CN108484180B - Method for preparing high-grade refractory material by using ferronickel smelting slag - Google Patents

Method for preparing high-grade refractory material by using ferronickel smelting slag Download PDF

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CN108484180B
CN108484180B CN201810250557.9A CN201810250557A CN108484180B CN 108484180 B CN108484180 B CN 108484180B CN 201810250557 A CN201810250557 A CN 201810250557A CN 108484180 B CN108484180 B CN 108484180B
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smelting slag
refractory material
ferronickel smelting
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ferronickel
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CN108484180A (en
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彭志伟
李光辉
姜涛
古佛全
张元波
饶明军
林小龙
颜加兴
李志忠
唐慧敏
范晓慧
郭宇峰
杨永斌
李骞
徐斌
杨凌志
易凌云
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Central South University
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

A method for preparing high-grade refractory material from ferronickel smelting slag comprises mixing ferronickel smelting slag, magnesia and chromic oxide, ball milling to obtain fine-grained uniform material, and synchronously regulating w (MgO)/w (SiO) in the uniform material2)＝1.37～1.40、w(MgO)/w(Cr2O3) 6.02-12.20, adding a bonding agent, and inducing phase and structure transformation of ferronickel smelting slag by controlling the sintering temperature of 1200-1500 ℃, so as to optimize a refractory phase (Mg)2SiO4、[Fe,Mg][Cr,Fe]2O4) The crystal form transformation process realizes the oriented transformation of phases and structures, and the refractory material with good crystallization and compact structure is obtained, so that the refractoriness and the compressive strength of the refractory material are improved, the refractoriness of the obtained refractory material reaches 1800-1860 ℃, and the refractory material also has the advantages of high compressive strength, large volume density and low apparent porosity, and can completely meet the industrial requirements of the refractory material. The method has the advantages of high resource utilization rate, high production efficiency, high added value of products, environmental friendliness, easy control of the process, low production cost and the like.

Description

Method for preparing high-grade refractory material by using ferronickel smelting slag
Technical Field
The invention belongs to the field of refractory materials, and particularly relates to a method for preparing a high-grade refractory material by using ferronickel smelting slag.
Background
The prereduction-electric furnace method (RKEF) is the mainstream process for producing ferronickel by taking laterite-nickel ore as a raw material in the world at present. According to incomplete statistics, the accumulated stockpiling amount of the laterite-nickel ore smelting slag in China exceeds 1 hundred million tons, and the accumulated stockpiling amount is still continuously increased at a speed of more than 1200 million tons every year. The large amount of stockpiling of ferronickel smelting slag occupies land, pollutes air and water sources, and has serious potential environmental hazard. Compared with the common iron and steel metallurgical slag, the ferronickel metallurgical slag has more complex chemical components, high magnesium oxide and silicon oxide contents (the contents of the magnesium oxide and the silicon oxide account for about 80 percent), contains 5 to 10 percent of ferrous oxide, 2 to 5 percent of aluminum oxide and a small amount of harmful heavy metal elements (such as Cr and the like), and has higher resource utilization difficulty. In view of the characteristics of the ferronickel smelting slag that the content of magnesium and silicon is high and the phase composition is mainly fayalite, researchers begin to research and utilize the fayalite to prepare the fayalite refractory material.
However, the conventional forsterite-type refractory has a refractoriness of 1650 to 1700 ℃, a compressive strength of 22.6 to 51MPa, an apparent porosity of 17.2 to 22.1%, and a bulk density of 2.43 to 2.67g/cm3. On the one hand, the current refractory materials are classified into common refractory materials1580-1770 ℃ for the material, 1770-2000 ℃ for the high-grade refractory material and more than 2000 ℃ for the super-grade refractory material. So that the refractoriness of the prepared forsterite type refractory material can only be used for common refractory materials. Meanwhile, the compressive strength is low, so that the application is greatly limited.
