CN115010485B - Refractory material for melting furnace and preparation method thereof - Google Patents
Refractory material for melting furnace and preparation method thereof Download PDFInfo
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/482—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
- C04B35/622—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
- C04B35/6303—Inorganic additives
- C04B35/6306—Binders based on phosphoric acids or phosphates
- C04B35/6309—Aluminium phosphates
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63472—Condensation polymers of aldehydes or ketones
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides 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
- C04B2235/30—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
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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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- 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
- C04B2235/3241—Chromium oxides, chromates, 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
- C04B2235/30—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
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- 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
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention discloses a refractory material for a melting furnace and a preparation method thereof, wherein the refractory material is prepared by mixing a framework comprising silica, chromium oxide, fused magnesia, yttrium oxide, a zirconia matrix and an adhesive; the mass percentages of the raw materials are as follows: 40-45% of zirconia, 10-15% of silica, 15-25% of chromium oxide, 5-10% of fused magnesia, 6-10% of alumina, 1-2% of yttrium oxide and 5-7% of adhesive, wherein the sum of the mass percentages of the raw materials is 100%. The preparation method has low sintering temperature, greatly shortens the sintering time, and the prepared refractory material has the functions of resisting slag erosion and reducing refractory brick cracks under the high-temperature condition, thereby meeting the requirements of a plasma gasification melting furnace.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to a refractory material for a melting furnace and a preparation method thereof.
Background
At present, the urban garbage treatment method generally adopts melting treatment to treat the incineration fly ash remained after incineration. The incineration fly ash is obtained by removing dust from the exhaust gas of the incinerator, and the main components thereof are a certain amount of calcium chloride hydrate, unreacted calcium hydroxide and salts such as hydrogen chloride, potassium chloride, limestone and the like.
The refractory materials used for melting furnaces in the prior art mainly comprise clay refractory materials and metal oxide materials, and for the common clay refractory materials, the allowable operation temperature of the melting furnaces is lower than 1000 ℃, for example, the special CN 114262233A 'novel glass melting furnace bottom large bricks and the preparation process' discloses a clay refractory material resistant to 1400 ℃; the high temperature resistance of the zirconia-corundum brick is superior to that of clay refractory materials, and can reach about 1700-2000 ℃, for example, patent CN 105016747A 'a thermal shock resistant refractory zirconia-corundum brick', which discloses a zirconia-corundum brick resistant to 1700 ℃, which can not be used in a plasma gasification melting furnace, and has weak resistance to incineration fly ash erosion and short service life.
The pH change of the incineration fly ash slag changes the reactivity and cohesiveness of the slag and the refractory material, and the reaction of the slag and the refractory material damages the refractory material, thereby affecting the refractory property of the refractory material. Therefore, when the mixed fly ash is melted, the influence of the pH change on the refractory of the melting furnace and the erosion of the slag on the refractory should be considered when considering the incineration fly ash treatment method.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a refractory material for a melting furnace and a preparation method thereof, wherein the preparation method has low sintering temperature, greatly shortens sintering time, and the prepared refractory material has the functions of resisting slag erosion and reducing refractory brick cracks under high temperature conditions, thereby meeting the requirements of a plasma gasification melting furnace.
Has the effect of slag erosion resistance under the high temperature condition, the temperature resistance degree is 2300-2600 ℃, and meets the requirements of a plasma gasification melting furnace.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a refractory material for a melting furnace, which is prepared by mixing a framework comprising silica, chromium oxide, fused magnesia, yttrium oxide, a zirconia matrix and an adhesive;
the mass percentages of the raw materials are as follows: 40-45% of zirconia, 10-15% of silica, 15-25% of chromium oxide, 5-10% of fused magnesia, 6-10% of alumina, 1-2% of yttrium oxide and 5-7% of adhesive, wherein the sum of the mass percentages of the raw materials is 100%.
Preferably, the refractory raw material consists of the following components in percentage by weight: 45% zirconia, 14% silica, 20% chromia, 7% fused magnesia, 8% alumina, 1% yttria, 6% binder.
Preferably, the mass fraction of magnesium oxide in the fused magnesia is more than or equal to 97%, the mass fraction of calcium oxide is more than or equal to 1%, and the fineness of the fused magnesia is less than 0.1 mm.
Preferably, the binder is a condensed aluminum phosphate or a phenolic resin.
Another object of the present application is to provide a method for preparing a refractory material for a melting furnace, comprising the steps of:
s1: according to the mass ratio of 100: 1-5, weighing magnesite and mixing with additives, and smelting to obtain high-calcium oxide fused magnesia;
s2: mixing silica, chromium oxide, fused magnesia, yttrium oxide and alumina uniformly in a mass ratio to form a framework, adding an adhesive, heating to 280-320 ℃ for high-temperature mixing, adding a zirconia-zirconia matrix, stirring uniformly, and then mixing at a high speed for 15-20min to obtain a mixed raw material;
s3: putting the mixed raw material obtained in the step S2 into a cold isostatic press, and pressing into wet blanks under ultrahigh pressure;
s4: and (3) drying the wet blank obtained in the step (S3) to obtain a blank, and sintering the blank at 1800-2000 ℃ for 14-16 hours to obtain the refractory material.
