Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D1/00—Casings; Linings; Walls; Roofs
  • F27D1/0003—Linings or walls
  • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
• • 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
  • C04B35/12—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 chromium oxide
• • 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
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
  • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/74—Construction of shells or jackets
• • 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
  • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
  • C04B2235/3206—Magnesium oxides 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
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
  • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
• • 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
  • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• • 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
  • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
  • C04B2235/3225—Yttrium oxide 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
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
  • C04B2235/3227—Lanthanum oxide 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
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
  • C04B2235/3229—Cerium oxides 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
  • C04B2235/32—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
  • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
• • 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
  • C04B2235/32—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
  • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
• • 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
  • C04B2235/349—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
  • C04B2235/02—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
  • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
  • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
• • 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
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
• • 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
• • 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
  • C04B2235/74—Physical characteristics
  • C04B2235/76—Crystal structural characteristics, e.g. symmetry
  • C04B2235/762—Cubic symmetry, e.g. beta-SiC
• • 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
  • C04B2235/74—Physical characteristics
  • C04B2235/77—Density
• • 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
  • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
  • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
  • C04B2235/9692—Acid, alkali or halogen resistance
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2200/00—Details of gasification apparatus
  • C10J2200/09—Mechanical details of gasifiers not otherwise provided for, e.g. sealing means

