CN109534788A - A kind of low chromium magnesite-chrome brick of glass furnace - Google Patents

A kind of low chromium magnesite-chrome brick of glass furnace Download PDF

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Publication number
CN109534788A
CN109534788A CN201811559656.1A CN201811559656A CN109534788A CN 109534788 A CN109534788 A CN 109534788A CN 201811559656 A CN201811559656 A CN 201811559656A CN 109534788 A CN109534788 A CN 109534788A
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magnesite
chrome
brick
granularity
fused magnesite
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CN109534788B (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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a kind of low chromium magnesite-chrome bricks of glass furnace, are indicated with mass percentage, the fused magnesite 25-10% of granularity 4-2mm；The fused magnesite 15-10% of granularity 2-1mm；The electric melting magnesium aluminum spinel 20-5% of granularity 2-1mm；The pre-synthesis magnesia-chrome sand 30-10% of granularity 1-0mm；The fused magnesite 40-30% of granularity < 0.088mm；In addition, the bonding agent for accounting for above-mentioned all total mass of raw materiales 3~5% is added.Glass furnace of the present invention has the performance characteristics that chromium content is low, consistency is high, intensity is high, corrosion resistance is strong and creep resistance is good with low chromium magnesite-chrome brick.The low chromium magnesite-chrome brick of the present invention is used for regenerator chamber of glass kiln, pollution of the Cr VI contained by residual brick to environment can be effectively relieved, and extend the service life of kiln simultaneously in the chromium content that refractory material is greatly reduced, the running rate for improving kiln, to obtain good economic benefit and social benefit.

