CN113999021B - Method for modifying impurities of magnesium-based refractory material with controllable morphology - Google Patents
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Abstract
The invention relates to a method for modifying impurities of a magnesium-based refractory material with controllable morphology, which comprises the following steps: 1) Preparing low-melting-point impurity phase calcium forsterite of the magnesium-based refractory material; 2) Adding a modifier La into the forsterite powder in the step 1) 2 O 3 Mixing and drying; 3) Putting the mixed materials into a tablet press for compression molding and drying; 4) And putting the dried sample into a high-temperature furnace with the temperature of more than 1300 ℃ for reaction and sintering. The invention has the advantages that: the process flow is simple, the cost is low, the appearance can be controlled, the impurity modification treatment is carried out on the low-grade magnesite, the comprehensive utilization rate is improved, and the energy is saved.
Description
Technical Field
The invention belongs to the field of refractory material impurity modification process control, and particularly relates to a morphology-controllable magnesium-based refractory material impurity modification method.
Background
Magnesium oxide (MgO) has the advantages of high melting point, strong resistance to corrosion by alkaline slag and the like, and is widely applied to industries such as ferrous metallurgy, non-ferrous metal smelting, cement and the like. Natural magnesite is one of the important sources for obtaining magnesium oxide. However, because of extensive management of magnesite resources, high-quality resources are relatively in short supply, and low-grade magnesite (magnesium oxide content is 35% -42%) occupying 1/3 of magnesite reserves in China is idle or stacked in waste, so that the resources are greatly wasted, and ecological damage and environmental pollution are caused. Therefore, the development and utilization of low-grade magnesite are imminent.
The low-grade magnesite has high content of impurities such as silicon, calcium and the like, so that the low-grade magnesite cannot meet the requirements of producing refractory materials and high-performance magnesium chemical materials and cannot be directly used. In the common magnesia refractory, the periclase grains are composed of a low-melting-point silicate phase and are continuously distributed among the periclase grains. The silicate phase with low melting point is softened or forms a liquid phase at first at high temperature, so that the high-temperature service performance and the slag corrosion resistance of the magnesia refractory material are obviously reduced. Therefore, the performance of the magnesia refractory material is fundamentally improved, the microstructure of the magnesia refractory material is designed and improved, and the periclase grain boundary phase in the magnesia is modified, namely, a low-melting-point silicate phase is reduced or eliminated, the continuous distribution state of the silicate phase among grains is changed, and the refractoriness of the silicate phase is improved. The method can improve the comprehensive utilization rate of the low-grade magnesite, broaden the application field of the magnesium material, save energy, reduce pollution and protect the environment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a magnesium-based refractory material impurity modification method with controllable morphology, which has the advantages of simple process flow, controllable morphology and capability of obtaining a novel impurity modification method with excellent modification effect and controllable microstructure morphology.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for modifying impurities of a magnesium-based refractory material with controllable morphology comprises the following steps:
1) Preparing low-melting-point impurity phase calcium forsterite of the magnesium-based refractory material;
2) Adding a modifier La into the forsterite powder in the step 1) 2 O 3 Mixing and drying;
3) Putting the mixed materials into a tablet press for compression molding and drying;
4) And placing the dried sample into a high-temperature furnace with the temperature of more than 1300 ℃ for reaction and sintering.
The calcium forsterite in the step 1) is prepared from CaO and SiO 2 MgO analytical reagent as raw materialSynthesized by adopting a high-temperature solid-phase reaction method according to the generation of CaO, mgO and SiO of the forsterite 2 The reaction equation (c) is as follows:
MgO+CaO+SiO 2 ＝CaO·MgO·SiO 2 。
the CaO and SiO 2 MgO analytical pure reagent according to the molar ratio n (CaO: siO) 2 MgO) =1, and the reaction temperature of the high-temperature solid-phase method is controlled to be 1400 +/-10 ℃, and is kept at 1400 +/-10 ℃ for more than 5 hours.