Definitions

• the invention concerns a gasifier reactor internal coating.
• reactors with fixed, fluidized or driven beds. These reactors differ in the mode of introduction of the reactants, the manner in which the fuel and the oxidizer are mixed, the temperature and pressure conditions, and the method of evacuating liquid residual slag or ash resulting from the reaction.
• the gasifier is coated with various layers of refractory products capable of withstanding the conditions of temperature, pressure and chemical environment to which they are subjected during gasification.
• the layers of refractory products thus protect the metal interior wall of the gasifier from heat and from corrosion by gases and slag.
• the refractory product at the hot face is more particularly subjected to erosion and chemical attack by ash or slag, which leads to the infiltration of compounds from the liquefied ash or slag into the pores of the refractory product. As a result of erosion and thermal cycling, this infiltration can cause spalling of the coating, and finally to shutting down of the reactor.
• the object of the invention is to satisfy this requirement.
• the above object is achieved by means of a gasifier internal refractory coating having at least one region of a sintered material containing at least 45% by weight of chromium oxide (Cr 2 O 3 ) and at least 1 %, preferably at least 2 %, and more preferably at least 3 %, by weight of zirconium oxide (ZrO 2 ), at least 20%, preferably at least 30 %, by weight of said zirconium oxide (ZrO 2 ) being stabilized in the cubic and/or quadratic form.
• chromium oxide Cr 2 O 3
• ZrO 2 zirconium oxide
• the presence of at least 1% zirconium oxide of which at least 20% by weight is stabilized in the cubic and/or quadratic form reduces infiltration and attack by slag without degrading the other functional properties of the coating.
• Said coating material of the invention preferably has one or more of the following optional features:
• At least 60% of the zirconium oxide is stabilized in the cubic and/or quadratic form.
• Said material contains at least one dopant, stabilizing or not stabilizing the zirconium oxide, selected from CaO, MgO, Y 2 O 3 and TiO 2 , the preferred dopant being CaO.
• the content of calcium oxide (CaO) of said material is preferably less than 1.0 % by weight.
• the dopant preferably stabilizes the zirconium oxide, at least in part.
• zirconium oxide (ZrO 2 ) is greater than 4.5%, preferably greater than 6% by weight, and/or less than 7% by weight.
• chromium oxide (Cr 2 O 3 ) is greater than 60% by weight and preferably greater than 80% by weight.
• - Said material has an aluminum oxide (AI 2 O 3 ) content greater than 1% by weight, preferably greater than 2% by weight, and/or less than 10% by weight, preferably less than 5% by weight, preferably less than 3.5% by weight.
• - Said material has a silica content greater than 0.5% by weight, preferably greater than 1% by weight, and/or less than 3% by weight, preferably less than 1.5% by weight.
• the sum of the contents of oxides of chromium (Cr 2 O 3 ), zirconium (ZrO 2 ), aluminum (AI 2 O 3 ), silicon (SiO 2 ) and calcium (CaO) is greater than 95%, preferably greater than 98%, by weight, the other constituents of the product being impurities.
• the impurities conventionally comprise iron essentially in the form of Fe 2 O 3 and oxides of alkali metals such as Na 2 O and K 2 O. Such contents of impurities are not considered to call into question the advantages obtained from using the material.
• the structure of the material features a granulate of chromium oxide bound by a matrix comprising grains including zirconium oxide and a dopant selected from
• the dopant stabilizing or not stabilizing the zirconium oxide, the percentage of zirconium oxide contained in said grains being greater than 1 %, preferably greater than 2.5%, by weight relative to the weight of the material.
• the dopant content in the grains containing zirconium oxide and a dopant is preferably from 1 % to 8% by weight relative to the weight of said grains.
• the material takes the form of a layer applied to the interior wall of a reactor of the gasifier or of an assembly of blocks arranged to protect said wall.
• the whole of the layer or all the blocks of the assembly preferably consist(s) of a material such as that defined hereinabove. In the present description, all percentages are percentages by weight unless otherwise indicated.
• composition of the slags in gasifiers typically consists of SiO 2 , FeO or
• a coating must be adapted to the corrosive conditions that it encounters.
• materials conforming to the invention include the materials described by Wang Zhe as ineffective for waste incineration furnaces. Surprisingly, the inventors have discovered that these materials are effective in an application to a gasifier coating.
• applications such as glassmaking furnaces or iron and steel furnaces, as described in the patent EP 0 404 610, for example, there are known in the art products consisting of zirconium oxide and chromium oxide. These products contain zirconium oxide in a proportion from 1 % to 9% by weight relative to the total composition.
• zirconium oxide it is essential that at least 80% of the zirconium oxide be in the monoclinic form, monoclinic zirconium being described as the "key ingredient" for improving resistance to thermal shocks.
• the inventors have discovered that, in the application to a gasifier coating, the presence of zirconium oxide stabilized to at least 20% is, on the contrary, advantageous.
