CN104557056A - Bauxite homogenizing material as Sialon raw material and production method of bauxite homogenizing material - Google Patents
Bauxite homogenizing material as Sialon raw material and production method of bauxite homogenizing material Download PDFInfo
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Abstract
The invention relates to a bauxite homogenizing material as a Sialon raw material and a production method of the bauxite homogenizing material, and belongs to the technical field of production of refractory materials. The homogenizing material is prepared by adding excessive metal aluminum powder to reduce SiO2, Fe2O3 and TiO2 in aluminum bauxite and coal gangue. The bauxite homogenizing material comprises active ingredients Al2O3, Si and Al and a small amount of Fe and Ti, wherein the amount of Al2O3 is 85 to 90wt%, the total amount of elemental Si and elemental Al is 8 to 12wt%, the weight ratio of elemental Si to elemental Al is (3-4): 1, and the bauxite homogenizing material is a very good raw material for synthesizing a Sialon material. When a refractory brick made from the homogenizing material is fired by nitriding, Sialon is formed in the matrix of the brick, and homogeneous Sialon can also be formed inside particles; and meanwhile, the homogenizing material is also a very good raw material for producing an iron runner material and a refractory brick with high refractoriness under load and low creep.
Description
Technical field
The invention belongs to refractory raw material production technical field, be specifically related to a kind of alumina homogenization material and the production method thereof that are used as Sialon raw material.
Background technology
The Sialon combined corundum brick of Savoie company of the large blast furnace common usage state production in the current whole world, this refractory brick take corundum as main raw material, and additional a certain amount of simple substance Si, simple substance Al, being greater than 150MPa forming under the pressure, at N
2burn till in atmosphere, simple substance Si and Al first nitrogenize formation Si in sintering process
3n
4with AlN, be greater than at 1400 DEG C of temperature, Al
2o
3be solid-solution in Si gradually
3n
4si is formed in lattice
6-Zal
zo
zn
8-Z(Sialon), because Sialon material has very high intensity, there is very excellent iron-resistant water, anti-molten slag erosional competency, there are extremely excellent thermal stability and alkali resistant erosional competency and antioxidant property, so Sialon combined corundum brick is current blast furnace hearth, the refractory materials that the harshest positions of working conditions such as bosh are best, a lot of universities and colleges after our country's the eighties in last century, a lot of research work has all been done by research department, publish thesis a nearly hundreds of section, if a Beijing University of Science & Technology flood man of virtue and ability, Sun Jialin etc., these achievements are assembled into " non-oxidized substance composite refractory " book, people are made to have had general understanding to Sialon material, China's researcher research Sialon material is all the research work launched with domestic existing raw material, be difficult to obtain stable performance in big scale Sialon combined corundum brick, reliably, equally distributed beta-Sialon phase.Sialon material is found at present near ISUZU company, and the Sialon product that energy and French Sialon combined corundum brick are waged a decisive campaign qualitatively do not appear in China all the time.The present inventor thinks that the key of problem is that we have ignored the most applicable development of raw materials work doing Sialon combined corundum, common corundum raw material adds simple substance Si, metal A l, be easy to obtain the good Sialon material of performance in matrix, and account for Sialon combined corundum brick quality granule interior over half also formed Sialon phase hardly may, raw material inside also needs equally distributed simple substance Si and Al and has Ti and the Fe of catalytic capability.The present invention is just in order to solve these problems of raw material.
Summary of the invention
The object of the invention there are provided a kind of alumina homogenization material and the production method thereof that are used as Sialon raw material.
Based on above-mentioned purpose, this invention takes following technical scheme: a kind of alumina homogenization material being used as Sialon raw material, it is by adding excess metal aluminium powder by the SiO in bauxitic clay and coal gangue
2, Fe
2o
3and TiO
2carry out reduction to obtain, the effective constituent of this alumina homogenization material is Al
2o
3, Si, Al, Fe and Ti, wherein Al
2o
3be 85 ~ 90wt%, simple substance Si and simple substance Al total amount are 8 ~ 12wt%, and the weight ratio of simple substance Si and simple substance Al is that (3 ~ 4): 1, Fe and Ti content are less, Ti 1 ~ 2%, Fe < 1.0%.
