CN108101516A - A kind of alumina-silica Cr refractory product and preparation method thereof - Google Patents
A kind of alumina-silica Cr refractory product and preparation method thereof Download PDFInfo
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- CN108101516A CN108101516A CN201810033831.7A CN201810033831A CN108101516A CN 108101516 A CN108101516 A CN 108101516A CN 201810033831 A CN201810033831 A CN 201810033831A CN 108101516 A CN108101516 A CN 108101516A
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Abstract
The invention belongs to fire resisting material fields, relate generally to a kind of aluminium oxide oxidation Cr refractory product and preparation method thereof.A kind of aluminium oxide oxidation Cr refractory product proposed, the raw material of aluminium oxide oxidation Cr refractory product include aggregate and matrix；Aggregate includes white fused alumina particle, Brown Alundum particle and chrome oxide particle；Matrix is the mixing of one or more of chromium oxide fine powder, chromium oxide micro mist, aluminum oxide fine powder or alumina powder；Also there is the aluminium chromium solid impurity particle of metal Al and metal Cr in aggregate added with addition；Fine powder, the micro mist of chromic salts slag are additionally added in matrix；The present invention hazardous waste has been carried out it is rationally effective utilize, the problem of improving traditional chrome corundum brick cost performance be low in the relatively low industrial production of some service temperature demands.
Description
Technical field
The invention belongs to fire resisting material fields, relate generally to a kind of alumina-silica Cr refractory product and preparation method thereof.
Background technology
Al2O3-Cr2O3Refractory material（Chrome corundum brick is commonly called as, hereafter referred to collectively as chrome corundum brick）It is with aluminium oxide, chromium oxide
For a kind of high-performance refractory material of main material production, with refractoriness height, physical strength height, good thermal shock stability, resist
The characteristics of erosiveness is strong, in industrial application resistance to erosion, resistant to corrosion, wear-resistant, anti-strip ability is strong.In nonferrous metallurgy, glass
Glass, petrochemical industry, carbon black, waste incineration industry extensive application.
Chrome corundum brick has excellent slag resistance, the reason is that：Al in two kinds of materials of aluminium oxide and chromium oxide3+And Cr3+
With approximate ionic radius and valence state, meet the condition to form continuous solid solution, the aluminium chromium solid solution structure of reacted formation
Stable, structural strength is promoted, erosive wear resistant ability is strong, is conducive to brick body and is resisted slag corrosion and mechanical stress damage；It is another
Aspect, Cr2O3Addition, can increase the angle of wetting between slag and refractory material, reduce slag wetability, and can be with slag
In SiO2And its salt action, viscosity coefficient of dross is improved, reduces the mobility of slag, is conducive to the infiltration that brick body resists slag.
Chrome corundum brick has very excellent slag resistance, can be served in the harsh Industrial Stoves of various conditions.Chromium is firm
Beautiful brick uses the high pure raw materials such as fused alumina and electric smelting chromium oxide, they are typically with high-purity alumina powder and chromium oxide powder
It is prepared for raw material through 2000 DEG C of electric smelting methods, these electric smelting raw materials have the spies such as advantages of good crystallization, the porosity are low, material character is stablized
Point, but production cost is high；Although and can start to be dissolved at 1200 DEG C between aluminium oxide and chromium oxide, from 1700 DEG C or more
Continuous solid solution can be formed, so the firing temperature of chrome corundum brick need to reach 1700 DEG C or more and long-time heat preservation.With this side
Chrome corundum brick cost of material prepared by method is high, and firing condition is harsh, and not high in face of some use environments and temperature requirement
Kiln in, have high-temperature behavior and slag resistance and be not in full use, seriously constrain the cost performance of chrome corundum brick.
Generated waste residue after aluminothermic process metal smelting chromium（Aluminium chromium slag is commonly called as, hereafter referred to collectively as aluminium chromium slag）In there are contents
Very high Al2O3And Cr2O3, other impurities content is low, and its Al2O3And Cr2O3Exist in the form of aluminium chromium solid solution, be a kind of
Outstanding raw material for refractory.In recent years, for the problem of cost of material is high existing for chrome corundum brick, by inserting in the feed
Aluminium chromium slag reduces the cost of material of chrome corundum brick, becomes a kind of approach that chrome corundum brick promotes cost performance.But due to aluminium chromium
Slag is the byproduct of thermit reaction metal smelting chromium, wherein there are the aluminium and chromium of metallic forms, metal simple-substance is in applied at elevated temperature mistake
Cheng Zhonghui forms plastic deformation phase, has a negative impact to the performance of chrome corundum brick.
