CN101580381A - Magnesium aluminate spinel- zirconium oxide-titanium oxide composite material and preparation method thereof - Google Patents
Magnesium aluminate spinel- zirconium oxide-titanium oxide composite material and preparation method thereof Download PDFInfo
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- CN101580381A CN101580381A CNA2009101498386A CN200910149838A CN101580381A CN 101580381 A CN101580381 A CN 101580381A CN A2009101498386 A CNA2009101498386 A CN A2009101498386A CN 200910149838 A CN200910149838 A CN 200910149838A CN 101580381 A CN101580381 A CN 101580381A
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Abstract
The invention relates to a magnesium aluminate spinel- zirconium oxide-titanium oxide composite material and a preparation method thereof, belonging to the field of refractory material. The composite material comprises the following materials by weight percentage: 28 to 31% of magnesite with particle size of less than or equal to 0.060mm, 56 to 62% of aluminium oxide with particle size of less than or equal to 0.060mm, 5 to 10% of zirconium oxide with particle size of less than or equal to 0.040mm and 2 to 6% of titanium oxide with particle size of less than or equal to 0.040mm. The preparation method comprises the following steps of: dry-mixing the materials for 1 minute, additionally adding 6 percent (weight percentage) of PVA solution, wet-mixing for 8 minutes, carrying out ageing mixture for 4 fours and obtaining blank, with the forming pressure of blank of more than or equal to 100MPa, drying the blank for 8 hours at the temperature of 60 to 100 DEG C, sintering at the temperature of 1600 DEG C, and holding the temperature for 3 to 5 hours. The composite material has excellent sintering performance, cement slag corrosion resistant performance and antistripping performance. The invention can provide a novel composite material for the field of refractory material used for the rotary kiln of the cement industry.
Description
Technical field
The invention belongs to fire resisting material field, be specifically related to a kind of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material and preparation method thereof.
Background technology
The present invention is a kind of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material that can be used for cement rotary kiln with fire resisting material field of exploitation, this matrix material can burn till preparation at 1600 ℃, has good sintering character, anti-cement clinker erosion performance and antistrip performance.
Magnesium chromium (MgO-Cr
2O
3) refractory materials is with the result of use of its good high temperature resistant, resisting cement clinker slag corrosion, establish magchrome refractory and be applied to the thermal zone irreplaceable status of large-scale cement rotary kiln.Yet, contain Cr
2O
3Basic refractory can produce can be carcinogenic hexavalent chromium (Cr
6+), magchrome refractory in producing or using, Cr
6+Can enter atmosphere with flue gas and cause environmental pollution.In addition, Cr
6+With the formed R of other oxide compound
2Cr
2O
3, RCrO
4Soluble in water, Cr in the residual brick of the magchrome refractory after the use
6+Dissolve, permeate the ground and cause water to pollute with rainwater.How to prevent Cr
6+To the problems such as environmental pollution at atmosphere and water source, become the important topic that world today's environmental protection and cement, refractory industry need to be resolved hurrily.
Cement rotary kiln is thermal zone in the world began to contain the chromium basic refractory with the non-chromium alkaline refractory materials is alternative from the eighties in 20th century, in the hope of stop Cr at all
6+Pollute.Abroad having adopted is the non-chromium alkaline refractory technology exploitation route of principal constituent with the periclasite, research and development magnesium oxide-aluminum oxide (MgO-Al
2O
3) and magnesium oxide-zirconium white (MgO-ZrO
2) two big class non-chromium alkaline refractory materialss, but firing temperature height, product cost costliness.Japan, West Europe and north america are modification refractory magnesia-alumina material, magnesium zirconia refractory because of the thermal zone refractory materials of cement rotary kiln of reasons such as resource research and development.
Late 1990s, China refractory technology personnel are to MgO-Al
2O
3, MgO-ZrO
2, the AlN-MgO based material explores, carried out aspects such as composition, structure and performance and studied.MgO-Al wherein
2O
3Magnesium-aluminium spinel (the MgAl of system
2O
4Being abbreviated as MA) fire resistant materials is as cement rotary kiln clinkering zone kiln lining, has a better effect.
But the MA fire resistant materials burn till the high temperature kiln that preparation needs 1700 ℃, its kiln investment and to burn till energy consumption big makes the production cost and the market value height of MA fire resistant materials, has restricted the process of China's Cement industry refractory materials environmental protection Chrome-freeization.Compare the magnesium chrome refractory, also remain resisting cement clinker slag corrosion performance, antistrip performance and the work-ing life of MA fire resistant materials further to be improved.