• Zirconium oxide can be stabilized by means of a stabilizing dopant and/or by heat treatment at very high temperature (typically greater than 1700 0 C). According to the invention at least 20% by weight of the zirconium oxide is stabilized in the cubic and/or quadratic form.
• a dopant selected from CaO, MgO, Y 2 O 3 and TiO 2 , acting or not acting as a stabilizer, is preferably present in the coating material of the invention.
• the refractory coating material of the invention consists of one or more granulates, i.e. particles having a particle size greater than 150 ⁇ m, surrounded by a binder matrix.
• the granulates may have diverse chemical compositions, in particular they can consist of chromium oxide, the total content of chromium oxide of the material being at least 45% by weight.
• the binder matrix comprises grains, i.e. particles having a particle size less than 150 ⁇ m, including zirconium oxide and a dopant.
• the zirconium oxide alone present in these grains preferably represents more than 2.5% of the total weight of the material.
• the dopant may have the function of stabilizing the zirconium oxide or not.
• the binder matrix may further comprise other grains, in particular grains of zirconium oxide with no dopant.
• the coating of the invention may be fabricated in the form of a layer obtained from a non-worked product or in the form of an assembly of refractory blocks.
• a base mixture is prepared of particles of chromium oxide and zirconia, and possibly other oxides, in proportions determined as a function of the composition of the required material.
• the dopant may be added to the mixture and/or be included with the zirconia, as a stabilizer.
• Forming additives may be added to facilitate use, preferably in a proportion of less than 7%.
• the manner of determining the proportions of the constituents of the base mixture is well known to the person skilled in the art.
• the person skilled in the art knows that the chromium, aluminum and zirconium oxides present in the base mixture are found in the sintered refractory material. Certain oxides of this material can also be introduced by the additives.
• the composition of the base mixture may therefore vary, in particular as a function of the quantities and the nature of the additives present.
• the chromium oxide may be added in the form of a mixture of sintered or fused chromium oxide particles.
• the aluminum oxide may be added in the form of a mixture of calcined or reactive particles of alumina, or even of white corundum.
• the zirconium oxide may be added in the form of commercially available unstabilized zirconia and/or in the form of stabilized zirconia, for example zirconia from Unitec, in powder form.
• a powder is made up of particles of which 90% by weight have a particle size less than 150 ⁇ m.
• the base mixture preferably includes at least 0.2% by weight of stabilized zirconia powder.
• the base mixture preferably includes:
• the base mixture is preferably homogenized and conditioned.
• a mixture of this kind is advantageously ready for use and may be applied to the interior wall of the reactor, for example by casting, vibrocasting or spraying, as a function of requirements and with great flexibility, and then sintered in situ during preheating of the reactor, to produce a refractory coating of the invention. Sintering occurs at atmospheric pressure, in an oxidizing atmosphere and at a temperature from 1300 0 C to 1600 0 C.
• a fabrication method may be used that includes the following successive steps: a) preparing a charge, b) forming said charge in a mold, c) casting said charge in the mold or compacting the charge by vibration and/or pressing and/or pounding of said charge in the mold to form a preform, d) removing the preform from the mold, e) drying said preform, preferably in air or a moisture-controlled atmosphere, and preferably so that the residual moisture content of the preform is from 0 to 0.5%, f) firing said preform in an oxidizing atmosphere at a temperature from
• the charge includes oxides determined as a function of the final composition of the block, precursors thereof and temporary forming additives.
• the steps a) to f) are steps conventionally employed in the art to fabricate sintered products.
• step a) the manner of determining the quantities of the constituents of the refractory product is well known to the person skilled in the art.
• the person skilled in the art knows that the chromium, aluminum and zirconium oxides present in the starting charge are found in the fabricated refractory product. Certain oxides may also be introduced by the additives.
• the composition of the starting charge may therefore vary, in particular as a function of the quantities and the nature of the additives present in the charge.
• the additives may be added to the starting charge to ensure that it is sufficiently plasticized during the step b) of forming it and to confer sufficient mechanical strength on the preform obtained at the end of the steps d) and e).
• Non- limiting examples of additives that may be used are: - organic temporary binders (i.e. binders that are eliminated wholly or in part during drying and firing steps), such as resins, derivatives of cellulose or lignone, polyvinyl alcohols; the quantity of temporary binder is preferably from 0.1% to 6% by weight relative to the weight of the particular mixture of the charge;
• - forming agents such as stearates of magnesium or calcium
• - hydraulic binders such as CaO aluminate cement
• - deflocculating agents such as alkaline polyphosphates or methacrylate derivatives
• the above additives introduce alumina and silica and a few oxides of alkali or alkaline-earth metals, even iron oxide, depending on the type of clay.