In recent years, a large amount of air storages of tailings containing chromium, the report for polluting animals and plants and underground water happen occasionally.Tailings containing chromium
Utility value and utilization ways need develop expand；Tailings containing chromium is the centre in Chemical Manufacture crome metal and chromic salts process
Body, it is a kind of leached-out chromium residue, is commonly called as chromic salts slag（Hereafter referred to collectively as chromic salts slag）；As crome metal and the centre of chromium salt production
Body, the principle that chromic salts slag generates are：In industrial production, by nature with Cr2O3Chromium is converted into Cr existing for form6+'s
Aqueous solution, then chromate or bichromate are precipitated by thermit reaction metal smelting chromium or direct crystallization, it produces in this process
It, all can inevitably there are Cr in raw waste liquid and waste residue6+, the production of chromic salts per ton all can output 2-3 in chromium salt production
The chromic salts slag of ton.
Chromic salts slag is as a kind of hazardous waste, and toxicity is extremely strong, wherein the Cr contained6+Water or some acid can be dissolved in, is easily passed through
The mode swallowed and sucked enters human body, there is very big threat, Long Term Contact to digestive system, respiratory tract, skin of human body etc.
Or sucking has carcinogenic danger.
The content of the invention
In order to solve the above technical problems, the purpose of the present invention is to propose to a kind of alumina-silica Cr refractory product and its systems
Preparation Method.
The present invention adopts the following technical scheme that complete above-mentioned purpose：
A kind of alumina-silica Cr refractory product, the raw material of the alumina-silica Cr refractory product include aggregate and base
Matter；The aggregate includes white fused alumina particle, Brown Alundum particle and chrome oxide particle；The matrix for chromium oxide fine powder,
The mixing of one or more of chromium oxide micro mist, aluminum oxide fine powder or alumina powder；It is also added with and adds in the aggregate
Enter to have the aluminium chromium solid impurity particle of metal Al and metal Cr；The aluminium chromium solid impurity particle is secondary caused by aluminothermic process metal smelting chromium
Product, Al in the aluminium chromium solid impurity particle2O3And Cr2O3Total mass fraction ＞ 90%, wherein Al2O3Mass fraction for 75~
80%、Cr2O3Mass fraction is 10~15%, metal Al, metal Cr total mass fraction are 1~3%, Fe2O3、MgO、CaO、SiO2's
Total mass fraction ＜ 5%, Na2O、K2The total mass fraction ＜ 1% of O；The fine powder, micro- of chromic salts slag is additionally added in the matrix
Powder；The chromic salts slag, is commercial production of metals chromium, the byproduct of chromic salts bichromate, Cr in the chromic salts slag2O3Matter
Amount fraction is 4~6%, Al2O3Mass fraction for 5~7%, Cr6+Mass fraction is 0.5~1.5%, its CaO mass fraction is
29~31%, MgO mass fractions are 24~26%, SiO2Mass fraction is 5~7, and particle size range is 44~74 μm.
The particle size range of the aluminium chromium solid impurity particle is 0.1~4mm.
Al in the aluminium chromium solid impurity particle2O3And Cr2O3Exist in the form of aluminium chromium solid solution, structural strength is big, resists molten
Scouring excellent performance is suitable as aggregate use；It is required that its Al2O3And Cr2O3Total mass fraction ＞ 90%, Fe2O3、MgO、
CaO、SiO2Total mass fraction ＜ 5%, Na2O、K2The total mass fraction ＜ 1% of O is since it is desired that controlling SiO in raw material2、
Na2O、K2The content of the substances such as O may generate eutectic at high temperature, reduce the performance of refractory material.
The white fused alumina particle, is a kind of electric smelting raw material, Al2O3Mass fraction >=99.0%, particle size range for 0.1 ~
4mm.White fused alumina particle manufactured by electric smelting method, advantages of good crystallization, stomata is few, and structural strength is big, is suitable as aggregate use；It is it is required that white
Corundum in granules has certain particle size range, is conducive to grain size distribution, makes matrix filling pore, the structure for making material is finer and close.
It is required that its Al2O3Mass fraction >=99% is because impurity can excessively generate complicated eutectic, influences the performance of refractory material.
The Brown Alundum particle, is a kind of electric smelting raw material, Al2O3Mass fraction >=95.0%, particle size range for 0.1~
4mm；It has compared with the more cheap price of white fused alumina particle, and due to being that electric smelting method is made, advantages of good crystallization, the porosity is low,
The aggregate of refractory material that can be relatively mild as use environment uses.
The chrome oxide particle, is a kind of electric smelting raw material, Cr2O3Mass fraction >=99.0%, particle size range for 0.1~
4mm；The made chrome oxide particle of electric smelting method, mechanical strength is high, advantages of good crystallization, and performance is stablized, and is suitable as aggregate use；It is required that its
Cr2O3Mass fraction >=99% is the influence in order to reduce the eutectic of impurity generation to material at high temperature performance.
