CN102718511A - Semi-lightweight high-zirconium refractory material - Google Patents
Semi-lightweight high-zirconium refractory material Download PDFInfo
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Abstract
The invention relates to a semi-lightweight high-zirconium refractory material, which is characterized by comprising the following components in percentage by weight: 70 to 80 percent of ZrO2, 10 to 25 percent of SiO2, 1 to 10 percent of Al2O3 and less than 1 percent of impurities. Compared with the prior art, the semi-lightweight high-zirconium refractory material has the following advantages and characteristics that 1, the material is semi-lightweight, has good thermal stability and is suitable for the hot repair; 2, the material has high zirconia content and has good corrosion resistance; 3, the material contains a few glass phases, ''ASZ high-viscosity liquid phase'' glaze is easily formed on a working surface in the using process of the semi-lightweight high-zirconium refractory material, the semi-lightweight high-zirconium refractory material is beneficial for the chemical invasion of furnace gas and the service life is prolonged; and 4, the semi-lightweight high-zirconium refractory material is beneficial for reducing the replacement frequency, reducing the influence on the production and promoting the production operating efficiency.
Description
Technical field
The present invention relates to the high Zr refractory material of a kind of half lightweight, belong to Industrial Stoves pure oxygen burning technical field.
Background technology
Along with the technology popularization of Industrial Stoves pure oxygen burning, saving energy in kiln exhaust gas emission total amount declines to a great extent.The concentration of admixtion component and glass metal salt volatile matter significantly raises in the kiln waste gas, and pure oxygen combustor flame ejiction opening produces negative pressure and kiln space atmosphere generates cyclone, constantly washes away refractory surface.In the conventional aluminium zirconium series fire resistive material product composition because of containing ZrO
2Measure lowly, a little less than anti-boron, the fluorine erosional competency, add Na
2The existence of O and part Si O
2Generate the lower melting point fused matter with glass batch component calcium, magnesium and run off, cause spray gun brick erosive velocity to be accelerated, work-ing life is very short.And the spray gun brick corrodes the back flame combustion state and changes, and kiln breastwork is on every side caused scaling loss, must change spray gun brick and part breastwork body of wall under the serious situation.
Summary of the invention
The object of the present invention is to provide on a kind of satisfied use technology with cost performance on requirement, and the high Zr refractory material of half lightweight with good thermal shock resistance property, erosion-resisting characteristics.
It is that the high Zr refractory material of this half lightweight contains ZrO that the present invention solves the problems of the technologies described above the technical scheme that is adopted
2, SiO
2, Al
2O
3, the physical parameter of the weight percentage of each component and the high Zr refractory material of said half lightweight is following:
ZrO
2 70~80%
SiO
2 10~25%
Al
2O
3 1~10%
Impurity < 1%
Volume density (g/cm
3) 3.0 ~ 3.5
Apparent porosity (%) 29 ~ 34
Compressive strength (MPa) >=35.
The heavy burden softening temperature of refractory materials according to the invention is >=1700 degree, life-time service temperature 1600 ~ 1650 degree.
Refractory materials of the present invention is with ZrO
2-Al
2O
3-SiO
2Element is the basis, ZrO
2The introducing ratio promotes the erosion performance of the resistance to acid basic slag that can obviously improve material, SiO
2Introducing is used as the material sticker, can promote forming materials and improve firing property, improves yield rate.Al
2O
3Introduce main solid state reaction and reduce silicon volatilization and free, the viscosity that increases liquid phase is simultaneously slowed down loss.
The present invention has improved zirconic ratio, and zirconium white introduces with the form of stabilised zirconia, and effectively control material crystal conversion rate obviously improves shaking property of heat.The raising of simultaneous oxidation zirconium ratio makes the material corrosion resistance significantly obtain to promote.
Sial part of the present invention is introduced as sticker, mainly introduces with the form of compound phase, has reduced the free and volatilization of elemental silicon, makes the hot structure of material keep stable.
The sial ratio that the present invention introduces is suitably adjusted, and can obtain the improvement on some use propertieies.
As preferably, the present invention contains ZrO
2, SiO
2, Al
2O
3, the physical parameter of the weight percentage of each component and the high Zr refractory material of said half lightweight is following:
ZrO
2 75~78%
SiO
2 15~17%
Al
2O
3 5~7%
Impurity < 1%
Volume density (g/cm
3) 3.1 ~ 3.3
Apparent porosity (%) 30 ~ 33
Compressive strength (MPa) >=35.
