CN111548171B - Silica refractory mortar with excellent high-temperature performance - Google Patents
Silica refractory mortar with excellent high-temperature performance Download PDFInfo
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a silica refractory mortar with excellent high-temperature performance, which comprises the following powder components in percentage by mass: 0.5-0mm of waste silicon brick powder, 20-50%; 0.3-0mm of quartz powder, 15-35%; 0.088-0mm of quartz powder, 25-45 percent; 1-3% of silicon carbide dust-extraction powder; 1-3% of silica micropowder; 1-1.5% of dextrin; 0.1-0.5% of carboxymethyl cellulose; 0.05-0.2% of a mineralizer; and water accounting for 27-30 wt% of the powder is added and mixed. The silica content of the silica refractory mortar provided by the invention is more than or equal to 94%, no raw clay, sodium bentonite and the like are added, the alumina content is low, the low-melting-point content is low, and the refractoriness under load is high. Meanwhile, the waste silicon brick powder is added, so that the secondary utilization of resources is realized, the waste silicon brick powder basically exists in a phosphorus quartz phase, the volume stability is good, the waste silicon brick powder is matched with the material of the laid silicon brick, the adhesion is good in a high-temperature use environment, and the surface is not broken.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to silica refractory mortar with excellent high-temperature performance.
Background
In the prior art, the siliceous refractory mortar is mainly used in various high-temperature kilns such as coke ovens, hot-blast stoves and the like to build siliceous refractory bricks. For example, in a modern coke oven, the usage amount of the silica brick reaches 60-70% of the whole refractory product, so that the usage amount of the silica refractory mortar in the process of building the silica brick also reaches about 3-5% of the total amount of the silica brick. The silica refractory mortar used for the coke oven needs to have the characteristics of higher refractoriness under load, higher thermal conductivity, good thermal shock resistance, high-temperature volume stability and the like. In the process of long-term high-temperature use, siliceous mud with poor quality at high temperature and silica bricks are not sintered into a whole, and brick joints of the silica brick masonry are easy to separate, so that the phenomena of cracking, brick falling and even collapse of the masonry are caused. In order to ensure good workability and workability, a certain amount of raw clay is added to the conventional silica refractory mortar. The main mineral phases of domestic raw clay belong to kaolinite, and the main chemical components are alumina, silicon dioxide and more low-melting impurities. Alumina in the siliceous refractory mortar is a harmful substance and can react with silicon dioxide at high temperature to generate a large amount of liquid phase, so that the siliceous refractory mortar has low refractoriness under load and large shrinkage after burning, and a furnace lining is easy to crack and collapse in the process of long-term high-temperature operation of a kiln. Therefore, the alumina content should be minimized in siliceous products.
CN201811033620.X discloses a silica refractory slurry produced by waste silica bricks, which adopts different particle size distribution to prepare the silica refractory slurry to have better performance; although a large amount of waste silica brick powder is used, resources are saved, the slurry used as powder has the possibility of causing shrinkage after firing and reducing the bonding strength of the slurry due to the large amount of waste silica brick powder with stable volume stability and chemical properties, and the content of silicon dioxide is lower. The clay is adopted to introduce alumina impurities and other low-melting substances.
CN200710062483.8 discloses a siliceous refractory mortar powder, which is prepared by matching waste silica brick powder, silica and clay with different particle sizes of raw materials to prepare siliceous refractory mortar matched with silica bricks; although the problem of mismatching of the materials of the silica refractory mortar and the silica brick is solved, the addition of raw clay, the introduction of alumina impurities and other low-melting substances has influence on the charge softness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the siliceous refractory mortar with high refractoriness under load and good high-temperature performance, which is free from clay, low in impurity content, high in refractoriness under load, good in high-temperature bonding performance and capable of meeting the long-term use of industrial kilns.
In order to achieve the purpose, the technical scheme is as follows:
the silica refractory mortar with excellent high-temperature performance comprises the following powder components in percentage by mass:
and water accounting for 27-30 wt% of the powder is added and mixed.
According to the scheme, the waste silicon brick powder is mainly prepared from waste silicon brick powderThe phase is a phosphorus quartz phase, is derived from defective products with defective shapes or cracks after the silica bricks are fired and qualified chemical components, and the silica bricks removed from industrial kilns such as coke ovens, hot blast stoves and the like are sorted and crushed into particles with the particle size of 0.5-0mm, wherein SiO is2The content is more than 94 wt%.
According to the scheme, the quartz powder is high-purity quartz sand without calcination, and SiO is obtained2The content is more than or equal to 98.5wt percent.
According to the scheme, the silicon carbide dust extraction powder is a smoke dust waste collected in the silicon carbide production process, the granularity is less than or equal to 20 mu m, and the content of silicon carbide is more than or equal to 95 wt%.
According to the scheme, the silicon dioxide micropowder is high-purity ultrafine micropowder with the silicon dioxide content of more than or equal to 99 wt% and the granularity d50 of about 0.15 um.
According to the scheme, the dextrin is yellow dextrin, and the binding power of the dextrin is more than 1.8kg/cm2The solubility in water at 15-17 ℃ is more than 96%.