The aluminium oxide is fused white corundum fine powder, sintering α-Al2O3The combination of one or both of micro mist,
Al2O3Mass fraction >=99.0%, the particle size range of fused white corundum fine powder is 44~74 μm, sintering α-Al2O3The grain of micro mist
Degree scope is D50=2~5 μm, fused white corundum fine powder can increase the structural strength of matrix to a certain extent, prevent material
Excessive shrinkage, sintering α-Al2O3The purpose of the addition of micro mist is that the high activity having can promote aluminium chromium solid solution reaction
It carries out, so as to promote the sintering of material at high temperature.
The chromium oxide, be electric smelting chromium oxide fine powder, chrome oxide green one or both combination, electric smelting chromium oxide is thin
Cr in powder2O3Mass fraction >=99.0%, Cr in chrome oxide green2O3Mass fraction >=99.2%, the grain of electric smelting chromium oxide fine powder
It is 44~74 μm to spend scope, and the particle size range of chrome oxide green is D50=2~8 μm, electric smelting chromium oxide fine powder and oxygen are inserted in matrix
Change the purpose of chrome green, primarily to promoting its high temperature firing, and pass through the stability of aluminium chromium solid solution reaction increase material structure.
A kind of preparation method of alumina-silica Cr refractory product, the preparation method are with chromium oxide, chromium oxide
One or more of fine powder or micro mist are used as matrix, and the fine powder or micro mist of chromic salts slag are added in matrix；Matrix is passed through
The abundant mixings of ball grinder ball milling 1-2h；With the combination of one or more of white fused alumina particle, Brown Alundum particle, chrome oxide particle
As aggregate, and aluminium chromium solid impurity particle is added in aggregate；Aggregate is put into simpson mill and is premixed, duration 5-
10min, and bonding agent is added in, bonding agent is made to be sufficiently adhering in aggregate, duration 5-10min；By the base portion Jing Guo mixing
It adds in simpson mill, is sufficiently stirred with aggregate and bonding agent, duration 15-30min；By the original by stirring and evenly mixing
Material spontaneously dries 12-24h at room temperature；Dried raw material is passed through into hydraulic press, friction press, vibrations pressure forming machine etc.
Compression moulding；Brick body after mechanical pressing is put into 110 DEG C of dry 4-6h in baking oven；Dried brick body is put into electric furnace or kiln
In burn till, 1400-1600 DEG C of maximum sintering temperature, heat preservation 3-6h burn till obtained Al2O3-Cr2O3Refractory product, it is obtained
Al2O3-Cr2O3In refractory product：Al2O3Mass fraction is 65~90%, Cr2O3 mass fractions are 10%~30%, Fe2O3, MgO,
CaO, SiO2, TiO2 total mass fraction are 0~5%, NaO, K2O total mass fraction are 0~1%, and apparent porosity is 13~19%.
The bonding agent is phenolic resin, and the amount of inserting is the 3-5% of raw material gross mass；It is the bonding of resin type organic
One kind of agent, bond strength is high, and material can be made not draw after burning till without having certain physical strength before burning till
Enter more impurity for influencing material at high temperature performance；On the other hand, due to the Cr in chromic salts slag6+With water solubility, can not use
Water-soluble binding agents, so selecting phenolic resin as bonding agent.
A kind of alumina-silica Cr refractory product proposed by the present invention and preparation method thereof, explores aluminium chromium slag, chromic salts slag
The Processes For Effective Conversion of waste residues is waited, utilizes Cr in the strong reducing property of aluminium chromium metal in the dreg Al and metal Cr and chromic salts slag6+It is strong
Oxidisability is passed to reaction generation Cr3+Or available oxide, insert white fused alumina, oxygen using chromic salts slag as additive
Change in the chrome corundum brick that chromium, aluminium chromium slag etc. burn till for primary raw material, can both partially remove plastic deformation compared with chrome corundum brick
The influence of performance, and during material preparation, to Cr6+It is reduced, eliminates its toxicity, hazardous waste is closed
Reason is effective to be utilized.On the other hand, by the adjustment to various raw material proportionings in material, can produce makes suitable for difference
With the chrome corundum brick of temperature and use environment, and ensure the stabilization of its performance, improve traditional chrome corundum brick and be on active service at some
The problem of cost performance is low in the relatively low industrial production of temperature requirements.
Specific embodiment
With reference to the embodiment provided, the present invention is illustrated, but does not form any limitation of the invention.