Al in described bauxitic clay
2o
3>=85 wt%, TiO
22.5 ~ 4 wt %, Fe
2o
3≤ 1.2 wt%; Al in described coal gangue
2o
3> 45 wt%, Al
2o
3+ SiO
2be 97 ~ 98 wt%.Although simple substance Fe is formed with katalysis to Sialon, in homogenization material, the content of simple substance Fe should control between 0.5 ~ 1%, is conducive to the Sialon product forming high-quality, therefore control Fe in alumina raw
2o
3≤ 1.2 wt%.Due to TiO in coal gangue
2and Fe
2o
3content do not affect the last component content of target product, can consider at this.
The production method of described alumina homogenization material, comprises the following steps: 1) by bauxitic clay and coal gangue powder process, carries out being mixed to get raw mixture with excessive metallic aluminium powder; 2) add rare resol, after wet stone roller, pressed compact are shaping, after being warming up to more than 1500 DEG C, the obtained alumina homogenization materials of insulation, are target product; Described rare resol mixes obtained by resol and organic solvent.The object that rare resol adds makes better to combine between material, plays the effect of bonding agent.
In step 1), described bauxitic clay and coal gangue are made 600 ~ 800 order powder or light-burned at 800 ~ 1000 DEG C after make 600 ~ 800 order powder.After the direct abrasive dust of alumina coal gangue raw material, burn till with aluminium powder mixing pressed compact, because constitution water in raw material can make aluminium powder oxidation, not easy-sintering and aluminium powder catalytic effect can be caused to reduce, thus aluminium powder consumption increases, cost is higher; If bauxitic clay, coal gangue are after 800 ~ 1000 DEG C of light-burned activation, in raw material, constitution water is removed, and more easy-sintering can obtain the better homogenization material of finer and close quality.
Al in bauxitic clay and coal gangue is detected respectively before batching
2o
3, SiO
2, Fe
2o
3, TiO
2content, if after light-burned, then need to detect the bauxitic clay after light-burned and coal gangue, then make simple substance Si and simple substance Al total amount in target product be 8 ~ 12wt% according to mass conservation law conversion feeding quantity, and the weight ratio of Si and Al is (3 ~ 4): 1.
Described organic solvent is alcohol organic solvent, affiliated alcohols particular methanol, ethanol or ethylene glycol.
Described alcohol organic solvent is ethanol, and the add-on of described rare resol is 4 ~ 6% of raw mixture weight, this rare resol by resol and ethanol by volume 1:4 mix obtained.
Step 2) in wet stone roller 25 ~ 35min.
Step 2) in the shaping pressure of pressed compact be 100 ~ 150MPa.
Step 2) in be warming up to 1500 ~ 1600 DEG C, temperature rise rate is 30 ~ 50 DEG C/h, insulation 8 ~ 24h.
The homogenization material that the present invention obtains is synthesis Sialon good raw material, not only has homodisperse elemental silicon and aluminium exists, and also has Ti and the Fe of the trace that can make catalyzer to exist, thus adopts homogenization material of the present invention at N
2in the process of atmosphere synthesis Sialon, matrix and granule interior all can stable, the reliable and equally distributed original position beta-Sialon phases of forming property.Its concrete forming process is: first, and metal A l powder is by the SiO of bauxitic clay and coal gangue inside
2, TiO
2, Fe
2o
3in-situ reducing is simple substance Si, Ti, Fe, the simple substance Si be reduced out is the amount of Si needed for synthesis homogenization material, the metal A l had more is just in time the amount of metal A l needed for synthesis Sialon, thus ensure that the Sialon forming original position in nitridation process, wherein, Si/Al=(3 ~ 4): 1, Al+Si accounts for 8 ~ 12% of homogenization material quality, ensure that this homogenization material forms in the process of Sialon the Si producing about 30% in nitrogenize
6-zal
zo
zn
8-zphase.
