid (6 g)
  • water 950 g
  • aqueous ammonium hydroxide 14.8 M, 70 g
  • Example 4 The procedure of Example 4 is repeated, except that alumina (DISPERAL® P2, available from Sasol, 20 g) is used.
  • alumina DISPERAL® P2, available from Sasol, 20 g
  • the extrudates are droopy as they exit the die face of the extruder and tend to stick to each other as they lay on a metal tray.
  • the calcined extrudate contains 1 wt% alumina and 99 wt% titania. Table 2
  • Example 1 The procedure of Example 1 is repeated, except that the formulation is as follows: DT51 (300 g), TAMOLTM 1 124 dispersant (5 g), WALOCELTM C cellulose (6 g), METHOCELTM K4M cellulose derivative (6 g), lactic acid (4.5 g), water (155 g), and aqueous ammonium hydroxide (14.8 M, 11 g).
  • the extrudates have smooth outer surface. Minimal feathering is observed. Almost no extrudate is observed to stick to others.
  • Example 6 The procedure of Example 6 is repeated, except that the formulation is shown in Table 3. The extrudates slump upon exiting the die. They stick to each other on the collection tray.
  • Example 6 The procedure of Example 6 is repeated, except that the formulation is shown in Table 3.
  • the extrudates do not tend to stick to each other after laying the on the collection tray. However, they appear to be feathering. Table 3
  • NaHCOa powder (27 g) is slowly added to an aqueous solution containing Na 2 PdCV3H 2 0 (31.4 g), NaAuCI 4 '2H 2 0 (11.3 g), and water (235.4 g). The mixture is stirred at room temperature for 10 min. The solution is sprayed with a pipette on calcined titania extrudates prepared in Example 1 (1000 g) while they are being tumbled in a rotating flask. Once the impregnation is finished, the rotating flask is heated to about 100°C with a heat gun. The impregnated extrudates are tumbled for another 30 min at 100°C, then placed in an oven at 80°C for 2 h before they are cooled to room temperature.
  • the dried extrudates are washed with warm water (50-80°C) until no chloride can be detected by mixing the wash filtrate solution with a 1 wt% silver nitrate solution to observe precipitation.
  • the catalyst is dried at 80 to 100°C to remove water. Then they are heated at 230°C for 3 h in air, and at 230°C for 30 min under a nitrogen flow. The temperature is raised to 500°C under a flow of 10 mol% hydrogen in nitrogen gas, and held for 3 h before it is cooled to room temperature.
  • the extrudates are washed with an aqueous solution containing 10 wt% potassium acetate and 1 wt% potassium hydroxide (10 L).
  • the washed extrudates are dried under nitrogen at 125°C for 2 h.
  • a palladium-gold catalyst is obtained. It contains 0.93 wt% Pd, 0.54 wt% Au, and 1.5 wt% K.
  • the palladium-gold catalyst prepared in Example 9 is tested for vinyl acetate production in a fixed-bed reactor (stainless steel, 1 inch O.D.).
  • the reactor is charged with a mixture of the catalyst (10 g) and an inert alpha alumina cylindrical pellets (1/8" in diameter, surface area 4 m 2 /g, pore volume 0.25 mUg, 25 g).
  • the feed contains 46.1 mol% helium, 33.9 mo!% ethylene, 11.48 mol% acetic acid, 4.2 mol% oxygen, and 4.2 mol% nitrogen.
  • the reactor pressure is 80 psig and the space velocity relative to the volume of the catalyst is 3050 h "1 at standard temperature and pressure.
  • the reactor is cooled using a fluidized sand bath, the temperature of which is set at 130°C.
  • the product stream is analyzed by gas chromatography (GC).
  • Oxygen conversion, oxygen selectivity, oxygen yield to vinyl acetate, and ethylene selectivity to vinyl acetate between 75 to 100 h on stream are calculated from the GC results and listed in Table 4.
  • Oxygen conversion is calculated by dividing the amount of oxygen consumed by the total amount of oxygen fed to the reactor.
  • Oxygen selectivity to vinyl acetate is the amount of oxygen consumed in making vinyl acetate divided by the total amount of oxygen consumed.
  • Oxygen yield to vinyl acetate is the product of oxygen conversion multiplied by oxygen selectivity.
  • Ethylene selectivity to vinyl acetate is the amount of ethylene consumed in making vinyl acetate divided by the total amount of ethylene consumed.
  • Catalyst productivity is the grams of vinyl acetate produced per liter of the catalyst per hour.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
  • Formation And Processing Of Food Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)