As more preferably, the present invention contains ZrO
2, SiO
2, Al
2O
3, the physical parameter of the weight percentage of each component and the high Zr refractory material of said half lightweight is following:
ZrO
2 75~78%
SiO
2 15~17%
Al
2O
3 5~7%
Impurity < 1%
Volume density (g/cm
3) 3.2
Apparent porosity (%) 30 ~ 33
Compressive strength (MPa) 35 ~ 45.
The method of manufacture of the high Zr refractory material of half lightweight according to the invention may further comprise the steps:
A, SiO
2, Al
2O
3Introduce ZrO with mullite phase form
2Part is introduced with the zirconium silicate form, and part is with ZrO
2Form is introduced, and allocates;
B, process " diaphragm " or " slurry casting " technology obtain idiosome;
C, idiosome leave oven dry moisture in the thermostatic drying chamber in, and dry idiosome moisture controlled is below 0.05%;
D, dry idiosome high temperature " shuttle kiln " the afterburner firing up of packing into, following temperature rise rate 10 degree of 900 degree/hour, 900 degree～1650 degree temperature rise rates 15 spend/hour; 1650 degree insulations begin the annealing cooling after 2 hours, the above annealing of 900 degree rate of temperature fall 30 degree/hour, 15 degree below 900 degree/hour, directly close down burner below 300 degree and lower the temperature naturally.
Burner according to the invention adopts LPG liquefied petroleum gas or Sweet natural gas to mix air combustion, heats up through adjustment gas flow and the empty ratio control of mixing.
The present invention has the following advantages and characteristics with existing compared with techniques: 1, half lightweight, have thermostability preferably, and adapt to hot repair.2, high proportion of zirconium-oxide has better resistance to fouling.3, contain a small amount of glassy phase, workplace is prone to form " ASZ HV liquid phase " glaze in the use, has to hinder in the invasion of furnace gas chemistry, prolongs life.4, help to reduce the replacing frequency, reduce influence, promote production operation efficiency producing.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, following examples are to explanation of the present invention and the present invention is not limited to following examples.Wherein embodiment component total content is slightly less than 100%, be appreciated that for residual volume be the minor components that trace impurity maybe can not analyze.
Embodiment: ZrO
2Preparing method: ZrO
2Preparation is purified through high-temperature electrolysis through mineral such as nature raw mineral materials zirconium sand, zircon, baddeleyites, obtains the higher ZrO of purity
2Raw material.Under 2000 degree conditions, zirconium white separates with quartz fully like zircon, thereby obtains high-purity mangesium oxide zirconium raw material.
SiO
2Preparing method: SiO
2Prepare simply relatively, the higher raw mineral materials of nature silicon content is a lot, as: quartzite, crystal, silica sand, sandstone etc., sandstone purity is high, is broken into particle and directly can introduces elemental silicon.
Al
2O
3Preparing method: Al
2O
3Preparation contains the higher raw mineral materials of aluminium through nature raw mineral materials kaolin, bauxitic clay etc., through high temperature or chemical purification technology, obtains the higher raw material of purity., carbon is decomposed the back obtain the higher Al of white cleanliness factor through calcining process like Coaseries kaolin
2O
3Raw material.
Therefore refractory materials mainly exists with compound phase form, prepares refractory materials and must consider that each oxide compound introduces with compound phase form, increases erosion-resistant performance.For example: silicon, zirconium slowly generate zirconium silicate under hot conditions, and sial generates the mullite crystalline phase under 1250 degree temperature condition.
Main raw material is zirconium white and aluminium, silicon, the compound phase form of zirconium among the present invention, and the method for manufacture of the high Zr refractory material of said half lightweight may further comprise the steps:
A, SiO
2, Al
2O
3Introduce ZrO with mullite phase form
2Part is introduced with the zirconium silicate form, and part is with ZrO
2Form is introduced, and allocates;
B, process " diaphragm " or " slurry casting " technology obtain idiosome;
C, idiosome leave oven dry moisture in the thermostatic drying chamber in, and dry idiosome moisture controlled is below 0.05%;
D, dry idiosome high temperature " shuttle kiln " the afterburner firing up of packing into, following temperature rise rate 10 degree of 900 degree/hour, 900 degree～1650 degree temperature rise rates 15 spend/hour; 1650 degree insulations begin the annealing cooling after 2 hours, the above annealing of 900 degree rate of temperature fall 30 degree/hour, 15 degree below 900 degree/hour, directly close down burner below 300 degree and lower the temperature naturally.
