CN113999021A - 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)2O3Mixing 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 alkaline slag corrosion resistance and the like, and is widely applied to the industries of 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 magnesite reserves 1/3 in China is left unused 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 is difficult to meet the requirements of producing refractory materials and high-performance magnesium chemical materials and cannot be directly used. The periclase crystal grains in the common magnesia refractory material are composed of a low-melting-point silicate phase and are continuously distributed among the periclase crystal 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)2O3Mixing 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 calcium forsterite in the step 1) is prepared from CaO and SiO2MgO analytically pure reagent is used as raw material, and is synthesized by adopting a high-temperature solid-phase reaction method according to the generation of calcium forsterite CaO, MgO and SiO2The reaction equation (2) is as follows:
MgO+CaO+SiO2＝CaO·MgO·SiO2。
the CaO and SiO2MgO analytical pure reagent according to the molar ratio n (CaO: SiO)2MgO) is mixed according to the proportion of 1:1:1, the reaction temperature of the high-temperature solid phase method is controlled at 1400 +/-10 ℃, and the temperature is kept at 1400 +/-10 ℃ for more than 5 hours.
The modifier La in the step 2)2O3Calcium-containing forsterite powder and modifier La2O3The 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 at the speed of 300-350 r/min for more than 5 h.
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 air atmosphere, wherein the heating rate is 3-5 ℃/min during sintering, and preserving 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·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+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·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+3MgO +2CaO by adjusting the modifier La2O3The novel impurity modification method with excellent modification effect and controllable microstructure morphology is obtained, and the method is easy to popularize and apply.
The invention makes full use of CaO and SiO in low-grade magnesite2The 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 morphology of the material4(SiO4)3O grows in rod-shaped crystals, i.e. CaLa4(SiO4)3The 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 phase4(SiO4)3And (5) a first micro-topography of O grains.
FIG. 2 is a hollow tubular CaLa generated in situ after modification of impurity phase4(SiO4)3And a second micro-topography of O grains.
FIG. 3 shows the rod-like CaLa generated in situ after modification of the impurity phase4(SiO4)3And (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, SiO2And MgO analytical reagent as raw materials, CaO and SiO2And MgO in a molar ratio n (CaO: SiO)2MgO is mixed in the ratio of 1:1:1, and the calcium-magnesium olivine (CaO, MgO, SiO) with impurity silicate phase generally existing in the magnesium material is prepared by adopting a high-temperature solid phase reaction method2)。
2) Adding 10 weight percent of modifier La into the impurity silicate phase calcium forsterite powder2O3(the content of the calcium forsterite powder is 90%, and La is contained2 O 310 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
The formed columnar sample is dried for 6-8 hours at the temperature of 110 ℃.
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 3 h.
In this example, a hollow tubular CaLa was obtained which was generated in situ after modification of the impurity phase4(SiO4)3And O crystal grains. Under the condition of high temperature, the modifier La2O3The impurity silicate phase calcium forsterite (CaO, MgO, SiO)2) Conversion to the high melting phase CaLa4(SiO4)3O, according to the reaction equation:
3(CaO·MgO·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+3MgO+2CaO
performing impurity modified reaction sintering to generate CaLa in situ4(SiO4)3The 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 grains play a certain toughening role in the magnesium-based refractory material and improveHigh-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, SiO2And MgO analytical reagent as raw materials, CaO and SiO2And MgO in a molar ratio n (CaO: SiO)2MgO is mixed in the ratio of 1:1:1, and the calcium-magnesium olivine (CaO, MgO, SiO) with impurity silicate phase generally existing in the magnesium material is prepared by adopting a high-temperature solid phase reaction method2)。
2) Adding 10 weight percent of modifier La into the impurity silicate phase calcium forsterite powder2O3(the content of the calcium forsterite powder is 90%, and La is contained2 O 310 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
The formed columnar sample is dried for 6-8 hours at the temperature of 110 ℃.
