CN112939618A - Anti-skinning zircon-based alkali-resistant brick for cement kiln and preparation method thereof - Google Patents

Anti-skinning zircon-based alkali-resistant brick for cement kiln and preparation method thereof Download PDF

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CN112939618A
CN112939618A CN202110292037.6A CN202110292037A CN112939618A CN 112939618 A CN112939618 A CN 112939618A CN 202110292037 A CN202110292037 A CN 202110292037A CN 112939618 A CN112939618 A CN 112939618A
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powder
zircon
skinning
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parts
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马淑龙
苏玉柱
周伟
丛江波
张康康
郝瑞
孟令汉
陈宝贵
席含博
李燕京
高长贺
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Beijing Jinyu Tongda Refractory Technology Co ltd
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Beijing Jinyu Tongda Refractory Technology Co ltd
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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
    • 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
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

The invention provides an anti-skinning zircon-based alkali-resistant brick for a cement kiln and a preparation method thereof, wherein the alkali-resistant brick is prepared from the following raw materials in parts by mass: 65-80 parts of single crystal phase mullite homogeneous material, 5-10 parts of zirconite powder, 5-15 parts of zircon powder, 1-3 parts of wollastonite powder, 1-3 parts of metal silicon powder, 5-8 parts of white mud and 3-4 parts of dextrin solution. The anti-skinning zircon-based alkali-resistant brick for the cement kiln, provided by the invention, has more excellent low porosity, high strength, high refractoriness under load, excellent alkali corrosion resistance and anti-skinning performance, can replace a silicon carbide product in the market to apply a preheater system which is easy to skin the cement kiln, overcomes the problem of hydration and oxidation of a silicon carbide brick, and greatly reduces the heat conductivity and the volume density of the material.

Description

Anti-skinning zircon-based alkali-resistant brick for cement kiln and preparation method thereof
Technical Field
The invention relates to the field of refractory materials, in particular to an anti-skinning zircon-based alkali-resistant brick for a cement kiln and a preparation method thereof.
Background
The cement kiln is used as main equipment for cooperatively treating industrial waste, household garbage, municipal sludge and other dangerous waste, and serious crust is easily formed because the waste contains a large amount of harmful components such as sulfur, alkali, chlorine and the like and is circularly enriched in a cement kiln preheater system. The skinning can cause the blockage of the preheater, seriously affect the running rate and the yield of the cement kiln and also seriously affect the quality of cement clinker. Therefore, solving the skinning problem of the preheater system of the cement kiln becomes a neck link to be solved urgently by a plurality of cement enterprises.
The anti-skinning system in the market at present mainly uses silicon carbide refractory castable and refractory bricks, and silicon carbide is used for preventing alkali salt from wetting and SiC is oxidized in the using process to form a layer of compact glass phase on the surface, so that the material has good skinning resistance. However, when the silicon carbide product is used for cooperatively treating municipal waste and sludge with large water content, the preheater system has high water content, and the refractory material (800-.
Disclosure of Invention
The embodiment of the invention provides an anti-skinning zirconium-based alkali-resistant brick for a cement kiln. The zirconium-based alkali-resistant brick provided by the invention has more excellent low porosity, high strength, high refractoriness under load, excellent alkali corrosion resistance and anti-skinning performance, can replace the silicon carbide products in the market to apply a preheater system which is easy to skin in a cement kiln, overcomes the problem of hydration and oxidation of the silicon carbide brick, greatly reduces the thermal conductivity and the volume density of the material, and effectively reduces the cost.
The embodiment of the invention provides an anti-skinning zirconium-based alkali-resistant brick for a cement kiln, which is prepared from the following raw materials in parts by mass: 65-80 parts of single crystal phase mullite homogeneous material, 5-10 parts of zirconite powder, 5-15 parts of zircon powder, 1-3 parts of wollastonite powder, 1-3 parts of metal silicon powder, 5-8 parts of white mud and 3-4 parts of dextrin solution. Aiming at the defects of the silicon carbide refractory material, the invention optimizes and develops the zirconium-based anti-skinning alkali-resistant brick without non-oxides such as silicon carbide and the like by utilizing the excellent alkali corrosion resistance of the alkali-resistant brick. On one hand, the zirconium oxide is generated by decomposing the zirconite and the zirconium kyanite, the alkali corrosion resistance of the product is improved by the mullite of the zirconium kyanite and a large amount of free silica of the zirconium kyanite, the liquid phase viscosity is improved, the alkali salt corrosion penetration is prevented, and the anti-skinning performance is improved. On the other hand, in order to further improve the silicon content and reduce the porosity of the product, dense single-crystal-phase mullite (namely mullite-high silica glass phase) is adopted, and superfine silica fume and metallic silicon are introduced to improve the SiO of the product2Content, and the porosity is reduced to improve the alkali corrosion resistance, and the anti-skinning performance is further optimized. The zircon-based alkali-resistant brick for resisting skinning also greatly reduces the heat conductivity and the volume density of a silicon carbide product, and has unique advantages in the aspects of energy conservation and light weight.
