CN102093063A - Magnesium-aluminum-zirconium composite spinel refractory material - Google Patents

Magnesium-aluminum-zirconium composite spinel refractory material Download PDF

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Publication number
CN102093063A
CN102093063A CN 201010582941 CN201010582941A CN102093063A CN 102093063 A CN102093063 A CN 102093063A CN 201010582941 CN201010582941 CN 201010582941 CN 201010582941 A CN201010582941 A CN 201010582941A CN 102093063 A CN102093063 A CN 102093063A
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granularity
magnesium
refractory
highly
magnalium
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CN102093063B (en
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刘锡俊
袁林
陈松林
王俊涛
叶亚红
胡世平
赵洪亮
翟耀杰
陈卫敏
刘昭
陈磊
吴兴胜
刘威
王庆朝
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HENAN RUITAI REFRACTORY TECHNOLOGY Co Ltd
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HENAN RUITAI REFRACTORY TECHNOLOGY Co Ltd
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Abstract

The invention relates to a magnesium-aluminum-zirconium composite spinel refractory material. The refractory material is prepared from the following raw materials in percentage by weight: 50 to 95 percent of high-purity magnesia of which the granularity is less than or equal to 5 millimeters, 5 to 25 percent of magnesia-aluminum spine of which the granularity is less than or equal to 4 millimeters, 1 to 25 percent of desilicated zirconium or zircon sand of which the granularity is less than or equal to 3 millimeters and 1 to 6 percent of bonding agent in the raw materials. The refractory material is suitable for high temperature zones of large and medium-sized cement kilns, has high service performance and long service life, can completely replace magnesium-chromium refractory material to be applied to the high temperature zone of a cement kiln, avoids environmental pollution caused by a magnesium-chromium brick after being used, and has very good economic benefit and social benefit.