The modifier La in the step 2) 2 O 3 Calcium-containing forsterite powder and modifier La 2 O 3 The weight percentage of the mixture is 10-30 wt%, absolute ethyl alcohol is used as a medium, and ball milling and mixing are carried out for more than 5 hours at the speed of 300-350 r/min.
In step 3) is pressed in a tablet press to form
The columnar sample of (2).
And 4) placing the dried sample in the step 4) into a high-temperature furnace, performing reactive sintering at 1300-1400 ℃ in an air atmosphere, wherein the temperature rise rate is 3-5 ℃/min during sintering, and preserving the heat for more than 5h at 1300-1400 ℃.
The reaction equation of the reaction sintering in the step 4) is as follows:
3(CaO·MgO·SiO 2 )+2La 2 O 3 ＝CaO·3SiO 2 ·2La 2 O 3 +3MgO+2CaO。
compared with the prior art, the invention has the beneficial effects that:
the method has simple process flow, low cost and controllable appearance, improves the comprehensive utilization rate of the low-grade magnesite by performing impurity modification treatment on the low-grade magnesite, saves energy, protects the environment, and is characterized in that:
3(CaO·MgO·SiO 2 )+2La 2 O 3 ＝CaO·3SiO 2 ·2La 2 O 3 +3MgO (+2CaO), by adjusting modifier La 2 O 3 The addition amount of the compound can obtain the novel impurity modification with excellent modification effect and controllable microstructure morphologyThe method is easy to popularize and apply.
The invention makes full use of CaO and SiO in low-grade magnesite 2 The main impurity components are obtained by introducing a modifier to modify the low-melting-point silicate impurity phase in the material into a high-melting-point rare earth-containing silicate phase. The CaLa generated by the in-situ reaction of the material is controlled by the microscopic appearance of the material 4 (SiO 4 ) 3 O grows in rod-shaped crystals, i.e. CaLa 4 (SiO 4 ) 3 The O crystal grains are transformed from hollow tubular crystal grains to rod-shaped crystal grains, so that the in-situ self-toughening effect is achieved, and the thermal shock resistance of the material is improved.
Drawings
FIG. 1 is a hollow tubular CaLa generated in situ after modification of impurity phase 4 (SiO 4 ) 3 And (5) a first micro-topography of O grains.
FIG. 2 is a hollow tubular CaLa generated in situ after modification of impurity phase 4 (SiO 4 ) 3 And a second micro-topography of O grains.
FIG. 3 shows the rod-like CaLa generated in situ after modification of the impurity phase 4 (SiO 4 ) 3 And (3) a micro-topography of O grains.
Figure 4 is an EDS spectrum at a in figure 3.
Figure 5 is an EDS spectrum at B in figure 3.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
The method for modifying impurities of the magnesium-based refractory material with controllable morphology comprises the following steps:
1) With CaO, siO 2 And MgO analytical reagent as raw materials, caO and SiO 2 And MgO in a molar ratio n (CaO: siO) 2 MgO) =1 2 )。
2) Adding 10 weight percent of modifier La into the impurity silicate phase calcium forsterite powder 2 O 3 (the content of the calcium forsterite powder is 90%, and La is contained 2 O 3 Accounting for 10 percent), using absolute ethyl alcohol as a medium, and carrying out planetary ball milling for 5 hours by using zirconia balls in a ball mill at the speed of 300r/min, sieving the obtained slurry by a 100-mesh sieve, and drying for 24 hours in a drying oven at the temperature of 60 ℃ to obtain uniformly mixed powder.
3) Pressing the uniformly mixed powder into
Drying the formed columnar sample at 110 ℃ for 6-8 hours.
4) And (3) placing the sample in a high-temperature furnace for sintering, wherein the heating rate is 5 ℃/min, heating to 1300 ℃, and keeping the temperature for 3h.
