CN110903076B - Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof - Google Patents
Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof Download PDFInfo
- Publication number
- CN110903076B CN110903076B CN201911220736.9A CN201911220736A CN110903076B CN 110903076 B CN110903076 B CN 110903076B CN 201911220736 A CN201911220736 A CN 201911220736A CN 110903076 B CN110903076 B CN 110903076B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- corundum
- hydrogen
- heating furnace
- tungsten
- 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.)
- Active
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
- 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
- C04B35/1015—Refractories from grain sized mixtures containing refractory metal compounds other than those covered by C04B35/103 - C04B35/106
-
- 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
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
-
- 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
- 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
- C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
-
- 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
- C04B2235/3258—Tungsten oxides, tungstates, 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/404—Refractory metals
-
- 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
- C04B2235/5427—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
-
- 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
Abstract
The invention belongs to the field of refractory materials, and provides a corundum refractory product for a hydrogen-filled molybdenum rod heating furnace and an application method thereof, which is a shaped refractory material subjected to high-temperature firing treatment, and the bulk density of the shaped refractory material is more than or equal to 3.15 g-cm‑1The normal temperature compressive strength is more than or equal to 60MPa, and the components comprise Al2O3The Al2O3 accounts for 96.0% or more and 98.5% or less, the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace contains one or two of tungsten and molybdenum elements, the sum of the mass fractions of the four elements of aluminum, oxygen, tungsten and molybdenum in the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is 99.0% or more, the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is composed of particles, fine powder and micro powder, the corundum refractory product is mainly applied to the hydrogen-introducing molybdenum rod heating furnace at the working temperature of 1600-1900 ℃, and H2 with the concentration of 99.0% or more is continuously introduced as protective gas during working.
Description
Technical Field
The invention belongs to the field of refractory materials, and mainly relates to a corundum refractory product for a hydrogen-filled molybdenum rod heating furnace and an application method thereof.
Background
Tungsten and molybdenum are the most commonly used refractory metals. The melting point of tungsten is 3410 + -20 deg.C, and the melting point of molybdenum is 2620 deg.C. The industrial hydrogen-introducing molybdenum rod heating furnace uses a metal rod material prepared from molybdenum or molybdenum-tungsten alloy as a resistance heating element, uses circulated hydrogen as protective gas to prevent tungsten and molybdenum from being oxidized, uses a refractory material as a furnace lining, and has the highest service temperature of 1900 ℃. The hydrogen-filled molybdenum rod heating furnace needs to be baked and air-fired after the refractory materials are built and the components of the furnace body are installed, in the process, hydrogen is continuously introduced to serve as protective gas, the temperature of the furnace is slowly raised to about 1850 ℃ from the room temperature, and then the furnace is slowly cooled, so that the moisture and volatile matters in the furnace are discharged, the residual stress is reduced, and the stability of the furnace in use is improved.
The furnace chamber of the hydrogen-feeding molybdenum rod heating furnace has high temperature, has high requirements on the wear resistance and high-temperature strength of the furnace lining, and the common fire-facing working layer refractory material is mainly high-purity corundum bricks. The brick Al2O3Greater than or equal to 99.0 percent, and the density of the body is greater than or equal to 3.15g cm-1The normal temperature compressive strength is more than or equal to 40MPa, and the high-temperature-resistant fused white corundum/plate-shaped corundum ceramic is prepared by pressing fused white corundum or plate-shaped corundum particles, alumina fine powder and micro powder as raw materials into a blank and firing the blank at 1600-1750 ℃. In order to improve the high temperature resistance of the corundum brick, the methods of improving the purity of the corundum brick material and the firing temperature of the corundum brick are adopted at present, such as Al which is the typical value of the corundum brick2O399.6%, and the sintering temperature is raised to 1800 ℃. But instead of the other end of the tubeAt present, the purity of the industrial alumina of 99.3 percent basically reaches the limit, and the further purification cost is extremely high; the high temperature burning at 1800 ℃ has large fuel loss and also can shorten the service life of a burning kiln sharply.
