WO2012062913A1 - Matériau de revêtement pour installations de gazéification constitué d'un matériau céramique oxyde résistant à la corrosion par les alcalis et aux changements de température, exempt d'oxyde de chrome et de carbone et son utilisation - Google Patents

Matériau de revêtement pour installations de gazéification constitué d'un matériau céramique oxyde résistant à la corrosion par les alcalis et aux changements de température, exempt d'oxyde de chrome et de carbone et son utilisation Download PDF

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Publication number
WO2012062913A1
WO2012062913A1 PCT/EP2011/069964 EP2011069964W WO2012062913A1 WO 2012062913 A1 WO2012062913 A1 WO 2012062913A1 EP 2011069964 W EP2011069964 W EP 2011069964W WO 2012062913 A1 WO2012062913 A1 WO 2012062913A1
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WIPO (PCT)
Prior art keywords
oxide
lining material
reducing conditions
mass
lining
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PCT/EP2011/069964
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German (de)
English (en)
Inventor
Christos G. Aneziris
Bernd Meyer
Patrick Gehre
Claudia Wenzel
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Technische Universität Bergakademie Freiberg
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Priority to DE112011103740T priority Critical patent/DE112011103740A5/de
Publication of WO2012062913A1 publication Critical patent/WO2012062913A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/135—Combustion residues, e.g. fly ash, incineration waste
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
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    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0058—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity open porosity
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M5/00—Casings; Linings; Walls
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    • 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
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • 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
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    • 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
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    • 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
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
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    • 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
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    • 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
    • C04B2235/652—Reduction treatment
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    • 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
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    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6587—Influencing the atmosphere by vaporising a solid material, e.g. by using a burying of sacrificial powder
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    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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    • 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
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    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M2900/00—Special features of, or arrangements for combustion chambers
    • F23M2900/05004—Special materials for walls or lining
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Definitions

  • Lining material for gasification plants consisting of an alkaline corrosion resistant and temperature change resistant chromoxide and carbon-free oxide ceramic material and its use
  • the invention relates to a lining material for gasification plants, which consists of an alkali corrosion resistant and temperature change resistant chromium oxide and carbon-free oxide ceramic material based on Al 2 0 3 .
  • the material is used as a lining material in gasification plants, in which under reducing conditions, and high temperatures and pressures from carbon carriers, eg. As brown coal, hard coal and petroleum coke, synthesis gas is produced.
  • the gasification temperatures are between 800 ° C and 1300 ° C (with temperature peaks of 1600 ° C).
  • the raw materials to be gasified may contain up to 50% by mass of inorganic constituents, which remain as ash during the gasification.
  • the gasifier compartment is usually lined with water-cooled refractory materials which protect the metallic carburettor shell throughout the process. If the gasification takes place above the melting temperature of the inorganic constituents of the carbon carriers, they melt and penetrate into the porous material as slag or flow down the refractory lining.
  • the refractory material Due to the extreme conditions in the gasifier room, the refractory material must meet a variety of requirements. In the gasification plants, the refractory material is exposed to a variety of extreme conditions, especially elevated temperatures and pressures, large and rapid temperature changes. It must be able to withstand erosion by particles and corrosion by molten ash (slag) as well as corrosion by hot process gases and variations in the chemical composition of the slag as a result of the changing composition of the starting material and changing oxidizing and reducing conditions.
  • slag molten ash
  • Conventional refractory ceramic carburettor linings may not be made of sintered / melt cast materials of alumina silica, high alumina Materials, co-existing chromium oxide, corundum magnesia spinel, corundum magnesia, chromium oxide corundum or silicon carbide.
  • the addition of at least 75% by weight of chromium oxide generally increases corrosion resistance [JP Bennett, "Refractory Liner Materials Used in Slagging Gasifiers", Journal of Refractories Application, Vol. 9 (2004), Iss. 5, pp. 20- 25].
  • Today Cr are mainly two 03-Al 2 03, Cr 2 03-Al 2 03-MgO used two 03-Zr02 and Cr materials and refractory lining in gasification plants, since they can withstand the extreme conditions of the gasification longest of all materials currently being tested.