Embodiment 1：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 10kg, granularity D of) >=99.0%50=3μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 10kg, granularity D50=5 μm,w(Cr2O3The chrome oxide green 5kg of) >=99.2%, grain
The chromic salts slag 5kg of 44 μm -74 μm of scope is spent, 1.5h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range is weighed respectively
The chemical composition of 0.1-4mm isw(Al2O3The white fused alumina particle 40kg of) >=99.0%, the wherein particle of particle size range 0.1-1mm
The particle 10kg of the particle 20kg of 10kg, particle size range 1-3mm, particle size range 3-4mm, weigh the change of particle size range 0.1-4mm
Learning composition isw(Cr2O3The particle 2kg of the chrome oxide particle 10kg of) >=99.0%, wherein particle size range 0.1-1mm, particle size range
The particle 3kg of the particle 5kg of 1-3mm, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90%
Aluminium chromium slag 10kg, wherein the particle 2kg of particle size range 0.1-1mm, the particle 5kg of particle size range 1-3mm, particle size range 3-
The particle 3kg of 4mm is added in simpson mill and is sufficiently stirred 5min；Bonding agent phenolic resin about 4kg is added in into particle simultaneously
Stir 5min；The matrix of premix is added in simpson mill and is sufficiently mixed 25min with particle, bonding agent, and at room temperature
Dry 12h；Friction press mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln and burns till for 1500 DEG C, heat preservation
5h。
Embodiment 2：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 10kg, granularity D of) >=99.0%50=3μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 6kg, granularity D50=5 μm,w(Cr2O3The chrome oxide green 4kg of) >=99.2%, grain
The chromic salts slag 5kg of 44 μm -74 μm of scope is spent, 1.5h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range is weighed respectively
The chemical composition of 0.1-4mm isw(Al2O3The white fused alumina particle 50kg of) >=99.0%, the wherein particle of particle size range 0.1-1mm
The particle 15kg of the particle 25kg of 10kg, particle size range 1-3mm, particle size range 3-4mm, weigh the change of particle size range 0.1-4mm
Learning composition isw(Cr2O3The particle 1.5kg of the chrome oxide particle 8kg of) >=99.0%, wherein particle size range 0.1-1mm, particle size range
The particle 2.5kg of the particle 4kg of 1-3mm, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞
90% aluminium chromium slag 7kg, the wherein particle 1.5kg of particle size range 0.1-1mm, the particle 3.5kg of particle size range 1-3mm, granularity model
The particle 2kg of 3-4mm is enclosed, adds in simpson mill and is sufficiently stirred 5min；Bonding agent phenolic resin is added in into particle about
3kg simultaneously stirs 5min；The matrix of premix is added in simpson mill and is sufficiently mixed 25min with particle, bonding agent, and in room
The lower dry 12h of temperature；Friction press mechanical pressing in an oven after 110 DEG C of dry 5h, is put into gas-combustion kiln and burns till for 1600 DEG C,
Keep the temperature 6h.
Embodiment 3：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 6kg, granularity D of) >=99.0%50=4μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 10kg, granularity D50=7 μm,w(Cr2O3The chrome oxide green 6kg of) >=99.2%, grain
The chromic salts slag 3kg of 44 μm -74 μm of scope is spent, 2h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 40kg of) >=99.0%, wherein the particle 10kg of particle size range 0.1-1mm,
The particle 10kg of the particle 20kg of particle size range 1-3mm, particle size range 3-4mm weigh the chemical composition of particle size range 0.1-4mm
Forw(Cr2O3The particle 1kg of the chrome oxide particle 5kg of) >=99.0%, wherein particle size range 0.1-1mm, particle size range 1-3mm's
The particle 1.5kg of particle 2.5kg, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90%
Aluminium chromium slag 20kg, wherein the particle 4kg of particle size range 0.1-1mm, the particle 10kg of particle size range 1-3mm, particle size range 3-4mm
Particle 6kg, add in simpson mill in be sufficiently stirred 10min；Bonding agent phenolic resin about 5kg is added in into particle and is stirred
Mix 10min；The matrix of premix is added in simpson mill and is sufficiently mixed 30min with particle, bonding agent, and is done at room temperature
It is dry for 24 hours；Friction press mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln and burns till for 1400 DEG C, keeps the temperature 3h.