The patent (CN107285778A) discloses a method for preparing a refractory forsterite type refractory material containing Cr2O3The nickel-iron slag is used as a raw material, the magnesite fine powder is used as an additive, the mineral phase reconstruction of the nickel-iron slag is induced, the crystal form transformation process is optimized, and the refractory material with the refractoriness of 1700-1780 ℃ and the compressive strength of 53.09-132.54 MPa is obtained. Although the refractoriness is improved, the refractory still belongs to common refractory materials, and the range of compressive strength is wide and unstable. And, when the refractoriness is in a high range, it corresponds to low strength. In addition, when the material is attempted to be applied to an environment of 1800 ℃, the strength is sharply reduced!
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a high-grade refractory material by using ferronickel smelting slag. The obtained high-grade refractory material has high refractoriness and high strength.
In order to achieve the purpose, the invention provides the following technical scheme:
mixing the ferronickel smelting slag, magnesia and chromic oxide, performing ball milling to obtain a fine-grained mixed material, adding a binding agent into the mixed material, uniformly mixing, performing compression molding, and performing drying treatment; sintering at 1200-1500 ℃ in an oxygen-containing atmosphere after treatment, and obtaining the high-grade refractory material after sintering;
the mass ratio of the components in the uniform mixture is as follows:
w(MgO)/w(SiO2)＝1.37～1.40；
w(MgO)/w(Cr2O3)＝6.02～12.20；
wherein w (MgO) is the mass percentage content of MgO in the mixed material, and w (SiO)2) For mixing SiO in the refining material2W (Cr) in mass percent2O3) Is Cr in the uniform material2O3The mass percentage content of (A).
In the present invention, chromium sesquioxide is added as a raw material for a refractory, in which Cr in the composition of the mixture is2O3I.e. containing Cr originating from ferronickel smelting slag2O3And additionally contains externally added Cr2O3。
In a preferred scheme, the mass ratio of the components in the mixture is as follows:
w(MgO)/w(SiO2)＝1.37～1.38；
w(MgO)/w(Cr2O3)＝7.07～8.80。
according to the preferable scheme, the ferronickel smelting slag comprises the following components in percentage by mass:
SiO238.65-50.75 wt%, MgO 25.41-35.88 wt%, FeO 5.09-11.16 wt%, Al2O32.26-6.53 wt% of Cr2O3The content is 1.31-4.01 wt%, and the balance is impurities.
Preferably, the sintering atmosphere is an air atmosphere.
In the preferable scheme, the adding amount of the magnesia is 15-35 wt% of the mass of the ferronickel smelting slag.
Preferably, the adding amount of the magnesia is 20-25 wt% of the mass of the ferronickel smelting slag.
In a preferable scheme, the content of magnesium oxide in the magnesia is more than or equal to 90 wt%.
In the preferable scheme, the addition amount of the chromium sesquioxide is 4-10 wt% of the mass of the ferronickel smelting slag.
Preferably, the addition amount of the chromium sesquioxide is 6-8 wt% of the mass of the ferronickel smelting slag.
Preferably, the purity of the chromium sesquioxide is more than 99%.
In the actual operation process, the components of the ferronickel smelting slag are detected before mixing, and then magnesia and chromic oxide with proper proportion are added to control the mass ratio relation of the components in the mixed material.
In the present invention, the ball milling may be performed by a ball mill commonly used by those skilled in the art, such as a planetary ball mill.
In a preferable scheme, the rotation speed of the ball mill is 300-600 r/min, the revolution speed is 50-80 r/min, the ball-material ratio is 5: 1-8: 1, and the time is 40-80 min.
Preferably, the rotation speed of the ball mill is 500-600 r/min, the revolution speed of the ball mill is 60-80 r/min, the ball-material ratio is 5: 1-8: 1, and the time is 60-80 min.
Preferably, the mass of the particles with the particle size of less than 0.074mm of the uniform material accounts for 90% or more of the total mass of the uniform amount.
More preferably, the mass of the particles with the particle size of less than 0.074mm in the blend accounts for 95% or more of the total mass of the blend.
In a preferred embodiment, the binding agent is a magnesium chloride solution.
In a preferable scheme, the concentration of the magnesium chloride solution is 1.35-1.4 g/cm3。
In the preferred scheme, the addition amount of the magnesium chloride solution is 6-7 wt% of the sum of the mass of the ferronickel smelting slag, the mass of the magnesia and the mass of the chromium sesquioxide.
