CN102731121B - High-performance magnesium-aluminum-chromium composite spinel brick and manufacturing method thereof - Google Patents

High-performance magnesium-aluminum-chromium composite spinel brick and manufacturing method thereof Download PDF

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CN102731121B
CN102731121B CN 201210239826 CN201210239826A CN102731121B CN 102731121 B CN102731121 B CN 102731121B CN 201210239826 CN201210239826 CN 201210239826 CN 201210239826 A CN201210239826 A CN 201210239826A CN 102731121 B CN102731121 B CN 102731121B
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chrome
fused magnesia
electrosmelted magnesite
low chromium
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CN102731121A (en
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苏广深
杨永刚
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Liaoning Zhongmei High-Temperature Materials Co Ltd
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Liaoning Zhongmei High-Temperature Materials Co Ltd
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Abstract

The invention relates to a high-performance magnesium-aluminum-chromium composite spinel brick for RH refining furnace dip pipes and non-ferrous smelting furnaces. The high-performance magnesium-aluminum-chromium composite spinel brick is characterized by comprising the following raw materials: 14.0-20.0 parts of low-chromium fused magnesium chromium sand (6-8% of Cr2O3, at least 78% of MgO), 71.6-82.0 parts of high-purity fused magnesite, 2.0-4.4 parts of nano Cr2O3 powder, 2.0-4.0 parts of uf-Al2O3 micropowder and 2-4 parts of binder. The manufacturing method comprises the following steps: mixing, molding, drying, firing and the like. The magnesium-aluminum-chromium composite spinel brick provided by the invention has the advantages of high sintering tendency, high crystal compactness, low porosity (at most 10%), high compressive strength (at least 100 MPa), high thermal shock stability (at least 18 times by 1100 DEG C water cooling) and the like. The Cr2O3 content of the product isat most 6%, thereby reducing the Cr2O3 content in the brick, lowering the production cost and finally effectively reducing the environmental pollution of waste magnesium-chromium bricks after use.

Description

High-performance magnesium-aluminium-chromium composite spinelle brick and manufacture method thereof
Technical field
The invention belongs to fire resisting material field, relate to a kind of RH refining furnace soaking tub and non-ferrous smelting furnace high-performance magnesium-aluminium-chromium composite spinelle brick and manufacture method thereof particularly.
Background technology
As everyone knows, magnesia chrome brick have excellent high-temperature intensity, high volume stability, anti-thermal shock stability and anti-ly wash away, characteristics such as anti-erosion, be widely used in Metal smelting and the cement rotary kiln.Many reasons such as owing to the chrome ore price increase, production cost increases in recent years, and the green wood fire resistant materials is alternative cause the consumption of magnesia chrome brick to reduce year by year; And that the underlying cause is can to produce Cr+6 with the discarded magnesia chrome brick in back is harmful, cause environmental pollution, so production and the use of magnesia chrome brick is all advocated to limit even cancel in countries in the world.
And external refining stove and non-ferrous metal smelting furnaces such as RH, VOD, AOD, owing to its high temperature and high speed metal liquid disturbance, wash away the magnesia chrome brick working lining.Step work technology of while, freezing air enters during standby, temperature decrease in the stove, this temperature fluctuation makes generation thermal stresses in the magnesia chrome brick and produces the internal fissure that is parallel to working face.Simultaneously, because infiltrating the molten steel of crackle in the refractory materials process of cooling on working face solidifies, because thermal expansivity is different, discontinuous stress produces layer in the operational layer brick that causes when temperature variation, has tangible harm its work-ing life to working lining with former brick interlayer on the turn.Slag causes structure spalling to the dissolving of periclasite and the infiltration in brick.Also has Cr 2O 3Volatility at high temperature causes magnesia chrome brick compactness to reduce, and influences its slag penetration resistance and erosion performance etc., and these factors have caused the damage of magnesia chrome brick.Under this harsh work processing condition, the refractory materials of other kind can't replace at all.As pointed in the 3rd the international refractory materials symposial, for the external refining refractory materials, the most erosion resistant magnesium chromium goods that are still can't substitute in the non-ferrous metal metallurgy especially.
Summary of the invention
In order to address the above problem, the invention provides a kind of high-performance magnesium-aluminium-chromium composite spinelle brick, it is that a kind of RH refining furnace soaking tub and non-ferrous smelting furnace hang down Cr refractory product with high-performance, reduce and reduce and contain the chromium goods to the pollution of environment, and improve its use properties, surmount existing work-ing life with refractory product.
Another object of the present invention provides a kind of manufacture method of high-performance magnesium-aluminium-chromium composite spinelle brick.