Preferably, the additive consists of the components with the mass ratio of 1: 2-10 of rare earth samarium-cerium-magnesium alloy and calcium oxide.
Preferably, in step S2, the molding pressure is 200 to 250MPa.
The invention has the beneficial effects that:
1. the chromium oxide has stable performance and good high temperature resistance, the incineration fly ash resistance is excellent, and the prepared refractory material has corrosion resistance and improves the high temperature resistance;
2. the fused magnesia can indirectly introduce CaO into the refractory bricks while providing a magnesium source, and the CaO in the magnesia can be uniformly dispersed in the framework, so that the fused magnesia can play a role in stabilizing zirconia, reducing cracks of the refractory bricks and effectively regulating the thermal shock resistance of the material;
3. adding inY of (2) 2 O 3 Will be in contact with ZrO 2 Formation (Y) 2 O 3 ) ZrO2 solid solution to reduce ZrO 2 The volume expansion associated with the high temperature cooling process causes ZrO in the refractory brick 2 The stability is better, and the generation of monoclinic phase and cracks is reduced; at the same time reduce MgO-ZrO 2 -Cr 2 O 3 The eutectic point of the system reduces the sintering temperature and promotes sintering.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
A refractory material for a melting furnace comprises the following raw materials in percentage by mass: 40% zirconia, 15% silica, 24% chromia, 7% fused magnesia, 8% alumina, 1% yttria, 5% condensed aluminium phosphate.
The preparation method comprises the following steps:
s1: mixing the following components in mass ratio 1:5, mixing the rare earth samarium-cerium-magnesium alloy with calcium oxide to form an additive;
s2: according to the mass ratio of 100:1, weighing magnesite and mixing with additives, and smelting to obtain high-calcium oxide fused magnesia;
s3: firstly, uniformly mixing silica, chromium oxide, fused magnesia, yttrium oxide and aluminum oxide according to mass ratio to be used as a framework, adding an adhesive, heating to 300 ℃ for high-temperature mixing, adding a zirconia matrix for uniform stirring, and then carrying out high-speed mixing for 20min to obtain a mixed raw material;
s4: putting the mixed raw material obtained in the step S3 into a cold isostatic press, and pressing into a wet blank under the ultra-high pressure of 200 Mpa;
s5: and (3) drying the wet blank obtained in the step (S4) at 120 ℃ to obtain a blank, and sintering the blank for 15 hours at 1800 ℃ to obtain the refractory material.
Example 2
A refractory material for a melting furnace comprises the following raw materials in percentage by mass: 40% of zirconia, 15% of silica, 20% of chromium oxide, 9% of fused magnesia, 8% of alumina, 2% of yttrium oxide and 6% of condensed aluminum phosphate.
The preparation method comprises the following steps:
s1: mixing the following components in mass ratio 1:5, mixing the rare earth samarium-cerium-magnesium alloy with calcium oxide to form an additive;
s2: according to the mass ratio of 100:1, weighing magnesite and mixing with additives, and smelting to obtain high-calcium oxide fused magnesia;
s3: firstly uniformly mixing silica, chromium oxide, fused magnesia, yttrium oxide and aluminum oxide according to the mass ratio to be used as a framework, adding an adhesive, heating to 300 ℃ for high-temperature mixing, adding a zirconia matrix for uniform stirring, and then carrying out high-speed mixing for 20min to obtain a mixed raw material;
s4: putting the mixed raw material obtained in the step S3 into a cold isostatic press, and pressing into a wet blank under the ultra-high pressure of 210 Mpa;
s5: and (3) drying the wet blank obtained in the step (S4) at 125 ℃ to obtain a blank, and sintering at 1800 ℃ for 15 hours to obtain the refractory material.
Example 3
A refractory material for a melting furnace comprises the following raw materials in percentage by mass: 45% zirconia, 14% silica, 20% chromia, 7% fused magnesia, 8% alumina, 1% yttria, 5% binder.
The preparation method comprises the following steps:
s1: mixing the following components in mass ratio 1:5, mixing the rare earth samarium-cerium-magnesium alloy with calcium oxide to form an additive;
s2: according to the mass ratio of 100:1, weighing magnesite and mixing with additives, and smelting to obtain high-calcium oxide fused magnesia;
s3: firstly uniformly mixing silica, chromium oxide, fused magnesia, yttrium oxide and aluminum oxide according to the mass ratio to be used as a framework, adding an adhesive, heating to 300 ℃ for high-temperature mixing, adding a zirconia matrix for uniform stirring, and then carrying out high-speed mixing for 20min to obtain a mixed raw material;
s4: putting the mixed raw material obtained in the step S3 into a cold isostatic press, and pressing into a wet blank under the ultra-high pressure of 210 Mpa;
s5: and (3) drying the wet blank obtained in the step (S4) at 125 ℃ to obtain a blank, and sintering at 1800 ℃ for 15 hours to obtain the refractory material.