In the preferable scheme, the pressure intensity of the compression molding is 80-100 MPa. More preferably, the pressure of the press molding is 90 to 100 MPa.
In the invention, the drying process is not limited too much, and the uniformly mixed material is dried only by adding water, for example, the pressed block mass is put into a 110 ℃ oven for drying for 12 hours.
In the preferable scheme, the sintering temperature is 1300-1350 ℃, and the sintering time is 2-3 h.
In the technical scheme of the invention, the refractoriness of the obtained high-grade refractory material is 1800-1860 ℃; the compressive strength is 135.83-160.6 Mpa, and the bulk density is 2.76-3.15 g/cm3The apparent porosity is 8.2 to 12.15%.
In the preferable scheme of the invention, the refractoriness of the obtained advanced refractory material is 1850-1860 ℃, the compressive strength is 145.38-160.6 MPa, and the bulk density is 2.87-3.15 g/cm3The apparent porosity is 8.2 to 9.51%.
The principle and advantages of the invention are as follows:
the invention takes the ferronickel smelting slag as the raw material for the first time, and successfully prepares the high-grade refractory material with high strength (namely the refractory material with the refractoriness of 1770-2000 ℃) by adding magnesia and chromium oxide, namely, the waste material which originally pollutes the environment is changed into the high-grade refractory material with high added value. Has great economic value and application value.
Chromium sesquioxide is a sintering raw material commonly used for refractory materials, such as common magnesite-chrome bricks and chrome corundum, but the compressive strength of the refractory materials is very low, usually only about 20MPa, and the strength is further reduced due to the increase of chromium content, mainly due to the fact that the volume of the refractory materials is sharply expanded and the compactness is poor along with the formation of a large amount of spinel phase, so that the application field of the refractory materials is limited only in some occasions with low compactness of the materials.
In the previous studies of the present invention, the inventors found that when ferronickel slag containing chromium trioxide is used as a raw material, MgO. Cr is generated in the ferronickel slag2O3The magnesium-chromium spinel can be cooperated with other phases to improve the refractoriness to a certain extent, but the same amount of magnesium-chromium spinel can cause volume expansion of the refractory material, so that the compactness of the refractory material is reduced, and the strength is reduced while the refractoriness is improved.
The inventor unexpectedly discovers through a large amount of experiments that the composition w (MgO)/w (SiO) is regulated and controlled by adding magnesia and chromic oxide2) 1.37 to 1.40, w (MgO)/w (Cr)2O3) 6.02-12.20, the refractoriness and strength are simultaneously and greatly improved, and the strength law is completely different from that of other chromium oxide-containing refractory materials, such as magnesite-chrome brick, when w (MgO)/w (Cr)2O3) The smaller the ratio of (i.e. Cr)2O3The higher the content of (A), the lower the strength of the magnesite-chrome brick, while in the present invention, the preferable embodiment thereof is w (MgO)/w (Cr)2O3) 7.07 to 8.80 in terms of Cr2O3Relative content isAt high temperatures, higher refractoriness and strength are obtained.
Later detection and analysis by the inventor show that the Cr is in the range of the proportion2O3Fe decomposed from fayalite under the action of2O3Will react with Cr2O3After combination, the magnesium oxide reacts with high-activity magnesium oxide formed by magnesia at high temperature to generate [ Fe, Mg ] with high refractoriness][Cr,Fe]2O4(the melting temperature was about 2350 ℃ C.). The liquid phase generated by the fayalite in the reaction process can accelerate the reaction speed, and meanwhile, because the iron oxide decomposed from the fayalite has the characteristic of being chromium oxide-philic, the fayalite and the iron oxide are combined to react with high-activity magnesium oxide [ Fe, Mg][Cr,Fe]2O4The method has the advantages of good crystallization and compact structure, and avoids directly generating the magnesia-chrome spinel phase, so that the refractory material not only has high refractoriness, but also has high volume density and compressive strength.
On the other hand, in the conventional preparation process of the refractory material, in order to obtain each fine material with accurate proportion, each raw material is respectively subjected to ball milling, and the invention adopts the steps of mixing the raw materials and then carrying out ball milling, so that the proportioning process is greatly simplified, and the inventor also unexpectedly discovers that the strength of the obtained high-grade refractory material is further improved, probably because the surface properties of the raw materials are changed under the interaction of several raw materials in the ball milling process, the high-grade refractory material has a better activation effect on the raw materials.
