CN111099843A - Medium-grade magnesia impurity modification method - Google Patents

Medium-grade magnesia impurity modification method Download PDF

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Publication number
CN111099843A
CN111099843A CN201911385137.2A CN201911385137A CN111099843A CN 111099843 A CN111099843 A CN 111099843A CN 201911385137 A CN201911385137 A CN 201911385137A CN 111099843 A CN111099843 A CN 111099843A
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medium
impurity
magnesite
magnesia
grade
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CN111099843B (en
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刘士军
罗旭东
杨孟孟
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Haicheng Zhonghao Magnesium Industry Co ltd
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Haicheng Zhonghao Magnesium Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • C04B2/102—Preheating, burning calcining or cooling of magnesia, e.g. dead burning
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • C04B2/104—Ingredients added before or during the burning process

Abstract

The invention relates to an impurity modification method of medium-grade magnesite, which comprises the steps of fine grinding, mixing, ball pressing, drying and nitriding calcination, 1) fine grinding light-burned magnesia powder to below 200 meshes, placing the fine ground material into a stirrer, and adding Zr (OH) in portions2Mixing the sol; 2) putting the mixed material into a ball press machine to press balls; 3) placing the formed magnesia balls in a dryer for drying; 4) and (3) placing the dried magnesite balls into a nitrogen atmosphere furnace with the temperature of more than 1400 ℃ for high-temperature calcination to obtain impurity modified medium-grade magnesite. The impurity modified medium-grade magnesia raw material prepared by the invention has the advantages of simple process flow, low cost, easy popularization and implementation, energy conservation and environmental protection.