In this example, a hollow tubular CaLa was obtained which was generated in situ after modification of the impurity phase 4 (SiO 4 ) 3 And O crystal grains. Under the condition of high temperature, the modifier La 2 O 3 The impurity silicate phase calcium forsterite (CaO, mgO, siO) 2 ) Conversion to the high melting phase CaLa 4 (SiO 4 ) 3 O, according to the reaction equation:
3(CaO·MgO·SiO 2 )+2La 2 O 3 ＝CaO·3SiO 2 ·2La 2 O 3 +3MgO+2CaO
performing impurity modified reaction sintering to generate in-situ CaLa 4 (SiO 4 ) 3 The O crystal grain is in a needle-shaped structure and is accompanied with a hollow tubular microscopic shape, and the needle-shaped and hollow tubular crystal plays a certain toughening role in the magnesium-based refractory material and improves the high-temperature mechanical property of the material. The needle-like and hollow tubular microstructures are shown in FIG. 1.
Example 2
The method for modifying impurities of the magnesium-based refractory material with controllable morphology comprises the following steps:
1) With CaO, siO 2 And MgO analytical reagent as raw materials, caO and SiO 2 And MgO in a molar ratio n (CaO: siO) 2 MgO) =1 2 )。
2) Adding 10 weight percent of modifier La into the impurity silicate phase calcium forsterite powder 2 O 3 (the content of the calcium forsterite powder is 90%, and La is contained 2 O 3 10 percent) and absolute ethyl alcohol as a medium, carrying out planetary ball milling for 5 hours by using zirconia balls in a ball mill at the speed of 300r/min, sieving the obtained slurry by using a 100-mesh sieve, and drying the slurry in a drying oven for 24 hours at the temperature of 60 ℃ to obtain uniformly mixed powder.
3) Pressing the uniformly mixed powder into powder
Drying the formed columnar sample at 110 ℃ for 6-8 hours.
4) And (3) placing the sample in a high-temperature furnace for sintering, wherein the heating rate is 5 ℃/min, heating to 1350 ℃, and preserving heat for 5 hours.
In this example, a hollow tubular CaLa was obtained which was generated in situ after modification of the impurity phase 4 (SiO 4 ) 3 And O crystal grains. Under the condition of high temperature, the modifier La 2 O 3 The impurity silicate phase calcium forsterite (CaO, mgO, siO) 2 ) Transformation into high melting phase CaLa 4 (SiO 4 ) 3 O, according to the reaction equation:
3(CaO·MgO·SiO 2 )+2La 2 O 3 ＝CaO·3SiO 2 ·2La 2 O 3 +3MgO+2CaO
performing impurity modified reaction sintering, and generating CaLa in situ along with the increase of temperature and the extension of heat preservation time 4 (SiO 4 ) 3 The O crystal grains grow from the previous needles to hollow tubular microscopic shape, and the tubular crystal plays a good toughening role on the magnesium-based refractory material and improves the high-temperature mechanical property of the material. The microstructure of the hollow tubular crystals is shown in FIG. 2.
Example 3
The method for modifying impurities of the magnesium-based refractory material with controllable morphology comprises the following steps:
1) With CaO, siO 2 And MgO analytical reagent as raw materials, caO and SiO 2 And MgO in a molar ratio n (CaO: siO) 2 MgO) =1 2 )。
2) Introducing 20 weight percent of modifier La 2 O 3 The method comprises the steps of taking absolute ethyl alcohol as a medium, carrying out planetary ball milling for 5 hours by using zirconia balls in a ball mill at the speed of 300-350 r/min, sieving the obtained slurry by using a 100-mesh sieve, and drying for 24 hours in a drying oven at the temperature of 60 ℃ to obtain uniformly mixed powder.
3) Pressing the uniformly mixed powder into powder
The formed columnar sample is dried for 6 to 8 hours at the temperature of 110 ℃.