Industrial kilns such as hydrogen-introducing molybdenum rod heating furnaces, tungsten-molybdenum product processing furnaces and the like mostly use corundum bricks and alumina hollow ball bricks as furnace linings, the used refractory bricks are polluted by tungsten and molybdenum, and the traditional recycling is limited. However, when the used refractory material is analyzed, the chemical components of the refractory material are mainly W and Mo elements except alumina, and the content of other impurities is low, so that the refractory material has extremely high recycling value.
Disclosure of Invention
The invention provides a corundum refractory product for a hydrogen-introducing molybdenum rod heating furnace and an application method thereof by deeply analyzing the working temperature, atmosphere and material field of the hydrogen-introducing molybdenum rod heating furnace, and aims to reduce the firing temperature of corundum bricks and save energy consumption on the premise of meeting the requirement of high-temperature use.
The invention adopts the following technical scheme for achieving the purpose:
a corundum refractory product for hydrogen-filled molybdenum rod heating furnace has a bulk density of 3.15 g-cm or more-1The normal temperature compressive strength is more than or equal to 60MPa, and the components comprise Al2O3Wherein the content of Al2O3 is 96.0% or more and 98.5% or less,
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace contains one or two of tungsten and molybdenum elements;
the sum of the mass fractions of the four elements of aluminum, oxygen, tungsten and molybdenum in the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is more than or equal to 99.0 percent;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace consists of particles, fine powder and micro powder;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is a refractory product subjected to high-temperature firing treatment, wherein the maximum firing temperature is more than or equal to 800 ℃, and the firing atmosphere is an oxidizing atmosphere.
Preferably, the tungsten and molybdenum elements can be present in the form of one of tungsten oxide, molybdenum oxide, simple substance tungsten, simple substance molybdenum or any combination of the tungsten oxide, the molybdenum oxide, the simple substance tungsten and the simple substance molybdenum.
Preferably, the mass of the tungsten oxide, the molybdenum oxide, the elemental tungsten and the elemental molybdenum accounts for 1-4% of the total mass of the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace.
Preferably, the particles in the corundum fire-resistant manufacturing process for the hydrogen-introducing molybdenum rod heating furnace can be artificially synthesized raw materials of electric-melting white corundum and tabular corundum, can also be particles of crushed waste refractory materials of high-purity corundum bricks contacting tungsten and molybdenum, or a combination of the above raw materials; the particle size range of the particles in the corundum refractory product is more than 0.2mm and less than or equal to 5 mm.
Preferably, the fine powder and the micro powder in the corundum fire-resistant manufacturing process for the hydrogen-introduced molybdenum rod heating furnace are a combination of fine powder of aluminum oxide, fine powder of aluminum oxide and fine powder containing tungsten and/or molybdenum elements; the particle size of the fine powder is less than or equal to 74 mu m and more than 10 mu m; the median diameter D of the micro powder50Less than or equal to 10 μm.
Preferably, the fine powder containing tungsten and/or molybdenum elements can be one or any combination of tungsten oxide, molybdenum oxide, simple substance tungsten and simple substance molybdenum, or can be powder obtained by crushing and grinding waste refractory materials after the waste refractory materials are used and contact with tungsten and molybdenum, or a combination of the powder and the high-purity corundum bricks and the aluminum oxide hollow ball bricks; the particle size of the fine powder containing tungsten and/or molybdenum elements is less than or equal to 74 mu m and more than 10 mu m.
Preferably, the composition proportion ranges of the particles, the fine powder and the micro powder in the corundum fire-resistant manufacturing process for the hydrogen-introducing molybdenum rod heating furnace are respectively 50% -75%, 20% -40% and 5% -20% in terms of the proportion of the total mass of the corundum fire-resistant product.
Preferably, the corundum refractory product for the hydrogen-filled molybdenum rod heating furnace has the operating environment that the operating temperature is 1600-1900 ℃, and H2 with the concentration of more than or equal to 99.0% is continuously introduced as protective gas during operation.