Embodiment 4：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 5kg, granularity D of) >=99.0%50=2μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 5kg, granularity D50=5 μm,w(Cr2O3The chrome oxide green 5kg of) >=99.2%, grain
The chromic salts slag 5kg of 44 μm -74 μm of scope is spent, 2h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 60kg of) >=99.0%, wherein the particle 15kg of particle size range 0.1-1mm,
The particle 20kg of the particle 25kg of particle size range 1-3mm, particle size range 3-4mm weigh the chemical composition of particle size range 0.1-4mm
Forw(Cr2O3The particle 1kg of the chrome oxide particle 5kg of) >=99.0%, wherein particle size range 0.1-1mm, particle size range 1-3mm's
The particle 1.5kg of particle 2.5kg, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90%
Aluminium chromium slag 5kg, wherein the particle 1kg of particle size range 0.1-1mm, the particle 2.5kg of particle size range 1-3mm, particle size range 3-4mm
Particle 1.5kg, add in simpson mill in be sufficiently stirred 10min；Bonding agent phenolic resin about 5kg is added in into particle simultaneously
Stir 10min；The matrix of premix is added in simpson mill and is sufficiently mixed 30min with particle, bonding agent, and at room temperature
Drying is for 24 hours；Friction press mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln and burns till for 1600 DEG C, heat preservation
6h。
Embodiment 5：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 8kg, granularity D of) >=99.0%50=3μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 8kg, granularity D50=5 μm,w(Cr2O3The chrome oxide green 5kg of) >=99.2%, grain
The chromic salts slag 4kg of 44 μm -74 μm of scope is spent, 1h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 45kg of) >=99.0%, wherein the particle 10kg of particle size range 0.1-1mm,
The particle 15kg of the particle 20kg of particle size range 1-3mm, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+
Cr2O3) ＞ 90% aluminium chromium slag 20kg, the wherein particle 4kg of particle size range 0.1-1mm, the particle 10kg of particle size range 1-3mm,
The particle 6kg of particle size range 3-4mm is added in simpson mill and is sufficiently stirred 10min；Bonding agent phenolic aldehyde is added in into particle
Resin about 4kg simultaneously stirs 10min；The matrix of premix is added in simpson mill and is sufficiently mixed with particle, bonding agent
30min, and it is dried at room temperature for 18h；Friction press mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln
1400 DEG C are burnt till, and keep the temperature 3h.
Embodiment 6：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 10kg, granularity D of) >=99.0%50=4μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 10kg, granularity D50=4 μm,w(Cr2O3The chrome oxide green 7kg of) >=99.2%, grain
The chromic salts slag 3kg of 44 μm -74 μm of scope is spent, 1h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 55kg of) >=99.0%, wherein the particle 10kg of particle size range 0.1-1mm,
The particle 15kg of the particle 30kg of particle size range 1-3mm, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+
Cr2O3) ＞ 90% aluminium chromium slag 5kg, the wherein particle 1kg of particle size range 0.1-1mm, the particle 2.5kg of particle size range 1-3mm,
The particle 1.5kg of particle size range 3-4mm is added in simpson mill and is sufficiently stirred 10min；Bonding agent phenol is added in into particle
Urea formaldehyde about 5kg simultaneously stirs 10min；The matrix of premix is added in simpson mill and is sufficiently mixed with particle, bonding agent
25min, and be dried at room temperature for for 24 hours；Friction press mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln
1500 DEG C are burnt till, and keep the temperature 4h.
Embodiment 7：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 5kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 5kg, granularity D of) >=99.0%50=2μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 5kg, granularity D50=3 μm,w(Cr2O3The chrome oxide green 5kg of) >=99.2%, grain
The chromic salts slag 5kg of 44 μm -74 μm of scope is spent, 2h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 68kg of) >=99.0%, wherein the particle 15kg of particle size range 0.1-1mm,
The particle 20kg of the particle 33kg of particle size range 1-3mm, particle size range 3-4mm, weigh particle size range 0.1-4mm'sw(Al2O3+
Cr2O3) ＞ 90% aluminium chromium slag 7kg, the wherein particle 1.5kg of particle size range 0.1-1mm, the particle of particle size range 1-3mm
The particle 2kg of 3.5kg, particle size range 3-4mm are added in simpson mill and are sufficiently stirred 10min；It adds in and combines into particle
Agent phenolic resin about 3kg simultaneously stirs 10min；The matrix of premix is added in fully mixed with particle, bonding agent in simpson mill
25min is closed, and is dried at room temperature for 12h；Friction press mechanical pressing in an oven after 110 DEG C of dry 4h, is put into gas-combustion kiln
Interior 1600 DEG C are burnt till, and keep the temperature 6h.
Embodiment 8：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 10kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 7kg, granularity D of) >=99.0%50=2μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 5kg, granularity D50=3 μm,w(Cr2O3The chrome oxide green 5kg of) >=99.2%, grain
The chromic salts slag 3kg of 44 μm -74 μm of scope is spent, 2h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range 0.1- is weighed respectively
The chemical composition of 4mm isw(Al2O3The white fused alumina particle 20kg of) >=99.0%, wherein the particle 4kg of particle size range 0.1-1mm, grain
The particle 10kg of scope 1-3mm, the particle 6kg of particle size range 3-4mm are spent, the chemical composition for weighing particle size range 0.1-4mm isw
(Al2O3The Brown Alundum particle 20kg of) >=95.0%, wherein the particle 4kg of particle size range 0.1-1mm, of particle size range 1-3mm
Grain 10kg, the particle 6kg of particle size range 3-4mm, the chemical composition for weighing particle size range 0.1-4mm isw(Cr2O3) >=99.0%
The particle 6kg of the particle 3kg of chrome oxide particle 12kg, wherein particle size range 0.1-1mm, particle size range 1-3mm, particle size range 3-
The particle 3kg of 4mm, weighs particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90% aluminium chromium slag 18kg, wherein particle size range
The particle 6kg of the particle 9kg of the particle 3kg of 0.1-1mm, particle size range 1-3mm, particle size range 3-4mm add in muller formula mulling
5min is sufficiently stirred in machine；Bonding agent phenolic resin about 5kg is added in into particle and stirs 10min；The matrix of premix is added in
25min is sufficiently mixed with particle, bonding agent in simpson mill, and is dried at room temperature for for 24 hours；Friction press machine is pressed into
Type in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln and burns till for 1500 DEG C, keeps the temperature 4h.