4) When the sample is placed in a high-temperature furnace for sintering, the temperature rise rate is 5 ℃/min, the temperature is raised to 1400 ℃, and the temperature is kept for 5h.
This example obtained a rod-like CaLa formed in situ after modification of the impurity phase 4 (SiO 4 ) 3 And O crystal grains. Under the condition of high temperature, the modifier La 2 O 3 The impurities of silicate phase calcium forsterite (CaO, mgO, siO) 2 ) Conversion to the high melting phase CaLa 4 (SiO 4 ) 3 O, according to the reaction equation:
3(CaO·MgO·SiO 2 )+2La 2 O 3 ＝CaO·3SiO 2 ·2La 2 O 3 +3MgO+2CaO
in this example, after the impurity modification treatment of the Mg-based refractory, the impurity low-melting-point phase calcium forsterite (CaO. MgO. SiO) is added under high temperature conditions 2 ) Conversion to the high melting phase CaLa 4 (SiO 4 ) 3 O, and, with increasing reaction temperature and increasing amount of modifier added, caLa generated in situ 4 (SiO 4 ) 3 The O hollow tubular crystal continuously grows to the tubular center to form the microscopic morphology of a rod-shaped crystal, the crystal grain is gradually coarse, and the bridging caused by the rod-shaped crystal plays a more remarkable toughening role on the magnesium-based refractory material and improves the high-temperature mechanical property of the material.The microstructures of the rod-shaped crystals are shown in FIGS. 3 to 5.
The invention utilizes CaO and SiO in low-grade magnesite 2 The main impurity components are modified into a high-melting-point rare earth-containing silicate phase by introducing a modifier, and the generated high-melting-point phase wraps the forsterite, so that the modification is effective.
Claims (4)
1. The method for modifying impurities of the magnesium-based refractory material with controllable morphology is characterized by comprising the following steps of:
1) Preparing low-melting-point impurity phase calcium forsterite of the magnesium-based refractory material;
the calcium forsterite is prepared from CaO and SiO 2 MgO analytically pure reagent as raw material is synthesized through high temperature solid phase reaction to produce CaO, mgO and SiO of forsterite 2 The reaction equation (c) is as follows:
MgO+CaO+SiO 2 =CaO·MgO·SiO 2 ；
2) Adding a modifier La into the forsterite powder in the step 1) 2 O 3 Mixing and drying;
modifier La 2 O 3 Calcium-occupying forsterite powder and modifier La 2 O 3 The weight percentage of the mixture is 10 to 30 percent, and the mixture is ball milled and mixed for more than 5 hours at the speed of 300 to 350r/min by taking absolute ethyl alcohol as a medium;
3) Putting the mixed materials into a tablet press for compression molding and drying;
4) Placing the dried sample into a high-temperature furnace, performing reactive sintering at 1300-1400 ℃ in air atmosphere, wherein the heating rate is 3-5 ℃/min during sintering, and keeping the temperature at 1300-1400 ℃ for more than 5 h; caLa 4 (SiO 4 ) 3 The O crystal grains are transformed from hollow tubular crystal grains to rod-shaped crystal grains, so that the in-situ self-toughening effect is achieved, and the thermal shock resistance of the material is improved.
2. The method for modifying impurities in a magnesium-based refractory material with controllable morphology as claimed in claim 1, wherein the method comprisesThe CaO and SiO 2 MgO analytical pure reagent according to molar ration(CaO:SiO 2 MgO) =1, and the reaction temperature of the high-temperature solid-phase reaction method is controlled to be 1400 +/-10 ℃, and is kept at 1400 +/-10 ℃ for more than 5 hours.
3. The method for modifying impurities in a magnesium-based refractory material with controllable morphology according to claim 1, characterized in that in step 3) the mixture is pressed into column shaped samples of Bronsted 20mm x 10mm on a tablet press.