Burner according to the invention adopts LPG liquefied petroleum gas or Sweet natural gas to mix air combustion, heats up through adjustment gas flow and the empty ratio control of mixing.
Sial introducing ratio is suitably adjusted in the refractory materials principal phase composition of the present invention, can obtain the improvement on some use propertieies.
Listed 8 embodiment of the present invention and Comparative Examples in table 1 to the table 2, wherein An represents embodiment, and Bn represents Comparative Examples.Each components contents of refractory materials is represented with weight percent in the table.For the advantage of the high Zr refractory material of the present invention's half lightweight is described; Provided 4 parameters in the table: volume density (g/cm3), apparent porosity (%), compressive strength (MPa); In work-ing life (moon), above-mentioned parameter and measuring method thereof are that the technician in present technique field knows.
Table 1:
| Numbering | B1 | B2 | B3 | A1 |
| ZrO 2（%） | 30.8 | 95 | 65 | 78 |
| SiO 2（%） | 14 | 2 | 35 | 15 |
| Al 2O 3（%） | 43 | 2 | \ | 7 |
| Fe 2O 3+ TiO 2（%） | 3 | \ | \ | \ |
| Na 2O（%） | 9 | \ | \ | \ |
| Volume density (g/cm 3） | 3.0 | 2.8 | 3.85 | 3.2 |
| Apparent porosity (%) | 32 | 38 | 18 | 32 |
| Compressive strength (MPa) | ≥35 | ≥25 | ≥100 | ≥35 |
| Work-ing life (moon) | 3 | 24 | Can't hotly change | 25 |
Table 2:
| Numbering | A2 | A3 | A4 | A5 |
| ZrO 2（%） | 70 | 75 | 80 | 72 |
| SiO 2（%） | 23 | 15 | 17 | 20 |
| Al 2O 3（%） | 7 | 10 | 3 | 8 |
| Fe 2O 3+ TiO 2（%） | \ | \ | \ | \ |
| Na 2O（%） | \ | \ | \ | \ |
| Volume density (g/cm 3） | 3.0 | 2.8 | 3.85 | 3.2 |
| Apparent porosity (%) | 32 | 38 | 18 | 32 |
| Compressive strength (MPa) | ≥35 | ≥35 | ≥35 | ≥35 |
| Work-ing life (moon) | 12 | 25 | 18 | 24 |
Contrast table 1: Comparative Examples B1 is that it is lower to contain the zirconium amount, Na with AZS aluminium zirconium product
2A little less than the higher hot use corrosion resistance of O content, the life-span is short.Comparative Examples B2 is that price is very high with the pure zirconium product of import " 1195 ".Comparative Examples B3 uses the zircon goods, and volume density is high, the hot replacing of incompatibility.Embodiment A 1 contains ZrO
2Near pure zirconium product, the performance of use satisfies processing requirement fully, and cost performance is significantly higher than the pure zirconium product of import.Contrast table 2: embodiment A 2 is because liquid phase is separated out the more stability that goods high temperature uses that influences, and life cycle is shorter.Although embodiment A 4 contains the zirconium amount and is higher than other embodiment, liquid phase precipitate viscosity is the very fast stability in use that influences goods equally of low-bleed very.Embodiment A 3 is approaching relatively with embodiment A 5 principal phase compositions, the liquid phase amount of separating out and precipitate viscosity ratio embodiment A 2 and embodiment A 4 ideals, and result of use is stablized life cycle and is reached more than 24 months.
Key point of the present invention mainly contains two: 1, the lifting of zirconium white ratio, and zirconium white is introduced with the form of stabilised zirconia, and effectively control material crystal conversion rate obviously improves shaking property of heat.The raising material corrosion resistance of simultaneous oxidation zirconium ratio significantly obtains to promote.2, the sial part is mainly introduced the free and volatilization that reduces elemental silicon with the form of compound phase as the introducing of sticker, and the hot structure of material keeps stable.
In addition, need to prove, the specific embodiment described in this specification sheets, its prescription, title that technology is named etc. can be different.Allly conceive equivalence or the simple change that described structure, characteristic and principle are done, include in the protection domain of patent of the present invention according to patent of the present invention.Person of ordinary skill in the field of the present invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment; Only otherwise depart from structure of the present invention or surmount the defined scope of these claims, all should belong to protection scope of the present invention.
Though the present invention with embodiment openly as above; But it is not in order to limit protection scope of the present invention; Any technician who is familiar with this technology, change and the retouching in not breaking away from design of the present invention and scope, done all should belong to protection scope of the present invention.