Description

Medium-grade magnesia impurity modification method
Technical Field
The invention belongs to the field of energy-saving equipment, and particularly relates to a method for modifying impurities in medium-grade magnesia.
Background
Magnesia is a high-grade magnesia refractory material and is one of important raw materials in the industries of steel, cement and the like. Magnesite is a kind of magnesia refractory material which is made by high-temperature calcination of magnesite mineral aggregate, and the main component of the magnesia refractory material is magnesia. China is one of the countries in the world where magnesite resources are abundant, the storage amount of magnesite resources in Liaoning province accounts for more than 80% of the total storage amount of the whole country, and the magnesite resources have the advantages of high taste, shallow buried layers, easiness in mining and the like. The medium-grade magnesite as a typical magnesite is made of magnesium stone with MgO mass fraction greater than 46.5% through reverse reactionLightly burning in a jet furnace, finely grinding, adding water, mixing with the solid fuel blocks, pressing into balls, mixing with the solid fuel blocks, and calcining in a shaft kiln to obtain magnesia with MgO content of about 95% and Al content2O3And CaO and other impurities are one of the most common raw materials for preparing the magnesia refractory product.
However, with the continuous development of the steel industry technology, the smelting strength and frequency are continuously improved, and the requirement on the high temperature of the refractory material is more severe. The magnesia refractory material, especially the low-grade medium-grade magnesia, contains impurity components such as CaO, SiO2, Al2O3 and the like, and the formed low-melting-point ore phase can obviously reduce the high-temperature service performance and the slag corrosion resistance of the magnesia material, thereby greatly limiting the application of the magnesia material in the fields of high temperature and even ultrahigh temperature. On the basis of medium-grade magnesite, a modified magnesite material with excellent performance is developed, and the problem of the defects of the medium-grade magnesite raw material is effectively solved by changing the composition of impurity phases, so that the key work in the industry is achieved. How to develop a modified impurity medium-grade magnesite, which changes the impurity phase in the medium-grade magnesite into a favorable phase with a higher melting point, improves the high-temperature performance of the medium-grade magnesite, and becomes one of the problems to be solved in the field of refractory materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for modifying impurities in medium-grade magnesite, which takes light-burned magnesia powder as a main raw material and Zr (OH)2The sol is taken as a reinforcing agent, nitrogen is taken as a reaction medium and a reactant, and the impurity modified medium-grade magnesite is obtained through the processes of fine grinding, mixing, ball pressing, drying and nitriding sintering.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the impurity modifying method of medium magnesia is characterized by using light-burned magnesia powder as main material and Zr (OH)2The sol is taken as a reinforcing agent, nitrogen is taken as a reaction medium and a reactant, and the impurity modified medium-grade magnesite is obtained through the procedures of fine grinding, mixing, ball pressing and nitriding calcination, and the specific operation steps are as follows:
1) fine grinding, namely fine grinding 94-97 parts by weight of light-burned magnesia powder to below 200 meshes;
2) mixing, finely grinding the materials, putting the materials into an NJ-160 type stirrer, and dividing 3-6 parts by weight of Zr (OH) with the concentration of 0.1-1 mol/L for 5-8 times2Adding the sol into a stirrer, and mixing for 10-30 minutes;
3) pressing balls, putting the mixed materials into a ball press machine, and pressing and forming under the pressure of 50-80 Mpa, wherein the diameter of the ball pressing material is 10-50 mm; drying the molded pellet pressing material for 12-24 hours at the temperature of 100-120 ℃ until the moisture of the pellet pressing material is less than 1%;
4) and nitriding and calcining, namely calcining the dried pellet pressing material in a nitrogen furnace at the temperature of 1400-1800 ℃ for 1-8 hours under the nitrogen pressure of 0.1-1.0 MPa to obtain the impurity modified medium-grade magnesia.
The light-burned magnesia powder in the step 1) is light-burned magnesia mixed powder produced by adopting any one of a multilayer furnace, a suspension kiln, a reflection kiln, a rotary kiln or a flash kiln or any two of the multilayer furnace, and the MgO content is 95% by weight.
Zr (OH) in the step 2)2The sol is prepared by taking zirconium oxychloride and hydrogen peroxide as raw materials, and the preparation equation is as follows:
ZrOCl2+2H2O=ZrO(OH)2+HCl （1）
2HCl+H2O2=Cl2+2H2O （2）
ZrO(OH)2+H2O=Zr(OH)4（3）。
in the step 4)
The nitrogen is commercial high-purity nitrogen, N2³99.999%。
Compared with the prior art, the invention has the beneficial effects that: 1) the invention takes light-burned magnesium powder as raw material and Zr (OH)2Mixing sol, and calcining in nitrogen atmosphere to obtain modified medium magnesia; 2) the invention has simple process flow and low cost, and the prepared medium-grade magnesia has low impurity content and is easy to popularize and apply. 3) The invention Zr (OH) at high temperature2The sol reacts with CaO in the impurities to generate calcium zirconate phase, and the nitrogen reacts with Al in the impurities2O3Reacting to form MgAlON phase, forming complex phase combinationThe magnesite converts an impurity phase into a favorable phase with a higher melting point, and improves the slag resistance, iron corrosion resistance and high-temperature mechanical properties of the medium-grade magnesite.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Comparative example 1: without addition of Zr (OH)2Sol and nitrogen
Comparative example 1 provides a method for modifying impurities in medium-grade magnesite, which comprises the following raw materials in parts by weight: 95g of light-burned magnesia powder prepared by a suspension furnace, 5g of water and nitrogen are used as a calcining medium and a reactant; the impurity modified medium magnesia is prepared by fine grinding, mixing, ball pressing, drying and nitriding calcination, and the specific operation steps are as follows:
finely grinding the light-burned magnesia powder to 200 meshes; putting the finely ground materials into an NJ-160 type stirrer, uniformly dividing for 5 times, adding the water into the stirrer, and mixing for 10 min; putting the mixed materials into a ball press machine, and pressing the balls under 50Mpa, wherein the diameter of each ball is about 40 mm; drying the magnesia balls for 12 hours at the temperature of 100 ℃ until the water content of the pressed ball materials is less than 1 percent; and (3) placing the dried magnesite balls into an atmosphere furnace with the nitrogen pressure of 0.3MPa, and calcining for 3 hours at 1500 ℃ to obtain impurity modified medium-grade magnesite.