Description

A kind of low chromium magnesite-chrome brick of glass furnace
Technical field
The invention belongs to technical field of refractory materials, and in particular to a kind of low chromium magnesite-chrome brick of regenerator chamber of glass kiln.
Background technique
With the rapid development of glass industry, the total output of China's plate glass occupies the first in the world.In recent years, glass row Industry faces the challenge of neutralizing excess capacity and transition and upgrade, whether float glass or container glass, in order to further decrease Cost has obtained large-area applications in glass industry using petroleum coke replacement for heavy as the technology of fuel.But it uses Bring is to corrode the significant shortening of aggravation and furnace service life to petroleum coke therewith.
Currently, the upper layer of regenerator chamber of glass kiln uses the magnesia brick of content of MgO about 97%；What regenerative chamber used originally at the middle and upper levels Magnesia brick a part of content of MgO about 95% is replaced by 97% magnesia brick, and a part is replaced by Direct bond magnesia-chrome brick；Regenerative chamber middle layer makes Use Direct bond magnesia-chrome brick；Regenerative chamber lower layer uses low stomata clay brick.Wherein, regenerative chamber be with middle layer at the middle and upper levels by load most Big section.On the one hand, the weight with middle layer checker by upper layer checker at the middle and upper levels；On the other hand, a large amount of saltcake from It is precipitated, condenses checker brick surface in middle level and is pierced inside brick in kiln gas, heavy corrosion is generated to checker brick.Sometimes, condensate It is in neutrality containing only saltcake；Sometimes condensate SO containing excess3In acidity；Sometimes condensate Na containing excess2O is in alkalinity.In addition, condensation CaO, SiO in object2Also brick body can be corroded with the help of saltcake.
CN102336539A discloses a kind of using useless regeneration baking-free magnesite-chrome brick and preparation method thereof, is by weight percent Useless magnesite-chrome brick particle 65% ~ 75%, fused magnesite 18% ~ 28%, magnesium aluminate spinel 2% ~ 4%, liquid thermosetting phenolic resin 3% ~ 5% Raw material is uniformly mixed, and compression moulding toasts for 24 hours at 200 DEG C, kiln discharge after natural cooling.This method sufficiently recycles The raw materials for production of magnesite-chrome brick, effectively alleviate environmental pollution.But this unburned magnesite-chrome brick, because raw material gives up crystal orientation inside brick Different, impurity content is unstable, causes unstable quality in use.CN102731121A discloses a kind of RH refining furnace dipping Pipe and non-ferrous smelting furnace high-performance magnesium-aluminium-chromium composite spinelle brick mainly use fused magnesia-chrome, fused magnesite for main original Material introduces nanoscale Cr2O3Powder and uf-Al2O3Micro mist uses spent pulping liquor for bonding agent, and product has easy-sintering, crystal The performances such as fine and close, low stomata, but the product is poor to the corrosion resistance for a large amount of saltcake being precipitated in regenerator chamber of glass kiln, easily causes and invades Dusting and peeling phenomenon after erosion.
Therefore, in order to guarantee service life of kiln, the preferable magnesite-chrome brick of corrosion resistance must still be used in the middle part of regenerator chamber of glass kiln. But the trivalent chromium in magnesite-chrome brick can transform into toxic and carcinogenic hexavalent chromium compound when in use.On the one hand, glass furnace Regenerative chamber is temporarily irreplaceable with magnesian-chrome efractoy；On the other hand, the residual brick of magnesium chromium matter being disassembled is caused to make environment again At serious pollution.Therefore, the pollution that the dismantled magnesite-chrome brick of glass furnace generates also becomes the problem of puzzlement glass industry.
Summary of the invention
The technical problem to be solved by the present invention is 1) Cr in regenerator chamber of glass kiln magnesite-chrome brick is greatly reduced2O3Content, The problem of to alleviate hexavalent chromium polluted environment in the residual brick of magnesium chromium；2) magnesite-chrome brick Cr is being reduced2O3Content while improve low chromium magnesium The service life of chrome brick.Therefore, it on the one hand needs to improve Cr in brick2O3Efficiency；On the other hand it needs that supplementary measures is taken to improve The corrosion resistance of refractory brick.To which the low chromium magnesite-chrome brick of glass furnace prepared using technical solution of the present invention can obtain reduction chromium Content and the purpose improved service life, obtain good economic and social benefit.
To solve the above-mentioned problems, the technical scheme adopted by the invention is as follows:
The present invention provides a kind of glass furnace low chromium magnesite-chrome brick, is indicated with mass percentage, the fused magnesite of granularity 4-2mm 10%-25%；The fused magnesite 10%-15% of granularity 2-1mm；The electric melting magnesium aluminum spinel 5%-20% of granularity 2-1mm；Granularity 1-0mm Pre-synthesis magnesia-chrome sand 10%-30%；The fused magnesite 30-40% of granularity < 0.088mm；In addition, being added, to account for above-mentioned all raw materials total The bonding agent of quality 3~5%.
Above-mentioned fused magnesite is the commercially available fused magnesite that content of MgO is more than or equal to 95%.
Above-mentioned magnesia-chrome sand system is by electric smelting pre-synthesis, Cr2O3Mass percentage≤20%, SiO2Content≤1.5% Product.
Above-mentioned electric melting magnesium aluminum spinel, the mass percentage of MgO are 25 ~ 35%, Al2O3Mass percentage be 60~75%。
Above-mentioned bonding agent is any one of lignosulfite, magnesium chloride solution or two kinds；The bonding agent Specific gravity is 1.20~1.45.
Above-mentioned low chromium magnesite-chrome brick, according to provide formula through weighing, mixing, molding, drying, at 1700-1760 DEG C through 5-8 Hour firing is made.