The refractory materials obtained in examples 1 to 3, the common clay refractory materials and the common zirconia corundum refractory materials in patent CN 105016747A were subjected to slag erosion resistance test, the unshaped refractory materials were prepared into test pieces with a size of 230mm x 114mm x 65mm according to YB/T5202.1, the test pieces were assembled into test panels with polygonal cross sections as rotary furnace linings, and the test was performed at 2500 ℃ by the rotary slag erosion method in the slag erosion resistance test method of GB T8931-2007, and the results are shown in table 1.
TABLE 1 slag erosion depth and penetration depth test results for refractory materials
The refractories obtained in examples 1 to 3, the common clay refractories and the common zirconia corundum refractories in patent CN 105016747a were subjected to refractoriness tests according to the method specified in GB/T7322-2007, and the test results shown in table 2 were obtained.
TABLE 2 results of refractoriness test
The refractory materials obtained in examples 1 to 3, the common clay refractory material and the common zirconia alumina refractory material in patent CN 105016747A were subjected to thermal shock resistance test according to the method specified in GB/T30873-2014, and the test results shown in table 3 were obtained.
In summary, the refractory material prepared by the technical scheme claimed in the application has the effect of resisting the erosion of slag under the high-temperature condition, as shown in table 1; the temperature resistance degree is 2300-2600 ℃, meets the requirements of a plasma gasification melting furnace, and is shown in table 2; the common zirconia corundum refractory material has better thermal shock resistance performance, but other performances are not as good as those of the common zirconia corundum refractory material, the sintering time can reach 70 hours, and the preparation method of the common zirconia corundum refractory material greatly shortens the sintering time and effectively adjusts the thermal shock resistance performance of the refractory material, as shown in table 3.
In the testing process, the surface condition of each refractory material is observed when the refractory material is close to the self temperature-resistant degree, and different degrees of cracks appear on the surfaces of the common zirconia-corundum refractory material and the clay refractory material.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (6)
1. A refractory material for a melting furnace is characterized by being prepared by mixing a framework comprising silica, chromium oxide, fused magnesia, yttrium oxide, a zirconia matrix and a binder;
the mass percentages of the raw materials are as follows: 40-45% of zirconia, 10-15% of silica, 15-25% of chromium oxide, 5-10% of fused magnesia, 6-10% of alumina, 1-2% of yttrium oxide and 5-7% of adhesive, wherein the sum of the mass percentages of the raw materials is 100%;
the preparation method of the refractory material for the melting furnace is characterized by comprising the following steps of:
s1: according to the mass ratio of 100: 1-5, weighing magnesite and mixing with additives, and smelting to obtain high-calcium oxide fused magnesia;
s2: mixing silica, chromium oxide, fused magnesia, yttrium oxide and alumina according to the mass ratio uniformly to form a framework, adding an adhesive, heating to 280-320 ℃ for high-temperature mixing, adding a zirconia matrix for uniform stirring, and then mixing at a high speed for 15-20min to obtain a mixing raw material;
s3: putting the mixed raw material obtained in the step S2 into a cold isostatic press, and pressing into wet blanks under ultrahigh pressure;
s4: and (3) drying the wet blank obtained in the step (S3) to obtain a blank, and sintering at 2000-2200 ℃ for 14-16 h to obtain the refractory material.
2. The refractory for a melting furnace according to claim 1, wherein the refractory raw material is composed of the following components in mass percent: 45% zirconia, 14% silica, 20% chromia, 7% fused magnesia, 8% alumina, 1% yttria, 5% binder.
3. The refractory for a melting furnace according to claim 1, wherein the mass fraction of magnesium oxide in the fused magnesia is not less than 97%, the mass fraction of calcium oxide is not less than 1%, and the fineness of the fused magnesia is not more than 0.1 mm.
4. A refractory for a melting furnace according to claim 1, wherein said binder is a condensed aluminum phosphate or a phenolic resin.
5. The refractory for a melting furnace according to claim 1, wherein the additive comprises the components in a mass ratio of 1: 2-10 of rare earth samarium-cerium-magnesium alloy and calcium oxide.
6. The refractory for a melting furnace according to claim 5, wherein in step S3, the molding pressure is 200 to 250MPa.
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| CN1521139A (en) * | 2003-02-13 | 2004-08-18 | 李葵荣 | Method for smelting high-calcium low-silicon fused magnesia |
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| CN105585322A (en) * | 2015-12-21 | 2016-05-18 | 洛阳利尔耐火材料有限公司 | Slag-corrosion-resistant magnesite-spinel brick and preparation method thereof |
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