This homogenization material is except Al intrinsic in bauxitic clay
2o
3outside, reduction Al has finally also become the Al in homogenization material
2o
3, all the other compositions are namely reduced into simple substance Si, Ti, Fe, and all the other compositions only have CaO, MgO, Na of the trace that can not be reduced in bauxitic clay and coal gangue
2o, K
2o, CaO+MgO+Na
2o+K
2o < 1.0%, and the composition of the homogenization material finally obtained: Al
2o
385 ~ 90%, Si+Al 8 ~ 12%, Ti 1 ~ 2%, Fe < 1.0% has been almost the high pure raw material of synthesis Sialon.
To sum up, beneficial effect of the present invention is: present method discloses makees reductive agent with excessive metallic aluminium powder, by the SiO in bauxitic clay
2, TiO
2, Fe
2o
3si, Ti, Fe of simple substance is reduced into Deng impurity, the Si be reduced is the source of the Si of target homogenization material, and unnecessary go out metallic aluminium Al, be the source of Al in target homogenization material, a small amount of Ti and Fe is just in time the catalyzer of synthesis Sialon material, and oxidized metallic aluminium is just in time the first principal component Al in alumina homogenization material
2o
3, this alumina homogenization material is the good raw material of synthesis Sialon material.Because this homogenization material does refractory brick, during Nitride firing not only brick matrix in can form Sialon, and granule interior can form homogeneous Sialon phase too, this homogenization material is also produce iron runner material and high RUL, the good raw material of low creep height refractory brick simultaneously.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, and the scope of this patent protection is only limitted to this by no means.
In following examples, bauxitic clay used and coal gangue first carry out the content detecting each component after light-burned, wherein Al in light-burned bauxitic clay
2o
388%, SiO
27%, TiO
23.5%, Fe
2o
31.2%; Al in light-burned coal gangue
2o
345.5%, SiO
252%, TiO
21.0%, Fe
2o
31.0%, but light-burned bauxitic clay and light-burned coal gangue are not limited to this, in the bauxitic clay under the varying environment effect of different areas and coal gangue, the content of each composition is different, in actual production, and Al in preferred bauxitic clay
2o
3>=85 wt%, TiO
22.5 ~ 4 wt %, Fe
2o
3≤ 1.2 wt%; Al in coal gangue
2o
3> 45 wt%, Al
2o
3+ SiO
2be 97 ~ 98 wt%.
embodiment
1
Target product: preparation Si+Al is the weight ratio of 10.2wt%, Si and Al is 3.08 alumina homogenization materials, and wherein, elemental silicon content is 7.7 wt %, and metal A l content is 2.5 wt % alumina homogenization materials.
First, adopt and with the following method the consumption of each raw material is calculated: the total amount of light-burned bauxitic clay and light-burned coal gangue is in 1000kg, and set light-burned bauxitic clay and light-burned coal gangue as x kg, y kg respectively, the consumption of aluminium powder is z kg.
If light-burned bauxitic clay and light-burned coal gangue are respectively x kg, y kg, then contain Al in the light-burned bauxitic clay of x kg and the light-burned coal gangue of y kg
2o
3(88%x+45.5%y) kg, containing SiO
2(7%x+52%y) kg, TiO
2(3.5%x+1.0% y) kg, Fe
2o
3(1.2% x+1.0%y) kg, the known SiO reducing 1kg respectively
2, TiO
2and Fe
2o
3need the amount of metal A l powder to be 0.6 kg, 0.45 kg, 0.34 kg, can obtain thus:
x+y=1000 （1）
7%x+52%y=7.7%×（1000+z）×
（2）
(7%x+52%y)×0.6+(3.5% x+1.0%y)×0.45 +(1.2% x+1.0%y)×0.34+(1000+z)×2.5%= z （3）
Separating this system of equations can to obtain x be 730 kg, y be 270 kg, z is 160kg, and namely the consumption of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder is respectively 730 kg, 270 kg, 160kg.
