CN109534788B - Low-chromium magnesia-chrome brick for glass kiln - Google Patents

Low-chromium magnesia-chrome brick for glass kiln Download PDF

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CN109534788B
CN109534788B CN201811559656.1A CN201811559656A CN109534788B CN 109534788 B CN109534788 B CN 109534788B CN 201811559656 A CN201811559656 A CN 201811559656A CN 109534788 B CN109534788 B CN 109534788B
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magnesia
chrome
granularity
brick
low
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CN109534788A (en
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徐琳琳
王俊涛
徐如林
魏瀚
闫昕
周严敦
王杰曾
袁林
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Ruitai 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
    • C04B35/01—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
    • C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/043—Refractories from grain sized mixtures
    • C04B35/047—Refractories from grain sized mixtures containing chromium oxide or chrome ore
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a low chrome magnesia chrome brick for a glass kiln, which is characterized in that the content of fused magnesia with the granularity of 4-2mm is 25-10 percent; 15-10% of fused magnesia with the granularity of 2-1 mm; 20-5% of fused magnesia-alumina spinel with the granularity of 2-1 mm; 30-10% of pre-synthesized magnesia-chrome sand with the granularity of 1-0 mm; 40-30% of fused magnesia with granularity less than 0.088 mm; in addition, a bonding agent accounting for 3-5% of the total mass of all the raw materials is added. The low-chromium magnesia chrome brick for the glass kiln has the performance characteristics of low chromium content, high density, high strength, strong erosion resistance and good creep resistance. The low-chromium magnesia chrome brick is used for a regenerative chamber of a glass kiln, can greatly reduce the chromium content of refractory materials, effectively relieve the pollution of hexavalent chromium contained in residual bricks to the environment, prolong the service life of the kiln, and improve the operation rate of the kiln, thereby obtaining good economic benefit and social benefit.