Abstract

La présente invention concerne un procédé pour préparer un catalyseur palladium-or contenant un extrudat de dioxyde de titane. L'extrudat de dioxyde de titane est produit en utilisant une carboxyalkylcellulose et une hydroxyalkylcellulose en tant qu'adjuvants d'extrusion. L'extrudat de dioxyde de titane a une aptitude au traitement et/ou des propriétés mécaniques améliorées. Après calcination, l'extrudat est utilisé en tant que support pour le catalyseur palladium-or. Le catalyseur est utile dans la production d'acétate de vinyle par oxydation d'éthylène avec de l'oxygène en présence d'acide acétique.
EP10779908A 2009-12-16 2010-11-19 Préparation de catalyseur palladium-or Ceased EP2512654A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/653,563 US8329611B2 (en) 2009-12-16 2009-12-16 Titania-containing extrudate
US12/653,592 US8273682B2 (en) 2009-12-16 2009-12-16 Preparation of palladium-gold catalyst
PCT/US2010/057373 WO2011075278A1 (fr) 2009-12-16 2010-11-19 Préparation de catalyseur palladium-or

Publications (1)

Publication Number Publication Date
EP2512654A1 true EP2512654A1 (fr) 2012-10-24

Family

ID=43466619

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10779908A Ceased EP2512654A1 (fr) 2009-12-16 2010-11-19 Préparation de catalyseur palladium-or
EP10787215A Ceased EP2512655A1 (fr) 2009-12-16 2010-11-19 Extrudat contenant du dioxyde de titane

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP10787215A Ceased EP2512655A1 (fr) 2009-12-16 2010-11-19 Extrudat contenant du dioxyde de titane

Country Status (8)

Country Link
EP (2) EP2512654A1 (fr)
JP (2) JP2013514174A (fr)
KR (2) KR20120102080A (fr)
CN (2) CN102740964A (fr)
BR (2) BR112012014795A2 (fr)
SG (4) SG181647A1 (fr)
TW (2) TW201129455A (fr)
WO (2) WO2011075277A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2512654A1 (fr) * 2009-12-16 2012-10-24 Lyondell Chemical Technology, L.P. Préparation de catalyseur palladium-or
US8273682B2 (en) 2009-12-16 2012-09-25 Lyondell Chemical Technology, L.P. Preparation of palladium-gold catalyst
US8329611B2 (en) 2009-12-16 2012-12-11 Lyondell Chemical Technology, L,P. Titania-containing extrudate
US8507720B2 (en) 2010-01-29 2013-08-13 Lyondell Chemical Technology, L.P. Titania-alumina supported palladium catalyst
EP2703078A1 (fr) * 2012-09-03 2014-03-05 Saudi Basic Industries Corporation Photocatalyseur comprenant un alliage or-palladium, procédé de préparation, système de photolyse
US20140081040A1 (en) * 2012-09-20 2014-03-20 Lyondell Chemical Technology, L.P. Process for pre-treatment of a catalyst support and catalyst prepared therefrom
KR101964275B1 (ko) 2015-09-01 2019-04-01 주식회사 엘지화학 아크릴산 제조용 촉매 제조방법 및 이로부터 제조되는 촉매
US11452995B2 (en) 2017-12-20 2022-09-27 Basf Se Catalyst and process for preparing dimethyl ether
CN112517065B (zh) * 2019-09-18 2023-05-02 中国石油化工股份有限公司 乙烯气相法醋酸乙烯工艺催化剂制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040127746A1 (en) * 2001-03-27 2004-07-01 Masahide Kondo Catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, method of preparing same, and method of synthesizing unsaturated aldehyde and unsaturated carboxylic acid with the catalyst