To achieve these goals, the technical solution used in the present invention is:
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, made by weight ratio by following raw material:
8 parts of 5mm~3mm electrosmelted magnesite clinker;
25 ~ 27 parts of 3mm~1mm electrosmelted magnesite clinker;
22 ~ 24 parts of≤1mm electrosmelted magnesite clinkers;
16.6 ~ 23.0 parts of≤0.074mm electrosmelted magnesite clinkers;
7 ~ 9 parts of the low chromium fused magnesia-chromes of 3mm~1mm;
4 ~ 6 parts of the low chromium fused magnesia-chromes of≤1mm;
3 ~ 5 parts of the low chromium fused magnesia-chromes of≤0.074mm;
10nm~50nm nanometer Cr 2O 32 ~ 4.4 parts of powders;
<1um uf-Al 2O 32 ~ 4 parts of micro mists;
2 ~ 4 parts of wedding agents;
Described wedding agent is lignosulfite.
A kind of manufacture method of high-performance magnesium-aluminium-chromium composite spinelle brick comprises the steps:
1) raw material pulverizing screening: with electrosmelted magnesite clinker, low chromium fused magnesia-chrome respectively after Hubei Province formula fragmentation and pair roller fragmentation, sieve and size classification, make granularity and be 5mm~3mm, 3mm~1mm ,≤the electrosmelted magnesite clinker particulate material of 1mm and≤0.074mm electrosmelted magnesite clinker fine powder, granularity be 3mm~1mm ,≤the low chromium fused magnesia-chrome particulate material of 1mm and≤the low chromium fused magnesia-chrome fine powder of 0.074mm;
2) powder premix: by weight ratio, take by weighing the nanometer Cr of electrosmelted magnesite clinker fine powder, low chromium fused magnesia-chrome fine powder, 10nm~50nm 2O 3Fine powder and granularity be<uf-Al of 1um 2O 3Micro mist mixes jointly through dry powder blender, and the fine powder material premix is even;
3) batch mixing: by weight ratio, take by weighing granularity be respectively 5mm~3mm, 3mm~1mm and≤the electrosmelted magnesite clinker particulate material of 1mm, granularity be respectively 3mm~1mm and≤the low chromium fused magnesia-chrome particulate material of 1mm, above-mentioned particulate material is added dried mixing 3~5 minutes in the sand mill, added the lignosulfite wet mixing then 3~7 minutes, add step 2 again) the uniform fine powder material of premix that obtains, mixed 8 ~ 12 minutes;
4) moulding: adopt friction press to be pressed into adobe;
5) drying: adobe is placed in the dry hole, and 110 ℃ are incubated 16 ~ 22 hours;
6) burn till: dried adobe is piled up on kiln car, send in the tunnel furnace, 1700 ℃ of firing temperatures, firing time 100 ~ 120 minutes.
Described low chromium fused magnesia-chrome adopts 15.4 parts of chromite ore fines, and 84.6 parts of light-burning magnesium powders fully mix through dry-mixed machine, stir, and puts in the electric smelter, and after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
Among the present invention, select the electrosmelted magnesite clinker of MgO content 〉=98% usually for use, MgO content 〉=78% and Cr 2O 3Content is at 6% ~ 8% low chromium fused magnesia-chrome, Cr 2O 3The nanometer Cr of content 〉=99% 2O 3Powder, Al 2O 3The uf-Al of content 〉=99% 2O 3Micro mist, Cr 2O 3The chromite ore fine of content 〉=52% and MgO content 〉=9%, the light-burning magnesium powder of MgO content 〉=92%.
The invention has the beneficial effects as follows, utilize existing electric smelting recombined magnesia-chrome brick technology, by introducing the nano level Cr of particle diameter between 10-50nm 2O 3Powder and fineness<1um uf-Al 2O 3Micro mist, reduce the segmentation specific surface area, reduce sintering temperature, promote its sintering, finer and close in the process of cooling crystallization, void content is lower, and the idiomorphic crystal of secondary spinel increases, and has strengthened the direct binding ability of brick, improved the erosion-resisting characteristics of brick, hot strength, heat-shock resistance is introduced uf-Al 2O 3Micro mist, not only can with Cr 2O 3, that MgO forms compound point is brilliant, can also effectively suppress magnesia chrome brick Cr at high temperature 2O 3Volatilization, and then improve the antistripping ability of brick; Again by adopting low chromium fused magnesia-chrome (Cr 2O 3, 6 ~ 8%), make it keep existing electric smelting again in conjunction with the performance of brick, when meeting or exceeding existing usefulness electric smelting recombined magnesia-chrome brick use properties, greatly reduce Cr in the brick 2O 3Content (Cr 2O 3≤ 6%), reduced production cost simultaneously, and the most basic purpose has been effectively to reduce with the pollution of the discarded magnesia chrome brick in back to environment.Adopt the preparation method of described low chromium fused magnesia-chrome to guarantee in the low chromium fused magnesia-chrome MgO content 〉=78% and make Cr 2O 3Content remains between 6% ~ 8%, has both strengthened the binding ability of brick, has also reduced simultaneously with the pollution of the discarded magnesia chrome brick in back to environment.