The modified medium magnesite prepared in comparative example 1 was treated with nitrogen and Al in impurities at high temperature2O3The reaction produces MgAlON phase, which has excellent slag and iron corrosion resistance and mechanical performance and can raise the performance of medium grade magnesite at high temperature.
Comparative example 2: adding Zr (OH)2Sol without addition of nitrogen
Comparative example 2 provides a method for modifying impurities in medium-grade magnesite, which comprises the following raw materials in parts by weight: 95g of light-burned magnesia powder prepared by using a suspension furnace, Zr (OH) having a concentration of 0.5mol/L25g of sol; the impurity modified medium magnesia is prepared by fine grinding, mixing, ball pressing, drying and calcining, and the specific operation steps are as follows:
finely grinding the light-burned magnesia powder to 200 meshes; placing the finely ground material into an NJ-160 type stirrerIn the mixer, divide equally 7 times the above Zr (OH)2Adding the sol into a stirrer, and mixing for 10 min; putting the mixed materials into a ball press machine, and pressing the balls under 50Mpa, wherein the diameter of each ball is about 40 mm; drying the magnesite balls for 12 hours at the temperature of 110 ℃ until the water content of the ball pressing material is less than 1 percent; and calcining the dried magnesia ball for 4 hours at 1600 ℃ to obtain the impurity modified medium-grade magnesia.
In the modified medium magnesite prepared in the comparative example 2, the zirconium oxide reacts with CaO in the impurities at a high temperature to generate a calcium zirconate phase (the melting point is 2550 ℃), so that the impurity phase is converted into a favorable phase with a higher melting point, and the high temperature performance of the medium magnesite is improved.
Example 1:
the invention provides a method for modifying impurities in medium magnesia, which adopts 95g of light-burned magnesia powder prepared by a multi-layer furnace and Zr (OH) with the concentration of 0.5mol/L25g of sol and nitrogen as a calcining medium and reactant, and preparing impurity modified medium magnesia by fine grinding, mixing, ball pressing, drying and nitriding calcination, wherein the specific operation steps are as follows:
finely grinding the light-burned magnesia powder to 200 meshes; putting the fine ground material into a NJ-160 type stirrer, and uniformly dividing the Zr (OH) for 8 times2Adding the sol into a stirrer, and mixing for 10 min; putting the mixed materials into a ball press machine, pressing the balls at 80Mpa, wherein the diameter of the balls is about 40 mm; drying the magnesia balls for 20 hours at the temperature of 110 ℃ until the water content of the pressed ball materials is less than 1 percent; and (3) placing the dried magnesite balls into an atmosphere furnace with the nitrogen pressure of 0.3MPa, and calcining for 3 hours at 1500 ℃ to obtain impurity modified medium-grade magnesite.
The impurity modified medium grade magnesite prepared in this example was Zr (OH) at high temperature2The sol reacts with CaO in the impurities to generate calcium zirconate phase, and the nitrogen reacts with Al in the impurities2O3The reaction generates a MgAlON phase to form a complex phase combined with the medium-grade magnesite, so that an impurity phase is converted into a favorable phase with a higher melting point, and the slag resistance, iron corrosion resistance and high-temperature mechanical properties of the medium-grade magnesite are improved.
Example 2:
the invention provides a method for modifying impurities in medium-grade magnesite, which adoptsLight-burned magnesia powder prepared in a Multi-layer furnace 95g, Zr (OH) in a concentration of 0.5mol/L25g of sol and nitrogen as a calcining medium and reactant, and preparing impurity modified medium magnesia by fine grinding, mixing, ball pressing, drying and nitriding calcination, wherein the specific operation steps are as follows:
finely grinding the light-burned magnesia powder to 200 meshes; placing the finely ground material into a NJ-160 type stirrer, and uniformly dividing the Zr (OH) for 6 times2Adding the sol into a stirrer, and mixing for 10 min; putting the mixed materials into a ball press machine, and pressing the balls under 50Mpa, wherein the diameter of each ball is about 40 mm; drying the magnesite balls for 24 hours at the temperature of 110 ℃ until the water content of the ball pressing material is less than 1%; and (3) placing the dried magnesite balls into an atmosphere furnace with the nitrogen pressure of 0.3MPa, and calcining for 4 hours at 1600 ℃ to obtain impurity modified medium-grade magnesite.
The impurity modified medium grade magnesite prepared in this example was Zr (OH) at high temperature2The sol reacts with CaO in the impurities to generate calcium zirconate phase, and the nitrogen reacts with Al in the impurities2O3The reaction generates a MgAlON phase to form a multiphase combined medium-grade magnesite, so that the impurity phase is converted into a favorable phase with a higher melting point, and the slag, iron corrosion and high-temperature mechanical properties of the medium-grade magnesite are improved.
Example 3:
the invention provides a method for modifying impurities in medium magnesia, which adopts 95g of light-burned magnesia powder prepared by a multi-layer furnace and Zr (OH) with the concentration of 0.75mol/L25g of sol and nitrogen as a calcining medium and reactant, and preparing impurity modified medium magnesia by fine grinding, mixing, ball pressing, drying and nitriding calcination, wherein the specific operation steps are as follows:
finely grinding the light-burned magnesia powder to 200 meshes; putting the fine ground material into a NJ-160 type stirrer, and uniformly dividing the Zr (OH) for 8 times2Adding the sol into a stirrer, and mixing for 10 min; putting the mixed materials into a ball press machine, and pressing the balls under 50Mpa, wherein the diameter of each ball is about 40 mm; drying the magnesite balls for 24 hours at the temperature of 110 ℃ until the water content of the ball pressing material is less than 1%; placing the dried magnesite balls into an atmosphere furnace with the nitrogen pressure of 1.0MPa, and calcining at 1800 DEG CAnd 5 hours, obtaining the impurity modified medium-grade magnesite.
The impurity modified medium grade magnesite prepared in this example was Zr (OH) at high temperature2The sol reacts with CaO in the impurities to generate calcium zirconate phase, and the nitrogen reacts with Al in the impurities2O3The reaction generates a MgAlON phase to form a multiphase combined medium-grade magnesite, so that the impurity phase is converted into a favorable phase with a higher melting point, and the slag, iron corrosion and high-temperature mechanical properties of the medium-grade magnesite are improved.