4. The method for modifying impurities in the magnesium-based refractory material with controllable morphology according to claim 1, wherein the reaction equation of the reaction sintering in the step 4) is as follows:
3(CaO·MgO·SiO 2 )+2La 2 O 3 =CaO·3SiO 2 ·2La 2 O 3 +3MgO+2CaO。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0375265A (en) * | 1989-08-17 | 1991-03-29 | Nippon Steel Corp | Magnesia-containing 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 |
| KR20130115906A (en) * | 2012-04-13 | 2013-10-22 | 케이에스씨 주식회사 | Method for manufacture of synthetic forsterite refractory |
| CN104058769A (en) * | 2014-07-18 | 2014-09-24 | 徐梅子 | Baffle wall for 100-ton tundish and preparation method of baffle wall |
| CN104909769A (en) * | 2015-06-03 | 2015-09-16 | 辽宁科技大学 | Magnesium-base composite refractory raw material and preparation method thereof |
| CN109929961A (en) * | 2019-04-03 | 2019-06-25 | 西宁特殊钢股份有限公司 | A kind of purposes for the technique and magnesium ball preparing magnesium ball with tundish paint |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314144A (en) * | 2004-04-27 | 2005-11-10 | Kurosaki Harima Corp | Chromium-free monolithic refractory for waste material melting furnace and waste material melting furnace lined with the same |
| US7960009B2 (en) * | 2008-02-29 | 2011-06-14 | Corning Incorporated | Dispersion-toughened cordierite for filter and substrate applications |
| US7964523B2 (en) * | 2008-06-19 | 2011-06-21 | Nihon Yamamura Glass Co., Ltd. | Composition for sealing glass |
| CN103964878A (en) * | 2014-05-28 | 2014-08-06 | 张婷 | Slag dam for 80-ton tundish and preparation method thereof |
| CN107522404B (en) * | 2017-09-15 | 2019-12-20 | 西安交通大学 | Dental lithium-aluminum-silicon microcrystalline glass and preparation method thereof |
| CN108117374B (en) * | 2017-11-28 | 2021-03-19 | 辽宁科技大学 | Heat storage material and preparation method thereof |
| 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 |
| CN109627022A (en) * | 2019-01-29 | 2019-04-16 | 四会市国耀铝业有限公司 | A kind of the furnace linings for energy-saving material and preparation method thereof |
| CN112608161A (en) * | 2021-01-04 | 2021-04-06 | 中国航空制造技术研究院 | Preparation method of metal toughening type rare earth silicate powder |
-
2021
- 2021-10-21 CN CN202111225499.2A patent/CN113999021B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0375265A (en) * | 1989-08-17 | 1991-03-29 | Nippon Steel Corp | Magnesia-containing 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 |
| KR20130115906A (en) * | 2012-04-13 | 2013-10-22 | 케이에스씨 주식회사 | Method for manufacture of synthetic forsterite refractory |
| CN104058769A (en) * | 2014-07-18 | 2014-09-24 | 徐梅子 | Baffle wall for 100-ton tundish and preparation method of baffle wall |
| CN104909769A (en) * | 2015-06-03 | 2015-09-16 | 辽宁科技大学 | Magnesium-base composite refractory raw material and preparation method thereof |
| CN109929961A (en) * | 2019-04-03 | 2019-06-25 | 西宁特殊钢股份有限公司 | A kind of purposes for the technique and magnesium ball preparing magnesium ball with tundish paint |
Non-Patent Citations (2)
| Title |
|---|
| Effect of La2O3 addition on the microstructural evolution and thermomechanical property of sintered low-grade magnesite;Yan Cui, et al.;《Ceramics International》;20200916;第47卷;第3137页左栏第1段和第2段、第3138页左栏第1段 * |
| 氧化镧对镁橄榄石晶体结构及性能的影响(英文);罗旭东等;《硅酸盐通报》;20130930;第32卷(第09期);第1709-1713、1718页 * |
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