Description of drawings
Fig. 1 is that the experiment of embodiment one slag resistance detects design sketch.
Fig. 2 is that the experiment of embodiment two slag resistance detects design sketch.
Fig. 3 is that the experiment of embodiment three slag resistance detects design sketch.
Fig. 4 is for now detecting design sketch with the experiment of electric smelting recombined magnesia-chrome brick slag resistance.
Embodiment
Embodiment 1
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, made by weight ratio by following raw material:
8 parts of 5mm~3mm electrosmelted magnesite clinker;
27 parts of 3mm~1mm electrosmelted magnesite clinker;
24 parts of≤1mm electrosmelted magnesite clinkers;
23 parts of≤0.074mm electrosmelted magnesite clinkers;
7 parts of the low chromium fused magnesia-chromes of 3mm~1mm;
4 parts of the low chromium fused magnesia-chromes of≤1mm;
3 parts of the low chromium fused magnesia-chromes of≤0.074mm;
10nm~50nm nanometer Cr 2O 32 parts of powders;
<1um uf-Al 2O 32 parts of micro mists;
2 ~ 4 parts of wedding agents;
Described wedding agent is lignosulfite.
A kind of manufacture method of high-performance magnesium-aluminium-chromium composite spinelle brick comprises the steps:
1) preparation of low chromium fused magnesia-chrome: adopt 15.4 parts of chromite ore fines, 84.6 parts of light-burning magnesium powders fully mix through dry-mixed machine, stir, and put in the electric smelter, and after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
2) raw material pulverizing screening: with electrosmelted magnesite clinker, low chromium fused magnesia-chrome respectively after Hubei Province formula fragmentation and pair roller fragmentation, sieve and size classification, make granularity and be 5mm~3mm, 3mm~1mm ,≤the electrosmelted magnesite clinker particulate material of 1mm and≤0.074mm electrosmelted magnesite clinker fine powder, granularity be 3mm~1mm ,≤the low chromium fused magnesia-chrome particulate material of 1mm and≤the low chromium fused magnesia-chrome fine powder of 0.074mm;
3) powder premix: by weight ratio, take by weighing the nanometer Cr of electrosmelted magnesite clinker fine powder, low chromium fused magnesia-chrome fine powder, 10nm~50nm 2O 3Fine powder and granularity be<uf-Al of 1um 2O 3Micro mist mixes jointly through dry powder blender, and the fine powder material premix is even;
4) batch mixing: by weight ratio, take by weighing granularity be respectively 5mm~3mm, 3mm~1mm and≤the electrosmelted magnesite clinker particulate material of 1mm, granularity be respectively 3mm~1mm and≤the low chromium fused magnesia-chrome particulate material of 1mm, above-mentioned particulate material is added dried mixing 3~5 minutes in the sand mill, added the lignosulfite wet mixing then 3~7 minutes, add step 2 again) the uniform fine powder material of premix that obtains, mixed 8 ~ 12 minutes;
5) moulding: adopt friction press to be pressed into adobe;
6) drying: adobe is placed in the dry hole, and 110 ℃ are incubated 18 hours;
7) burn till: dried adobe is piled up on kiln car, send in the tunnel furnace, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
Finished product test the results are shown in Table 1.
Embodiment 2
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, made by weight ratio by following raw material:
8 parts of 5mm~3mm electrosmelted magnesite clinker;
26 parts of 3mm~1mm electrosmelted magnesite clinker;
23 parts of 1mm~0mm electrosmelted magnesite clinker;
19.8 parts of≤0.074mm electrosmelted magnesite clinkers;
8 parts of the low chromium fused magnesia-chromes of 3mm~1mm;
5 parts of the low chromium fused magnesia-chromes of 1mm~0mm;
4 parts of the low chromium fused magnesia-chromes of≤0.074mm;
10nm~50nm nanometer Cr 2O 33.2 parts of powders;
<1um uf-Al 2O 33 parts of micro mists;
2 ~ 4 parts of wedding agents;
Described wedding agent is lignosulfite.