Embodiment 9：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 8kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3Electric smelting chromium oxide the fine powder 7kg, granularity D of) >=99.0%50=2μm、w
(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 8kg, granularity D50=3 μm,w(Cr2O3The chrome oxide green 7kg of) >=99.2%, grain
The chromic salts slag 5kg of 44 μm -74 μm of scope is spent, 1.5h is sufficiently mixed through ball mill, is prepared into matrix；Particle size range is weighed respectively
The chemical composition of 0.1-4mm isw(Al2O3The white fused alumina particle 28kg of) >=99.0%, the wherein particle of particle size range 0.1-1mm
The particle 8kg of the particle 14kg of 6kg, particle size range 1-3mm, particle size range 3-4mm weigh the chemistry of particle size range 0.1-4mm
It forms and isw(Al2O3The Brown Alundum particle 22kg of) >=95.0%, wherein the particle 5kg of particle size range 0.1-1mm, particle size range 1-
The particle 7kg of the particle 10kg of 3mm, particle size range 3-4mm, the chemical composition for weighing particle size range 0.1-4mm arew(Cr2O3)≥
The particle 4kg of the particle 1.5kg of 99.0% chrome oxide particle 8kg, wherein particle size range 0.1-1mm, particle size range 1-3mm, grain
The particle 2.5kg of scope 3-4mm is spent, weighs particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90% aluminium chromium slag 7kg,
The particle 2kg of the particle 3.5kg of the particle 1.5kg of middle particle size range 0.1-1mm, particle size range 1-3mm, particle size range 3-4mm,
It adds in simpson mill and is sufficiently stirred 7min；Bonding agent phenolic resin about 3kg is added in into particle and stirs 10min；It will
The matrix of premix adds in simpson mill and is sufficiently mixed 15min with particle, bonding agent, and is dried at room temperature for 12h；Friction
Brick machine mechanical pressing in an oven after 110 DEG C of dry 6h, is put into gas-combustion kiln and burns till for 1500 DEG C, keeps the temperature 4h.
Embodiment 10：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 15kg of) >=99.0%,
Granularity D50=5μm、w(Al2O3Sintering α-the Al of) >=99.0%2O3Micro mist 10kg, granularity D50=5 μm,w(Cr2O3The oxygen of) >=99.2%
Change chrome green 12kg, the chromic salts slag 3kg of 44 μm -74 μm of particle size range is sufficiently mixed 1h through ball mill, is prepared into matrix；Claim respectively
The chemical composition for taking particle size range 0.1-4mm isw(Al2O3The Brown Alundum particle 55kg of) >=95.0%, wherein particle size range 0.1-
The particle 18kg of the particle 27kg of the particle 10kg of 1mm, particle size range 1-3mm, particle size range 3-4mm, weigh particle size range
0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90% aluminium chromium slag 5kg, the wherein particle 1kg of particle size range 0.1-1mm, particle size range
The particle 1.5kg of the particle 2.5kg of 1-3mm, particle size range 3-4mm are added in simpson mill and are sufficiently stirred 10min；To
Bonding agent phenolic resin about 5kg is added in particle and stirs 10min；By the matrix of premix add in simpson mill with
Grain, bonding agent are sufficiently mixed 25min, and are dried at room temperature for for 24 hours；Friction press mechanical pressing, in an oven 110 DEG C of dryings
It after 6h, is put into gas-combustion kiln and burns till for 1600 DEG C, keep the temperature 6h.
Embodiment 11：
The chemical composition for weighing 44 μm -74 μm of particle size range respectively isw(Al2O3The fused white corundum fine powder 15kg of) >=99.0%,
The chemical composition that 44 μm -74 μm of particle size range isw(Cr2O3The electric smelting chromium oxide fine powder 10kg of) >=99.0%, granularity D50=5 μm,w
(Cr2O3The chrome oxide green 5kg of) >=99.2%, the chromic salts slag 5kg of 44 μm -74 μm of particle size range, 1h is sufficiently mixed through ball mill, system
It is standby into matrix；The chemical composition for weighing particle size range 0.1-4mm respectively isw(Al2O3The Brown Alundum particle 40kg of) >=95.0%,
The particle 10kg of the particle 20kg of the particle 10kg of middle particle size range 0.1-1mm, particle size range 1-3mm, particle size range 3-4mm,
Weigh particle size range 0.1-4mm'sw(Al2O3+Cr2O3) ＞ 90% aluminium chromium slag 25kg, the wherein particle of particle size range 0.1-1mm
The particle 9kg of the particle 15kg of 6kg, particle size range 1-3mm, particle size range 3-4mm are added in simpson mill and are sufficiently stirred
10min；Bonding agent phenolic resin about 4kg is added in into particle and stirs 10min；The matrix of premix is added in into simpson mill
In with particle, bonding agent be sufficiently mixed 30min, and be dried at room temperature for 18h；Friction press mechanical pressing, in an oven 110
After DEG C dry 5h, it is put into gas-combustion kiln and burns till for 1400 DEG C, keep the temperature 3h.