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8028A (en) * 1851-04-08 Hokse-poweb
US4366259A (en) * 1981-10-29 1982-12-28 Texaco, Inc. Production of acetic acid and propionic acid and their esters
US4551295A (en) * 1984-04-26 1985-11-05 Corning Glass Works Process for mixing and extruding ceramic materials
DE4012479A1 (de) * 1990-04-19 1991-10-24 Degussa Titandioxidpresslinge, verfahren zu ihrer herstellung sowie ihre verwendung
US5582670A (en) * 1992-08-11 1996-12-10 E. Khashoggi Industries Methods for the manufacture of sheets having a highly inorganically filled organic polymer matrix
GB9305066D0 (en) * 1993-03-12 1993-04-28 British American Tobacco Co Improvements relating to filtration materials
JP3833731B2 (ja) * 1995-01-20 2006-10-18 触媒化成工業株式会社 アンモニアの分解方法
US5710089A (en) * 1995-06-07 1998-01-20 Phillips Petroleum Company Sorbent compositions
US6022823A (en) 1995-11-07 2000-02-08 Millennium Petrochemicals, Inc. Process for the production of supported palladium-gold catalysts
US5884138A (en) 1996-06-10 1999-03-16 Corning Incorporated Method for improving the stiffness of extrudates
JP3636912B2 (ja) * 1997-12-25 2005-04-06 株式会社日本触媒 エチレンオキシド製造用触媒の製造方法
DE19828491A1 (de) 1998-06-26 1999-12-30 Degussa Formkörper auf Basis von Siliciumdioxid
US6709570B1 (en) 1999-09-27 2004-03-23 Shell Oil Company Method for preparing a catalyst
EP1205493A1 (fr) * 2000-11-14 2002-05-15 ATOFINA Research Systèmes catalytiques pour la polymérisation et leur préparation
US6797669B2 (en) * 2000-12-29 2004-09-28 China Petroleum & Chemical Corporation Catalyst for selective hydrogenation, its preparation process and application
DE10163180A1 (de) * 2001-12-21 2003-07-10 Degussa Trägerkatalysator
US6677261B1 (en) * 2002-07-31 2004-01-13 Corning Incorporated Alumina-bound high strength ceramic honeycombs
US8227369B2 (en) * 2005-05-25 2012-07-24 Celanese International Corp. Layered composition and processes for preparing and using the composition
US8168562B2 (en) * 2006-02-02 2012-05-01 Lyondell Chemical Technology, L.P. Preparation of palladium-gold catalysts
DE102006022866A1 (de) * 2006-05-16 2007-11-22 Glatt Systemtechnik Gmbh Kohlenstoff-Granulat, Verfahren zu dessen Herstellung und dessen Verwendung
DE102006058800A1 (de) * 2006-12-13 2008-06-19 Wacker Chemie Ag Verfahren zur Herstellung von Katalysatoren und deren Verwendung für die Gasphasenoxidation von Olefinen
US7825204B2 (en) 2006-12-19 2010-11-02 Lyondell Chemical Technology, L.P. Inorganic oxide extrudates
US7563740B2 (en) * 2006-12-19 2009-07-21 Lyondell Chemical Technology, L.P. Direct epoxidation process
US7811968B2 (en) * 2007-05-11 2010-10-12 Lyondell Chemical Technology, L.P. Preparation of palladium-gold catalysts
US20090274866A1 (en) * 2008-04-30 2009-11-05 Michelle Dawn Fabian Ceramic article and method for making it
CN100594978C (zh) * 2008-08-22 2010-03-24 中国石化扬子石油化工有限公司 用于对羧基苯甲醛加氢过程的Pd/TiO2催化剂的制备方法
CN101474580B (zh) * 2009-02-13 2014-04-23 江苏龙源催化剂有限公司 一种用于负载高粉尘烟气条件下催化剂的载体及其制备方法
CN101513620A (zh) * 2009-04-07 2009-08-26 南京大学 一种二氧化钛基催化剂载体的制备方法
EP2512654A1 (fr) * 2009-12-16 2012-10-24 Lyondell Chemical Technology, L.P. Préparation de catalyseur palladium-or