Description

Magnalium zirconium composite spinelle refractory materials
Technical field
The present invention relates to fire resisting material field, be specifically related to a kind of magnalium zirconium composite spinelle refractory materials.
Background technology
Magnesia chrome brick has good refractoriness under load, hot strength, resistance to fouling, thermal shock resistance etc., is widely used in the high temperature kiln such as thermal zone, coloured industrial zinc metallurgy, copper metallurgy of cement kiln.
But a large amount of uses of magnesia chrome brick have brought problems: on the one hand, because the magnesium chrome refractory after using makes original Cr in the material under high temperature, alkalescence and oxidizing atmosphere 3+Be converted into the Cr that contains with the residual brick in back 6+, and Cr 6+Contain severe toxicity, cause severe contamination to pollute environment; On the other hand, China's chromium ore resource poorness, a large amount of chrome ore of import is wanted in the consumption of a large amount of magnesia chrome bricks, consumes a large amount of foreign exchanges, also aggravates the contradiction of China's chrome ore poorness.
Magnalium zirconium composite spinelle brick has good performance: excellent high-temperature flame-proof performance, erosion-resisting characteristics is good, good thermal shock stability, refractoriness under load are high, can substitute the magnesium chrome refractory, be used for cement, high temperature kiln such as coloured, be environmental friendliness basic refractory of new generation.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of magnalium zirconium composite spinelle refractory materials, this material has excellent high-temperature flame-proof performance, thermal shock resistance energy, erosion-resisting characteristics etc., can replace the magnesium chrome refractory (magnesia chrome brick) that environment is polluted, be used for the environmental friendliness basic refractory of cement, high temperature kiln such as coloured.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of magnalium zirconium composite spinelle refractory materials, by percentage to the quality, its preparation raw material is as follows: highly-purity magnesite 50～95wt % of granularity≤5mm, magnesium-aluminium spinel 4～25wt% of granularity≤4mm, granularity≤3mm desilicated zirconia or zircon sand 1～25wt% add the wedding agent that accounts for above-mentioned raw materials gross weight 1～6wt%.
Highly-purity magnesite is to select for use natural superfine giobertite flotation to purify to form MgO content 〉=96wt% through light-burned, fine grinding, pressure ball, the calcining of ultrahigh-temperature oil shaft furnace; Magnesium-aluminium spinel (MgOAl 2O 3) have high melt point, thermal expansion is little, thermal stresses is low, heat is shaken good stability, it has than stable chemical property simultaneously, basic slag is had stronger resistivity, is the core point that the magnalium green brick is used, and is one of key substance that improves the life-span.Zircon sand is a kind of silicate (Zr with zirconium 2SiO 4) be the main mineral of forming.
Add ZrO 2Can play: 1. in refractory brick, generate tiny crack, improve heat-shock resistance; 2. ZrO 2But isolated silicon hydrochlorate phase makes it to reduce wetting to MgO; 3. cracked ZrO 2Absorb CaO, SiO in the liquid phase 2To put crystalline distribution.Therefore, can improve the thermal shock resistance energy and the erosion-resisting characteristics of material.
Described wedding agent is lignosulfite, bittern (MgCl 26H 2O) at least a in, its proportion is 1.0～1.6g/cm 3
MgO content 〉=95wt% in the described highly-purity magnesite.
Described magnalium zirconium composite spinelle refractory materials is via batching, the wet stone roller, moulding, drying, burns till step and makes, and wherein, drying temperature is 80 ℃～130 ℃, and time of drying 〉=12h, firing temperature are 1600 ℃～1730 ℃.
The present invention has actively useful effect:
Magnalium zirconium composite spinelle brick involved in the present invention is the multiple phase refractory material that contains periclasite-magnesia alumina spinel-zirconia-zirconium.Its chemical ingredients is: MgO 80～90%, Al 2O 33～19%, ZrO 21～18%.
1. the ZrO of product of the present invention by adding 2At high temperature, in material, produce tiny crack, improve the thermal shock resistance of material, but while isolated silicon hydrochlorate phase has improved the erosion-resisting characteristics of material, thereby made goods have the excellent high-temperature use properties by phase transformation; The integrated performance index of this material is as shown in table 1.
2. refractory materials of the present invention is applicable to big-and-middle-sized cement kiln high-temperature band, has use properties and work-ing life preferably, can replace the application of magchrome refractory fully, avoid having good economic benefits and social benefit with back magnesia chrome brick pollution on the environment at the cement kiln high-temperature band.
Table 1 performance index
Volume density Apparent porosity Cold crushing strength Thermal shock resistance Erosion-resisting characteristics Refractoriness Refractoriness under load
g/cm 3 % Mpa 1100 ℃, water-cooled ? ℃ T 0.6/℃
≥3.00 ≤16.5 ≥80 >10 Excellent >1750 >1700
Embodiment
1 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 34wt%, granularity 3～1mm highly-purity magnesite (25wt% of MgO content 〉=96wt%), granularity＜0.088mm highly-purity magnesite 33wt%, granularity 3～1mm magnesium-aluminium spinel 6wt%, granularity 1～0mm desilicated zirconia 2wt% adds lignosulfite (the proportion 1.4g/cm that accounts for above-mentioned raw materials gross weight 4wt% 3), through behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, behind 110 ℃ of oven dry 18h, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 2 in dry kiln.
Table 2 performance index
2 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 32wt%, granularity 3～0mm highly-purity magnesite 20 wt%, granularity＜0.088mm highly-purity magnesite 31 wt %, granularity 4～1mm magnesium-aluminium spinel 12wt %, granularity 1～0mm zircon sand 5wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 3wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 18h after, through the magnalium zirconium composite spinelle product of 1650 ℃ high-temperature heat treatment systems, its performance index see Table 3.
 
Table 3 performance index
3 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 32wt%, granularity 3～0mm highly-purity magnesite 20wt %, granularity＜0.088mm highly-purity magnesite 30wt%, granularity 4～1mm magnesium-aluminium spinel 8wt%, granularity＜0.088mm zircon sand 10wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 5wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 28h after, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 4.
Table 4 performance index
4 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt 5～3mm highly-purity magnesite 32wt%, granularity 3～0mm highly-purity magnesite 20 wt %, granularity＜0.088mm highly-purity magnesite 30 wt %, granularity 4～1mm magnesium-aluminium spinel 8wt %, granularity＜0.088mm desilicated zirconia 10wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 6wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 24h after, through the magnalium zirconium composite spinelle product of 1690 ℃ high-temperature heat treatment systems, its performance index see Table 5.
Table 5 performance index
5 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt the highly-purity magnesite 32wt% of granularity 5～3mm, granularity 3～0mm highly-purity magnesite 20wt%, granularity＜0.088mm highly-purity magnesite 30wt%, granularity 4～1mm magnesium-aluminium spinel 8wt%, granularity 1～0mm desilicated zirconia 10wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 1.5wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 18h after, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 6.
Table 6 performance index
6 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 34wt%, granularity 3～0mm highly-purity magnesite 10wt%, granularity＜0.088mm highly-purity magnesite 30wt %, granularity 4～1mm magnesium-aluminium spinel 18wt%, granularity 1～0mm desilicated zirconia 8wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 3wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 18h after, through the magnalium zirconium composite spinelle product of 1730 ℃ high-temperature heat treatment systems, its performance index see Table 7.
Table 7 performance index
7 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt the highly-purity magnesite 32wt% of granularity 5～3mm, granularity 3～0mm highly-purity magnesite 20wt%, granularity＜0.088mm highly-purity magnesite 30wt%, granularity 4～1mm magnesium-aluminium spinel 10wt%, granularity 1～0mm desilicated zirconia 10wt% adds bittern (the proportion 1.3g/cm that accounts for above-mentioned raw materials gross weight 1.5wt% 3), through behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, behind 110 ℃ of oven dry 18h, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 1 in dry kiln.
8 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 32wt%, granularity 3～0mm highly-purity magnesite 20wt%, granularity＜0.088mm highly-purity magnesite 30wt%, granularity 4～1mm magnesium-aluminium spinel 8wt%, granularity＜0.088mm zircon sand 10wt%, add the lignosulfite that accounts for above-mentioned raw materials gross weight 5wt%, behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, in dry kiln 110 ℃ the oven dry 28h after, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 1.
9 one kinds of magnalium zirconiums of embodiment composite spinelle refractory materials, adopt granularity 5～3mm highly-purity magnesite 32wt%, granularity 3～1mm highly-purity magnesite 30wt%, granularity＜0.088mm highly-purity magnesite 30wt%, granularity 3～1mm magnesium-aluminium spinel 6wt%, granularity 1～0mm zircon sand 2wt% adds bittern (the proportion 1.4g/cm that accounts for above-mentioned raw materials gross weight 4wt% 3), through behind the edge runner-wet mill batch mixing, adopt the pressing machine moulding, behind 110 ℃ of oven dry 18h, through the magnalium zirconium composite spinelle product of 1680 ℃ high-temperature heat treatment systems, its performance index see Table 2 in dry kiln.