Properties of product prepared by embodiment 1-11 are as shown in the table, and apparent porosity, bulk density, chemical composition analysis are adopted
It is tested with national standard method.Embodiment 1-11 products are suitable with market high purity product on sale in terms of physical property；Resistance to slag
Energy aspect, crucible and commercially available high-purity alumina chrome brick prepared by embodiment 1-11 products（w(Cr2O3)=10%~30%）Prepared
Crucible carries out across comparison anti-slag experiment, and anti-permeability performance is close to commercial product, penetration depth 5%-20%s more compared with commercial product,
Erosion degree is slightly above commercial product, shows that its anti-slag ability is still very outstanding, and relatively low kiln is required in some service temperatures
In stove, there is higher cost performance.
Claims (10)
1. a kind of alumina-silica Cr refractory product, the raw material of the alumina-silica Cr refractory product includes aggregate and base
Matter；The aggregate includes white fused alumina particle, Brown Alundum particle and chrome oxide particle；The matrix for chromium oxide fine powder,
The mixing of one or more of chromium oxide micro mist, aluminum oxide fine powder or alumina powder；It is characterized in that：In the aggregate
Also there is the aluminium chromium solid impurity particle of metal Al and metal Cr added with addition；The aluminium chromium solid impurity particle is aluminothermic process metal smelting chromium
Generated byproduct, Al in the aluminium chromium solid impurity particle2O3And Cr2O3Total mass fraction ＞ 90%, wherein Al2O3Quality point
Number is 75~80%, Cr2O3Mass fraction is 10~15%, metal Al, metal Cr total mass fraction are 1~3%, Fe2O3、MgO、
CaO、SiO2Total mass fraction ＜ 5%, Na2O、K2The total mass fraction ＜ 1% of O；Chromic salts slag has been additionally added in the matrix
Fine powder, micro mist；The chromic salts slag, is commercial production of metals chromium, the byproduct of chromic salts bichromate, in the chromic salts slag
Cr2O3Mass fraction be 4~6%, Al2O3Mass fraction for 5~7%, Cr6+Mass fraction is 0.5~1.5%, its CaO matter
Amount fraction is 29~31%, MgO mass fractions are 24~26%, SiO2Mass fraction is 5~7, and particle size range is 44~74 μm.
2. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The granularity of the aluminium chromium solid impurity particle
Scope is 0.1~4mm.
3. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：In the aluminium chromium solid impurity particle
Al2O3And Cr2O3Exist in the form of aluminium chromium solid solution.
4. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The white fused alumina particle, is one
Kind electric smelting raw material, Al2O3Mass fraction >=99.0%, particle size range are 0.1~4mm.
5. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The Brown Alundum particle, is one
Kind electric smelting raw material, Al2O3Mass fraction >=95.0%, particle size range are 0.1~4mm.
6. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The chrome oxide particle is one
Kind electric smelting raw material, Cr2O3Mass fraction >=99.0%, particle size range are 0.1~4mm.
7. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The aluminium oxide is that electric smelting is white
Corundum fine powder, sintering α-Al2O3The combination of one or both of micro mist, Al2O3Mass fraction >=99.0%, electric smelting is firm in vain
The particle size range of beautiful fine powder is 44~74 μm, sintering α-Al2O3The particle size range of micro mist is D50=2~5 μm.
8. alumina-silica Cr refractory product as described in claim 1, it is characterised in that：The chromium oxide is electric smelting oxygen
Change chromium fine powder, chrome oxide green one or both combination, Cr in electric smelting chromium oxide fine powder2O3Mass fraction >=99.0%, oxygen
Change Cr in chrome green2O3Mass fraction >=99.2%, the particle size range of electric smelting chromium oxide fine powder is 44~74 μm, the grain of chrome oxide green
Degree scope is D50=2~8 μm.