Claims (4)

1. The impurity modifying method of medium magnesia is characterized by using light-burned magnesia powder as main material and Zr (OH)2The sol is taken as a reinforcing agent, nitrogen is taken as a reaction medium and a reactant, and the impurity modified medium-grade magnesite is obtained through the procedures of fine grinding, mixing, ball pressing and nitriding calcination, and the specific operation steps are as follows:
1) fine grinding, namely fine grinding 94-97 parts by weight of light-burned magnesia powder to below 200 meshes;
2) mixing, finely grinding the materials, putting the materials into an NJ-160 type stirrer, and dividing 3-6 parts by weight of Zr (OH) with the concentration of 0.1-1 mol/L for 5-8 times2Adding the sol into a stirrer, and mixing for 10-30 minutes;
3) pressing balls, putting the mixed materials into a ball press machine, and pressing and forming under the pressure of 50-80 Mpa, wherein the diameter of the ball pressing material is 10-50 mm; drying the molded pellet pressing material for 12-24 hours at the temperature of 100-120 ℃ until the moisture of the pellet pressing material is less than 1%;
4) and nitriding and calcining, namely calcining the dried pellet pressing material in a nitrogen furnace at the temperature of 1400-1800 ℃ for 1-8 hours under the nitrogen pressure of 0.1-1.0 MPa to obtain the impurity modified medium-grade magnesia.
2. The impurity modification method for medium-grade magnesite clinker according to claim 1, wherein the light-burned magnesia powder in step 1) is a light-burned magnesia mixed powder produced by any one or two of a multi-layer furnace, a suspension furnace, a reflection furnace, a rotary kiln and a flash furnace, and the MgO content is 95% through labor.
3. The impurity modification method of medium magnesite clinker as claimed in claim 1, wherein Zr (OH) is added in step 2)2The sol is prepared by taking zirconium oxychloride and hydrogen peroxide as raw materials, and the preparation equation is as follows:
ZrOCl2+2H2O=ZrO(OH)2+HCl （1）
2HCl+H2O2=Cl2+2H2O （2）
ZrO(OH)2+H2O=Zr(OH)4（3）。
4. the method for modifying impurities in medium magnesite according to claim 1, wherein the step 4) is performed by a method comprising
The nitrogen is commercial high-purity nitrogen, N2³99.999%。
CN201911385137.2A 2019-12-28 2019-12-28 Medium-grade magnesia impurity modification method Active CN111099843B (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
AT317154B (en) * 1971-02-13 1974-08-12 Kali & Salz Ag Process for the production of magnesium oxide or hydroxide from burned dolomite and magnesium chloride
CN104072168A (en) * 2014-07-01 2014-10-01 辽宁科技大学 Composite magnesia stable in high-temperature vacuum conditions and preparation method of composite magnesia
CN106186740A (en) * 2016-07-12 2016-12-07 海城市恒镁科技有限公司 A kind of method utilizing magnesite concentrate one one-step baking highly-purity magnesite
CN205774134U (en) * 2016-07-12 2016-12-07 海城市恒镁科技有限公司 A kind of production line utilizing magnesite concentrate one one-step baking highly-purity magnesite
CN107540391A (en) * 2017-08-22 2018-01-05 东北大学 A kind of preparation method of high-strength compact zirconium oxide forsterite composite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT317154B (en) * 1971-02-13 1974-08-12 Kali & Salz Ag Process for the production of magnesium oxide or hydroxide from burned dolomite and magnesium chloride
CN104072168A (en) * 2014-07-01 2014-10-01 辽宁科技大学 Composite magnesia stable in high-temperature vacuum conditions and preparation method of composite magnesia
CN106186740A (en) * 2016-07-12 2016-12-07 海城市恒镁科技有限公司 A kind of method utilizing magnesite concentrate one one-step baking highly-purity magnesite
CN205774134U (en) * 2016-07-12 2016-12-07 海城市恒镁科技有限公司 A kind of production line utilizing magnesite concentrate one one-step baking highly-purity magnesite
CN107540391A (en) * 2017-08-22 2018-01-05 东北大学 A kind of preparation method of high-strength compact zirconium oxide forsterite composite

Non-Patent Citations (5)

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Title
中国冶金百科全书总编辑委员会《耐火材料》卷编辑委员会等: "《中国冶金百科全书：耐火材料》", 31 October 1997, 冶金工业出版社 *
全跃: "《镁质材料生产与应用》", 29 February 2008, 冶金工业出版社 *
栾舰等: "添加Al的MgO-MA材料的相组成和显微结构", 《耐火材料》 *
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