The invention has the characteristics of simple process, low production cost and environmental friendliness. The high-grade refractory material prepared from the ferronickel smelting slag has the advantages of high refractoriness, high compressive strength, good stability, large volume density, low apparent porosity and the like, and has good application prospect.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments, and it is apparent that the embodiments described are only a part of the embodiments of the present invention, rather than the whole embodiments, and all other embodiments obtained by those skilled in the art without inventive labor based on the embodiments of the present invention belong to the protection scope of the present invention.
In order to avoid repetition, the raw materials related to this specific embodiment are described below in a unified manner, and are not described in detail in the specific embodiment:
the ferronickel smelting slag comprises the following components in percentage by mass:
SiO238.65-50.75 wt%, MgO 25.41-35.88 wt%, FeO 5.09-11.16 wt%, Al2O32.26-6.53 wt% of Cr2O3The content is 1.31-4.01 wt%, and the balance is impurities.
The content of magnesium oxide in the magnesite is more than 90%.
The purity of the chromic oxide is more than 99%.
Example 1
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 80min in a planetary ball mill under the conditions that the rotation speed is 600r/min, the revolution speed is 80r/min and the ball-to-material ratio is 8:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 95% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 25 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 6 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.38，
w(MgO)/w(Cr2O3)＝7.07。
adding magnesium chloride solution, mixing, press-forming under 100MPa, and drying; and sintering at 1350 ℃ for 3h after treatment to obtain the high-grade refractory material.
The concentration of the magnesium chloride solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This example 1 utilizes the high-grade refractory material of ferronickel smelting slag preparation: its refractoriness is 1860 deg.C, and its compression strength is 160.60MPaVolume density of 3.15g/cm3The apparent porosity was 8.20%.
Example 2
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 80min in a planetary ball mill under the conditions that the rotation speed is 300r/min, the revolution speed is 50r/min and the ball-to-material ratio is 5:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 95% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 30 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 4 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.37，
w(MgO)/w(Cr2O3)＝12.20。
then adding magnesium chloride solution, uniformly mixing, pressing and forming under the pressure of 90MPa, and drying; and sintering at 1350 ℃ for 2.5h after treatment to obtain the high-grade refractory material.
The concentration of the magnesium chloride solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This embodiment 2 utilizes the senior refractory material of ferronickel smelting slag preparation: the refractoriness is 1800 ℃, the compressive strength is 156.06Mpa, and the bulk density is 2.92g/cm3The apparent porosity was 9.82%.
Example 3
And finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 60min in a planetary ball mill under the conditions that the rotation speed is 500r/min, the revolution speed is 70r/min and the ball-to-material ratio is 6:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 95% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 20 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 8 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.40，
w(MgO)/w(Cr2O3)＝6.02。
adding magnesium chloride solution, mixing, press-forming under 100MPa, and drying; and sintering at 1300 ℃ for 3h after treatment to obtain the high-grade refractory material.
The particle size of the mixture after the ferronickel smelting slag, the magnesia and the chromium sesquioxide are finely ground is 95 percent less than 0.074 mm.
The concentration of the magnesium solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This embodiment 3 utilizes the senior refractory material of ferronickel smelting slag preparation: the refractoriness is 1850 ℃, the compressive strength is 135.83Mpa, and the bulk density is 2.76g/cm3The apparent porosity was 12.15%.
Example 4
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 80min in a planetary ball mill under the conditions that the rotation speed is 600r/min, the revolution speed is 60r/min and the ball-to-material ratio is 5:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 98% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 25 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 7 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.38，
w(MgO)/w(Cr2O3)＝8.80。
adding magnesium chloride solution, mixing, press-forming under 80MPa, and drying; and sintering at 1300 ℃ for 2h after treatment, and obtaining the high-grade refractory material after sintering.
The concentration of the magnesium chloride solution is 1.35g/cm3。
The addition amount of the magnesium chloride solution is 7 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This embodiment 4 utilizes the senior refractory material of ferronickel smelting slag preparation: the refractoriness is 1850 ℃, the compressive strength is 145.38Mpa, and the bulk density is 2.87g/cm3The apparent porosity was 9.51%.