According to the embodiment of the invention, the skinning-resistant zirconium-based alkali-resistant brick for the cement kiln comprises Al in the single-crystal-phase mullite homogeneous material2O3Preferably, the mass content of the mullite is 40-48%, and Al in the single-crystal-phase mullite homogeneous material is preferably2O342-45% by mass of SiO250-55% by mass of K2The mass content of O is less than 0.5 percent; the volume density of the single-crystal-phase mullite homogeneous material is more than 2.35g/cm3Preferably 2.45 to 2.50g/cm3. In the invention, K is reduced by controlling the aluminum content in the formula2O、Na2The material has compact sintering, good crystal phase development, low porosity and high strength, and the temperature resistance, wear resistance and erosion resistance of the product can be further improved by optimizing the single-crystal-phase mullite.
According to the embodiment of the invention, the anti-skinning zirconium-based alkali-resistant brick for the cement kiln is characterized in that the grain size distribution of the single-crystal-phase mullite homogeneous material is as follows: d is not less than 3mm1＜5mm、1mm≤d2＜3mm、0.074mm≤d3< 1mm and 0mm < d4The mass ratio of less than 0.074mm is 4-8: 35-45: 15-25: 5 to 20. In the invention, by controlling the particle size distribution range, the particles can be tightly packed, and the porosity of the material is reduced, and the erosion resistance is effectively improved.
According to the embodiment of the invention, the crust-resistant zirconium-based alkali-resistant brick for the cement kiln is provided, wherein ZrO in the zircon powder2The mass content of (A) is more than 60 percent; in the zirconium sapphire powder, Al2O345-55% by mass of ZrO2The mass content of (A) is more than 5 percent; in the silica fume powder, SiO2The mass content of (A) is more than 92 percent; in the metal silicon powder, the mass content of Si is more than 97 percent; in the white mud, Al2O3In mass fraction of>28 percent, and the white mud is preferably Guangxi white mud. Preferably, ZrO in the zircon powder2The mass content of (A) is more than 65%; in the silica fume powder, SiO2In mass fraction of>95 percent; in the Guangxi white mud, Al2O330-35% by mass of K2O+Na2O content less than 0.4% by mass, Fe2O3The mass content of (A) is less than 1.5%. In the present invention, the zirconium source is introduced on the one hand by controlling the zirconium source (zircon and zirconium kyanite). In addition, the influence of impurities on the decomposition of the zircon is reduced, the mullite of the amorphous quartz decomposed by the zircon is facilitated, and the anti-skinning performance is further improved; the preferred white mud is mainly used for controlling the content of impurities, ensuring the good plasticity index of the material and contributing to the densification of products.
According to the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, in the zircon powder, the particle size of the zircon powder is that d is more than 0mm and less than 0.074 mm; the particle size of the zirconium cyanite powder is more than 0mm and less than 0.074 mm; the particle size of the silicon ash powder is more than 0mm and less than d and 0.010 mm; and/or the particle size of the metal silicon powder is more than 0mm and less than d1 and less than 0.074 mm; the granularity of the Guangxi white mud is more than 0mm and less than 0.074 mm. In the invention, by controlling the proper particle size range, the decomposition of the zirconite is controllable, and the physical and chemical performance indexes of the material, such as strength, wear resistance, erosion resistance and the like, are effectively improved on the basis of ensuring the anti-skinning effect in the using process.
According to the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, in the zircon powder, the dextrin solution is a dextrin aqueous solution; preferably, the mass ratio of the maltodextrin to the water is 1: 1-2, the specific gravity of the dextrin aqueous solution is 1.1-1.2 g/cm3。
In the invention, by adopting maltodextrin, particularly the preferable dextrin water solution, the pug has good forming performance and green brick strength, and the environmental problem caused by the pulp waste liquid adopted in the market is avoided.