This patent proposes to introduce small amounts zirconium and titanium oxide in the MA material, can burn till a kind of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material of preparation 1600 ℃ of lesser tempss, this matrix material has good sintering character, anti-cement clinker erosion performance and antistrip performance.This patent can be China's Cement industry rotary kiln and provides a kind of advanced composite material with fire resisting material field.
Summary of the invention
Goal of the invention of the present invention is above-mentioned deficiency of the prior art, provides a kind of and can burn till and have magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material of good sintering character, anti-cement clinker erosion performance and antistrip performance and preparation method thereof at 1600 ℃.
Technical scheme of the present invention and technical characterictic are:
The present invention is a kind of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material and preparation method thereof, it is characterized in that this matrix material weight percent raw materials used and raw material is: magnesia 28～31%, aluminum oxide 56～62%, zirconium white 5～10%, titanium oxide 2～6%.This Composite Preparation may further comprise the steps: the blank preparation; Blank forming is with dry; Base substrate high temperature burns till.
The used magnesia raw material of this matrix material is electrosmelted magnesite clinker or magnesite clinker or caustic-calcined magnesite, and the weight percent of above-mentioned magnesia material purity is MgO 〉=97%; Particle diameter≤the 0.060mm of above-mentioned magnesia raw material.
The used alumina raw material of this matrix material is commercial alumina or Alpha-alumina or Calcined polishing aluminum oxide or aluminium hydroxide, and the weight percent of above-mentioned alumina raw material purity is Al
2O
3〉=97%; Particle diameter≤the 0.060mm of above-mentioned alumina raw material.
The used zirconium white raw material of this matrix material is fully stabilized zirconia or PSZ or astable zirconium white, and the weight percent of above-mentioned zirconium white material purity is ZrO
2〉=90%; The particle diameter 0.040mm of above-mentioned zirconium white raw material.
The used raw titanium oxide material of this matrix material is Rutile type Titanium Dioxide or Detitanium-ore-type titanium dioxide, and the weight percent of above-mentioned raw titanium oxide material purity is TiO
2〉=95%; Particle diameter≤the 0.040mm of above-mentioned raw titanium oxide material.
The blank preparation method of this matrix material is: magnesia raw material, alumina raw material, zirconium white, titanium oxide are measured the back respectively did mixed 1 minute, add PVA solution 6% (weight percent then, add) wet mixing 8 minutes, material obtains blank for blank forming through ageing mixture again after the wet mixing after 4 hours.
The blank forming and the drying means of this matrix material are: base substrate adopts hydraulic press or friction press moulding, and blank forming pressure is 〉=100MPa, and base substrate obtains the base substrate that Gong burns till through 100 ℃ of dryings again through 60 ℃ of dryings 4 hours after the moulding after 4 hours.
The base substrate high temperature process for calcining of this matrix material is: dry back base substrate burns till through 1600 ℃ of high temperature, is incubated and obtains magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material after 3～5 hours.
Embodiment
Embodiment 1
The blank of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material is formed weight percent: the magnesite clinker 30% of≤0.060mm, the Calcined polishing aluminum oxide 59% of≤0.060mm, the fully stabilized zirconia 7% of≤0.040mm, the Rutile type Titanium Dioxide 4% of≤0.040mm.Above-mentioned each raw material is measured the back respectively did mixed 1 minute, add PVA solution 6% (weight percent adds) wet mixing 8 minutes then, material obtains to supply the blank of blank forming again after the wet mixing after 4 hours through ageing mixture.Adopt hydraulic press or friction press moulding, blank forming pressure is 〉=100MPa, and base substrate obtains the base substrate that Gong burns till through 100 ℃ of dryings again through 60 ℃ of dryings 2 hours after the moulding after 2 hours.Dry back base substrate burns till through 1600 ℃ of high temperature, is incubated and obtains magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material after 5 hours.
The tensile strength of this matrix material is 52.8MPa (the contrast sample that does not add zirconium white and titanium oxide is 42.2MPa), and apparent porosity is 11.4% (the contrast sample that does not add zirconium white and ferric oxide is 26.1%).