Example 5
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 40min in a planetary ball mill under the conditions that the rotation speed is 600r/min, the revolution speed is 50r/min and the ball-to-material ratio is 7:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 90% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 20 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 4 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.40，
w(MgO)/w(Cr2O3)＝10.22。
adding magnesium chloride solution, mixing, press-forming under 100MPa, and drying; and sintering at 1350 ℃ for 2h after treatment to obtain the high-grade refractory material.
The concentration of the magnesium solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This example 5 utilizes the high-grade refractory material of ferronickel smelting slag preparation: the refractoriness is 1830 ℃, the compressive strength is 155.11Mpa, and the bulk density is 3.01g/cm3The apparent porosity was 8.93%.
Example 6
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 80min in a planetary ball mill under the conditions that the rotation speed is 600r/min, the revolution speed is 80r/min and the ball-to-material ratio is 8:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 95% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 25 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 6 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.38，
w(MgO)/w(Cr2O3)＝7.07。
adding magnesium chloride solution, mixing, press-forming under 100MPa, and drying; and sintering at 1500 ℃ for 2h after treatment, and obtaining the high-grade refractory material after sintering.
The concentration of the magnesium chloride solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This embodiment 6 utilizes the senior refractory material of ferronickel smelting slag preparation: the refractoriness is 1840 ℃, the compressive strength is 155.06Mpa, and the bulk density is 3.08g/cm3The apparent porosity was 9.12%.
Example 7
And (2) finely grinding the ferronickel smelting slag, the magnesia and the chromium sesquioxide for 40min in a planetary ball mill under the conditions that the rotation speed is 600r/min, the revolution speed is 50r/min and the ball-to-material ratio is 7:1 to obtain fine-grained mixed material, wherein the mass of particles with the grain diameter of less than 0.074mm accounts for 90% or more of the total mass of the mixed material.
Wherein the adding amount of the magnesia is 20 wt% of the mass of the ferronickel smelting slag, and the adding amount of the chromium sesquioxide is 4 wt% of the mass of the ferronickel smelting slag, so that in the uniform mixture, the mass ratio relation of each component is as follows:
w(MgO)/w(SiO2)＝1.40，
w(MgO)/w(Cr2O3)＝10.22。
adding magnesium chloride solution, mixing, press-forming under 100MPa, and drying; and sintering at 1200 ℃ for 3h after treatment to obtain the high-grade refractory material.
The concentration of the magnesium solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This embodiment 7 utilizes the senior refractory material of ferronickel smelting slag preparation: the refractoriness is 1800 ℃, the compressive strength is 140.02Mpa, and the bulk density is 2.78g/cm3The apparent porosity was 11.13%.
In the following comparative examples, the ball milling parameters were set within the following ball milling parameter ranges: the rotation speed of the ball mill is 300-600 r/min, the revolution speed of the ball mill is 50-80 r/min, the ball-material ratio is 5: 1-8: 1, and the time is 40-80 min.
Comparative example 1
Finely grinding the ferronickel smelting slag, magnesia and chromic oxide in a planetary ball mill uniformly to obtain a fine-grained uniform mixed material, adding a bonding agent, uniformly mixing, performing compression molding under the pressure of 100MPa, and drying; and sintering at 1350 ℃ for 3h after treatment to obtain the refractory material.
The mass ratio of each component in the uniform mixture is as follows:
w(MgO)/w(SiO2)＝1.35，
w(MgO)/w(Cr2O3)＝5.81。
the particle size of 90% of the mixture after the ferronickel smelting slag, the magnesia and the chromium oxide are finely ground is less than 0.074 mm.
The concentration of the magnesium solution is 1.35g/cm3。
The addition amount of the magnesium chloride solution is 6 wt% of the sum of the quality of the ferronickel smelting slag, the quality of the magnesite and the quality of the chromium oxide.
This comparative example 1 utilizes refractory material that ferronickel smelting slag prepared: the refractoriness is 1730 ℃, the compressive strength is 68.28Mpa, and the bulk density is 2.94g/cm3The apparent porosity was 8.59%.