A kind of manufacture method of high-performance magnesium-aluminium-chromium composite spinelle brick comprises the steps:
1) preparation of low chromium fused magnesia-chrome: adopt 15.4 parts of chromite ore fines, 84.6 parts of light-burning magnesium powders fully mix through dry-mixed machine, stir, and put in the electric smelter, and after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
2) raw material pulverizing screening: with electrosmelted magnesite clinker, low chromium fused magnesia-chrome respectively after Hubei Province formula fragmentation and pair roller fragmentation, sieve and size classification, make granularity and be 5mm~3mm, 3mm~1mm ,≤the electrosmelted magnesite clinker particulate material of 1mm and≤0.074mm electrosmelted magnesite clinker fine powder, granularity be 3mm~1mm ,≤the low chromium fused magnesia-chrome particulate material of 1mm and≤the low chromium fused magnesia-chrome fine powder of 0.074mm;
3) powder premix: by weight ratio, take by weighing the nanometer Cr of electrosmelted magnesite clinker fine powder, low chromium fused magnesia-chrome fine powder, 10nm~50nm 2O 3Fine powder and granularity be<uf-Al of 1um 2O 3Micro mist mixes jointly through dry powder blender, and the fine powder material premix is even;
4) batch mixing: by weight ratio, take by weighing granularity be respectively 5mm~3mm, 3mm~1mm and≤the electrosmelted magnesite clinker particulate material of 1mm, granularity be respectively 3mm~1mm and≤the low chromium fused magnesia-chrome particulate material of 1mm, above-mentioned particulate material is added dried mixing 3~5 minutes in the sand mill, added the lignosulfite wet mixing then 3~7 minutes, add step 2 again) the uniform fine powder material of premix that obtains, mixed 8 ~ 12 minutes;
5) moulding: adopt friction press to be pressed into adobe;
6) drying: adobe is placed in the dry hole, and 110 ℃ are incubated 18 hours;
7) burn till: dried adobe is piled up on kiln car, send in the tunnel furnace, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
Finished product test the results are shown in Table 1.
Embodiment 3
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, made by weight ratio by following raw material:
8 parts of 5mm~3mm electrosmelted magnesite clinker;
25 parts of 3mm~1mm electrosmelted magnesite clinker;
22 parts of≤1mm electrosmelted magnesite clinkers;
16.6 parts of≤0.074mm electrosmelted magnesite clinkers;
9 parts of the low chromium fused magnesia-chromes of 3mm~1mm;
6 parts of the low chromium fused magnesia-chromes of≤1mm;
5 parts of the low chromium fused magnesia-chromes of≤0.074mm;
10nm~50nm nanometer Cr 2O 34.4 parts of powders;
<1um uf-Al 2O 34 parts of micro mists;
2 ~ 4 parts of wedding agents;
Described wedding agent is lignosulfite.
A kind of manufacture method of high-performance magnesium-aluminium-chromium composite spinelle brick comprises the steps:
1) preparation of low chromium fused magnesia-chrome: adopt 15.4 parts of chromite ore fines, 84.6 parts of light-burning magnesium powders fully mix through dry-mixed machine, stir, and put in the electric smelter, and after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
2) raw material pulverizing screening: with electrosmelted magnesite clinker, low chromium fused magnesia-chrome respectively after Hubei Province formula fragmentation and pair roller fragmentation, sieve and size classification, make granularity and be 5mm~3mm, 3mm~1mm ,≤the electrosmelted magnesite clinker particulate material of 1mm and≤0.074mm electrosmelted magnesite clinker fine powder, granularity be 3mm~1mm ,≤the low chromium fused magnesia-chrome particulate material of 1mm and≤the low chromium fused magnesia-chrome fine powder of 0.074mm;
3) powder premix: by weight ratio, take by weighing the nanometer Cr of electrosmelted magnesite clinker fine powder, low chromium fused magnesia-chrome fine powder, 10nm~50nm 2O 3Fine powder and granularity be<uf-Al of 1um 2O 3Micro mist mixes jointly through dry powder blender, and the fine powder material premix is even;
4) batch mixing: by weight ratio, take by weighing granularity be respectively 5mm~3mm, 3mm~1mm and≤the electrosmelted magnesite clinker particulate material of 1mm, granularity be respectively 3mm~1mm and≤the low chromium fused magnesia-chrome particulate material of 1mm, above-mentioned particulate material is added dried mixing 3~5 minutes in the sand mill, added the lignosulfite wet mixing then 3~7 minutes, add step 2 again) the uniform fine powder material of premix that obtains, mixed 8 ~ 12 minutes;
5) moulding: adopt friction press to be pressed into adobe;
6) drying: adobe is placed in the dry hole, and 110 ℃ are incubated 18 hours;
7) burn till: dried adobe is piled up on kiln car, send in the tunnel furnace, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
Finished product test the results are shown in Table 1.