Advantageous effects
1. According to the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace, the refractory metal elements such as W, Mo are added into the raw materials of the corundum brick, and the corundum brick is sintered at the temperature higher than the melting point of the oxide in the oxidizing atmosphere, so that liquid phases of the refractory metal oxides are generated inside the corundum brick during sintering, the liquid phases promote the combination growth of alumina fine powder and micro powder grains, and the microstructure densification and the mechanical strength improvement of the corundum brick during low-temperature sintering are facilitated.
2. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace is characterized in that corundum bricks are built in the hydrogen-filled molybdenum rod heating furnace in the presence of H2WO in the brick at a high temperature of 1600-1900 ℃ in a gas environment3And MoO3Quilt H2Reducing the metal W and Mo into metal W and Mo, and remaining in the corundum brick to form the refractory metal phase composite corundum brick which not only has high use temperature, but also has good thermal shock resistance.
3. Compared with the traditional corundum refractory material, the firing temperature of the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is reduced by 100-900 ℃, the low-temperature firing effect is achieved, and the method has the advantage of low production energy consumption; meanwhile, the product can use the waste refractory materials of the used high-purity corundum bricks and alumina hollow ball bricks which are contacted with tungsten and molybdenum as raw materials, and can realize the resource recycling of the waste refractory materials.
Detailed Description
A corundum refractory product for hydrogen-filled molybdenum rod heating furnace has a bulk density of 3.15 g-cm or more-1The normal temperature compressive strength is more than or equal to 60MPa, and the components comprise Al2O3Wherein the content of Al2O3 is 96.0% or more and 98.5% or less,
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace contains one or two of tungsten and molybdenum elements;
the sum of the mass fractions of the four elements of aluminum, oxygen, tungsten and molybdenum in the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is more than or equal to 99.0 percent;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace consists of particles, fine powder and micro powder, wherein the composition proportion ranges from 50% to 75%, 20% to 40% and 5% to 20% in terms of the total mass of the corundum refractory product;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is a refractory product subjected to high-temperature firing treatment, wherein the maximum firing temperature is more than or equal to 800 ℃, and the firing atmosphere is an oxidizing atmosphere.
Specifically, the tungsten and molybdenum elements can be present in the form of one of tungsten oxide, molybdenum oxide, simple substance tungsten, simple substance molybdenum or any combination of the tungsten oxide, the molybdenum oxide, the simple substance tungsten and the simple substance molybdenum.
Specifically, the mass of the tungsten oxide, the molybdenum oxide, the elemental tungsten and the elemental molybdenum accounts for 1-4% of the total mass of the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace.
Specifically, the particles in the corundum fire-resistant manufacturing process for the hydrogen-introducing molybdenum rod heating furnace can be artificially synthesized raw materials of electro-fused white corundum and tabular corundum, can also be particles of crushed waste refractory materials of high-purity corundum bricks contacting tungsten and molybdenum, or a combination of the above raw materials; the particle size range of the particles in the corundum refractory product is more than 0.2mm and less than or equal to 5 mm.
Specifically, the fine powder and the micro powder in the corundum fire-resistant preparation for the hydrogen-introduced molybdenum rod heating furnace are a combination of alumina fine powder, alumina micro powder and fine powder containing tungsten and/or molybdenum elements; the particle size of the fine powder is less than or equal to 74 mu m and more than 10 mu m; the median diameter D of the micro powder50Less than or equal to 10 μm.
Specifically, the fine powder containing tungsten and/or molybdenum elements may be one or any combination of tungsten oxide, molybdenum oxide, simple substance tungsten and simple substance molybdenum, or may be powder obtained by crushing and grinding waste refractory materials after use of high-purity corundum bricks and alumina hollow ball bricks which contact tungsten and molybdenum, or a combination of the above materials; the particle size of the fine powder containing tungsten and/or molybdenum elements is less than or equal to 74 mu m and more than 10 mu m.