  • a high-chromium oxide-containing material with improved corrosion resistance to coal slags is described in US Pat. No. 6,815,386.
  • the refractory material consists of a coarse graining and a binding matrix containing at least 60 Ma.% Chromium oxide and 1 -10 Ma.% Phosphate compounds. Further oxides, eg ZrO 2 and Al 2 O 3 , can be introduced into the binding matrix in order to improve the mechanical properties of the matrix.
  • the starting raw materials are mixed, shaped and cured at elevated temperatures and sintered.
  • the phosphate compounds react with chromium oxide and aluminum oxide to form chromium phosphate (CrPO 4 ) and aluminum phosphate (AIPO 4 ).
  • CrPO 4 chromium phosphate
  • AIPO 4 aluminum phosphate
  • I refer to a calcined chromium-containing refractory of high purity and low levels of soluble chromium.
  • the addition of titanium dioxide, boric acid, carbon black, silicon dioxide, zirconium dioxide and / or molybdenum oxide reduced the chromium solubility to ⁇ 5 ppm.
  • the patent application WO 2008/109222 likewise describes a refractory material with a chromium oxide content of> 60 Ma.% With improved resistance to slag infiltration.
  • the porosity of the pre-fired stones is 20-50%.
  • a suspension consisting of alumina, chromia, silica, rare earth oxides, titania, mullite, zirconia, zirconium silicate, yttria, magnesia, iron oxide and mixtures thereof is infiltrated into the open pores by infiltration (spraying, dipping, coating or vacuum ) introduced as protective material.
  • the refractory bricks are then treated at temperatures of 100-1000 ° C to remove the solvent.
  • DE 725 525 relates to the production of ref temperature-resistant refractory products (stones, ramming masses and mortar) from mixtures of chrome ore and magnesia. They are characterized in that chromium or magnesia in amounts of 30-70 Ma.% Mixed with a cellulose-containing slurry and a feinstgemahlenem mixture of manganese compounds with chromium or iron compounds or both, molded and fired at temperatures of> 1 400 ° C. The process is also characterized by the fact that the products are fired in a reducing atmosphere.
  • US 2008/0254967 A1 discloses a chromium oxide-free refractory ceramic based on magnesium-rich magnesium-aluminum spinel, which has in particular a high resistance to aggressive slag.
  • the starting materials are ground to a particle size of less than 50 ⁇ m.
  • the ceramic is fired at 1700 ° C.
  • Patent DD 299 527 describes a process for sintering oxide-ceramic materials.
  • the materials are fired until the onset of high grain growth in a reducing atmosphere and then at a higher oxygen partial pressure.
  • the materials produced in this way have a high sintering density and a small grain size.
  • the materials are intended for use as indexable inserts or as implants. It is known that the inorganic constituents of the carbonaceous raw materials to be gasified react with the refractory lining of the carburetor. It creates new chemical compounds that have a lower density than the refractory material. This can cause spalling and exfoliation of the refractory during gasification.
  • the invention is based on the technical object of developing a chromium-oxide-free refractory lining of gasification reactors on the basis of readily available and inexpensive raw materials, which are distinguished by high thermal shock resistance and good corrosion resistance under gasification conditions.
  • the object is achieved by lining material for gasification plants, in particular for gasification plants, in which work is carried out under reducing conditions, which consists of an oxide-ceramic material based on aluminum oxide.
  • the oxide-ceramic material contains
  • At least one oxide additive selected from oxides of the alkali metals, oxides of alkaline earth metals, titanium dioxide, zirconium dioxide (preferably titanium oxide and zirconium dioxide), brown coal ash, coal coke or mixtures thereof.
  • the oxide-ceramic material according to the invention is characterized in that it has been fired or heat-treated under reducing conditions.
  • the burning (sintering) or the heat treatment take place before the lining of the gasification plant with the lining material according to the invention.
  • the invention is based on the observation that lining materials for gasification plants, which were produced by sintering under oxidizing conditions, when used in gasification plants, in which operating under reducing conditions, their material properties (eg, the phase composition and temperature resistance) adversely affect.