Comparative example 2
Finely grinding the ferronickel smelting slag, magnesia and chromic oxide in a planetary ball mill uniformly to obtain a fine-grained uniform mixed material, adding a bonding agent, uniformly mixing, performing compression molding under the pressure of 100MPa, and drying; and sintering at 1350 ℃ for 3h after treatment to obtain the refractory material.
The mixed material comprises the following components in relation:
w(MgO)/w(SiO2)＝1.43，
w(MgO)/w(Cr2O3)＝12.25。
the particle size of 90% of the mixture after the ferronickel smelting slag, the magnesia and the chromium oxide are finely ground is less than 0.074 mm.
The concentration of the magnesium solution is 1.35g/cm3。
The addition amount of the magnesium chloride solution is 6 wt% of the sum of the quality of the ferronickel smelting slag, the quality of the magnesite and the quality of the chromium oxide.
This comparative example 2 utilizes the refractory material of ferronickel smelting slag preparation: the refractoriness is 1750 ℃, the compressive strength is 33.14Mpa, and the bulk density is 2.54g/cm3The apparent porosity was 28.99%.
Comparative example 3
Finely grinding the ferronickel smelting slag, magnesia and chromic oxide in a planetary ball mill uniformly to obtain a fine-grained uniform mixed material, adding a bonding agent, uniformly mixing, performing compression molding under the pressure of 100MPa, and drying; and sintering at 1350 ℃ for 3h after treatment to obtain the refractory material.
The mixed material comprises the following components in relation:
w(MgO)/w(SiO2)＝1.35，
w(MgO)/w(Cr2O3)＝12.25。
the particle size of 90% of the mixture after the ferronickel smelting slag, the magnesia and the chromium oxide are finely ground is less than 0.074 mm.
The concentration of the magnesium solution is 1.35g/cm3。
The addition amount of the magnesium chloride solution is 6 wt% of the sum of the quality of the ferronickel smelting slag, the quality of the magnesite and the quality of the chromium oxide.
This comparative example 3 utilizes the refractory material of ferronickel smelting slag preparation: the refractoriness is 1700 ℃, the compressive strength is 73.14Mpa, and the bulk density is 2.96g/cm3The apparent porosity was 7.88%.
Comparative example 4
Finely grinding the ferronickel smelting slag, magnesia and chromic oxide in a planetary ball mill to obtain a fine-grained uniform mixture, adding a bonding agent to mix uniformly, performing compression molding under the pressure of 90MPa, and drying; and sintering at 1300 ℃ for 2h after treatment, and obtaining the refractory material after sintering.
The mixed material comprises the following components in relation:
w(MgO)/w(SiO2)＝1.43，
w(MgO)/w(Cr2O3)＝5.81。
the particle size of 90% of the mixture after the ferronickel smelting slag, the magnesia and the chromium oxide are finely ground is less than 0.074 mm.
The concentration of the magnesium solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 7 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This comparative example 4 utilizes the refractory material of ferronickel smelting slag preparation: the refractoriness is 1760 ℃, the compressive strength is 21.49Mpa, and the bulk density is 2.41g/cm3The apparent porosity was 30.12%.
Comparative example 5
Fine grinding the ferronickel smelting slag, magnesia and chromic oxide respectively, then uniformly mixing to obtain a fine-grained uniform material, adding a bonding agent, uniformly mixing, pressing and molding under the pressure of 100MPa, and drying; and sintering at 1350 ℃ for 3h after treatment to obtain the refractory material.
The mixed material comprises the following components in relation:
w(MgO)/w(SiO2)＝1.38，
w(MgO)/w(Cr2O3)＝7.07。
the particle size of the mixture after the ferronickel smelting slag, the magnesia and the chromium oxide are finely ground is 95 percent less than 0.074 mm.
The concentration of the magnesium solution is 1.4g/cm3。
The addition amount of the magnesium chloride solution is 6.5 wt% of the total mass of the ferronickel smelting slag, the magnesia and the chromium oxide.
This comparative example 5 utilizes the refractory material of ferronickel smelting slag preparation: the refractoriness is 1720 ℃, the compressive strength is 95.36Mpa, and the bulk density is 2.51g/cm3The apparent porosity was 23.74%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that the present embodiments be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments in each example may be appropriately combined to form other embodiments that may be understood by those skilled in the art.