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 phase4(SiO4)3And O crystal grains. Under the condition of high temperature, the modifier La2O3The impurity silicate phase calcium forsterite (CaO, MgO, SiO)2) Conversion to the high melting phase CaLa4(SiO4)3O, according to the reaction equation:
3(CaO·MgO·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+3MgO+2CaO
carrying out impurity modified reaction sintering, and generating in situ along with the increase of temperature and the extension of heat preservation timeCaLa of4(SiO4)3The O crystal grains grow from the prior needle shape into a 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, SiO2And MgO analytical reagent as raw materials, CaO and SiO2And MgO in a molar ratio n (CaO: SiO)2MgO is mixed in the ratio of 1:1:1, and the calcium-magnesium olivine (CaO, MgO, SiO) with impurity silicate phase generally existing in the magnesium material is prepared by adopting a high-temperature solid phase reaction method2)。
2) Introducing a modifier La with the weight percentage of 20 percent2O3The 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
The formed columnar sample is dried for 6-8 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 5 h.
This example obtained a rod-like CaLa formed in situ after modification of the impurity phase4(SiO4)3And O crystal grains. Under the condition of high temperature, the modifier La2O3The impurity silicate phase calcium forsterite (CaO, MgO, SiO)2) Conversion to the high melting phase CaLa4(SiO4)3O, according to the reaction equation:
3(CaO·MgO·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+3MgO+2CaO
this example is refractory to magnesium baseAfter the material impurity modification treatment, the impurity low-melting point phase calcium forsterite (CaO, MgO, SiO) is added under the high temperature condition2) Conversion to the high melting phase CaLa4(SiO4)3O, and, with increasing reaction temperature and increasing amount of modifier added, CaLa generated in situ4(SiO4)3The 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 magnesite2The 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 (7)
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;
2) adding a modifier La into the forsterite powder in the step 1)2O3Mixing 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.
2. The method for modifying impurities in the magnesium-based refractory material with controllable morphology as claimed in claim 1, wherein the calcium forsterite in step 1) is selected from CaO and SiO2MgO analytically pure reagent is used as raw material, and is synthesized by adopting a high-temperature solid-phase reaction method according to the generation of calcium forsterite CaO, MgO and SiO2The reaction equation (2) is as follows:
MgO+CaO+SiO2＝CaO·MgO·SiO2。
3. the method for impurity modification of magnesium-based refractory material with controllable morphology as claimed in claim 2, wherein the CaO and SiO are added2MgO analytical pure reagent according to the molar ratio n (CaO: SiO)2MgO) is mixed in a ratio of 1:1:1, the reaction temperature of the high-temperature solid phase method is controlled at 1400 +/-10 ℃, and the temperature is kept at 1400 +/-10 ℃ for more than 5 hours.
4. The method for modifying impurities in the magnesium-based refractory material with controllable morphology as claimed in claim 1, wherein the modifier La in step 2) or 2) is La2O3Calcium-containing forsterite powder and modifier La2O3The 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 at the speed of 300-350 r/min for more than 5 h.
5. The method for modifying impurities in the magnesium-based refractory material with controllable morphology as claimed in claim 1, wherein the magnesium-based refractory material is pressed into the magnesium-based refractory material in step 3) in a tablet press
The columnar sample of (2).
6. The impurity modification method of the magnesium-based refractory material with controllable morphology according to claim 1, characterized in that the sample dried in the step 4) is placed in a high temperature furnace, and is subjected to reactive sintering at 1300-1400 ℃ in an air atmosphere, wherein the temperature rise rate during sintering is 3-5 ℃/min, and the temperature is kept at 1300-1400 ℃ for more than 5 h.
7. 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·SiO2)+2La2O3＝CaO·3SiO2·2La2O3+3MgO+2CaO。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0375265A (en) * | 1989-08-17 | 1991-03-29 | Nippon Steel Corp | Magnesia-containing refractory |
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