Specifically, the corundum refractory product for the hydrogen-filled molybdenum rod heating furnace has the operating environment requirement that the operating temperature is 1600-1900 ℃, and H2 with the concentration of more than or equal to 99.0% is continuously introduced as protective gas during operation.
The invention is illustrated by the examples given, but is not to be construed as being in any way limited thereto.
Example 1: respectively weighing fused white corundum (Al) with particle size of 5mm or less and more than 0.2mm2O3Not less than 99.2%) 50kg of fine alumina powder (Al) having a particle size of 74 μm or less and 10 μm or more2O3Not less than 99.2%) 26kg of tungsten oxide fine powder having a particle size of 74 μm or less and more than 10 μm (WO)3Not less than 99.5%) 4kg, median diameter D50Fine alumina powder (Al) of 10 μm2O3Not less than 99.5 percent) of 20kg and PVA binder with the mass fraction of 5 percent of 4kg, and the materials are fully and uniformly mixed in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the maximum temperature of 800 ℃ for 5h for sintering, adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 96.0 percent and the volume density of 3.15g cm-1The room-temperature compressive strength was 60MPa, and W (Al + O + W + Mo) was 99.3%. The product is a working lining refractory material of a heating furnace with hydrogen-filled molybdenum rods at the working temperature of 1800 ℃.
Example 2: weighing plate-shaped corundum (Al) with granularity of 3mm or less and more than 0.2mm2O3Not less than 99.3%) 60kg of fine alumina powder (Al) having a particle size of 74 μm or less and 10 μm or more2O399.5%) 22kg of molybdenum oxide fine powder (MoO) with particle size of 74 μm or less and 10 μm or more3Not less than 99.5%) 3kg, median diameter D50Fine alumina powder (Al) of 5 μm2O3Not less than 99.5 percent) and 15kg of PVA binder with the mass fraction of 5 percent, and the materials are fully and uniformly mixed in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 12h, then preserving the heat in a gas kiln at the highest temperature of 1000 ℃ for 5h, and adjusting the air-fuel ratio during firing to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 97.0 percent and the volume density of 3.20g cm-1The room-temperature compressive strength was 75MPa, and W (Al + O + W + Mo) was 99.7%. The product is a working lining refractory material of a heating furnace with a hydrogen-filled molybdenum rod at the working temperature of 1900 ℃.
Examples3: respectively weighing fused white corundum (Al) with granularity of less than or equal to 4mm and more than 1mm2O3Not less than 99.2 percent) 40kg of waste corundum brick crushed granules (Al) with the granularity of not more than 2mm and more than 0.2mm2O396.2% and 3.1% of W, 30kg of fine alumina powder (Al) having a particle size of 43 μm or less and a particle size of 10 μm or more2O3Not less than 99.2%) 20kg of broken fine powder (Al) of waste corundum brick with granularity not more than 74 μm and more than 10 μm2O396.2% W3.1%) of tungsten oxide fine powder having a particle size of 74 μm or less and a particle size of 10 μm or more (WO)3Not less than 99.5%) 1kg, median diameter D50Fine alumina powder (Al) of 1 μm2O3Not less than 99.5%) 10kg, and pulp waste liquor binder with mass fraction of 10% 5kg, and mixing the above materials in a roller mill. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 400 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the maximum temperature of 1200 ℃ for 3h to sinter, adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the kiln in an oxidizing atmosphere. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 98.0 percent and the volume density of 3.25g cm-1The room-temperature compressive strength was 80MPa, and W (Al + O + W + Mo) was 99.2%. The product is a working lining refractory material of a hydrogen-filled molybdenum rod heating furnace with the working temperature of 1850 ℃.