Then, be prepared into target product, method is:
1) by bauxitic clay and coal gangue at 800 ~ 1000 DEG C of light-burned rear system 600 ~ 800 order powder, be carry out butt batching mixing at 730: 270: 160 by the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder;
2) add rare resol with 5% of ingredients mixture weight, wet grind pressed compact under 30min, 120MPa shaping after, the obtained alumina homogenization material of calcining.Wherein, the temperature rise rate in calcination process is 30 ~ 50 DEG C/h, when temperature rises to 1500 DEG C, carries out insulation 20 ~ 24h, and rare resol mixes obtained by 1:4 by resol and ethanol.
In ultimate aim product homogenization material: Al
2o
3=
=87.3%
Si=7.7%
Al=2.5%
Ti=
=1.46%
Fe=
=0.69%
embodiment
2
Target product: preparation Si+Al is the weight ratio of 12wt%, Si and Al is the alumina homogenization material of 4:1, and wherein, elemental silicon content is 9.6 wt %, and metal A l content is 2.4wt % alumina homogenization material.
Calculate according to the method for embodiment 1 consumption proportion of each raw material, the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder is 611.3: 388.7: 190.6.
Its preparation method is:
1) by bauxitic clay and coal gangue at 800 ~ 1000 DEG C of light-burned rear system 600 ~ 700 order powder, be carry out butt batching mixing at 611.3: 388.7: 190.6 by the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder;
2) add rare resol with 4% of ingredients mixture weight, wet grind pressed compact under 30min, 100MPa shaping after, one-step calcination obtains alumina homogenization material.Wherein, the temperature rise rate in one-step calcination process is 30 ~ 40 DEG C/h, when temperature rises to 1600 DEG C, carries out insulation 8 ~ 12h, and rare resol mixes obtained by 1:4 by resol and ethanol.
In ultimate aim product homogenization material: Al
2o
3be 0.66% for 85.7wt%, Si be 9.6 wt %, Al be 2.4wt %, Ti are 1.27%, Fe.
embodiment
3
Target product: preparation Si+Al is the weight ratio of 8 wt%, Si and Al is the alumina homogenization material of 3:1, and wherein, elemental silicon content is 6 wt %, and metal A l content is 2 wt % alumina homogenization materials.
Calculate according to the method for embodiment 1 consumption proportion of each raw material, the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder is 833: 167: 129.
Its preparation method is:
1) by bauxitic clay and coal gangue at 800 ~ 1000 DEG C of light-burned rear system 700 ~ 800 order powder, be carry out butt batching mixing at 833: 167: 129 by the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder;
2) add rare resol with 6% of ingredients mixture weight, wet grind pressed compact under 25min, 150MPa shaping after, the obtained alumina homogenization material of calcining.Wherein, the temperature rise rate in calcination process is 30 ~ 40 DEG C/h, when temperature rises to 1600 DEG C, carries out insulation 12 ~ 14h, and rare resol mixes obtained by 1:4 by resol and ethanol.
In ultimate aim product homogenization material: Al
2o
3be 0.70% for 89.7wt%, Si be 6wt %, Al be 2wt %, Ti are 1.64%, Fe.
embodiment
4
Target product: preparation Si+Al is the weight ratio of 12 wt%, Si and Al is the alumina homogenization material of 3:1, and wherein, elemental silicon content is 9 wt %, and metal A l content is 3 wt % alumina homogenization materials.
Calculate according to the method for embodiment 1 consumption proportion of each raw material, the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder is 646: 354: 188.