The embodiment of the invention also provides a preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, which comprises the following steps: mixing the single crystal phase mullite homogeneous material, zircon powder, silica fume, metal silicon, dextrin water solution, zirconium cyanite powder and Guangxi white mud according to the proportion to prepare a green brick, and drying, sintering and cooling the green brick.
The preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, comprises the following steps:
1) preparing a single-crystal-phase mullite homogeneous material, zircon powder, silica fume, metal silicon, a dextrin aqueous solution, zirconium cyanite powder and Guangxi white mud according to a ratio;
2) pre-mixing zircon powder with the particle size of more than 0mm and less than 0.074mm, silica fume powder with the particle size of more than 0mm and less than 0.010mm and metal silicon powder with the particle size of more than 0mm and less than 0.074mm, which are prepared in the step 1), to obtain mixed powder;
3) d is the grain diameter of 3mm or less1＜5mm、1mm≤d2D is less than 3mm and the particle diameter is not less than 0.074mm3Dry-mixing the single-crystal-phase mullite homogeneous material with the diameter less than 1mm, then adding a dextrin solution for mixing, and then adding the mixed powder obtained in the step 2) and Guangxi white mud for mixing to obtain mud;
4) pressing the pug obtained in the step 3) into green bricks, drying and sintering, and then cooling to room temperature.
According to the preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, in the step 4), the drying temperature is 100-180 ℃, and the drying time is 12-24 hours; preferably, drying is carried out by adopting a drying kiln, and the temperature at the inlet of the drying kiln is preferably 30-60 ℃; the volume density of the green brick is 2.40-2.60 g/cm3。
According to the preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, in the step 4), the firing temperature is 1300-1450 ℃, and the temperature is kept for 4-10 h at the firing temperature; raising the temperature from room temperature to 1450 ℃, and preserving the temperature for 4-10 h at 1450 ℃.
According to the embodiment of the invention, the anti-skinning zirconium-based alkali-resistant brick for the cement kiln or the anti-skinning zirconium-based alkali-resistant brick for the cement kiln obtained by the preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln is used as an anti-skinning zirconium-based alkali-resistant brick for co-processing waste in the cement kiln. According to the invention, the alkali-resistant brick is innovatively optimized and promoted, the zirconium kyanite, the zirconite and the monocrystalline mullite are matched, and the silicon content of the system is further reduced by introducing the ultrafine silica fume and the metallic silicon, so that the porosity is reduced, and the product density is improved. Compared with the common alkali-resistant brick, the zirconium-based alkali-resistant brick is a new system alkali-resistant brick, and has more excellent low porosity, high strength, high refractoriness under load, excellent alkali erosion resistance and excellent anti-skinning performance. The anti-skinning zirconium-based alkali-resistant brick can replace the silicon carbide products in the market, is applied to a preheater system which is easy to skinne in a cement kiln, overcomes the problem of hydration and oxidation of the silicon carbide brick, and greatly reduces the heat conductivity and the volume density of the material.