Example 4: respectively weighing the waste corundum brick crushed granules (Al) with the granularity of less than or equal to 4mm and more than 0.2mm2O398.2% of Mo, 1.3%) and crushed fine powder of waste corundum brick (Al) with particle size of 43 μm or less and 10 μm or more2O398.2%, Mo 1.3%) 20kg, median diameter D50Fine alumina powder (Al) of 3 μm2O3Not less than 99.5%) 5kg, and pulp waste liquor binder with mass fraction of 10% 5kg, and mixing the above materials in a roller mill. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 400 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the highest temperature of 1400 ℃ for 6h for sintering, and adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1 percent and keep the kiln in an oxidizing atmosphere.Naturally cooling to obtain the corundum refractory product w (Al)2O3) 98.5 percent, and the volume density is 3.25g cm-1The room-temperature compressive strength was 93MPa, and W (Al + O + W + Mo) was 99.3%. The product is a working lining refractory material of a hydrogen-filled molybdenum rod heating furnace with the working temperature of 1600 ℃.
Example 5: weighing plate-shaped corundum (Al) with granularity of 3mm or less and more than 0.2mm2O3Not less than 99.3 percent) of 20kg of waste corundum brick crushed granules (Al) with the granularity of not more than 3mm and more than 0.2mm2O395.8% of fine alumina powder (Al), 1.1% of W, and 2.3% of Mo), and a particle size of 74 μm or less and 10 μm or more2O3Not less than 99.2%) 20kg of broken fine powder (Al) of waste corundum brick with granularity not more than 74 μm and more than 10 μm2O395.8%, W1.1%, Mo 2.3%) 40kg, median diameter D50Fine alumina powder (Al) of 5 μm2O3Not less than 99.5 percent) of 10kg and PVA binder with the mass fraction of 5 percent of 3.5kg, and the materials are fully and uniformly mixed in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 24h, then preserving the heat in a gas kiln at the highest temperature of 1600 ℃ for 5h, and adjusting the air-fuel ratio during firing to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 97.0 percent and the volume density of 3.30g cm-1The room-temperature compressive strength was 125MPa, and W (Al + O + W + Mo) was 99.2%. The product is a working lining refractory material of a hydrogen-filled molybdenum rod heating furnace with the working temperature of 1850 ℃.
Example 6: respectively weighing fused white corundum (Al) with granularity of less than or equal to 5mm and more than 3mm2O3Not less than 99.0%) 35kg of tabular corundum (Al) with granularity not more than 3mm and more than 0.2mm2O3Not less than 99.3%) 30kg of fine alumina powder (Al) having a particle size of 74 μm or less and 10 μm or more2O399.5%) 22kg of molybdenum oxide fine powder (MoO) with particle size of 74 μm or less and 10 μm or more3Not less than 99.5%) 2kg of fine molybdenum powder (MoO) having particle size of 74 μm or less and 10 μm or more3≥99.5%) 1kg, median diameter D50Fine alumina powder (Al) of 0.8 μm2O3Not less than 99.5 percent) of 10kg and PVA binder with the mass fraction of 5 percent of 3.5kg, and the materials are fully and uniformly mixed in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the maximum temperature of 1500 ℃ for 5h to sinter, adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 96.6%, volume density 3.35g cm-1The room-temperature compressive strength was 110MPa, and W (Al + O + W + Mo) was 99.7%. The product is a working lining refractory material of a heating furnace with a hydrogen-filled molybdenum rod at the working temperature of 1900 ℃.
Example 7: respectively weighing the waste corundum brick crushed granules (Al) with the granularity of less than or equal to 4mm and more than 0.2mm2O3＝96.8％、MoO30.8% of Mo and 1.3% of Mo, and 70kg of fine alumina powder (Al) having a particle size of 74 μm or less and a particle size of 10 μm or more2O3Not less than 99.2%) 18kg of tungsten oxide with particle size not more than 74 μm and more than 10 μm (WO)3Not less than 99.5%) 0.5kg of molybdenum oxide (MoO) with particle size of 74 μm or less and more than 10 μm3Not less than 99.5%) 1.5kg, median diameter D50Fine alumina powder (Al) of 3 μm2O3Not less than 99.5 percent) of 10kg and PVA binder with the mass fraction of 5 percent of 4.5kg, and the materials are fully and uniformly mixed in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the maximum temperature of 1500 ℃ for 8h for sintering, adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 96.1%, volume density 3.25g cm-1The room-temperature compressive strength was 103MPa, and W (Al + O + W + Mo) was 99.5%. The product is a working lining refractory material of a hydrogen-filled molybdenum rod heating furnace with the working temperature of 1850 ℃.