According to the scheme, the cellulose content in the carboxymethyl cellulose is more than or equal to 97.5 wt%.
According to the scheme, the mineralizer is the combination of iron scale powder and borax; the iron scale powder is derived from scale-shaped objects formed by the oxidation and falling off of the surfaces of steel products in the heating and rolling processes, the particle size range is 0.044-0mm, and the mass ratio of the iron scale powder to borax is 1 (1-3).
The waste silica brick used in the invention is completely transformed in crystal form due to high-temperature calcination under strict temperature control, and the main crystal phase is a phosphorite phase, so that the volume stability is good, and the high-temperature performance is good.
The quartz powder used in the invention has low price, high refractoriness, high silicon dioxide content and less impurities, is a necessary raw material for preparing the silica refractory slurry, and because the slurry is composed of a large amount of fine powder, the slurry is easy to shrink after high-temperature sintering, and the shrinkage during sintering can be reduced by adding the quartz powder.
The silicon carbide dust-extraction powder used in the invention belongs to industrial waste, but the silicon carbide content is high, the granularity is superfine, loose dust-like accumulation is presented, and the workability of the silica refractory slurry is improved. And the silicon carbide has high heat conductivity coefficient, and is beneficial to improving the heat conductivity of the silica refractory mortar.
The silicon dioxide micropowder used in the invention has superfine granularity and good dispersibility, and can suspend refractory mortar in the silica refractory mortar, so that the refractory mortar has better workability and is not precipitated, and the content of silicon dioxide in the silica refractory mortar can be increased due to ultrahigh content of silicon dioxide. The sintering can be promoted at the medium-high temperature stage, and the slurry bonding strength is improved.
Dextrin acts to increase the workability of the refractory mortar and to increase the bond strength after baking.
The carboxymethyl cellulose plays a role in retaining water in the refractory mortar, increases the suspension property of the refractory mortar, ensures that the mortar has certain plasticity, and ensures that mortar joints are full.
The scale powder used in the invention is iron scale produced in the steel rolling process, and the main component of the scale powder is Fe2O3FeO and the like, the granularity is 0.044-0mm, and the TFe content is more than or equal to 90 wt%; borax, sodium borate, is a chemical agent that is readily soluble in water and has a relatively low melting point. The combination of the scaly iron powder and the boric acid is used as a mineralizer to promote sintering in the siliceous refractory slurry, so that raw quartz powder can start to be converted into a large amount of phosphorosilicate in the sintering process at a lower temperature, the volume stability of the siliceous slurry is favorably improved, and the formed phosphorosilicate is spearhead-shaped bicrystals which are staggered with each other, and the strength of the slurry is favorably improved.
Compared with the prior art, the invention has the beneficial effects that:
the silica content of the silica refractory mortar provided by the invention is more than or equal to 94%, no raw clay, sodium bentonite and the like are added, the alumina content is low, the low-melting-point content is low, and the refractoriness under load is high.
The silicon carbide waste is added, so that the resource is saved, and the temperature conductivity of the silica refractory slurry is improved.
The waste silicon brick powder is added, so that the secondary utilization of resources is realized, the waste silicon brick powder basically exists in a phosphorus quartz phase, the volume stability is good, the waste silicon brick powder is matched with the material of the laid silicon brick, the adhesion is good in a high-temperature use environment, and the surface is not broken.
A certain amount of mineralizer is added in a compounding way, so that a large amount of quartz powder (the basic phase is beta-quartz) in the siliceous mud can be converted into tridymite phase at a lower temperature in the heating process, and cristobalite phase with larger volume expansion is not directly generated, and the refractory mud is favorable for not generating too large expansion in the high-temperature use process.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
In the following examples, the raw material indexes used are:
the particle size of the waste silicon brick powder is 0-0.5mm, and the SiO of the waste silicon brick powder2The content was 94.5 wt%;
the particle size of the quartz powder is 0-0.3mm, and 0.088-0mm, SiO2The content is 99 wt%;
the dust particle size of the silicon carbide is less than or equal to 20um, and the content of the silicon carbide is 95.2 wt%;
the average particle size of the silicon dioxide micro powder is about 0.15um, and the silicon dioxide content is 99.3 wt%;
the dextrin is yellow dextrin with binding power greater than 1.8kg/cm2The solubility in water at 15-17 deg.C is greater than 96%, and the acidity is less than 35%.
The mineralizer is formed by compounding or independently adding the iron scale powder and the borax. Wherein, the TFe content in the scaly iron powder is 93.5 percent.
Example 1
The silica refractory mortar comprises the following components in percentage by weight:
the results of the performance index test of the silica refractory mortar provided in this example are shown in Table 1
Example 2
The silica refractory mortar comprises the following components in percentage by weight:
the results of the performance index test of the silica refractory mortar provided in this example are shown in Table 1
Example 3
The silica refractory mortar comprises the following components in percentage by weight:
the results of the performance index test of the silica refractory mortar provided in this example are shown in Table 1
Example 4
The silica refractory mortar comprises the following components in percentage by weight:
the results of the performance index test of the silica refractory mortar provided in this example are shown in Table 1
Example 5
The silica refractory mortar comprises the following components in percentage by weight:
the results of the performance index test of the silica refractory mortar provided in this example are shown in Table 1.