The invention has the beneficial effects that: the invention adopts the zirconium kyanite, the zirconite and the single crystal phase mullite as the main raw materials, and on one hand, the free SiO is generated by utilizing the high-temperature decomposition of the zirconium kyanite and the zirconite2The silicon carbide is oxidized to generate the silicon dioxide anti-skinning effect, and the zirconium kyanite is mullite to reduce the porosity. Secondly, the single crystal phase mullite is a mullite-high silica glass complex phase material by utilizing the self structural characteristics of the single crystal phase mullite, and the needle column-shaped mullite phases are mutually crossed to form the mullite-high silica glass complex phase materialThe high silica glass phase is filled in the mullite crystal phase, the aluminum content is close to that of flint clay, the structure is compact, the alkali corrosion resistance of the material can be effectively improved due to the high silica glass phase, and the material has good high-temperature mechanical resistance and higher wear resistance compared with low bauxite clinker and flint clay. The existence of high-activity silica fume and metallic silicon can further reduce the porosity of the material and improve the SiO2The content of the additive is further improved, the corrosion resistance and the adhesion resistance of the material to alkali and cement dust are further improved, and the anti-skinning performance of the material is further improved. The volume density of the zirconium-based alkali-resistant brick prepared by the invention is about 2.3-2.5g/cm3The volume density of the silicon carbide-based castable and the silicon carbide brick is 2.5-2.7g/cm3Compared with the prior art, the volume density is greatly reduced, and the thermal conductivity coefficient of the material at 1000 ℃ is 9-10W (m.K)-1Reduce 1-1.5W (m.K)-1The temperature of the cylinder can be reduced by more than 50 ℃, the use of the refractory brick is reduced by 10 percent, and the cost can be effectively reduced. The zircon-based alkali-resistant brick solves the problem of low-temperature hydration and oxidation of a silicon carbide product, solves the problem of anti-skinning of the alkali-resistant brick, improves the high-temperature resistance and the wear resistance, and prolongs the service life to more than 3 years. Al in zirconium-based alkali-resistant brick prepared by the invention2O3ZrO in an amount of about 30 to 40%2The content is 3-10%, the porosity is less than 16%, and the alkali resistance and the anti-skinning performance of the material are effectively improved. It is a kind of excellent anti-erosion, anti-wear, high temperature resistant, anti-skinning refractory product.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples, single crystal phase mullite homogeneous material Al2O344.25% by mass of SiO252.36% by mass of K2The mass content of O is less than 0.38 percent; the bulk density is 2.47g/cm3. Among zircon powders, ZrO265.52% by mass; in the zirconium sapphire powder, Al2O351.48% by mass of ZrO26.58 percent; in the silica fume powder, SiO295.43% by mass; in the metal silicon powder, the mass content of Si is 97.67%; in the Guangxi white mud, Al2O331.38% by mass of (A), K2O+Na20.32% of O and Fe2O31.26% by mass.
The preparation method of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln, provided by the embodiment of the invention, comprises the following steps:
1) preparing a single-crystal-phase mullite homogeneous material, zircon powder, silica fume, metal silicon, a dextrin aqueous solution, zirconium cyanite powder and Guangxi white mud according to a ratio;
2) pre-mixing zircon powder with the particle size of more than 0mm and less than 0.074mm, silica fume powder with the particle size of more than 0mm and less than 0.010mm and metal silicon powder with the particle size of more than 0mm and less than 0.074mm, which are prepared in the step 1), to obtain mixed powder;
3) d is the grain diameter of 3mm or less1＜5mm、1mm≤d2D is less than 3mm and the particle diameter is not less than 0.074mm3Dry-mixing the single-crystal-phase mullite homogeneous material with the diameter less than 1mm, then adding a dextrin solution for mixing, and then adding the mixed powder obtained in the step 2) and Guangxi white mud for mixing to obtain mud;
4) preparing the pug obtained in the step 3) into pug with the bulk density of 2.40-2 by adopting a press.60g/cm3Drying the green bricks by using a drying kiln, wherein the temperature at the inlet of the drying kiln is 30-60 ℃, the drying temperature is 100-180 ℃, and the drying time is 12-24 hours; heating the high-temperature kiln from room temperature to 1450 ℃, and preserving the heat for 4-10 h at 1450 ℃; then cooled to room temperature.
Example 1
The embodiment provides an anti-skinning zirconium-based alkali-resistant brick (single-crystal-phase mullite brick) for a cement kiln, which is prepared from the following raw materials in parts by mass: 80 parts of single crystal phase mullite (homogeneous material), 5 parts of zircon powder, 5 parts of zirconium cyanite powder, 2 parts of wollastonite powder, 2 parts of metal silicon powder, 6 parts of Guangxi white mud and 4 parts of dextrin water solution.
Wherein the grain size distribution of the single crystal phase mullite homogeneous material is as follows: d is not less than 3mm1＜5mm、1mm≤d1＜3mm、0.074mm≤d1< 1mm and 0mm < d1The mass ratio of less than 0.074mm is 5: 35: 20: 20.
TABLE 1 criteria for testing item selection
Figure BDA0002982582240000071
The performance of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln prepared in the embodiment is detected as follows: the detection is carried out according to the existing national relevant standards, and the detection items are shown in table 1. The detection results are as follows: al in the prepared single crystal phase mullite brick2O3Content of 38.2% ZrO2The content is 3.8 percent, the apparent porosity is 15.8 percent, and the volume density is 2.36g/cm3The normal temperature compressive strength is 67.4MPa, the refractoriness under load is 1562 ℃, the thermal shock stability (1100 ℃, water cooling) is more than 15 times, and the thermal conductivity coefficient at 1000 ℃ is 1.06W (m.K)-1。
Example 2
The embodiment provides an anti-skinning zirconium-based alkali-resistant brick for a cement kiln, which is prepared by the same method as the embodiment 1, and is characterized in that: the feed is prepared from the following raw materials in parts by mass: 72 parts of single-crystal-phase mullite homogeneous material, 10 parts of zircon powder, 10 parts of zirconium blue spar powder, 1 part of wollastonite powder, 2 parts of metal silicon powder, 5 parts of Guangxi white mud and 3.5 parts of dextrin water solution.