• the charge is formed and disposed in a mold.
• step c) in the case of forming by pressing, a specific pressure of 400 to 800 kg/cm 2 is appropriate. Pressing is preferably effected uniaxially or isostatically, for example by means of a hydraulic press. It may advantageously be preceded by an operation of manual or pneumatic ramming and/or of vibration.
• the drying of the step e) may be effected at a moderately high temperature. It is preferably effected at a temperature from 110 0 C to 200 0 C. It conventionally takes from ten hours to one week, depending on the format of the preform, continuing until the residual moisture content of the preform is less than 0.5%. The dried preform is then fired (step f)).
• the firing time from approximately three days to approximately 15 days from cold to cold, varies as a function of the materials but also as a function of the size and the shape of the parts.
• the firing cycle is preferably effected in the conventional manner, in air, at a temperature from 1300°C to 1600°C.
• the fashioned refractory product obtained at the end of the step f) has proved particularly resistant to the stresses encountered inside gasifier reactors, in particular to infiltration by fused ash or slag.
• the process steps a) to e) described above are used, but at least part of the firing step f) is effected after assembling the blocks in the reactor.
• the blocks are assembled by means of appropriate expansion joints, using techniques well known to the person skilled in the art.
• (D50) is less than 2 microns, calcined or micronized alumina powder with a median diameter of 5 microns, monoclinic zirconia powder from ZIRPRO having the characteristics set out in table 1 below (powder P1 ), - additives: magnesium or calcium stearates, temporary binders (derivatives of cellulose or lignone), chemical binders (phosphoric acid, derivatives of aluminum monophosphate), stabilized zirconia powder from UNITEC, with the characteristics set out in table 1 below (powder P2), clay with a content of alumina >30%.
• a the raw materials were mixed and 3% water added. This was followed by the process steps: b) forming the charge in a mold, c) compacting the charge in the mold at a pressure of 600 kg/cm 2 to form a preform, d) removing the preform from the mold, e) drying the preform, in air, to obtain a residual moisture content of the material less than or equal to 0.5%, f) firing said preform in an oxidizing atmosphere at a temperature from 1400 0 C to 1600 0 C to form a fashioned refractory product.
• the contents of aluminum, chromium, silicon and calcium oxides in the sintered final product were calculated from the chemical composition of the raw materials used for the starting charge.
• microstructure of the products of the invention shows that they consist of a granulate of chromium oxide surrounded by a binder matrix that contains, for the products 2 to 5, grains of ZrO 2 -CaO.
• Microprobe analysis identifies the content of the elements of the grains of ZrO 2 -CaO coming from the powder P1 or P2.
• the density and open porosity were measured on the products before any corrosion had occurred and in accordance with the standard ISO 5017.
• SiO 2 approximately 30-50%
• Fe 2 O 3 Or FeO: 15-25%
• CaO approximately 10-20%
• the base index B of this slag i.e. the (CaO + MgO + Fe 2 O 3 ) / (SiO 2 + AI 2 O 3 ) mass ratio, was typically of the order of 0.6.
• the CaO/SiO 2 mass ratio was of the order of 0.4.
• the corrosion indicator is equal to the following ratio: loss of section of the sample of the product tested at the atmosphere /slag triple point loss of section of the reference sample at the atmosphere /slag triple point
• the corrosion indicator is therefore 100 for the reference product and a value lower than 100 indicates better corrosion resistance than the reference product.
• the depth of penetration of the CaO of the slag was measured by means of a microprobe on a metallographic section.
• the coating of the invention may be subjected in service to high stresses following thermal shocks, the inventors also measured the change in the modulus of rupture in bending of the products subjected to a thermal shock.
• Composition No. 1 is the reference composition.
• Table 2 indicates that: o
• the presence of more than 0.5% silicon oxide is not harmful to corrosion resistance.
• the presence of aluminum oxide may be favorable to resistance to calcium oxide infiltration, as is indicated by comparing compositions 2 and 3.
• the calcium oxide added in particular by the source of the zirconia is not particularly harmful to the required properties.
• the products of the invention have better corrosion resistance than the reference product.
• Composition 3 offers the best compromise for the required properties and is preferred over all the others.
• the coating of the invention advantageously reduces infiltration and attack by the slags encountered in gasifier reactors, without other functional properties thereof being degraded.
• the invention also concerns a reactor, in particular a gasifier, comprising an interior wall on which a layer is applied, or an interior wall protected by an assembly of blocks, said layer or said blocks having at least one region of a sintered material containing : i) at least 25% by weight of chromium oxide Cr 2 O 3 ; and ii) at least 1% by weight of zirconium oxide, wherein at least 20% by weight of said zirconium oxide ZrO 2 is stabilized in the cubic and/or quadratic form.
• this reactor in particular gasifier, is designated as a reactor "according to the new developments".