Description

Low-chromium magnesia-chrome brick for glass kiln
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a low-chromium magnesia chrome brick for a regenerative chamber of a glass kiln.
Background
With the rapid development of the glass industry, the total production of the plate glass in China is the first in the world. In recent years, the glass industry faces the challenges of excess capacity and transformation upgrading, and in order to further reduce the cost, the technology of replacing heavy oil with petroleum coke as fuel has been widely applied to the glass industry, no matter float glass or bottle and can glass. But the use of petroleum coke is accompanied by increased erosion and a significant reduction in kiln life.
At present, the upper layer of a regenerative chamber of a glass kiln uses magnesia bricks with the MgO content of about 97 percent; one part of magnesia bricks with the MgO content of about 95 percent originally used in the upper layer of the regenerator is replaced by 97 percent magnesia bricks, and the other part of magnesia bricks is replaced by directly combined magnesia-chrome bricks; the middle layer of the regenerator is directly bonded with magnesia-chrome bricks; the lower layer of the regenerator is made of low-porosity clay bricks. Wherein, the upper layer and the middle layer in the regenerator are the sections with the largest load. On the one hand, the middle upper layer and the middle layer lattice body are stressed by the upper layer lattice body; on the other hand, a large amount of mirabilite is separated out from the kiln gas, condensed on the surface of the middle checker brick and drilled into the brick, and severe corrosion is generated on the checker brick. Sometimes, the condensate contains only mirabilite and is neutral(ii) a Sometimes the condensate contains excess SO3Is acidic; sometimes the condensate contains excess Na2O is basic. In addition, CaO, SiO in the condensate2The brick body is also eroded with the help of mirabilite.
CN102336539A discloses a baking-free magnesia-chrome brick prepared by using waste regeneration and a preparation method thereof, wherein raw materials comprising 65-75% of waste magnesia-chrome brick particles, 18-28% of fused magnesia, 2-4% of magnesia-alumina spinel and 3-5% of liquid thermosetting phenolic resin by weight percent are uniformly mixed, pressed and formed, baked for 24 hours at 200 ℃, and taken out of a kiln after natural cooling. The method fully recycles the production raw materials of the magnesia-chrome brick, and effectively reduces the environmental pollution. However, the unburned magnesite-chrome brick has unstable quality in use due to different crystal orientations and unstable impurity content in the waste bricks. CN102731121A discloses a high-performance Mg-Al-Cr composite spinel brick for a dip pipe of an RH refining furnace and a nonferrous smelting furnace, which mainly adopts fused magnesia-chrome sand and fused magnesia sand as main raw materials and introduces nanoscale Cr2O3Powder and uf-Al2O3The product has the properties of easy sintering, compact crystal, low air hole and the like by adopting the pulp waste liquid as a bonding agent, but has poor erosion resistance to a large amount of mirabilite separated out from a regenerative chamber of a glass kiln, and is easy to cause pulverization and peeling after erosion.
Therefore, in order to ensure the service life of the kiln, the middle part of the regenerative chamber of the glass kiln still needs to adopt the magnesia-chrome brick with better erosion resistance. However, trivalent chromium in magnesite chrome bricks is converted into toxic and carcinogenic hexavalent chromium compounds during use. On one hand, the regenerative chamber of the glass kiln can not be replaced by the magnesia-chrome refractory material temporarily; on the other hand, the detached magnesia-chromite residual bricks cause serious pollution to the environment. Therefore, the pollution caused by the magnesia-chrome bricks disassembled from the glass kiln also becomes a difficult problem which troubles the glass industry.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: 1) greatly reducing Cr in magnesia-chrome brick for glass kiln regenerator2O3The content of (2) so as to relieve the problem that hexavalent chromium in the magnesium-chromium residual brick pollutes the environment; 2) reducing Cr in magnesia-chrome brick2O3While increasing the content of low chromium magnesiumThe service life of the chrome brick. Therefore, there is a need to increase Cr in bricks2O3The efficiency of (c); on the other hand, the corrosion resistance of the refractory brick needs to be improved by adopting matching measures. Therefore, the low-chromium magnesia chrome brick for the glass kiln, which is prepared by the technical scheme of the invention, can achieve the purposes of reducing the chromium content and prolonging the service life, and obtain good economic and social benefits.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a low chrome magnesia chrome brick for a glass kiln, which is characterized in that the content of fused magnesia with the granularity of 4-2mm is 10% -25% by weight; 10% -15% of fused magnesia with the granularity of 2-1 mm; 5% -20% of fused magnesia-alumina spinel with the granularity of 2-1 mm; 10-30% of pre-synthesized magnesia-chrome sand with granularity of 1-0 mm; 30-40% of fused magnesia with granularity less than 0.088 mm; in addition, a bonding agent accounting for 3-5% of the total mass of all the raw materials is added.
The fused magnesite is commercially available fused magnesite with the MgO content of more than or equal to 95 percent.
The above-mentioned magnesite-chrome sand system is pre-synthesized by electric smelting, Cr2O3The mass percentage of the SiO is less than or equal to 20 percent2The content is less than or equal to 1.5 percent.
The fused magnesia-alumina spinel comprises 25-35% of MgO and Al in percentage by mass2O3The mass percentage of the component (A) is 60-75%.
The bonding agent is one or two of sulfite pulp waste liquid and magnesium chloride solution; the specific gravity of the bonding agent is 1.20-1.45.
The low-chromium magnesium chromium brick is prepared by weighing, mixing, molding, drying and sintering at 1700-1760 ℃ for 5-8 hours according to the given formula.
The invention has the following positive beneficial effects: 1) greatly reduce the content of chromium oxide and Cr in the brick2O3The content is reduced from 16-8% to about 5%, and the pollution of residual brick hexavalent chromium to the environment is remarkably relieved; 2) the service life of the checker bricks is remarkably prolonged from 1-3 years after the petroleum coke is used to 5-8 years, and the service life reaches the level when the petroleum coke is not used.