Its preparation method is:
1) by bauxitic clay and coal gangue at 800 ~ 1000 DEG C of light-burned rear system 700 ~ 800 order powder, be carry out butt batching mixing at 646: 354: 188 by the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder;
2) add rare resol with 6% of ingredients mixture weight, wet grind pressed compact under 35min, 150MPa shaping after, the obtained alumina homogenization material of calcining.Wherein, the temperature rise rate in calcination process is 30 ~ 40 DEG C/h, when temperature rises to 1600 DEG C, carries out insulation 12 ~ 14h, and rare resol mixes obtained by 1:4 by resol and ethanol.
In ultimate aim product homogenization material: Al
2o
3be 0.67% for 85.6wt%, Si be 9wt %, Al be 3wt %, Ti are 1.32%, Fe.
embodiment
5
Target product: preparation Si+Al is the weight ratio of 8wt%, Si and Al is the alumina homogenization material of 4:1, and wherein, elemental silicon content is 6.4 wt %, and metal A l content is 1.6wt % alumina homogenization material.
Calculate according to the method for embodiment 1 consumption proportion of each raw material, the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder is 812: 188: 127.
Its preparation method is:
1) by bauxitic clay and coal gangue at 800 ~ 1000 DEG C of light-burned rear system 700 ~ 800 order powder, be carry out butt batching mixing at 812: 188: 127 by the weight ratio of light-burned bauxitic clay, light-burned coal gangue and metallic aluminium powder;
2) add rare resol with 6% of ingredients mixture weight, wet grind pressed compact under 30min, 100MPa shaping after, the obtained alumina homogenization material of calcining.Wherein, the temperature rise rate in calcination process is 30 ~ 40 DEG C/h, when temperature rises to 1600 DEG C, carries out insulation 12 ~ 14h, and rare resol mixes obtained by 1:4 by resol and ethanol.
In ultimate aim product homogenization material: Al
2o
3be 0.62% for 89.2wt%, Si be 6.4wt %, Al be 1.6wt %, Ti are 1.61%, Fe.
In actual production, for the ease of calculating, also can adopt rough method, concrete grammar is: i) according to mass conservation law, the mass balance calculation bauxitic clay of Si and the addition of coal gangue before and after reaction; Ii) the consumption of metal A l powder is on the known basis of the addition of bauxitic clay and coal gangue, can by SiO contained in bauxitic clay and coal gangue according to Al powder
2, Fe
2o
3, TiO
2restore All and reach simple substance Si and simple substance Al total amount is 8 ~ 12wt% in target product, and the weight ratio of simple substance Si and simple substance Al is (3 ~ 4): the requirement of 1 calculates.
Calculate to reduce the light-burned alumina of 1000kg and light-burned coal shale in brick making, be specially (to prepare the target product of embodiment 1):
If light-burned bauxitic clay and light-burned coal gangue are respectively x kg, y kg then
x+y=1000 (1)
7%x+52%y=7.7%×1000×
(4)
Solve x=788.89kg ≈ 789kg y=211.11kg ≈ 211kg
And contain Al in the light-burned bauxitic clay of 789kg and the light-burned coal gangue of 211kg
2o
3790.325kg, containing SiO
2164.95kg, TiO
229.725, Fe
2o
311.58kg, reduce these SiO
2, TiO
2, Fe
2o
3need metal A l powder=98.97+13.38+3.91+2.5% × 1000=141.26kg, generate new Al
2o
3=186.94+25.27+7.39=219.6kg, forms simple substance Si76.98kg, metal Ti 16.35 kg, simple substance Fe8.106kg respectively.
Al in the final homogenization material of ∴
2o
3=
=
=88.87%
Si=
=6.77%
Al=
=2.2%
Ti=
=1.44%
Fe=
=0.713%。
Claims (10)
1. be used as an alumina homogenization material for Sialon raw material, it is characterized in that, it is by adding excessive metallic aluminium powder by the SiO in bauxitic clay and coal gangue
2, Fe
2o
3and TiO
2reduction is obtained, and the effective constituent of this alumina homogenization material is Al
2o
3, Si, Al, Fe and Ti, wherein Al
2o
3be 85 ~ 90wt%, simple substance Si and simple substance Al total amount are 8 ~ 12wt%, and the weight ratio of simple substance Si and simple substance Al is (3 ~ 4): 1.
