CN104402470A - Composite high-temperature refractory material and making method thereof - Google Patents
Composite high-temperature refractory material and making method thereof Download PDFInfo
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- CN104402470A CN104402470A CN201410647375.7A CN201410647375A CN104402470A CN 104402470 A CN104402470 A CN 104402470A CN 201410647375 A CN201410647375 A CN 201410647375A CN 104402470 A CN104402470 A CN 104402470A
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Abstract
The invention provides a composite high-temperature refractory material and a making method thereof. The composite high-temperature refractory material is composed of anorthite, calcium hexaluminate, corundum and perovskite. The composite high-temperature refractory material mainly comprises the following chemical components by mass: 61.44%-62.86% of Al2O3, 14.85%-19.30% of SiO2 and 19.26%-22.29% of CaO. The method comprises the steps of: mixing, by mass percentage, 48%-76% of alumina slag, 20%-50% of white corundum powder and 2%-6% of a carbon black pore-forming agent evenly and conducting molding to obtain a composite high-temperature refractory material green body; drying the composite high-temperature refractory material green body; and calcining the dried composite high-temperature refractory material green body, thus obtaining the composite high-temperature refractory material. According to the invention, the composite high-temperature refractory material with excellent performance can be made.
Description
Technical field
The invention belongs to fire resisting material field, more particularly, the present invention relates to a kind of combined high temperature refractory materials and manufacture method thereof.
Background technology
High swage bauxite accounts for more than 30% of China's bauxite resource total amount, mainly be distributed in the ground such as the Guigang in Guangxi, Heng County, Binyang, guest, Wuming, the ground such as Shanxi Baode, Henan, Guizhou, Chongqing, Hainan, Fujian also has high-iron bauxite to distribute in addition, and national high swage bauxite resource amount reaches more than 1,500,000,000 tons.High swage bauxite can obtain high granulated iron recovery rate and high-grade aluminum oxide slag after coal-based direct reduction melts point, high-quality granulated iron directly can be used as the steel-making refrigerant of converter or electric furnace, and high-grade aluminum oxide slag is never effectively fully utilized.
Summary of the invention
One object of the present invention is to provide a kind of combined high temperature refractory materials and the manufacture method thereof that effectively can utilize aluminum oxide slag.
According to the present invention, provide a kind of combined high temperature refractory materials, described combined high temperature refractory materials can be made up of lime feldspar, calcium hexaluminate, corundum and uhligite, and wherein, the chemical composition of described combined high temperature refractory materials is mainly the Al of 61.44% ~ 62.86% by mass percentage
2o
3, 14.85% ~ 19.30% SiO
2with 19.26% ~ 22.29% CaO.
According to an aspect of the present invention, with the total weight of described combined high temperature refractory materials, described combined high temperature refractory materials can by 28.0% ~ 30.02% lime feldspar, the calcium hexaluminate of 49.28% ~ 50.91%, the corundum of 12.22% ~ 13.09% and 7.61% ~ 8.88% uhligite form.
According to an aspect of the present invention, the volume density of described combined high temperature refractory materials can be 1.75g/cm
3~ 1.92g/cm
3, reheating linear change rate on reheating can be-0.4% ~ 0.2%, and compressive strength can be 145MPa ~ 190MPa, and refractoriness can be 1600 DEG C ~ 1650 DEG C, and the thermal conductivity 800 DEG C time can be 0.37W/mk ~ 0.45W/mk.
According to the present invention, provide a kind of method manufacturing combined high temperature refractory materials, described method can comprise the following steps: (a) by be the aluminum oxide slag of 48% ~ 76% by mass percentage, the white alundum powder of 20% ~ 50% and 2% ~ 6% carbon black pore-forming material to mix and shaping, obtain combined high temperature refractory materials green compact; B () carries out drying to combined high temperature refractory materials green compact; C () calcines dried combined high temperature refractory materials green compact, obtain described combined high temperature refractory materials, wherein, aluminum oxide slag is made up of corundum, gehlenite and calcium hexaluminate, wherein, described combined high temperature refractory materials is made up of lime feldspar, calcium hexaluminate, corundum and uhligite, and wherein, the chemical composition of described combined high temperature refractory materials is mainly the Al of 61.44% ~ 62.86% by mass percentage
2o
3, 14.85% ~ 19.30% SiO
2with 19.26% ~ 22.29% CaO.