The invention uses the fused magnesia to replace the sintered magnesia, thereby greatly slowing down the SiO2CaO reacts with the magnesite to form forsterite M2S, forsterite CMS, magadite C3MS2The reaction of (1); meanwhile, the free SO of the brick is greatly improved3、V2O5And the like.
The invention replaces the magnesite-chrome ore with the fused magnesite-chrome sand, because the magnesite-chrome ore fully reacts with the light-burned magnesia during electric melting, the magnesia-chrome spinel is formed, which is not only beneficial to sintering and forming compact brick bodies, but also avoids the green chromite contained in the burned bricks, thereby greatly improving the erosion resistance of the brick material. If the brick contains raw chromite, the chromite will react with magnesia to form magnesia-chromite spinel with the help of mirabilite, and the expansion associated with the formation of magnesia-chromite spinel will result in loose structure and rapid erosion damage.
The invention still retains a part of the fine-grained magnesia-chrome sand. When sintering, chromium oxide is diffused from the magnesia-chrome sand to form periclase solid solution in the matrix of the brick, and magnesia-chrome spinel is formed when cooling, so that direct combination is formed, a silicate phase becomes an isolated island, and the high temperature resistance, creep resistance and erosion resistance of the brick are greatly improved.
The material developed by the invention has good erosion resistance and creep resistance, and is used for a glass kiln to solve the problem that the service life of the kiln is greatly reduced after petroleum coke is used; meanwhile, because the chromium content in the brick is low, the pollution of hexavalent chromium is greatly reduced, thereby obtaining remarkable social and economic benefits.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The mass percentage content of MgO in the fused magnesia adopted in the following examples is more than or equal to 95 percent; cr in the magnesia-chrome sand2O3The mass percentage of the SiO is less than or equal to 20 percent2The content is less than or equal to 1.0 percent; the mass percentage of MgO in the fused magnesia-alumina spinel is 25-35%, and Al is2O3The mass percentage of the binder is 50-65%, and the binder is one or two of sulfite pulp waste liquor and magnesium chloride solution; the specific gravity of the bonding agent is 1.20-1.45.
Example 1:
the low chrome-magnesia chrome brick comprises the following raw materials in percentage by mass: 20 percent of fused magnesia with the granularity of 4-2mm, 12 percent of fused magnesia with the granularity of 2-1mm, 10 percent of fused magnesia-alumina spinel with the granularity of 2-1mm, 26 percent of magnesia-chrome sand with the granularity of 1-0mm and 32 percent of fused magnesia with the granularity of less than 0.088mm, and in addition, a bonding agent, namely sulfite pulp waste liquor and a magnesium chloride solution (the specific gravity of the bonding agent is 1.25) which account for 3.5 percent of the total mass of all the raw materials are added, and the raw materials in the formula are weighed, mixed, molded, dried and sintered at 1700 ℃ for 8 hours to obtain the magnesium-containing fused magnesia-alumina spinel.
Example 2:
the low chrome-magnesia chrome brick of the invention is expressed by mass percentage, and comprises the following raw materials: 18 percent of fused magnesia with the granularity of 4-2mm, 11 percent of fused magnesia with the granularity of 2-1mm, 17 percent of fused magnesia-alumina spinel with the granularity of 2-1mm, 23 percent of magnesia-chrome sand with the granularity of 1-0mm and 31 percent of fused magnesia with the granularity of less than 0.088 mm; and adding a binding agent sulfite pulp waste liquid (the specific gravity of the binding agent is 1.35) accounting for 4% of the total mass of all the raw materials, weighing the raw materials of the formula, mixing, molding, drying, and sintering at 1750 ℃ for 7 hours to obtain the modified sulfite pulp waste liquid.
Example 3:
the low chrome-magnesia chrome brick of the invention is expressed by mass percentage, and comprises the following raw materials: 16% of fused magnesia with the granularity of 4-2mm, 10% of fused magnesia with the granularity of 2-1mm and 16% of fused magnesia-alumina spinel with the granularity of 2-1 mm; 23% of 1-0mm magnesia-chrome sand and 35% of fused magnesia with the grain size less than 0.088 mm; adding a bonding agent magnesium chloride solution (the specific gravity of the bonding agent is 1.30) accounting for 4.5 percent of the total mass of all the raw materials, weighing the raw materials of the formula, mixing, molding, drying, and firing at 1760 ℃ for 5 hours to obtain the magnesium chloride-based composite material.
Example 4:
the low chrome-magnesia chrome brick of the invention is expressed by mass percentage, and comprises the following raw materials: 22% of fused magnesia with the granularity of 4-2mm, 13% of fused magnesia with the granularity of 2-1mm and 14% of fused magnesia-alumina spinel with the granularity of 2-1 mm; 18 percent of magnesite-chrome sand with the diameter of 1-0mm and 33 percent of fused magnesite with the diameter less than 0.088 mm; and adding a combined sulfite pulp waste liquid (the specific gravity of the binder is 1.20) accounting for 3.2 percent of the total mass of all the raw materials, weighing the raw materials with the formula, mixing, molding, drying, and sintering at 1720 ℃ for 6 hours to obtain the product.
Example 5:
the low chrome-magnesia chrome brick of the invention is expressed by mass percentage, and comprises the following raw materials: 14% of fused magnesia with the granularity of 4-2mm, 15% of fused magnesia with the granularity of 2-1mm and 12% of fused magnesia-alumina spinel with the granularity of 2-1 mm; 25 percent of magnesite-chrome sand with the diameter of 1-0mm and 34 percent of fused magnesite sand with the diameter less than 0.088 mm; and adding a bonding agent magnesium chloride solution and sulfurous acid pulp waste liquor (the specific gravity of the bonding agent is 1.40) which account for 4.8 percent of the total mass of all the raw materials, weighing the raw materials in the formula, mixing, molding, drying, and firing at 1710 ℃ for 6.5 hours to obtain the composite material.
The properties of the low chrome magnesite chrome bricks obtained in the above examples 1 to 5 are shown in Table 1.
TABLE 1 relevant Performance test data for products prepared in examples 1 to 5 of the present invention
Figure 278890DEST_PATH_IMAGE001
As shown in Table 1, Cr of the product2O3The content is reduced from 8-16% to about 5%, and the chromium-containing chromium complex has good physical properties, and the product has good effect after being tried for more than 3 years in a glass plant, and can be expected to reach the service life of 5-8 years, thereby achieving the purposes of prolonging the service life and greatly reducing the chromium content of the material.