Example 8: respectively weighing waste corundum with granularity less than or equal to 4mm and more than 0.2mmBroken brick granule (Al)2O3＝96.6％、MoO3＝0.2％、Mo＝0.7％、WO30.6% and 1.3% of W, and fine powder (Al) obtained by grinding waste corundum bricks having particle size of 43 μm or less and larger than 10 μm after crushing2O3＝96.6％、MoO3＝0.2％、Mo＝0.7％、WO30.6% and 1.3% of W, and fine powder (Al) obtained by crushing and grinding waste alumina hollow ball bricks with particle size of 43 μm or less and more than 10 μm2O397.2%, Mo 0.9%, W1.6%) 5kg, median diameter D50Fine alumina powder (Al) of 3 μm2O3Not less than 99.5%) 15kg and 5kg of PVA binder with the mass fraction of 5%, and fully and uniformly mixing the materials in a roller type sand mixer. The mixed material is molded into standard bricks of 230mm multiplied by 114mm multiplied by 65mm on a 630 ton friction brick press. Drying the green body at 110 ℃ for 12h, then keeping the temperature in a gas kiln at the highest temperature of 1650 ℃ for 5h for sintering, adjusting the air-fuel ratio during sintering to ensure that the CO concentration in the flue gas is less than 0.1%, and keeping the oxidizing atmosphere in the kiln. Naturally cooling to obtain the corundum refractory product w (Al)2O3) 96.8 percent, and the volume density of 3.25g cm-1The room-temperature compressive strength was 135MPa, and W (Al + O + W + Mo) was 99.0%. The product is a working lining refractory material of a heating furnace with hydrogen-filled molybdenum rods at the working temperature of 1800 ℃.
Claims (6)
1. A corundum refractory product for hydrogen-filled molybdenum rod heating furnace has a bulk density of 3.15 g-cm or more-1The normal temperature compressive strength is more than or equal to 60MPa, and the components comprise Al2O3Said Al2O3The ratio is more than or equal to 96.0% and less than or equal to 98.5%, and the characteristics are that:
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace contains one or two of tungsten and molybdenum elements;
the sum of the mass fractions of the four elements of aluminum, oxygen, tungsten and molybdenum in the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is more than or equal to 99.0 percent;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace comprises particles, fine powder and micro powder, wherein the composition proportion ranges from 50% to 75%, 20% to 40% and 5% to 20% in terms of the total mass of the corundum refractory product;
the particles in the corundum fire-resistant manufacturing process for the hydrogen-introducing molybdenum rod heating furnace can be artificially synthesized raw materials of electro-fused white corundum and plate-shaped corundum, can also be particles of waste refractory materials after high-purity corundum bricks contacting tungsten and molybdenum are used and crushed, or the combination of the raw materials and the waste refractory materials;
the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace is a refractory product subjected to high-temperature firing treatment, wherein the maximum firing temperature is more than or equal to 800 ℃, and the firing atmosphere is an oxidizing atmosphere;
the corundum refractory product for the hydrogen-filled molybdenum rod heating furnace has the operating environment requirement that the operating temperature is 1600-1900 ℃, and H with the concentration of more than or equal to 99.0 percent is continuously filled in the corundum refractory product during operation2To protect the gas.
2. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace according to claim 1, which is characterized in that: the tungsten and molybdenum elements can be one of tungsten oxide, molybdenum oxide, simple substance tungsten and simple substance molybdenum or any combination of the tungsten oxide, the molybdenum oxide, the simple substance tungsten and the simple substance molybdenum.
3. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace according to claim 2, which is characterized in that: the mass of the tungsten oxide, the molybdenum oxide, the elemental tungsten and the elemental molybdenum accounts for 1-4% of the total mass of the corundum refractory product for the hydrogen-introducing molybdenum rod heating furnace.
4. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace according to claim 1, which is characterized in that: the particle size range of the particles in the corundum refractory product is more than 0.2mm and less than or equal to 5 mm.
5. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace according to claim 1, which is characterized in that: the fine powder and the micro powder in the corundum fire-resistant preparation for the hydrogen-filled molybdenum rod heating furnace are a combination of alumina fine powder, alumina micro powder and fine powder containing tungsten and/or molybdenum elements; the particle size of the fine powder is less than or equal to 74 mum, greater than 10 μm; the median diameter D of the micro powder50Less than or equal to 10 μm.
6. The corundum refractory product for the hydrogen-filled molybdenum rod heating furnace according to claim 5, which is characterized in that: the fine powder containing tungsten and/or molybdenum elements can be one or any combination of tungsten oxide, molybdenum oxide, simple substance tungsten and simple substance molybdenum, or powder obtained by crushing and grinding waste refractory materials after the waste refractory materials are used and contact with tungsten and molybdenum, or the combination of the powder and the high-purity corundum bricks and the aluminum oxide hollow ball bricks; the particle size of the fine powder containing tungsten and/or molybdenum elements is less than or equal to 74 mu m and more than 10 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220736.9A CN110903076B (en) | 2019-12-03 | 2019-12-03 | Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220736.9A CN110903076B (en) | 2019-12-03 | 2019-12-03 | Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110903076A CN110903076A (en) | 2020-03-24 |
| CN110903076B true CN110903076B (en) | 2020-12-25 |
Family
ID=69821976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911220736.9A Active CN110903076B (en) | 2019-12-03 | 2019-12-03 | Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110903076B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143678A (en) * | 1997-06-26 | 2000-11-07 | Ngk Spark Plug Co., Ltd. | Sintered alumina-based ceramics and process for producing same |
| CN101148352A (en) * | 2007-09-04 | 2008-03-26 | 桂林工学院 | Tungsten corundum ceramic material and low temperature sintering method |
| CN101182190A (en) * | 2007-09-04 | 2008-05-21 | 桂林工学院 | Mo-corundum ceramic material and low-temperature sintering method |
| WO2014002306A1 (en) * | 2012-06-25 | 2014-01-03 | 京セラ株式会社 | Alumina ceramic, and ceramic wiring substrate and ceramic package using same |
| CN105906353A (en) * | 2016-04-20 | 2016-08-31 | 湖北神雾热能技术有限公司 | Wear-resistant and high-temperature-resistant composite ceramic material |
| CN106145906A (en) * | 2016-07-04 | 2016-11-23 | 浙江工贸职业技术学院 | A kind of low-temperature sintering Environment-friendlyceramic ceramic material and preparation technology thereof |
| CN109437863A (en) * | 2018-12-28 | 2019-03-08 | 江苏省宜兴电子器件总厂有限公司 | A kind of high intensity HTCC ceramic material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069264A (en) * | 1992-06-25 | 1994-01-18 | Nippon Steel Corp | Wc-al2o3 sintered composite compact |
| EP3029006B1 (en) * | 2014-12-02 | 2017-03-08 | Refractory Intellectual Property GmbH & Co. KG | Refractory product, raw batch for producing the product, method producing the product and use thereof. |
-
2019
- 2019-12-03 CN CN201911220736.9A patent/CN110903076B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143678A (en) * | 1997-06-26 | 2000-11-07 | Ngk Spark Plug Co., Ltd. | Sintered alumina-based ceramics and process for producing same |