Embodiment 2
The blank of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material is formed weight percent: the caustic-calcined magnesite 30% of≤0.060mm, the Calcined polishing aluminum oxide 59% of≤0.060mm, the fully stabilized zirconia 6% of≤0.040mm, the Detitanium-ore-type titanium dioxide 5% of≤0.040mm.Above-mentioned each raw material is measured the back respectively did mixed 1 minute, add PVA solution 6% (weight percent adds) wet mixing 8 minutes then, material obtains to supply the blank of blank forming again after the wet mixing after 4 hours through ageing mixture.Adopt hydraulic press or friction press moulding, blank forming pressure is 〉=100MPa, and base substrate obtains the base substrate that Gong burns till through 100 ℃ of dryings again through 60 ℃ of dryings 2 hours after the moulding after 2 hours.Dry back base substrate burns till through 1600 ℃ of high temperature, is incubated and obtains magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material after 5 hours.
The tensile strength of this matrix material is 54.9MPa (the contrast sample that does not add zirconium white and titanium oxide is 42.2MPa), and apparent porosity is 10.7% (the contrast sample that does not add zirconium white and ferric oxide is 26.1%).
Claims (8)
1, a kind of magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material and preparation method thereof, it is characterized in that this matrix material weight percent raw materials used and raw material is: magnesia 28～31%, aluminum oxide 56～62%, zirconium white 5～10%, titanium oxide 2～6%.This Composite Preparation may further comprise the steps: the blank preparation; Blank forming is with dry; Base substrate high temperature burns till.
2, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that used magnesia raw material is electrosmelted magnesite clinker or magnesite clinker or caustic-calcined magnesite, the weight percent of above-mentioned magnesia material purity is MgO 〉=97%; Particle diameter≤the 0.060mm of above-mentioned magnesia raw material.
3, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that used alumina raw material is commercial alumina or Alpha-alumina or Calcined polishing aluminum oxide or aluminium hydroxide, the weight percent of above-mentioned alumina raw material purity is Al
2O
3〉=97%; Particle diameter≤the 0.060mm of above-mentioned alumina raw material.
4, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that used zirconium white raw material is fully stabilized zirconia or PSZ or astable zirconium white, the weight percent of above-mentioned zirconium white material purity is ZrO
2〉=90%; Particle diameter≤the 0.040mm of above-mentioned zirconium white raw material.
5, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof is characterized in that used raw titanium oxide material is Rutile type Titanium Dioxide or Detitanium-ore-type titanium dioxide, and the weight percent of above-mentioned raw titanium oxide material purity is TiO
2〉=95%; Particle diameter≤the 0.040mm of above-mentioned raw titanium oxide material.
6, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that the blank preparation method is: magnesia raw material, alumina raw material, zirconium white, titanium oxide are measured the back respectively did mixed 1 minute, add PVA solution 6% (weight percent then, add) wet mixing 8 minutes, material obtains blank for blank forming through ageing mixture again after the wet mixing after 4 hours.
7, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that blank forming and drying means are: base substrate adopts hydraulic press or friction press moulding, blank forming pressure is 〉=100MPa, base substrate is through 60 ℃ of dryings 4 hours after the moulding, obtains the base substrate that Gong burns till after 4 hours through 100 ℃ of dryings again.
8, magnesia alumina spinel-zirconia-zirconium as claimed in claim 1-titanium oxide matrix material and preparation method thereof, it is characterized in that base substrate high temperature process for calcining is: dry back base substrate burns till through 1600 ℃ of high temperature, is incubated and obtains magnesia alumina spinel-zirconia-zirconium-titanium oxide matrix material after 3～5 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093063A (en) * | 2010-12-10 | 2011-06-15 | 河南瑞泰耐火材料科技有限公司 | Magnesium-aluminum-zirconium composite spinel refractory material |