  • the inventors have found that, in the case of direct firing (sintering) of oxide-ceramic lining materials under reducing conditions (for example in coke beds or under a carbon monoxide atmosphere), the thermal shock resistance of the materials is advantageous over the sintering process nt improved wi rd.
  • Thermal shock resistance of the material significantly improved. It has also been found to be advantageous to heat treat materials fired under oxidizing conditions again before use as lining material under reducing conditions, so that the phase transformation processes are completed prior to installation in the gasification plant.
  • reducing conditions are understood as meaning a combustion air ratio ⁇ of less than 1 (lack of air).
  • Suitable reducing conditions are the sintering in coke beds (for example, in a bed of petroleum coke, while a carbon monoxide sintering atmosphere is formed) or under carbon monoxide atmosphere.
  • the firing process is preferably carried out at temperatures between 1200 and 1700 ° C., more preferably at 1300 to 1550 ° C.
  • the material under oxidizing conditions As an alternative to direct firing of the material under reducing conditions, it is also possible, less preferably, to burn the material under oxidizing conditions, this being preferably carried out at temperatures between 1200 and 1700 ° C., more preferably at 1300 to 1550 ° C. , The fired material thus obtained can be stored in this form.
  • the material fired under oxidizing conditions is again submerged heat-treated reducing conditions, preferably at temperatures between 600 and 1500 ° C. Only then is the material intended for use with lining material.
  • the phase transformation processes in the material take place even before installation in the gasification plant, so that further conversion processes and changes in material properties during the gasification process are minimized.
  • heat treatment is therefore understood as meaning that an oxide-ceramic material which has been fired under oxidizing conditions is used for the production of the gasification apparatus under reducing conditions at high temperatures, preferably 600 to 1500 ° C. is treated to achieve the desired beneficial properties of the material.
  • oxidizing conditions excess air
  • ⁇ ⁇ combustion air ratio
  • a lining material according to the invention is therefore obtained directly by sintering under reducing conditions.
  • the oxide-ceramic material of which the lining material according to the invention for gasification plants contains at least 50% by mass of aluminum oxide.
  • the content of aluminum oxide is preferably at least 60% by mass, more preferably at least 70% by mass, most preferably at least 80% by mass.
  • Aluminum oxide contents of between 85 and 99% by weight are particularly preferred.
  • the aluminum oxide can be used in the form of Al 2 O 3 (alumina) or as compounds with oxides of another metal, in particular oxides of alkaline earth metals. Preference is given to the use of mixed oxides of aluminum with magnesium (Magnesiumaluminatspinell) or with calcium (calcium hexaaluminate). In this case, the mass percentages given above relate to the content of Al2O3 on the oxide ceramic material.
  • the other oxidic additives contained in the oxide ceramic material are contained in total at least 0.8 to 50 wt .-%. Levels of further oxidic additives of from 1 to 15% by weight are preferred. The following contents of the oxide-ceramic material are preferred for the respective oxidic additives:
  • alkali metals preferably sodium oxide or potassium oxide, more preferably Na 2 O
  • 5 to 10 wt .-% particularly preferably 5 to 15 wt .-%
  • alkaline earth metals preferably magnesium oxide or calcium oxide
  • Titanium dioxide at 0.4 to 20% by mass, particularly preferably 0.4 to 5% by mass;
  • Zirconia at 0.4 to 20% by mass, particularly preferably 0.4 to 5% by mass, titanium dioxide and zirconium dioxide preferably being used in combination with one another;
  • Lignite ash at 5 to 50% by mass, more preferably at 5 to 15% by mass;
  • the brown coal ash and / or coal coke used preferably have at least the following constituents: 40-80% by weight SiO 2 , 7-35% by weight Al 2 O 3 , 5-33% by mass CaO, 0-6 Ma. % MgO, 0-7 mass% SO 3 , 2-25 mass% Fe 2 O 3 .
  • Alumina with 5-10% by mass of sodium oxide (beta-alumina)
  • An advantage of the lining material according to the invention for gasification plants is that during fire or heat treatment under reducing conditions, the new phase formation of the oxide ceramic material is largely completed before use in the gasifier and thus stresses within the refractory material, which can lead to flaking or flaking be prevented during the gasification process.