Wherein the grain size distribution of the single crystal phase mullite homogeneous material is as follows: d is not less than 3mm1＜5mm、1mm≤d1＜3mm、0.074mm≤d1< 1mm and 0mm < d1The mass ratio of less than 0.074mm is 5: 32: 25: 15.
the performance of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln prepared in the embodiment is detected, and the detection result is as follows: al in the prepared single crystal phase mullite brick2O3Content of 36.8% ZrO2The content is 6.9 percent, the apparent porosity is 15.3 percent, and the volume density is 2.40g/cm3The normal temperature compressive strength is 57.4MPa, the refractoriness under load is 1552 ℃, the thermal shock stability (1100 ℃, water cooling) is more than 15 times, and the thermal conductivity coefficient at 1000 ℃ is 1.24W (m.K)-1。
Example 3
The embodiment provides an anti-skinning zirconium-based alkali-resistant brick for a cement kiln, which is prepared by the same method as the embodiment 1, and is characterized in that: the feed is prepared from the following raw materials in parts by mass: 65 parts of single-crystal-phase mullite homogeneous material, 12 parts of zircon powder, 10 parts of zirconium blue spar powder, 3 parts of wollastonite powder, 1 part of metal silicon powder, 8 parts of Guangxi white mud and 3.5 parts of dextrin aqueous solution.
Wherein the grain size distribution of the single crystal phase mullite homogeneous material is as follows: the mass ratio of d1 which is more than or equal to 3mm and less than 5mm, d1 which is more than or equal to 1mm and less than or equal to 3mm, d1 which is more than or equal to 0.074mm and d1 which is more than 0mm and less than 0.074mm is 5: 35: 20: 10.
the performance of the anti-skinning zirconium-based alkali-resistant brick for the cement kiln prepared in the embodiment is detected, and the detection result is as follows: al in the prepared single crystal phase mullite brick2O3Content of 33.1% ZrO2The content is 8.4 percent, the apparent porosity is 15.7 percent, and the volume density is 2.44g/cm3Normal temperature compression strength 53.4MPa, refractoriness under load 1522 ℃, thermal shock stability (1100 ℃, water cooling) more than 15 times, and thermal conductivity coefficient of 1.33W (m.K) at 1000 DEG C-1。
Example 4
The embodiment provides an anti-skinning zirconium-based alkali-resistant brick for a cement kiln, which is prepared by the same method as the embodiment 1, and is characterized in that: the feed is prepared from the following raw materials in parts by mass: 65 parts of single-crystal-phase mullite homogeneous material, 10 parts of zircon powder, 15 parts of zirconium blue spar powder, 2 parts of wollastonite powder, 2 parts of metal silicon powder, 6 parts of Guangxi white mud and 3.5 parts of dextrin aqueous solution.
Wherein the grain size distribution of the single crystal phase mullite homogeneous material is as follows: the mass ratio of d1 which is more than or equal to 3mm and less than 5mm, d1 which is more than or equal to 1mm and less than or equal to 3mm, d1 which is more than or equal to 0.074mm and d1 which is more than 0mm and less than 0.074mm is 5: 30: 25: 5.