• the sintered material of a reactor according to the new developments may have one or several of the characteristics of the "sintered material of the gasifier internal refractory coating which is described here above" (i.e. already described in the original US patent application No. 11/166,275).
• the silica SiC> 2 content is less than 9.5%, less than 9 %, less than 8 %, less than 6 %, less than 5 %, or less than 4.5 % by weight.
• the zirconium oxide ZrC> 2 content is less than 25 %, less than 20 %, less than
• At least 70%, at least 95 %, at least 90 %, at least 95 %, or even substantially 100 % of said zirconium oxide is stabilized in the cubic and/or quadratic form.
• the chromium oxide Cr 2 O 3 content is more than 30%, more than 35%, more than 40%, more than 45%, more than 50%, more than 65%, more than 70%, more than 75%, or even more than 85%, by weight.
• the structure of the material features a granulate bound by a matrix.
• the granulate may comprise chromium oxide, ZrO 2 , AI 2 O 3 , in particular corundum, AI 2 O 3 -ZrO 2 -SiO 2 , AI 3 O 3 -ZrO 2 -SiO 2 -Cr 2 O 3 particles, or mixture of said particles.
• the content of Cr 2 O 3 in the granulate may be 15 % or more, or 20 % or more, on the basis of the oxides of the sintered material (granulate + matrix).
• the content of Cr 2 O 3 in the matrix may be 10 % or more, or 15% or more, on the basis of the oxides of the sintered material.
• the sintered material of a reactor according to the new developments may have lower chromium oxide Cr 2 O 3 content.
• the difference in the chromium oxide Cr 2 O 3 content may be compensated by alumina, in particular corundum and/or zirconia and/or silica and/or magnesia and/or spinel and/or, more generally, crystallographic forms containing the element Aluminum.
• the choice of the substitute to the chromium oxide may depend on the intended application and in particular on the desired refractoriness.
• the total content of AI 2 O 3 + ZrO 2 may be more than 5 %, more than 20 %, more than 30 %, more than 35 %, and/or less than 70 %, less than 60 %, or less than 50 %, in percentages by weight on the basis of the oxides.
• Said layer or said blocks may be fabricated according to the method described here above used in order to fabricate a gasifier internal refractory coating of the invention, provided that the starting charge is adapted, according to the conventional practice.
• the starting charge contains more than 3%, preferably more than 5 %, and/or less than 15%, preferably less than 10% of clay, in percentages on the basis of the wet starting charge.
• the clay may be ball clay for instance or bentonite, or other natural aluminosilicates or even artificial aluminosilicates.
• the invention also concerns a sintered material containing: at least 25% by weight of chromium oxide Cr 2 O 3 ;and at least 0.5% by weight and less than 9.5% of silica SiO 2 ; and at least 1% by weight of zirconium oxide, at least 20% by weight of said zirconium oxide ZrO 2 being stabilized in the cubic and/or quadratic form.
• this sintered material is designated as a "sintered material according to the further new developments".
• silica may confer to a sintered material according to the further new developments good resistance to corrosion, in particular in the environment encountered in gasifiers, and very good mechanical properties.
• Said sintered material contains more than 30%, more than 35%, more than
• chromium oxide Cr 2 O 3 40%, more than 45%, more than 50%, and/or less than 70%, less than 60%, less than 55%, by weight, of chromium oxide Cr 2 O 3 .
• a chromium oxide Cr 2 O 3 content of about 53% by weight is very well adapted.
• Said sintered material contains more than 3%, more than 4%, more than 5%, and/or less than 9%, less than 8%, less than 7%, less than 6%, by weight, of silica SiO 2 .
• a silica SiO 2 content of about 5.5% by weight is very well adapted.
• the total content of AI 2 O 3 + ZrO 2 may be more than 5 %, more than 20 %, more than 30 %, more than 35 %, and/or less than 70 %, less than 60 %, or less than 50 %, in percentages by weight on the basis of the oxides.
• Said sintered material contains more than 10%, more than 12%, more than 15%, more than 17%, more than 19%, and/or less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, or less than 22%, by weight, of aluminum oxide AI 2 O 3 .
• Said sintered material contains more than 10%, more than 12%, more than
• zirconium oxide ZrO 2 15%, more than 17%, more than 19%, and/or less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, or less than 22%, by weight, of zirconium oxide ZrO 2 .
• said zirconium oxide ZrO 2 is stabilized in the cubic and/or quadratic form.
• Said sintered material contains at least one dopant, stabilizing or not stabilizing the zirconium oxide, selected from CaO, MgO, Y 2 O 3 , TiO 2 , and rare earth oxides like CeO 2 , Er 2 O 3 , La 2 O 3 , the preferred dopant being CaO.
• the content of calcium oxide (CaO) is preferably less than 1.0 % by weight.
• the dopant preferably stabilizes the zirconium oxide, at least in part.
• the sum of the contents of oxides of chromium (Cr 2 O 3 ), zirconium (ZrO 2 ), aluminum (AI 2 O 3 ), silicon (SiO 2 ) and calcium (CaO) is greater than 95%, preferably greater than 98%, preferably greater than 99%, by weight, the other constituents being preferably impurities.
• the impurities conventionally comprise iron essentially in the form of Fe 2 O 3 and oxides of alkali metals such as Na 2 O and K 2 O, in particular when clay is introduced in the starting charge. Such contents of impurities are not considered to call into question the advantages obtained from using the sintered material.
• the structure of the material features a granulate bound by a matrix.