  • Another advantage of the lining material according to the invention lies in the fact that the material during the sintering fire in a reducing atmosphere entschlie excellent thermal shock and alkali corrosion resistance to slags and hot process gases lt.
  • the invention also includes a method for producing the lining material according to the invention for gasification plants.
  • the method according to the invention comprises the steps:
  • binders are silica sol or cements, such as calcium aluminate cement (eg 27% by weight CaO and 72% by weight Al 2 O 3).
  • Preferred dispersants are dispersing alumina, such as the products ADW, ADS (minimum constituents Al 2 0 3 , Na 2 0, B 2 0 3 and CaO).
  • Preferred liquefying agents are synthetic polymers or polyelectrolytes, in particular polycarboxylate ethers (for example VP65).
  • Additives are preferably added to a total weight fraction of 0.5 to 5 wt .-% (based on the total mass of the dry mixture), more preferably to a weight proportion of 0.9 to 2 wt .-%.
  • the mixing of the oxidic starting materials is preferably carried out in a mixer (for example a tumble mixer).
  • a mixer for example a tumble mixer.
  • at least one additive is added at the beginning, it is either added to the oxidic starting materials at the beginning or mixed in after the dry mixture has been obtained.
  • the porosity of the material obtained can be adjusted.
  • the porosity of the material obtained can be adjusted.
  • between 4 and 60% by weight of water is added.
  • the open porosity indicates all externally accessible pores and is u.a. determinable according to DIN EN 993-1.
  • lining materials with an open porosity of less than 20% preferably 5 to 10% by mass of water is added to the dry mixture.
  • at least one liquefying agent is preferably added as an additive. Lining materials having an open porosity of less than 20% are particularly preferred.
  • lining materials with an open porosity of at least 20%, preferably 6 to 60% by mass of water, more preferably 30 to 50% by mass of water, is added to the dry mixture.
  • at least one binder is added as an additive.
  • the flowable mass obtained after the addition of water is placed in a mold (preferably a metal mold), preferably this is done by means of Casting technology or by vibration (for example on vibration tables).
  • the set mass is demolded and then dried to an anhydrous molded body (green compact) at preferably 100 to 150 ° C.
  • the dried form bodies are then fired (sintered). This is done according to the invention either under reducing conditions (preferred variant), preferably in coke bed or under reducing CO gas atmosphere, or under oxidizing conditions with subsequent heat treatment under reducing conditions.
  • the S in te ru ngwi rd, under oxidizing or reducing conditions preferably at 1200 and 1700 ° C, preferably carried out at a maximum of 1500 ° C.
  • the temperature increase in the sintering or in the heat treatment is preferably carried out at 0.5 to 1, 5 K / min. After reaching the target temperature, this is preferably fired or heat treated for four to ten hours, more preferably four to six hours.
  • a preferred process for producing the oxide-ceramic chromium oxide and carbon-free refractories is via casting technology.
  • alum inium oxide and the other starting materials or ash components are mixed together and processed using other additives at room temperature to give a castable or vibrational mass.
  • the thus prepared refractory chromium oxide and carbon-free materials are cementitious (CAC), phosphate bound, silica or non-cemented (reactive clay) bound.
  • the production of lining materials according to the invention in the form of large-sized components with an open porosity of up to 20%.
  • the starting materials are premixed and with addition of binder, preferably calcium aluminate cement and / or reactive clay, and other additives for controlling the bondability and / or improving the flow properties and 5-10 Ma .% Water to a vibration or flowable mass processed in a mixer.
  • inventive lining materials in the form of large-sized components with an open porosity of over 20% is possible.
  • the starting materials are premixed and likewise with the addition of B, preferably calcium aluminate cement and / or reactive clay, and further additives for controlling the setting behavior and / or improving the flow properties and 6-60 Ma.% water processed into a vibration or flowable mass in a mixer.
  • the shaping takes place in both variants via vibration (on vibration table) or pouring of self-flowing masses into metallic molds. After about 12 hours, the green compacts can be demolded and dried at 1 10 ° C. Subsequently, the components are fired in a reducing atmosphere (e.g., in a coke bed) at temperatures of up to 1500 ° C.