Claims (5)

1. The utility model provides a glass kiln regenerator is with low chromium magnesium chrome brick which characterized in that: 25-10% of fused magnesia with the granularity of 4-2mm in a brick making formula expressed by mass percentage; 15% -10% of fused magnesia with the granularity of 2-1 mm; 20% -5% of electric melting magnesia-alumina spinel with the granularity of 2-1 mm; 30-10% of pre-synthesized magnesia-chrome sand with the granularity of 1-0 mm; 40-30% of fused magnesia with granularity less than 0.088 mm; in addition, adding a bonding agent which accounts for 3-5% of the total mass of all the raw materials; the presynthesized magnesia-chrome sand is synthesized by electric melting, and Cr of the presynthesized magnesia-chrome sand2O3The mass percentage of the SiO is less than or equal to 20 percent2The mass percentage content is less than or equal to 1.5 percent.
2. The low chrome magnesia brick of claim 1, wherein: the electric melting magnesite is the commercial electric melting magnesite with the MgO content more than or equal to 95 percent.
3. The low chrome magnesia brick of claim 1, wherein: the mass percentage of MgO in the fused magnesia-alumina spinel is 25-35%, and Al is2O3The mass percentage of the component (A) is 60-75%.
4. The low chrome magnesia brick of claim 1, wherein: the binding agent is one or two of sulfite pulp waste liquid and magnesium chloride solution; the specific gravity of the bonding agent is 1.20-1.45.
5. The low chrome magnesia brick of claim 1, wherein: the material is prepared by weighing, mixing, molding, drying and sintering at 1700-1760 ℃ for 5-8 hours according to the formula.
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CN112456969B (en) * 2020-12-16 2022-03-18 中南大学 Method for reinforcing performance of complex phase refractory material by microwave precalcination-sintering two steps
CN113354396A (en) * 2021-06-15 2021-09-07 郑州海迈高温材料研究院有限公司 Production method of periclase brick for regenerator of large float glass melting furnace
CN115433016A (en) * 2022-09-29 2022-12-06 河南瑞泰耐火材料科技有限公司 Magnesium-iron-chromium brick for kiln car and preparation method thereof
CN117362015B (en) * 2023-10-27 2024-04-12 河南省瑞泰科实业集团有限公司 High-purity corundum brick and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062334A (en) * 1991-05-28 1992-07-01 冶金工业部辽宁镁矿公司 A kind of burnt Ma-Al-Cr refractory brick and manufacture method thereof
CN101708987A (en) * 2009-11-23 2010-05-19 海城市中兴高档镁质砖有限公司 Compound advanced magnesia-chromite brick for RH dip pipes and production method thereof
CN104591752A (en) * 2014-12-11 2015-05-06 浙江自立股份有限公司 Burnt magnesia spinel brick for RH refining furnace dip pipe and circulating pipe and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062334A (en) * 1991-05-28 1992-07-01 冶金工业部辽宁镁矿公司 A kind of burnt Ma-Al-Cr refractory brick and manufacture method thereof
CN101708987A (en) * 2009-11-23 2010-05-19 海城市中兴高档镁质砖有限公司 Compound advanced magnesia-chromite brick for RH dip pipes and production method thereof
CN104591752A (en) * 2014-12-11 2015-05-06 浙江自立股份有限公司 Burnt magnesia spinel brick for RH refining furnace dip pipe and circulating pipe and preparation method thereof

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