TABLE 1 Performance index testing of silica refractory slurries of examples 1-5
Table 1 shows that the silica refractory slurries provided in embodiments 1 to 3 of the present invention, without adding raw clay, adopt high purity silica micropowder and ultrafine silicon carbide dust extraction powder to improve the workability of the materials, have high silica content, low impurity content, high temperature bonding strength and high refractoriness under load starting point, and effectively improve the high temperature service performance of the silica refractory slurries.
The mineralizer is added in a certain amount in a compounding way, after the mixture is fired at 1300 ℃ for 5 hours, the true density of the slurry is reduced, which shows that the residual quartz is less, and the mineralizer is beneficial to the great conversion of quartz phase into phosphorus quartz phase with good high-temperature volume stability.
Claims (6)
1. The silica refractory mortar with excellent high-temperature performance is characterized in that the powder comprises the following components in percentage by mass:
adding water accounting for 27-30 wt% of the powder material, and mixing;
the mineralizer is the combination of iron scale powder and borax; the iron scale powder is derived from scale-shaped objects formed by the oxidation and falling off of the surfaces of steel products in the heating and rolling processes, the particle size range is 0.044-0mm, and the mass ratio of the iron scale powder to borax is 1 (1-3);
the silicon carbide dust extraction powder is a smoke dust waste collected in the silicon carbide production process, the granularity is less than or equal to 20 mu m, and the content of silicon carbide is more than or equal to 95 wt%.
2. The silica refractory mortar of claim 1, wherein the main phases of the waste silica bricks are a phosphosilicate phase derived from defective shapes or cracks after firing silica bricks and from defective products having a satisfactory chemical composition, and silica bricks removed from coke ovens or hot blast furnaces and sorted by crushing the silica bricks into particles having a particle size of 0.5 to 0mm,wherein SiO is2The content is more than 94 wt%.
3. The silica refractory slurry having excellent high-temperature characteristics as claimed in claim 1, wherein the silica powder is a high-purity silica sand containing SiO as an uncalcined component2The content is more than or equal to 98.5wt percent.
4. The silica refractory mortar of claim 1, wherein the fine silica powder is a high-purity ultrafine powder having a silica content of 99 wt% or more and a particle size d50 of 0.15 μm.
5. The silica refractory mortar of claim 1, wherein the dextrin is a yellow dextrin having a cohesive strength of greater than 1.8kg/cm2The solubility in water at 15-17 ℃ is more than 96%.
6. The silica refractory mortar of claim 1, wherein the carboxymethyl cellulose has a cellulose content of 97.5 wt% or more.
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| CN113800916A (en) * | 2021-09-08 | 2021-12-17 | 中冶武汉冶金建筑研究院有限公司 | Silicon carbide refractory mortar for prebuilt construction |
| CN114057497B (en) * | 2021-11-22 | 2023-06-02 | 郑州安耐克实业有限公司 | High-strength siliceous refractory slurry for hot blast stoves and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06345547A (en) * | 1993-06-02 | 1994-12-20 | Shinagawa Refract Co Ltd | Cushioning silica mortar |
| CN1887805A (en) * | 2006-07-24 | 2007-01-03 | 孙邢哲 | Heat repairing quartzy material and its usage |
| CN105000896A (en) * | 2015-07-23 | 2015-10-28 | 郑州市科源耐火材料有限公司 | Universal siliceous castable |
| CN106045528A (en) * | 2016-05-31 | 2016-10-26 | 中国冶集团有限公司 | Iron runner ramming material containing 90% of waste refractories or above |
| JP2019099706A (en) * | 2017-12-05 | 2019-06-24 | 品川リフラクトリーズ株式会社 | Repairing material for furnace bottom of coke oven |
-
2020
- 2020-04-30 CN CN202010361981.8A patent/CN111548171B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06345547A (en) * | 1993-06-02 | 1994-12-20 | Shinagawa Refract Co Ltd | Cushioning silica mortar |
| CN1887805A (en) * | 2006-07-24 | 2007-01-03 | 孙邢哲 | Heat repairing quartzy material and its usage |
| CN105000896A (en) * | 2015-07-23 | 2015-10-28 | 郑州市科源耐火材料有限公司 | Universal siliceous castable |
| CN106045528A (en) * | 2016-05-31 | 2016-10-26 | 中国冶集团有限公司 | Iron runner ramming material containing 90% of waste refractories or above |
| JP2019099706A (en) * | 2017-12-05 | 2019-06-24 | 品川リフラクトリーズ株式会社 | Repairing material for furnace bottom of coke oven |
Non-Patent Citations (1)
| Title |
|---|
| 热风炉用高强度硅质泥浆的研制;林佩玉等;《第十三届全国耐火材料青年学术报告会暨2012年六省市金属（冶金）学会耐火材料学术交流会论文集》;20121019;引言第2段，1.1试验，表1-2 * |
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