• the granulate may comprise chromium oxide, ZrO 2 , AI 2 O 3 , in particular corundum, AI 2 O 3 -ZrO 2 -SiO 2 , AI 3 O 3 -ZrO 2 -SiO 2 -Cr 2 O 3 particles, or mixture of said particles.
• the content of Cr 2 O 3 in the granulate may be 15 % or more, or 20 % or more, on the basis of the oxides of the sintered material (granulate + matrix).
• the content of Cr 2 O 3 in the matrix may be 10 % or more, or 15 % or more, on the basis of the oxides of the sintered material.
• the structure of the material features a granulate of chromium oxide bound by a matrix comprising grains including zirconium oxide and a dopant selected from CaO, MgO, Y2O3, TiO 2 , and rare earth oxides like CeO 2 , Er 2 O 3 , La 2 O 3 , the dopant, stabilizing or not stabilizing the zirconium oxide, the percentage of zirconium oxide contained in said grains being greater than 1%, preferably greater than 2.5%, by weight relative to the weight of the material.
• the dopant content in the grains containing zirconium oxide and a dopant is preferably from 1% to 8% by weight relative to the weight of said grains.
• the material takes the form of a layer applied to the interior wall of a reactor, in particular of the gasifier, or of an assembly of blocks arranged to protect said wall.
• the whole of the layer or all the blocks of the assembly preferably consist(s) of a sintered material according to the further new developments.
• the sintered material according to the further new developments may be fabricated according to the method described here above used in order to fabricate a gasifier internal refractory coating of the invention, provided that the starting charge is adapted, according to the conventional practice, so as to obtain this sintered material.
• the starting charge contains between more than 3%, preferably more than 5 %, and/or less than 15%, preferably less than 10% of clay, more preferably less than 7% in percentages on the basis of the wet starting charge.
• the clay may be ball clay for instance or bentonite, or other natural aluminosilicates or even artificial aluminosilicates.
• the invention also concerns a reactor, and in particular a gasifier, comprising an interior wall on which a layer is applied, or an interior wall protected by an assembly of blocks, said layer or said blocks having at least one region of a sintered material according to the further new developments of the invention.
• a reactor and in particular a gasifier, comprising an interior wall on which a layer is applied, or an interior wall protected by an assembly of blocks, said layer or said blocks having at least one region of a sintered material according to the further new developments of the invention.
• particulate mixture of particles ER2161 said particles mainly being composed of chromium, aluminum and zirconium oxides, sold by SEPR (France) with the following average composition : AI 2 O 3 : 28%, ZrO 2 : 27%, Cr 2 O 3 : 27%, SiO 2 : 15%, impurities : complement to 100%.
• This mixture comprises at least 90% by weight of particles having a size greater than 20 microns and less than 20 mm; particulate mixture of particles ER1681 , said particles mainly being composed of aluminum, zirconium and silicon oxides, sold by SEPR (France) with the following average composition : AI 2 O 3 : 51%, ZrO 2 : 32.5%, SiO 2 : 15%, impurities : complement to 100%.
• This mixture comprises at least 90% by weight of particles having a size greater than 20 microns and less than 20 mm; calcined alumina with a median diameter less than 150 ⁇ m.
• Examples 6 to 10 were fabricated and tested in the same way as examples 1 to 5.
• Table 3 also shows that products 7 and 9, comprising more than 3% of silica are preferable to products 6 and 8, respectively. Indeed, the products 7 and 9 of the invention may be compared to the products 6 and 8, respectively, which present similar chromium oxide contents and similar densities. Table 3 shows that the products 7 and 9 exhibit better resistance to corrosion, i.e. lower corrosion indicators. This is surprising since the products 7 and 9 have higher silica content than the products 6 and 8, respectively. Moreover, advantageously the products 7 and 9 exhibit a lower depth of
• the product 9 is preferred.
• example 10 A comparison of example 10 with example 7, presenting similar chromium oxide content, shows that silica content higher than 10% is detrimental to the corrosion resistance.
• the corrosion indicator and the depth of CaO infiltration of example 10 are significantly higher.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Organic Chemistry (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Oxide Ceramics (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=41349977

Family Applications (1)

Country Status (10)

Families Citing this family (9)

Citations (10)

Family Cites Families (7)

• 2008
  • 2008-07-02 US US12/167,074 patent/US8173564B2/en active Active
• 2009
  • 2009-07-02 RU RU2010154051/05A patent/RU2537621C2/ru active
  • 2009-07-02 KR KR1020117001165A patent/KR101644943B1/ko not_active Expired - Fee Related
  • 2009-07-02 JP JP2011515716A patent/JP2011526541A/ja active Pending
  • 2009-07-02 CN CN2009801259595A patent/CN102083527A/zh active Pending
  • 2009-07-02 BR BRPI0913861A patent/BRPI0913861B1/pt not_active IP Right Cessation
  • 2009-07-02 CA CA2729754A patent/CA2729754A1/en not_active Abandoned
  • 2009-07-02 EP EP09773015.4A patent/EP2307131B1/en not_active Not-in-force
  • 2009-07-02 WO PCT/IB2009/052884 patent/WO2010001355A1/en not_active Ceased
• 2011
  • 2011-01-03 ZA ZA2011/00039A patent/ZA201100039B/en unknown

Patent Citations (10)

Also Published As

Similar Documents

Legal Events