Claims (4)

1. magnalium zirconium composite spinelle refractory materials, it is characterized in that, by percentage to the quality, its preparation raw material is as follows: highly-purity magnesite 50～95wt % of granularity≤5mm, magnesium-aluminium spinel 4～25wt% of granularity≤4mm, granularity≤3mm desilicated zirconia or zircon sand 1～25wt% add the wedding agent that accounts for above-mentioned raw materials gross weight 1～6wt%.
2. according to the described magnalium zirconium of claim 1 composite spinelle refractory materials, it is characterized in that described wedding agent is at least a in lignosulfite, the bittern, its proportion is 1.0～1.6g/cm 3
3. according to the described magnalium zirconium of claim 1 composite spinelle refractory materials, it is characterized in that the MgO content 〉=95wt% in the described highly-purity magnesite.
4. according to the described magnalium zirconium of claim 1 composite spinelle refractory materials, it is characterized in that, described magnalium zirconium composite spinelle refractory materials is via batching, the wet stone roller, moulding, drying, burn till step and make, wherein, drying temperature is 80 ℃～130 ℃, and time of drying 〉=12h, firing temperature are 1600 ℃～1730 ℃.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102353253A (en) * 2011-08-17 2012-02-15 通达耐火技术股份有限公司 Rotary cement kiln
CN104108944A (en) * 2014-08-11 2014-10-22 辽宁中镁控股股份有限公司 Magnesium-zirconium spinel ramming material for furnace bottom
CN104177102A (en) * 2014-08-28 2014-12-03 洛阳利尔耐火材料有限公司 Furnace bottom ramming material of RH refining furnace
CN106278324A (en) * 2016-08-22 2017-01-04 大石桥市中建镁砖有限公司 A kind of modified high-purity magnesium-aluminum spinel composite brick and preparation method thereof
CN106631061A (en) * 2016-12-15 2017-05-10 河南瑞泰耐火材料科技有限公司 High-thermal-conductivity magnesium-rich spinel composite brick for flue wall and preparation method of composite brick
CN107365150A (en) * 2017-06-29 2017-11-21 通达耐火技术股份有限公司 One kind is low to lead magnesium-aluminum-zirconium composite brick and preparation method thereof
CN107540351A (en) * 2017-08-28 2018-01-05 江苏诺明高温材料股份有限公司 A kind of high-purity composite of seawater magnesia magnesium aluminate spinel zirconium oxide
CN107759214A (en) * 2017-12-02 2018-03-06 芜湖乾凯材料科技有限公司 A kind of high thermal shock resistance magnesia-spinel brick and preparation method thereof
CN107793165A (en) * 2017-12-02 2018-03-13 芜湖乾凯材料科技有限公司 A kind of anti-erosion cement kiln clinkering zone refractory brick and preparation method thereof
CN107935609A (en) * 2017-12-02 2018-04-20 芜湖乾凯材料科技有限公司 High chemical stability cement kiln clinkering zone refractory brick and preparation method thereof
CN107935562A (en) * 2017-12-02 2018-04-20 山东鲁桥新材料股份有限公司 A kind of dry-process cement rotary kiln height temperate zone chromium-free brick and preparation method thereof
CN109400121A (en) * 2018-12-29 2019-03-01 河南新拓耐火材料有限公司 A kind of steel ladle sliding water gap does not soak magnalium slide plate and preparation method thereof with not burning
CN109592970A (en) * 2018-12-20 2019-04-09 瑞泰科技股份有限公司 A kind of low chromium electric smelting recombined magnesia-chrome brick

