CN102731121A - 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 PDFInfo
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- CN102731121A CN102731121A CN2012102398264A CN201210239826A CN102731121A CN 102731121 A CN102731121 A CN 102731121A CN 2012102398264 A CN2012102398264 A CN 2012102398264A CN 201210239826 A CN201210239826 A CN 201210239826A CN 102731121 A CN102731121 A CN 102731121A
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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 is at 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
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 particularly with high-performance magnesium-aluminium-chromium composite spinelle brick and method of manufacture thereof.
Background technology
As everyone knows, magnesia chrome brick has excellent high-temperature intensity, high volume stability, anti-thermal shock is stable 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 back depleted magnesia chrome brick is harmful, cause environmental pollution, so the 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 gets into 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 workplace.Simultaneously; Because on workplace, infiltrating the molten steel of crackle in the refractory materials process of cooling solidifies; Because thermal expansivity is different, discontinuous stress produces layer in the operational layer brick that when temperature variation, causes, and 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 present 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; Minimizing and reduction contain the pollution of chromium goods to environment, and improve its use properties, surmount existing work-ing life with refractory product.
Another object of the present invention provides a kind of method of manufacture of high-performance magnesium-aluminium-chromium composite spinelle brick.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, process 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 a lignosulfite.
A kind of method of manufacture 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; Process 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, through the dry powder blender mixed together, that 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 is respectively the low chromium fused magnesia-chrome particulate material of 3mm～1mm and≤1mm, above-mentioned particulate material is added to do in the sand mill mixed 3～5 minutes, adds 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, 1700 ℃ of firing temperatures, firing time 100 ~ 120 minutes.
Said low chromium fused magnesia-chrome adopts 15.4 parts of chromite ore fines, and 84.6 parts of light-burning magnesium powders through the dry-mixed machine thorough mixing, 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, through introducing the nano level Cr of particle diameter between 10-50nm
2O
3Powder and fineness＜1um uf-Al
2O
3Micro mist reduces the segmentation specific surface area, reduces 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, has 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 through adopting low chromium fused magnesia-chrome (Cr
2O
3, 6 ~ 8%), make it keep the performance that existing electric smelting combines brick again, meet or exceed existing with electric smelting recombined magnesia-chrome brick use properties in, 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 said 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 detect design sketch with the experiment of electric smelting recombined magnesia-chrome brick slag resistance at present.
Embodiment
Embodiment 1
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, process 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 a lignosulfite.
A kind of method of manufacture 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 through the dry-mixed machine thorough mixing, 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; Process 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, through the dry powder blender mixed together, that 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 is respectively the low chromium fused magnesia-chrome particulate material of 3mm～1mm and≤1mm, above-mentioned particulate material is added to do in the sand mill mixed 3～5 minutes, adds 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, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
The finished product test result sees table 1.
Embodiment 2
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, process 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 a lignosulfite.
A kind of method of manufacture 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 through the dry-mixed machine thorough mixing, 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; Process 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, through the dry powder blender mixed together, that 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 is respectively the low chromium fused magnesia-chrome particulate material of 3mm～1mm and≤1mm, above-mentioned particulate material is added to do in the sand mill mixed 3～5 minutes, adds 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, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
The finished product test result sees table 1.
Embodiment 3
A kind of high-performance magnesium-aluminium-chromium composite spinelle brick, process 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 a lignosulfite.
A kind of method of manufacture 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 through the dry-mixed machine thorough mixing, 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; Process 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, through the dry powder blender mixed together, that 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 is respectively the low chromium fused magnesia-chrome particulate material of 3mm～1mm and≤1mm, above-mentioned particulate material is added to do in the sand mill mixed 3～5 minutes, adds 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, 1700 ℃ of firing temperatures, firing time 120 minutes.
8) after the cooling, after selection, packing, go into stockyard.
The finished product test result sees table 1.
Table 1 embodiment contrasts with use electric smelting recombined magnesia-chrome brick (DMGe-20) physical and chemical index at present
Referring to Fig. 1 to Fig. 4, embodiment becomes a partner more as shown in table 2 than effect with use the experiment of electric smelting recombined magnesia-chrome brick (DMGe-20) slag resistance at present.
Table 2 embodiment tests the ratio of becoming a partner with use electric smelting recombined magnesia-chrome brick (DMGe-20) slag resistance at present
。
The key technical indexes I that table 3 the present invention reaches
The key technical indexes II that table 4 the present invention reaches
Claims (3)
1. high-performance magnesium-aluminium-chromium composite spinelle brick is characterized in that being processed 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 a lignosulfite.
2. the method for manufacture of the described high-performance magnesium-aluminium-chromium composite spinelle brick of claim 1 is characterized in that comprising 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; Process 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, through the dry powder blender mixed together, that 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 is respectively the low chromium fused magnesia-chrome particulate material of 3mm～1mm and≤1mm, above-mentioned particulate material is added to do in the sand mill mixed 3～5 minutes, adds 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, 1700 ℃ of firing temperatures, firing time 100 ~ 120 minutes.
3. the method for manufacture of a high-performance magnesium-aluminium-chromium composite spinelle brick as claimed in claim 2; It is characterized in that: said low chromium fused magnesia-chrome adopts 15.4 parts of chromite ore fines, and 84.6 parts of light-burning magnesium powders are through the dry-mixed machine thorough mixing; Stir; Put in the electric smelter, after 10.5 hours, the naturally cooling selection makes through 2800 ℃ of insulations.
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