Claims (8)

1. A method for preparing a high-grade refractory material by using ferronickel smelting slag, which is characterized in that,
mixing the ferronickel smelting slag, magnesia and chromic oxide, performing ball milling to obtain a fine-grained mixed material, adding a binding agent into the mixed material, uniformly mixing, performing compression molding, and performing drying treatment; sintering at 1200-1500 ℃ in an oxygen-containing atmosphere after treatment, and obtaining the high-grade refractory material after sintering;
the mass ratio of the components in the uniform mixture is as follows:
w(MgO)/w(SiO2)＝1.37～1.38；
w(MgO)/w(Cr2O3)＝7.07～8.80；
the rotation speed of the ball mill is 300-600 r/min, the revolution speed of the ball mill is 50-80 r/min, the ball-material ratio is 5: 1-8: 1, and the time is 40-80 min.
2. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that:
the content of magnesium oxide in the magnesite is more than or equal to 90 wt%;
the adding amount of the magnesia is 15-35 wt% of the mass of the ferronickel smelting slag;
the addition amount of the chromium sesquioxide is 4-10 wt% of the mass of the ferronickel smelting slag.
3. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that:
the adding amount of the magnesia is 20-25 wt% of the mass of the ferronickel smelting slag;
the addition amount of the chromium sesquioxide is 6-8 wt% of the mass of the ferronickel smelting slag.
4. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that: the mass of the particles with the particle size of less than 0.074mm of the uniform mixture accounts for 90 percent or more of the total mass of the uniform mixture.
5. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that: the mass of the particles with the particle size of less than 0.074mm of the uniform mixture accounts for 95 percent or more of the total mass of the uniform mixture.
6. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that:
the binding agent is magnesium chloride solution;
the concentration of the magnesium chloride solution is 1.35-1.4 g/cm3；
The addition amount of the magnesium chloride solution is 6-7 wt% of the sum of the ferronickel smelting slag, the magnesia and the chromium oxide.
7. The method for preparing advanced refractory material by using ferronickel smelting slag according to claim 1, characterized in that: the sintering temperature is 1300-1350 ℃, the sintering time is 2-3 h, and the sintering atmosphere is air atmosphere.
8. The method for preparing advanced refractory material by ferronickel slag according to any one of claims 1 to 7, characterized in that: the refractoriness of the obtained high-grade refractory material is 1800-1860 ℃; the compressive strength is 135.83-160.6 Mpa, and the bulk density is 2.76-3.15 g/cm3The apparent porosity is 8.2 to 12.15%.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062334A (en) * 1991-05-28 1992-07-01 冶金工业部辽宁镁矿公司 A kind of burnt Ma-Al-Cr refractory brick and manufacture method thereof
KR20130043284A (en) * 2011-10-20 2013-04-30 주식회사 에스엔엔씨 Refractories for electric furnaces
CN107285778A (en) * 2017-06-27 2017-10-24 中南大学 A kind of preparation method of high temperature resistant forsterite type refractory material
CN107793176A (en) * 2017-11-01 2018-03-13 江苏省冶金设计院有限公司 The method for handling ferronickel slag
CN107827439A (en) * 2017-11-23 2018-03-23 江苏省冶金设计院有限公司 Handle the method and Ceramic Tiles of ferronickel slag

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1062334A (en) * 1991-05-28 1992-07-01 冶金工业部辽宁镁矿公司 A kind of burnt Ma-Al-Cr refractory brick and manufacture method thereof
KR20130043284A (en) * 2011-10-20 2013-04-30 주식회사 에스엔엔씨 Refractories for electric furnaces
CN107285778A (en) * 2017-06-27 2017-10-24 中南大学 A kind of preparation method of high temperature resistant forsterite type refractory material
CN107793176A (en) * 2017-11-01 2018-03-13 江苏省冶金设计院有限公司 The method for handling ferronickel slag
CN107827439A (en) * 2017-11-23 2018-03-23 江苏省冶金设计院有限公司 Handle the method and Ceramic Tiles of ferronickel slag

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