| CN102503456A (en) * | 2011-10-20 | 2012-06-20 | 陈复生 | Fully-closed fire-resistant hollow brick and manufacturing method thereof |
| CN104355603A (en) * | 2014-10-29 | 2015-02-18 | 安徽省皖捷液压科技有限公司 | Composite alumina/zirconia ceramic nozzle and manufacturing method thereof |
| CN104387033A (en) * | 2014-10-29 | 2015-03-04 | 安徽省皖捷液压科技有限公司 | High-cost-performance special ceramic nozzle and manufacturing method thereof |
| CN104692816A (en) * | 2015-02-10 | 2015-06-10 | 东北大学 | Compact aluminum, magnesium, calcium grog refractory and preparation method thereof |
| CN105036716A (en) * | 2015-07-09 | 2015-11-11 | 长兴泓矿炉料有限公司 | Corrosion-resistant refractory material and preparation method therefor |
| CN104355603B (en) * | 2014-10-29 | 2017-01-04 | 安徽省皖捷液压科技有限公司 | Ceramic nozzle that a kind of alumina-zirconia is compound and preparation method thereof |
| CN106631119A (en) * | 2016-12-28 | 2017-05-10 | 河南和成无机新材料股份有限公司 | High-strength lightweight microporous spinel and preparation method thereof and high temperature resistant brick |
| CN107522485A (en) * | 2017-08-24 | 2017-12-29 | 浙江科屹耐火材料有限公司 | A kind of spinel fibre oxidation Zr refractory material and its preparation technology |
| CN112723864A (en) * | 2020-12-28 | 2021-04-30 | 郑州汇特耐火材料有限公司 | Microcrystal periclase composite spinel titanium refractory material and manufacturing method thereof |
| CN115650747A (en) * | 2022-11-16 | 2023-01-31 | 鞍山钢铁冶金炉材科技有限公司 | Magnesia-hercynite ladle wall gunning mix and preparation method thereof |
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| CN1335281A (en) * | 2001-08-10 | 2002-02-13 | 宝山钢铁股份有限公司 | Sliding sprue tile for smelting high-oxygen steel and calcium treated steel |
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Patent Citations (1)
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| CN1335281A (en) * | 2001-08-10 | 2002-02-13 | 宝山钢铁股份有限公司 | Sliding sprue tile for smelting high-oxygen steel and calcium treated steel |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093063B (en) * | 2010-12-10 | 2013-09-18 | 河南瑞泰耐火材料科技有限公司 | Magnesium-aluminum-zirconium composite spinel refractory material |
| CN102093063A (en) * | 2010-12-10 | 2011-06-15 | 河南瑞泰耐火材料科技有限公司 | Magnesium-aluminum-zirconium composite spinel refractory material |
| CN102503456A (en) * | 2011-10-20 | 2012-06-20 | 陈复生 | Fully-closed fire-resistant hollow brick and manufacturing method thereof |
| CN104355603B (en) * | 2014-10-29 | 2017-01-04 | 安徽省皖捷液压科技有限公司 | Ceramic nozzle that a kind of alumina-zirconia is compound and preparation method thereof |
| CN104355603A (en) * | 2014-10-29 | 2015-02-18 | 安徽省皖捷液压科技有限公司 | Composite alumina/zirconia ceramic nozzle and manufacturing method thereof |
| CN104387033A (en) * | 2014-10-29 | 2015-03-04 | 安徽省皖捷液压科技有限公司 | High-cost-performance special ceramic nozzle and manufacturing method thereof |
| CN104692816A (en) * | 2015-02-10 | 2015-06-10 | 东北大学 | Compact aluminum, magnesium, calcium grog refractory and preparation method thereof |
| CN105036716A (en) * | 2015-07-09 | 2015-11-11 | 长兴泓矿炉料有限公司 | Corrosion-resistant refractory material and preparation method therefor |
| CN105036716B (en) * | 2015-07-09 | 2017-09-22 | 青岛西海岸高新材料有限公司 | A kind of corrosion-proof fire-resistant material and preparation method thereof |
| CN106631119A (en) * | 2016-12-28 | 2017-05-10 | 河南和成无机新材料股份有限公司 | High-strength lightweight microporous spinel and preparation method thereof and high temperature resistant brick |
| CN107522485A (en) * | 2017-08-24 | 2017-12-29 | 浙江科屹耐火材料有限公司 | A kind of spinel fibre oxidation Zr refractory material and its preparation technology |
| CN107522485B (en) * | 2017-08-24 | 2020-09-01 | 马长江 | Spinel fiber reinforced zirconia refractory material and preparation process thereof |
| CN112723864A (en) * | 2020-12-28 | 2021-04-30 | 郑州汇特耐火材料有限公司 | Microcrystal periclase composite spinel titanium refractory material and manufacturing method thereof |
| CN115650747A (en) * | 2022-11-16 | 2023-01-31 | 鞍山钢铁冶金炉材科技有限公司 | Magnesia-hercynite ladle wall gunning mix and preparation method thereof |
| CN115650747B (en) * | 2022-11-16 | 2023-12-15 | 鞍山钢铁冶金炉材科技有限公司 | Magnesia-hercynite steel ladle wall gunning material and preparation method thereof |
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Application publication date: 20091118 |