Positive beneficial effect of the invention: 1) chromic oxide content in brick, Cr is greatly reduced2O3Content is reduced to 5% from 16-8% Left and right, significantly alleviates pollution of the residual brick Cr VI to environment；2) significantly extend the checker brick service life, the 1- after using petroleum coke It extends to 5-8 within 3 years, has reached level when unused petroleum coke.
The present invention replaces magnesite clinker with fused magnesite, substantially slows down SiO2, CaO and magnesia act on, form magnesium olive Stone M2S, monticellite CMS, manganolite C3MS2Reaction；Meanwhile brick material greatly improved to free SO3、V2O5Equal acid The corrosion resistance of property substance.
The present invention replaces picrochromite with fused magnesia-chrome, and picrochromite is sufficiently reacted with light calcined magnesia when due to electric smelting, shape It at magnesia chrome spinel, not only contributes to be sintered and forms fine and close brick body, and avoid after burning in brick containing raw chromite, To which the corrosion resistance of brick material greatly improved.If brick material contains raw chromite, with the help of saltcake, chromite will be with magnesium Sand reacts to form magnesia chrome spinel, and forms the adjoint expansion of magnesia chrome spinel, will lead to short texture and quickly corrodes damage It ruins.
The present invention still retains a part of particulate magnesia-chrome sand.When sintering, chromium oxide will be diffused out from magnesia-chrome sand, in brick Matrix in form periclase solid solution, form magnesia chrome spinel when cooling, bound directly to be formed, become silicate phase " isolated island " greatly improves the high temperature resistant, creep resistant, erosion resisting of brick.
The material that the present invention is developed has good corrosion resistance, good creep resistance, solves for glass furnace The problem being greatly reduced using furnace service life after petroleum coke；Simultaneously because in brick chromium content it is relatively low, the dirt of Cr VI is greatly reduced Dye, to achieve significant economic results in society.
Specific embodiment
The present invention is further explained with reference to embodiments, but is not intended to limit the contents of the present invention.
The mass percentage of MgO is >=95% in the fused magnesite used in following embodiment；Cr in the magnesia-chrome sand2O3 Mass percentage≤20%, SiO2Content≤1.0%；In the electric melting magnesium aluminum spinel mass percentage of MgO be 25 ~ 35%, Al2O3Mass percentage be 50 ~ 65%, bonding agent be any one of lignosulfite, magnesium chloride solution or Two kinds；The specific gravity of the bonding agent is 1.20~1.45.
Embodiment 1:
A kind of low chromium magnesite-chrome brick, is indicated with mass percentage, raw material composition are as follows: granularity 4-2mm fused magnesite 20%, 2- 1mm fused magnesite 12%, 2-1mm electric melting magnesium aluminum spinel 10%, 1-0mm magnesia-chrome sand 26%, < 0.088mm fused magnesite 32%, Additionally incorporate the bonding agent lignosulfite for accounting for above-mentioned all total mass of raw materiales 3.5% and magnesium chloride solution (bonding agent specific gravity For 1.25), by the raw material of above-mentioned formula through weighing, mixing, molding, drying, be made through firing in 8 hours at 1700 DEG C.
Embodiment 2:
The low chromium magnesite-chrome brick of the present invention, is indicated with mass percentage, raw material composition are as follows: granularity 4-2mm fused magnesite 18%, 2- 1mm fused magnesite 11%, 2-1mm electric melting magnesium aluminum spinel 17%, 1-0mm magnesia-chrome sand 23%, < 0.088mm fused magnesite 31%； The bonding agent lignosulfite (bonding agent specific gravity is 1.35) for accounting for above-mentioned all total mass of raw materiales 4% is additionally incorporated, it will be above-mentioned The raw material of formula through weighing, mixing, molding, drying, 1750 DEG C through 7 hours firing be made.
Embodiment 3:
The low chromium magnesite-chrome brick of the present invention, is indicated with mass percentage, raw material composition are as follows: granularity 4-2mm fused magnesite 16%, 2- 1mm fused magnesite 10%, 2-1mm electric melting magnesium aluminum spinel 16%,；1-0mm magnesia-chrome sand 23%, < 0.088mm fused magnesite 35%；The bonding agent magnesium chloride solution (bonding agent specific gravity is 1.30) for accounting for above-mentioned all total mass of raw materiales 4.5% is additionally incorporated, it will be upper State the raw material of formula through weighing, mixing, molding, drying, be made through firing in 5 hours at 1760 DEG C.
Embodiment 4:
The low chromium magnesite-chrome brick of the present invention, is indicated with mass percentage, raw material composition are as follows: granularity 4-2mm fused magnesite 22%, 2- 1mm fused magnesite 13%, 2-1mm electric melting magnesium aluminum spinel 14%,；1-0mm magnesia-chrome sand 18%, < 0.088mm fused magnesite 33%；The combination sulfurous acid agent spent pulping liquor (bonding agent specific gravity is 1.20) for accounting for above-mentioned all total mass of raw materiales 3.2% is additionally incorporated, By the raw material of above-mentioned formula through weighing, mixing, molding, drying, 1720 DEG C through 6 hours firing be made.
Embodiment 5:
The low chromium magnesite-chrome brick of the present invention, is indicated with mass percentage, raw material composition are as follows: granularity 4-2mm fused magnesite 14%, 2- 1mm fused magnesite 15%, 2-1mm electric melting magnesium aluminum spinel 12%,；1-0mm magnesia-chrome sand 25%, < 0.088mm fused magnesite 34%；Additionally incorporate the bonding agent magnesium chloride solution and lignosulfite (bonding agent for accounting for above-mentioned all total mass of raw materiales 4.8% Specific gravity be 1.40), by the raw material of above-mentioned formula through weighing, mixing, molding, drying, 1710 DEG C through 6.5 hours firing be made.
The performance of the low chromium magnesite-chrome brick made from above-described embodiment 1-5 is as shown in table 1.
The correlated performance detection data of product prepared by 1 embodiment of the present invention 1 ~ 5 of table
As shown in Table 1, the Cr of product2O3Content is reduced to 5% or so from 8-16%, and has good physical behavior, and product is in glass Glass factory works well more after trying out 3 years, it is contemplated that can achieve the 5-8 service life, has reached and not only improved service life but also substantially Reduce the purpose of material chromium content.