Table 1 embodiment contrasts with now using electric smelting recombined magnesia-chrome brick (DMGe-20) physical and chemical index
Figure 165554DEST_PATH_IMAGE001
Referring to Fig. 1 to Fig. 4, embodiment becomes a partner more as shown in table 2 than effect with now using the experiment of electric smelting recombined magnesia-chrome brick (DMGe-20) slag resistance.
Table 2 embodiment tests the ratio of becoming a partner with now using electric smelting recombined magnesia-chrome brick (DMGe-20) slag resistance
Figure 82695DEST_PATH_IMAGE002
The key technical indexes I that table 3 the present invention reaches
Figure 675481DEST_PATH_IMAGE003
The key technical indexes II that table 4 the present invention reaches
Figure 70690DEST_PATH_IMAGE004

Claims (2)

1. the manufacture method of a high-performance magnesium-aluminium-chromium composite spinelle brick is characterized in that it being to adopt following composition of raw materials:
8 parts of 5mm~3mm electrosmelted magnesite clinker;
25 ~ 27 parts of 3mm~1mm electrosmelted magnesite clinker;
22 ~ 24 parts of≤1mm electrosmelted magnesite clinkers;
16.6 ~ 23.0 parts of≤0.074mm electrosmelted magnesite clinkers;
7 ~ 9 parts of the low chromium fused magnesia-chromes of 3mm~1mm;
4 ~ 6 parts of the low chromium fused magnesia-chromes of≤1mm;
3 ~ 5 parts of the low chromium fused magnesia-chromes of≤0.074mm;
10nm~50nm nanometer Cr 2O 32 ~ 4.4 parts of powders;
<1 μ m uf-Al 2O 32 ~ 4 parts of micro mists;
2 ~ 4 parts of wedding agents;
Described wedding agent is lignosulfite;
In the described raw material, MgO content 〉=98% in the electrosmelted magnesite clinker, MgO content 〉=78% and Cr in the low chromium fused magnesia-chrome 2O 3Content is 6% ~ 8%, nanometer Cr 2O 3Cr in the powder 2O 3Content 〉=99%, uf-Al 2O 3Al in the micro mist 2O 3Content 〉=99%;
Described manufacture method comprises the steps:
1) raw material pulverizing screening: with above-mentioned electrosmelted magnesite clinker, low chromium fused magnesia-chrome respectively after Hubei Province formula fragmentation and pair roller fragmentation, sieve and size classification, make granularity and be 5mm~3mm, 3mm~1mm ,≤the electrosmelted magnesite clinker particulate material of 1mm and≤0.074mm electrosmelted magnesite clinker fine powder, granularity be 3mm~1mm ,≤the low chromium fused magnesia-chrome particulate material of 1mm and≤the low chromium fused magnesia-chrome fine powder of 0.074mm;
2) powder premix: by weight ratio, take by weighing the nanometer Cr of electrosmelted magnesite clinker fine powder, low chromium fused magnesia-chrome fine powder, 10nm~50nm 2O 3Fine powder and granularity are the uf-Al of<1 μ m 2O 3Micro mist mixes jointly through dry powder blender, and the fine powder material premix is even;
3) batch mixing: by weight ratio, take by weighing granularity be respectively 5mm~3mm, 3mm~1mm and≤the electrosmelted magnesite clinker particulate material of 1mm, granularity be respectively 3mm~1mm and≤the low chromium fused magnesia-chrome particulate material of 1mm, above-mentioned particulate material is added dried mixing 3~5 minutes in the sand mill, added the lignosulfite wet mixing then 3~7 minutes, add step 2 again) the uniform fine powder material of premix that obtains, mixed 8 ~ 12 minutes;
4) moulding: adopt friction press to be pressed into adobe;
5) drying: adobe is placed in the dry hole, and 110 ℃ are incubated 16 ~ 22 hours;
6) burn till: dried adobe is piled up on kiln car, send in the tunnel furnace, 1700 ℃ of firing temperatures, firing time 100 ~ 120 minutes.
2. the manufacture method of a kind of high-performance magnesium-aluminium-chromium composite spinelle brick as claimed in claim 1, it is characterized in that: described low chromium fused magnesia-chrome adopts 15.4 parts of chromite ore fines, 84.6 parts of light-burning magnesium powders, fully mix through dry-mixed machine, stir, put in the electric smelter, after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
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