the single crystal phase mullite brick prepared in the embodiment is subjected to performance detection, and the detection result is as follows: al in the prepared single crystal phase mullite brick2O3Content of 32.9% ZrO2The content is 7.1 percent, the apparent porosity is 14.1 percent, and the volume density is 2.49g/cm3Normal temperature compression strength 63.4MPa, refractoriness under load 1522 ℃, thermal shock stability (1100 ℃, water cooling) more than 15 times, and thermal conductivity coefficient of 1.50W (m.K) at 1000 DEG C-1。
The existing cement kiln preheater system anti-skinning material usually adopts silicon carbide castable and silicon carbide bricks with the silicon carbide content reaching 30-80%. With the increase of the types and the quantity of the waste treated by the cement kiln, particularly waste acid with large water content, waste alkali, municipal sludge and the like, the silicon carbide products are easy to be oxidized by steam at low temperature, and the use effect is influenced by the damage of refractory materials. The invention considers the actual working condition of high alkali content of the preheater system, utilizes the mechanism of zircon decomposition and anti-skinning, adopts single-crystal phase mullite to replace alumina and flint clay, introduces silica fume and metallic silicon, adopts the high-temperature oxidation of superfine powder and metallic silicon to further reduce the porosity of the product, improves the silicon content, further improves the alkali corrosion resistance, finally improves the anti-skinning performance, improves the strength and the wear resistance, prolongs the service life under severe working conditions, and has good application prospect.
The anti-skinning zirconium-based alkali-resistant brick for the cement kiln, which is prepared in the embodiment, has excellent performance, the embodiment 4 has the best performance, and meanwhile, the brick has the advantages of low porosity, high strength, high zirconia content and better anti-skinning comprehensive performance.
Comparative example 1
This comparative example provides an anti-spalling high alumina brick, which differs from example 4 in that: introduction of alumina clinker (Al)2O3Content greater than 80%) of the substitute single crystalPhase mullite, which is also an indicator of zircon as a zirconium source, is resistant to Al of the high-alumina brick2O3A content of more than 65 percent, ZrO25-10% of content, 18-20% of apparent porosity and 2.65-2.80g/cm of volume density3Normal temperature compression strength 60-90MPa, refractoriness under load 1550--1. The anti-stripping high-alumina brick has a certain anti-skinning effect according to related papers, but compared with a zircon brick, the anti-skinning performance is poorer, and the anti-skinning requirement of a cement kiln at the present stage, particularly a co-processing cement kiln, cannot be met. In addition, the volume density is large, the heat conductivity is high, the alkali corrosion resistance is poor, and the manufacturing cost and the energy-saving effect are also obviously reduced.
Comparative example 2
The comparative example provides a low thermal conductivity single crystal phase mullite brick, which adopts single crystal phase mullite (Al) as the raw material2O340% -48%) and is different from that of example 4 in that the other raw materials are different (no zircon powder, zirconium blue-crystal powder and other zirconium source powder are added in the single-crystal-phase mullite brick, the single-crystal-phase mullite brick and the blue-crystal powder are adopted in the composition, and the activity rho-Al is2O3The powder is matched to prepare a low-aluminum pure mullite system. The detection result of the single crystal phase mullite brick is as follows: al (Al)2O3About 35-45%, porosity less than 16%, and volume density of 2.3-2.45g/cm3The strength is more than 50MPa, the thermal shock stability is more than 15 times, and the refractoriness under load is more than 1500 ℃. The product is mainly applied to a wear-resistant, high-temperature-resistant and excellent low-heat-conduction refractory product of a cement kiln and a tertiary air duct. However, compared with the anti-skinning zirconium-based alkali-resistant brick, the anti-skinning performance of the brick is poor, even the brick has no anti-skinning functionality, cannot meet the anti-skinning requirement of the existing cement kiln, particularly areas for cooperatively treating a cement kiln preheater, a smoke chamber, a discharging pipe and the like, and is completely different from the using areas and the using functionalities of the brick.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The anti-skinning zircon-based alkali-resistant brick for the cement kiln is characterized by being prepared from the following raw materials in parts by mass: 65-80 parts of single crystal phase mullite homogeneous material, 5-10 parts of zirconite powder, 5-15 parts of zircon powder, 1-3 parts of wollastonite powder, 1-3 parts of metal silicon powder, 5-8 parts of white mud and 3-4 parts of dextrin solution.
2. The anti-skinning zircon-based alkali-resistant brick for cement kiln as claimed in claim 1, wherein Al in the single crystal phase mullite homogeneous material2O3Preferably, the mass content of the mullite is 40-48%, and Al in the single-crystal-phase mullite homogeneous material is preferably2O342-45% by mass of SiO250-55% by mass of K2The mass content of O is less than 0.5 percent; the volume density of the single-crystal-phase mullite homogeneous material is more than 2.35g/cm3Preferably 2.45 to 2.50g/cm3。
3. The anti-skinning zircon-based alkali-resistant brick for cement kiln according to claim 2, wherein the grain size distribution of the single crystal phase mullite homogenate is as follows: d is not less than 3mm1＜5mm、1mm≤d2＜3mm、0.074mm≤d3< 1mm and 0mm < d4The mass ratio of less than 0.074mm is 4-8: 35-45: 15-25: 5 to 20.