  • a reducing atmosphere e.g., in a coke bed
  • the lining of the gasification plants, Verbrennungsan and rotary kilns from the cast and pre-burned under reducing conditions oxide ceramic stones or cast with casting compounds from the materials described and then heated under reducing conditions.
  • Fireproof bricks of the composition according to the invention fired under oxidizing conditions can be used under reducing conditions after a heat treatment.
  • Fabrication of the materials under reducing conditions causes changes in the phase balance and creates voids in the microstructure, providing sufficiently good mechanical and thermo-mechanical and excellent thermal shock properties as well as improved corrosion resistance to overprinting and hot stamping Process gases of the gasification can be achieved.
  • Embodiment 1 Oxide ceramic chromium and carbon-free refractory material based on Al umi niumoxid with additions of lignite coal ash Table 1 below contains exemplary ash compositions of an acidic or basic brown coal ash:
  • Table 2 contains a mixture for the preparation of an alumina-based refractory component with additions of brown coal ash.
  • Aluminum oxide (alumina) from Almatis GmbH was used (Tabular Alumina T60), the particle size distribution (in mm, unless otherwise stated) also being indicated in the following table.
  • alumina and the brown coal ash were dry pre-mixed in a mixer.
  • the average particle size (sieve fraction or laser granulometer) of the ceramic matrix was between 3 and 8 ⁇ m, and the mean grain size of the coarse grain was between 55 and 4250 ⁇ m.
  • the additives were added and the dry mix processed in a mixer with the addition of 4.9 Ma.% Water to a pourable self-flowing mass.
  • specimens were prepared in metal molds. The dried samples were fired at a rate of 1 K / min at 1300 ° C in a reducing atmosphere (by embedding in petroleum coke) and a hold time of 300 m in. Petroleum coke burns from about 500 ° C to form CO.
  • Table 4 shows the mechanical and thermo-mechanical properties of the materials obtained.
  • Table 5 shows a mixture for the preparation of an alumina-based refractory with added ZrO2 and T1O2.
  • Alumina and reactive clays were used analogously to Example 1 of Almatis GmbH.
  • alumina, zirconium dioxide and titanium dioxide were premixed dry in a mixer.
  • the mean grain size of the ceramic matrix was between 3 and 8 ⁇ m, the mean grain size of the coarse grain was 55 to 4250 ⁇ m.
  • the additives were added and the dry mix was processed in a mixer with the addition of 4.9 Ma.% Water to a pourable self-flowing mass.
  • specimens were prepared in metal molds. The dried samples were fired at a rate of 1 K / min at 1300 ° C in a reducing atmosphere (analogous to Example 1) and a hold time of 300 min.
  • a comparative example was a mixture of identical composition fired under oxidizing conditions (air).
  • Table 6 shows the mechanical and thermo-mechanical properties of the AZT materials (determined as in Example 1).
  • the phase composition and phase proportions of cast cement bonded AZT devices are shown in Table 7.
  • Exemplary Embodiment 3 Oxide-ceramic chromium-free and carbon-free refractory material based on aluminum oxide with additions of sodium oxide Table 8 below shows a mixture for the production of a refractory component from ⁇ -alumina.
  • reactive clay was dry-premixed with ⁇ -alumina (contains sodium oxide) and the additives in a mixer.
  • the mean grain size of the ceramic matrix was between 7 and 14 ⁇ m, the mean grain size of the coarse grain was 38 to 2020 ⁇ .
  • the dry mixture was processed in a mixer with the addition of 45.0 Ma.% Water to a viable mass.
  • specimens were prepared in metal molds. The dried samples were fired at a rate of 1, 0 K / min at 1500 ° C in a reducing atmosphere (analogous to Example 1) and a holding time of 300 m in.
  • a mixture of identical composition was fired under oxidizing conditions (air).
  • Embodiment 4 Oxide Ceramics Chromium and Carbon-Free Refractory Material Based on Aluminum Oxide with Magnesium Oxide Additives
  • Table 10 shows a mixture for the production of an aluminum oxide-based refractory component with 24 Ma.% Magnesium aluminate spinel additives (composition of the magnesium aluminate spinel 74% Al 2 O 3 , 26% MgO).