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040127746A1 (en) * 2001-03-27 2004-07-01 Masahide Kondo Catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, method of preparing same, and method of synthesizing unsaturated aldehyde and unsaturated carboxylic acid with the catalyst

Also Published As

Publication number Publication date
BR112012014795A2 (pt) 2016-06-21
BR112012014697A2 (pt) 2016-04-12
JP2013514175A (ja) 2013-04-25
WO2011075277A1 (fr) 2011-06-23
KR20120102080A (ko) 2012-09-17
SG181640A1 (en) 2012-07-30
TW201129455A (en) 2011-09-01
EP2512655A1 (fr) 2012-10-24
CN102740964A (zh) 2012-10-17
WO2011075278A1 (fr) 2011-06-23
JP2013514174A (ja) 2013-04-25
TW201129642A (en) 2011-09-01
SG188923A1 (en) 2013-04-30
KR20120102079A (ko) 2012-09-17
SG181647A1 (en) 2012-07-30
CN102725063A (zh) 2012-10-10
SG189707A1 (en) 2013-05-31

Similar Documents

Publication Publication Date Title
US20110190533A1 (en) Titania-alumina supported palladium catalyst
WO2011075278A1 (fr) Préparation de catalyseur palladium-or
US8501984B2 (en) Preparation of palladium-gold catalyst
KR100658383B1 (ko) 에틸렌과 아세트산의 비닐 아세테이트로의 기상 산화용 촉매 및 이의 제조방법
US7811968B2 (en) Preparation of palladium-gold catalysts
US8513152B2 (en) Titania-containing extrudate
CN108472626A (zh) 多孔成型金属-碳产品
JP2000093797A (ja) ビニルモノマ―の製造用担持触媒、その製造方法及びその使用
JP2000000473A (ja) 酢酸ビニルの製造における触媒およびその使用
US20110306748A1 (en) Titania-alumina-tungsta extrudate and its use
EP2544815B1 (fr) Procédé de production d'acétate de vinyl en présence d'un catalyseur au palladium ayant un support à base de titane et d'alumine.
CN102753265B (zh) 二氧化钛-氧化铝负载钯催化剂
CN112517065B (zh) 乙烯气相法醋酸乙烯工艺催化剂制备方法
JP4507247B2 (ja) α，β−不飽和アルデヒド及び／またはα，β−不飽和カルボン酸製造用触媒、その製造方法及びその使用法
CN114177938A (zh) 醋酸乙烯催化剂及其应用
JP2005224657A (ja) パラジウム含有担持触媒及びその製造方法、並びに、α，β−不飽和カルボン酸の製造方法
CN114425444A (zh) 乙烯法合成醋酸乙烯催化剂及其制备方法
JP2006075819A (ja) α，β−不飽和カルボン酸製造用触媒及びその製造方法、並びに、α，β−不飽和カルボン酸の製造方法
JP2009297634A (ja) 貴金属含有触媒、その製造方法、およびα，β−不飽和カルボン酸の製造方法
JP2009136836A (ja) パラジウム含有触媒およびその製造方法、並びに、α，β−不飽和カルボン酸の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120613

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130902

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20150919