Claims (3)
1. the high Zr refractory material of one and half lightweights is characterized in that containing ZrO
2, SiO
2, Al
2O
3, the weight percentage of each component is following:
ZrO
2 70~80%
SiO
2 10~25%
Al
2O
3 1~10%
Impurity < 1%.
2. according to the high Zr refractory material of described half lightweight of claim 1, it is characterized in that containing ZrO
2, SiO
2, Al
2O
3, the weight percentage of each component is following:
ZrO
2 75~78%
SiO
2 15~17%
Al
2O
3 5~7%
Impurity < 1%.
3. the method for manufacture of claim 1 or the high Zr refractory material of 2 said half lightweights is characterized in that may further comprise the steps:
A, SiO
2, Al
2O
3Introduce ZrO with mullite phase form
2Part is introduced with the zirconium silicate form, and part is with ZrO
2Form is introduced, and allocates;
B, process " diaphragm " or " slurry casting " technology obtain idiosome;
C, idiosome leave oven dry moisture in the thermostatic drying chamber in, and dry idiosome moisture controlled is below 0.05%;
D, dry idiosome high temperature " shuttle kiln " the afterburner firing up of packing into, following temperature rise rate 10 degree of 900 degree/hour, 900 degree～1650 degree temperature rise rates 15 spend/hour; 1650 degree insulations begin the annealing cooling after 2 hours, the above annealing of 900 degree rate of temperature fall 30 degree/hour, 15 degree below 900 degree/hour, directly close down burner below 300 degree and lower the temperature naturally.
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|---|---|---|---|
| CN2012102146259A CN102718511A (en) | 2012-06-27 | 2012-06-27 | Semi-lightweight high-zirconium refractory material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102146259A CN102718511A (en) | 2012-06-27 | 2012-06-27 | Semi-lightweight high-zirconium refractory material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033796A (en) * | 2017-12-08 | 2018-05-15 | 安徽雷萨重工机械有限公司 | A kind of refractory material of high-strength mechanical properties |
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|---|---|---|---|---|
| CN1048025A (en) * | 1989-06-15 | 1990-12-26 | 欧洲耐火材料公司 | Fused and cast refractory products with high zirconium dioxide content |
| CN1187178A (en) * | 1995-06-09 | 1998-07-08 | 福斯伯尔国际有限公司 | Process for forming refractory repair mass |
| CN1319572A (en) * | 2000-01-31 | 2001-10-31 | 欧洲耐火材料公司 | Aluminium oxide-zirconium oxide-silicon oxide based electric fused products with improved microstructure |
| CN1807352A (en) * | 2005-08-04 | 2006-07-26 | 淄博工陶耐火材料有限公司 | Higly oxidized zirconia refractory preparation method |
| CN1902142A (en) * | 2004-01-02 | 2007-01-24 | 维苏维尤斯·克鲁斯布公司 | Fusion-cast refractory with high electrical resistivity |
| CN101652337A (en) * | 2007-02-23 | 2010-02-17 | 法商圣高拜欧洲实验及研究中心 | Molten and cast refractory block having a high zirconia content |
-
2012
- 2012-06-27 CN CN2012102146259A patent/CN102718511A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048025A (en) * | 1989-06-15 | 1990-12-26 | 欧洲耐火材料公司 | Fused and cast refractory products with high zirconium dioxide content |
| CN1187178A (en) * | 1995-06-09 | 1998-07-08 | 福斯伯尔国际有限公司 | Process for forming refractory repair mass |
| CN1319572A (en) * | 2000-01-31 | 2001-10-31 | 欧洲耐火材料公司 | Aluminium oxide-zirconium oxide-silicon oxide based electric fused products with improved microstructure |
| CN1902142A (en) * | 2004-01-02 | 2007-01-24 | 维苏维尤斯·克鲁斯布公司 | Fusion-cast refractory with high electrical resistivity |
| CN1807352A (en) * | 2005-08-04 | 2006-07-26 | 淄博工陶耐火材料有限公司 | Higly oxidized zirconia refractory preparation method |
| CN101652337A (en) * | 2007-02-23 | 2010-02-17 | 法商圣高拜欧洲实验及研究中心 | Molten and cast refractory block having a high zirconia content |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033796A (en) * | 2017-12-08 | 2018-05-15 | 安徽雷萨重工机械有限公司 | A kind of refractory material of high-strength mechanical properties |
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Application publication date: 20121010 |