  • the casting compound was prepared as described in Example 2.
  • the water requirement was 4.5 Ma.%.
  • the mean grain size of the matrix was 1.7 to 20 ⁇ m and the mean grain size of the coarse grain was between 20 and 4250 ⁇ m.
  • the produced self-flowing mass was introduced into metallic molds. Of the Fire of the samples was carried out as in Example 2.
  • the mechanical and thermo-mechanical properties and the phase composition with the corresponding proportions are listed in Tables 1 1 and 12.
  • Embodiment 5 Oxide ceramic chromium and carbon-free refractory material based on aluminum oxide with magnesium oxide additives
  • Table 13 contains a mixture for the preparation of a refractory component based on aluminum oxide with magnesium aluminate spinel additives (analogous to Example 4).
  • the casting compound was prepared as described in Example 2.
  • the water requirement was 5.0 Ma.%.
  • the mean grain size of the matrix was 1.7 to 20 ⁇ m and the mean grain size of the coarse grain was between 20 and 4250 ⁇ m.
  • the produced self-flowing mass was introduced into metallic molds.
  • the firing of the samples was carried out as in Example 2.
  • the mechanical and thermo-mechanical properties and the phase composition with the corresponding proportions are listed in Tables 14 and 15. Table 14
  • Embodiment 6 Oxide ceramic chromium- and carbon-free refractory material based on aluminum oxide with additions of calcium oxide
  • Table 16 contains a mixture for the preparation of an alumina-based refractory with ceria-hexaluminate (CAe) additives.
  • CAe ceria-hexaluminate
  • Table 18 shows the mechanical and thermo-mechanical properties of the materials obtained.

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Abstract

L'invention concerne un matériau de revêtement pour installations de gazéification, en particulier pour des installations de gazéification, dans lesquelles un gaz de synthèse est généré dans des conditions réductrices. Le matériau de revêtement selon l'invention pour installations de gazéification est constitué par un matériau céramique oxyde à base d'oxyde d'aluminium. Selon l'invention, le matériau céramique oxyde contient a) au moins 50% en masse (Ma.-%) d'oxyde d'aluminium, b) au moins un additif oxyde, choisi parmi les oxydes des métaux alcalins, les oxydes des métaux alcalino-terreux, le dioxyde de titane, le dioxyde de zirconium, les cendres de lignite, les cendres de houille ou leurs mélanges. En outre, le matériau céramique oxyde se caractérise selon l'invention en ce qu'il a été calciné ou traité thermiquement dans des conditions réductrices. L'invention comprend également un procédé de fabrication d'un matériau de revêtement selon l'invention pour installations de gazéification, ainsi que son utilisation.
PCT/EP2011/069964 2010-11-12 2011-11-11 Matériau de revêtement pour installations de gazéification constitué d'un matériau céramique oxyde résistant à la corrosion par les alcalis et aux changements de température, exempt d'oxyde de chrome et de carbone et son utilisation WO2012062913A1 (fr)

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WO2015108795A1 (fr) * 2014-01-15 2015-07-23 Corning Incorporated Procédé de préparation de feuilles de verre avec prétraitement gazeux de matériaux réfractaires
US10047000B2 (en) 2014-01-15 2018-08-14 Corning Incorporated Method of making glass sheets with vehicle pretreatment of refractory

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015108795A1 (fr) * 2014-01-15 2015-07-23 Corning Incorporated Procédé de préparation de feuilles de verre avec prétraitement gazeux de matériaux réfractaires
CN106103366A (zh) * 2014-01-15 2016-11-09 康宁股份有限公司 利用耐火材料的气体预处理的玻璃板制造方法
US10047000B2 (en) 2014-01-15 2018-08-14 Corning Incorporated Method of making glass sheets with vehicle pretreatment of refractory
CN106103366B (zh) * 2014-01-15 2019-06-07 康宁股份有限公司 利用耐火材料的气体预处理的玻璃板制造方法
US10435323B2 (en) 2014-01-15 2019-10-08 Corning Incorporated Method of making glass sheets with gas pretreatment of refractory

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