Claims (6)

1. a kind of low chromium magnesite-chrome brick of regenerator chamber of glass kiln, it is characterised in that: the brick-making formula indicated with mass percentage, grain Spend the fused magnesite 25%-10% of 4-2mm；The fused magnesite 15%-10% of granularity 2-1mm；The electric melting magnesium aluminum spinel of granularity 2-1mm 20%-5%；The pre-synthesis magnesia-chrome sand 30-10% of granularity 1-0mm；The fused magnesite 40-30% of granularity < 0.088mm；In addition, being added Account for the bonding agent of above-mentioned all total mass of raw materiales 3~5%.
2. fused magnesite according to claim 1 is the commercially available fused magnesite that content of MgO is more than or equal to 95%.
3. magnesia-chrome sand system according to claim 1 is by electric smelting pre-synthesis, Cr2O3Mass percentage≤20%, SiO2The product of content≤1.5%.
4. electric melting magnesium aluminum spinel according to claim 1, it is characterised in that the mass percentage of MgO is 25 ~ 35%, Al2O3's Mass percentage is 60 ~ 75%.
5. low chromium magnesite-chrome brick according to claim 1, it is characterised in that: the bonding agent is lignosulfite, chlorine Change any one of magnesium solution or two kinds；The specific gravity of the bonding agent is 1.20~1.45.
6. according to low chromium magnesite-chrome brick described in claim 1, it is characterised in that: according to above-mentioned formula through weighing, mixing, molding, dry It is dry, obtained through firing in 5-8 hours at 1700-1760 DEG C.
CN201811559656.1A 2018-12-20 2018-12-20 Low-chromium magnesia-chrome brick for glass kiln Active CN109534788B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112456969A (en) * 2020-12-16 2021-03-09 中南大学 Method for strengthening performance of complex phase refractory material by precalcination-sintering microwave two-step method
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
CN117362015A (en) * 2023-10-27 2024-01-09 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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112456969A (en) * 2020-12-16 2021-03-09 中南大学 Method for strengthening performance of complex phase refractory material by precalcination-sintering microwave two-step method
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
CN117362015A (en) * 2023-10-27 2024-01-09 河南省瑞泰科实业集团有限公司 High-purity corundum brick 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

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