2. alumina homogenization material as claimed in claim 1, is characterized in that, Al in described bauxitic clay
2o
3>=85 wt%, TiO
22.5 ~ 4 wt %, Fe
2o
3≤ 1.2 wt%; Al in described coal gangue
2o
3> 45 wt%, Al
2o
3+ SiO
2be 97 ~ 98 wt%.
3. the production method of alumina homogenization material as claimed in claim 1 or 2, is characterized in that, comprise the following steps: 1) by bauxitic clay and coal gangue powder process, carry out being mixed to get raw mixture with excessive metallic aluminium powder; 2) add rare resol, after wet stone roller, pressed compact are shaping, after being warming up to more than 1500 DEG C, the obtained alumina homogenization materials of insulation, are target product; Described rare resol mixes obtained by resol and organic solvent.
4. the production method of alumina homogenization material as claimed in claim 3, is characterized in that, in step 1), described bauxitic clay and coal gangue are made 600 ~ 800 order powder or light-burned at 800 ~ 1000 DEG C after make 600 ~ 800 order powder.
5. the production method of alumina homogenization material as claimed in claim 4, is characterized in that, detect Al in bauxitic clay and coal gangue respectively before batching
2o
3, SiO
2, Fe
2o
3, TiO
2content, make simple substance Si and simple substance Al total amount in target product be 8 ~ 12wt% according to mass conservation law conversion feeding quantity, and the weight ratio of Si and Al is (3 ~ 4): 1.
6. the production method of alumina homogenization material as claimed in claim 5, it is characterized in that, described organic solvent is alcohol organic solvent.
7. the production method of alumina homogenization material as claimed in claim 3, it is characterized in that, described alcohol organic solvent is ethanol, and the add-on of described rare resol is 4 ~ 6% of raw mixture weight, this rare resol by resol and ethanol by volume 1:4 mix obtained.
8. the production method of alumina homogenization material as claimed in claim 3, is characterized in that, step 2) in wet stone roller 25 ~ 35min.
9. the production method of alumina homogenization material as claimed in claim 3, is characterized in that, step 2) in the shaping pressure of pressed compact be 100 ~ 150MPa.
10. the production method of alumina homogenization material as claimed in claim 3, is characterized in that, step 2) in be warming up to 1500 ~ 1600 DEG C, temperature rise rate is 30 ~ 50 DEG C/h, insulation 8 ~ 24h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002852A (en) * | 2016-10-28 | 2018-05-08 | 河南智联寰宇知识产权运营有限公司 | Refractory brick containing alumina homogenization material and preparation method thereof |
| CN108276017A (en) * | 2018-01-31 | 2018-07-13 | 景德镇陶瓷大学 | It is a kind of to utilize corundum-silicon carbide whisker composite ceramic material and preparation method thereof that natural minerals are raw material |
| CN108585882A (en) * | 2018-05-15 | 2018-09-28 | 李明建 | A kind of raw material and its production method of function alundum |
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| CN1724472A (en) * | 2005-03-31 | 2006-01-25 | 北京科技大学 | Compound phose material of beta cellulose and alpha cellulose and its preparation technology |
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| 侯新梅: "铝、硅、碳还原剂对合成矾土基Sialon的作用及机理探讨", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002852A (en) * | 2016-10-28 | 2018-05-08 | 河南智联寰宇知识产权运营有限公司 | Refractory brick containing alumina homogenization material and preparation method thereof |
| CN108276017A (en) * | 2018-01-31 | 2018-07-13 | 景德镇陶瓷大学 | It is a kind of to utilize corundum-silicon carbide whisker composite ceramic material and preparation method thereof that natural minerals are raw material |
| CN108585882A (en) * | 2018-05-15 | 2018-09-28 | 李明建 | A kind of raw material and its production method of function alundum |
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