4. The anti-skinning zircon-based alkali-resistant brick for cement kiln according to claim 3, wherein the zircon powder is ZrO 22The mass content of (A) is more than 60 percent; in the zirconium sapphire powder, Al2O345-55% by mass of ZrO2The mass content of (A) is more than 5 percent; in the silica fume powder，SiO2The mass content of (A) is more than 92 percent; in the metal silicon powder, the mass content of Si is more than 97 percent; in the white mud, Al2O3In mass fraction of>28%, wherein the white mud is preferably Guangxi white mud;
preferably, ZrO in the zircon powder2The mass content of (A) is more than 65%; in the silica fume powder, SiO2In mass fraction of>95 percent; in the Guangxi white mud, Al2O330-35% by mass of K2O+Na2O content less than 0.4% by mass, Fe2O3The mass content of (A) is less than 1.5%.
5. The anti-skinning zircon-based alkali-resistant brick for a cement kiln according to claim 4, wherein the zircon powder has a particle size of 0mm < d < 0.074 mm; the particle size of the zirconium cyanite powder is more than 0mm and less than 0.074 mm; the particle size of the silicon ash powder is more than 0mm and less than d and 0.010 mm; and/or the particle size of the metal silicon powder is more than 0mm and less than d1 and less than 0.074 mm; the granularity of the Guangxi white mud is more than 0mm and less than 0.074 mm.
6. The anti-skinning zircon-based alkali-resistant brick for cement kiln according to any one of claims 1 to 5, wherein the dextrin solution is an aqueous dextrin solution; preferably, the mass ratio of the maltodextrin to the water is 1: 1-2, the specific gravity of the dextrin aqueous solution is 1.1-1.2 g/cm3。
7. The method for preparing the anti-skinning zircon-based alkali-proof brick for the cement kiln as claimed in any one of claims 1 to 6, is characterized by comprising the following steps: mixing the single crystal phase mullite homogeneous material, zircon powder, silica fume, metal silicon, dextrin water solution, zirconium cyanite powder and Guangxi white mud according to the proportion to prepare a green brick, and drying, sintering and cooling the green brick.
8. The method for preparing the anti-skinning zircon-based alkali-resistant brick for the cement kiln according to claim 7, comprising the steps of:
1) preparing a single-crystal-phase mullite homogeneous material, zircon powder, silica fume, metal silicon, a dextrin aqueous solution, zirconium cyanite powder and Guangxi white mud according to a ratio;
2) pre-mixing zircon powder with the particle size of more than 0mm and less than 0.074mm, silica fume powder with the particle size of more than 0mm and less than 0.010mm and metal silicon powder with the particle size of more than 0mm and less than 0.074mm, which are prepared in the step 1), to obtain mixed powder;
3) d is the grain diameter of 3mm or less1＜5mm、1mm≤d2D is less than 3mm and the particle diameter is not less than 0.074mm3Dry-mixing the single-crystal-phase mullite homogeneous material with the diameter less than 1mm, then adding a dextrin solution for mixing, and then adding the mixed powder obtained in the step 2) and Guangxi white mud for mixing to obtain mud;
4) pressing the pug obtained in the step 3) into green bricks, drying and sintering, and then cooling to room temperature.
9. The method for preparing the anti-skinning zircon based alkali-resistant brick for the cement kiln according to claim 8, wherein in the step 4), the drying temperature is 100 to 180 ℃ and the drying time is 12 to 24 hours; preferably, drying is carried out by adopting a drying kiln, and the temperature at the inlet of the drying kiln is preferably 30-60 ℃; the volume density of the green brick is 2.40-2.60 g/cm3。
10. The method for preparing the anti-skinning zircon based alkali-resistant brick for the cement kiln according to claim 8 or 9, wherein in the step 4), the firing temperature is 1300-1450 ℃, and the temperature is kept at the firing temperature for 4-10 h; preferably, the temperature is raised from room temperature to 1450 ℃, and the temperature is kept at 1450 ℃ for 4-10 h.
CN202110292037.6A 2021-03-18 2021-03-18 Anti-skinning zircon-based alkali-resistant brick for cement kiln and preparation method thereof Pending CN112939618A (en)

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