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CN101665367A (en) * 2009-10-20 2010-03-10 瑞泰科技股份有限公司 Thermal shock resistant corundum-magnesium aluminum spinel pouring material
CN101811880A (en) * 2010-04-20 2010-08-25 中民驰远实业有限公司 Carbon-free refractory bricks and preparation method thereof

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CN1657485A (en) * 2005-03-22 2005-08-24 北京瑞泰高温材料科技股份有限公司 Sintered magnesing complex-phase refractory
CN101412629A (en) * 2008-08-29 2009-04-22 瑞泰科技股份有限公司 Periclase-magnesium aluminate spinel composite refractory brick and technique for producing the same
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CN101665367A (en) * 2009-10-20 2010-03-10 瑞泰科技股份有限公司 Thermal shock resistant corundum-magnesium aluminum spinel pouring material
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102353253A (en) * 2011-08-17 2012-02-15 通达耐火技术股份有限公司 Rotary cement kiln
CN104108944A (en) * 2014-08-11 2014-10-22 辽宁中镁控股股份有限公司 Magnesium-zirconium spinel ramming material for furnace bottom
CN104108944B (en) * 2014-08-11 2017-12-26 辽宁中镁控股股份有限公司 A kind of magnesium zirconium spinel matter furnace bottom ramming mass
CN104177102A (en) * 2014-08-28 2014-12-03 洛阳利尔耐火材料有限公司 Furnace bottom ramming material of RH refining furnace
CN106278324A (en) * 2016-08-22 2017-01-04 大石桥市中建镁砖有限公司 A kind of modified high-purity magnesium-aluminum spinel composite brick and preparation method thereof
CN106631061A (en) * 2016-12-15 2017-05-10 河南瑞泰耐火材料科技有限公司 High-thermal-conductivity magnesium-rich spinel composite brick for flue wall and preparation method of composite brick
CN106631061B (en) * 2016-12-15 2019-08-23 河南瑞泰耐火材料科技有限公司 A kind of flue wall high thermal conductivity magnesium-rich spinel composite brick and preparation method thereof
CN107365150A (en) * 2017-06-29 2017-11-21 通达耐火技术股份有限公司 One kind is low to lead magnesium-aluminum-zirconium composite brick and preparation method thereof
CN107540351A (en) * 2017-08-28 2018-01-05 江苏诺明高温材料股份有限公司 A kind of high-purity composite of seawater magnesia magnesium aluminate spinel zirconium oxide
CN107793165A (en) * 2017-12-02 2018-03-13 芜湖乾凯材料科技有限公司 A kind of anti-erosion cement kiln clinkering zone refractory brick and preparation method thereof
CN107935609A (en) * 2017-12-02 2018-04-20 芜湖乾凯材料科技有限公司 High chemical stability cement kiln clinkering zone refractory brick and preparation method thereof
CN107935562A (en) * 2017-12-02 2018-04-20 山东鲁桥新材料股份有限公司 A kind of dry-process cement rotary kiln height temperate zone chromium-free brick and preparation method thereof
CN107935562B (en) * 2017-12-02 2020-09-25 山东鲁桥新材料股份有限公司 Chromium-free brick for high-temperature zone of dry-process cement kiln and preparation method thereof
CN107759214A (en) * 2017-12-02 2018-03-06 芜湖乾凯材料科技有限公司 A kind of high thermal shock resistance magnesia-spinel brick and preparation method thereof
CN109592970A (en) * 2018-12-20 2019-04-09 瑞泰科技股份有限公司 A kind of low chromium electric smelting recombined magnesia-chrome brick
CN109592970B (en) * 2018-12-20 2021-10-26 瑞泰科技股份有限公司 Low-chromium electric melting recombination magnesia-chrome brick
CN109592970B8 (en) * 2018-12-20 2021-12-03 瑞泰科技股份有限公司 Low-chromium electric melting recombination magnesia-chrome brick
CN109400121A (en) * 2018-12-29 2019-03-01 河南新拓耐火材料有限公司 A kind of steel ladle sliding water gap does not soak magnalium slide plate and preparation method thereof with not burning

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