| CN101148352A (en) * | 2007-09-04 | 2008-03-26 | 桂林工学院 | Tungsten corundum ceramic material and low temperature sintering method |
| CN101182190A (en) * | 2007-09-04 | 2008-05-21 | 桂林工学院 | Mo-corundum ceramic material and low-temperature sintering method |
| WO2014002306A1 (en) * | 2012-06-25 | 2014-01-03 | 京セラ株式会社 | Alumina ceramic, and ceramic wiring substrate and ceramic package using same |
| CN105906353A (en) * | 2016-04-20 | 2016-08-31 | 湖北神雾热能技术有限公司 | Wear-resistant and high-temperature-resistant composite ceramic material |
| CN106145906A (en) * | 2016-07-04 | 2016-11-23 | 浙江工贸职业技术学院 | A kind of low-temperature sintering Environment-friendlyceramic ceramic material and preparation technology thereof |
| CN109437863A (en) * | 2018-12-28 | 2019-03-08 | 江苏省宜兴电子器件总厂有限公司 | A kind of high intensity HTCC ceramic material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110903076A (en) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112125651B (en) | Preparation method of compact calcium hexaluminate-corundum complex phase ceramic | |
| CN1326804C (en) | Alumina base mullite homogeneous material preparation method | |
| CN107935575B (en) | High-purity low-creep fused mullite brick and preparation method thereof | |
| US3753744A (en) | Graphite-alumina-silicon carbide base refractory | |
| CN109369181B (en) | Volume-stable high-purity zirconia refractory product | |
| CN109081697A (en) | It is a kind of to prepare B4The method of C/SiC composite ceramic | |
| CN102826851A (en) | Preparation method of zirconium boride-silicon carbide complex phase high temperature resistance powder material | |
| CN108083765A (en) | Low heat conduction anti-strip brick and preparation method thereof | |
| CN108395218A (en) | A kind of low carbon magnesia carbon brick and preparation method thereof prepared using modified magnesia | |
| CN108610071A (en) | A kind of self-bonding Tercod and its liquid-phase sintering preparation method | |
| CN101007730A (en) | Alumina-spinel flame-proof material for refining aluminium furnace and its production method | |
| CN110483023A (en) | A kind of microporous corundum brick and preparation method thereof | |
| Zhi et al. | Effect of Al (OH) 3 particle size on microstructures and strengths of porous MgAl2O4 ceramics | |
| CN110903076B (en) | Corundum refractory product for hydrogen-filled molybdenum rod heating furnace and application method thereof | |
| CN112745108A (en) | High-density chromium corundum brick for hazardous waste disposal rotary kiln | |
| CN107043265A (en) | A kind of metallurgical, coloured smelting furnace is not with burning magnesite-chrome brick and preparation method thereof | |
| Kumar et al. | Improvement in thermomechanical properties of off‐grade natural magnesite by addition of Y2O3 | |
| CN114315379B (en) | Glass phase coated zirconia spherical powder and preparation method thereof | |
| CN106810283B (en) | Mullite-chromium lightweight castable | |
| CN104987076A (en) | High-toughness silicon carbide ceramic and low-temperature sintering technology thereof | |
| CN107417286A (en) | One kind enhancing Ultra-low carbon Al2O3‑ZrO2The preparation method of SiC C refractory materials | |
| CN105503193B (en) | It is a kind of to prepare Sialon/Si using kyanite milltailings transition phase inversion3N4The preparation method of-SiC complex phase high-temperature resistant materials | |
| CN107417271A (en) | A kind of preparation method of the bar-shaped brilliant enhancing dimension stone of magnesia alumina spinel of rare earth aluminium (silicon) hydrochlorate | |
| CN112745111A (en) | High-density chromium-zirconium-corundum brick for hazardous waste disposal rotary kiln | |
| CN112745110A (en) | High-density zirconia-corundum brick for hazardous waste disposal rotary kiln |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 313100 No. 2, North Ding Road, Dingjia Bridge, Jiapu Town, Changxing County, Huzhou City, Zhejiang Province Patentee after: Zhejiang Keao High Temperature Technology Integration Co.,Ltd. Address before: Jiapu Yueming village, Changxing County, Huzhou City, Zhejiang Province Patentee before: ZHEJIANG KEAO CERAMIC INDUSTRY CO.,LTD. |