9. prepare a kind of preparation method of alumina-silica Cr refractory product described in claim 1, it is characterised in that：Described
Preparation method is using one or more of chromium oxide, the fine powder of chromium oxide or micro mist as matrix, and chromium is added in matrix
The fine powder or micro mist of salt slag；Matrix is passed through into the abundant mixings of ball grinder ball milling 1-2h；With white fused alumina particle, Brown Alundum particle, oxygen
Change the combination of one or more of chromium particle as aggregate, and aluminium chromium solid impurity particle is added in aggregate；Aggregate is put into muller
It is premixed in formula sand mixer, duration 5-10min, and adds in bonding agent, bonding agent is made to be sufficiently adhering in aggregate, duration 5-
10min；Base portion Jing Guo mixing is added in simpson mill, is sufficiently stirred with aggregate and bonding agent, duration
15-30min；12-24h will be spontaneously dried at room temperature by the raw material stirred and evenly mixed；By dried raw material by hydraulic press,
The compression mouldings such as friction press, vibrations pressure forming machine；Brick body after mechanical pressing is put into 110 DEG C of dry 4- in baking oven
6h；Dried brick body is put into electric furnace or kiln and is burnt till, 1400-1600 DEG C of maximum sintering temperature, heat preservation 3-6h burns till obtained
Al2O3-Cr2O3Refractory product, obtained Al2O3-Cr2O3In refractory product：Al2O3Mass fraction is 65~90%, Cr2O3 matter
Amount fraction is 10%~30%, Fe2O3, MgO, CaO, SiO2, TiO2 total mass fraction are 0~5%, NaO, K2O total mass fraction are
0~1%, apparent porosity is 13~19%.
10. a kind of preparation method of alumina-silica Cr refractory product as claimed in claim 9, it is characterised in that：The knot
Mixture is phenolic resin, and addition is the 3-5% of raw material gross mass.
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| CN109020570A (en) * | 2018-08-23 | 2018-12-18 | 北京科技大学 | A kind of Chromium oxide fireproof material and preparation method thereof |
| CN109265150A (en) * | 2018-10-15 | 2019-01-25 | 郑州市瑞沃耐火材料有限公司 | The prefabricated slide brick of heating furnace |
| CN110698190A (en) * | 2019-10-12 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Single-phase replacement solid solution oxide ceramic coating and preparation method thereof |
| CN113173795A (en) * | 2021-06-09 | 2021-07-27 | 江苏君耀耐磨耐火材料有限公司 | Chromium corundum brick for sulfur recovery acid gas incinerator and preparation process thereof |
| CN113185306A (en) * | 2021-04-01 | 2021-07-30 | 张福生 | Method for preparing high-resistance aluminum-chromium brick by doping zirconium boride |
| CN113416083A (en) * | 2021-07-19 | 2021-09-21 | 安庆市徽富防火材料有限公司 | High-temperature refractory material and preparation method thereof |
| CN109320219B (en) * | 2018-11-13 | 2021-12-28 | 辽宁中镁高温材料有限公司 | High-performance aluminum-chromium refractory material and manufacturing method and application thereof |
| CN117362015A (en) * | 2023-10-27 | 2024-01-09 | 河南省瑞泰科实业集团有限公司 | High-purity corundum brick and preparation method thereof |
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| CN109020570A (en) * | 2018-08-23 | 2018-12-18 | 北京科技大学 | A kind of Chromium oxide fireproof material and preparation method thereof |
| CN109265150A (en) * | 2018-10-15 | 2019-01-25 | 郑州市瑞沃耐火材料有限公司 | The prefabricated slide brick of heating furnace |
| CN109320219B (en) * | 2018-11-13 | 2021-12-28 | 辽宁中镁高温材料有限公司 | High-performance aluminum-chromium refractory material and manufacturing method and application thereof |
| CN110698190A (en) * | 2019-10-12 | 2020-01-17 | 中国科学院上海硅酸盐研究所 | Single-phase replacement solid solution oxide ceramic coating and preparation method thereof |
| CN110698190B (en) * | 2019-10-12 | 2021-06-15 | 中国科学院上海硅酸盐研究所 | Single-phase replacement solid solution oxide ceramic coating and preparation method thereof |
| CN113185306A (en) * | 2021-04-01 | 2021-07-30 | 张福生 | Method for preparing high-resistance aluminum-chromium brick by doping zirconium boride |
| CN113173795A (en) * | 2021-06-09 | 2021-07-27 | 江苏君耀耐磨耐火材料有限公司 | Chromium corundum brick for sulfur recovery acid gas incinerator and preparation process thereof |
| CN113416083A (en) * | 2021-07-19 | 2021-09-21 | 安庆市徽富防火材料有限公司 | High-temperature refractory material and preparation method thereof |
| CN117362015A (en) * | 2023-10-27 | 2024-01-09 | 河南省瑞泰科实业集团有限公司 | High-purity corundum brick and preparation method thereof |
| CN117362015B (en) * | 2023-10-27 | 2024-04-12 | 河南省瑞泰科实业集团有限公司 | High-purity corundum brick and preparation method thereof |
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