According to an aspect of the present invention, described aluminum oxide slag by mass percentage can by the SiO of 20.69% ~ 23.09%
2, the CaO of 23.06% ~ the 31.05% and Al of 41.14% ~ 45.91%
2o
3, 1.55% ~ 1.73% FeO, the MnO of 2.70% ~ 3.01%, the TiO of 2.50% ~ 2.79%
2with 0.37% ~ 0.41% V
2o
5composition, wherein, the fineness of aluminum oxide slag is 40 ~ 60 orders, and the fineness of white alundum powder is 60 order ~ 80 orders, and the fineness of carbon black pore-forming material is 300 order ~ 350 orders.
According to an aspect of the present invention, by carrying out coal-based direct reduction molten point of aluminum oxide slag obtained in described step (a) to high-iron bauxite.
According to an aspect of the present invention, carry out molten point of coal-based direct reduction to high-iron bauxite can comprise the following steps: by mass percentage by the high-iron bauxite breeze of 74.39% ~ 78.63%, the coal dust of 9.45% ~ 9.98% and 11.39% ~ 16.16% slaked lime mixing after manufacture pelletizing; Dried by pelletizing, bake out temperature is 200 DEG C ~ 240 DEG C, and drying time is 3 hours ~ 5 hours; Sent in pushed bat kiln by pelletizing after drying, carry out molten point of reduction when nitrogen protection, nitrogen flow is 5.0L/min ~ 7.0L/min, and the molten point temperature of reduction is 1400 DEG C ~ 1450 DEG C, and the reduction molten point time is 25min ~ 35min; To the pelletizing deironing after molten point of reduction, obtain the aluminum oxide slag described in step (a).
According to an aspect of the present invention, can comprise: pelletizing is crushed to 5mm ~ 10mm to the step of the pelletizing deironing after molten point of reduction, the granulated iron of magnetic separation removing more than 0.3mm, obtains the first aluminum oxide slag; By levigate for the first aluminum oxide slag to 40 order ~ 60 orders, carry out low intensity magnetic separation deironing after obtain the aluminum oxide slag described in step (a), wherein, low intensity magnetic separation use magnetic induction density be 0.14T ~ 0.16T.
According to an aspect of the present invention, carry out dry step to combined high temperature refractory materials green compact can comprise: by green compact seasoning 12 hours ~ 24 hours; Then green compact are dried in the drying kiln of 50 DEG C ~ 200 DEG C.
According to an aspect of the present invention, 800 DEG C ~ 1000 DEG C calcinings 2 ~ 3 hours can be included in the step that combined high temperature refractory materials green compact are calcined, calcine 3 ~ 4 hours for 1100 DEG C ~ 1200 DEG C, then 1400 DEG C ~ 1500 DEG C calcinings 4 hours ~ 6 hours.
According to combined high temperature refractory materials of the present invention, have that thermal conductivity is low, good stability under high-temperature reductibility atmosphere, alkali resistant erosional competency and slag corrosion resistance ability is good, intensity is high, the life-span is long, energy-saving efficiency is a high feature.
According to combined high temperature refractory materials manufacture method of the present invention, the aluminum oxide slag obtained after can effectively utilizing high-iron bauxite direct-reduction to melt point, can realize the comprehensive utilization of aluminium in high-iron bauxite.
Accompanying drawing explanation
By the detailed description of carrying out below in conjunction with accompanying drawing, above and other objects of the present invention, feature and advantage will become apparent, in the accompanying drawings:
Fig. 1 shows the XRD figure of combined high temperature refractory materials according to an exemplary embodiment of the present invention;
Fig. 2 A shows the SEM figure of combined high temperature refractory materials according to an exemplary embodiment of the present invention;
Fig. 2 B shows the SEM figure of combined high temperature refractory materials according to an exemplary embodiment of the present invention;
Fig. 3 shows the parison of combined high temperature refractory materials according to an exemplary embodiment of the present invention;
Fig. 4 shows the process flow sheet manufacturing combined high temperature refractory materials according to an exemplary embodiment of the present invention.
Embodiment
Hereinafter, with reference to the accompanying drawings exemplary embodiment of the present invention is described more fully.But they can be implemented in different forms, and should not be construed as the embodiment being confined to set forth here.On the contrary, provide these embodiments to make the disclosure to be thoroughly with complete, and the scope example embodiment is conveyed to those skilled in the art fully.
Hereinafter, will describe according to a kind of combined high temperature refractory materials of exemplary embodiment of the present invention and manufacture method thereof.
The invention provides a kind of combined high temperature refractory materials, this combined high temperature refractory materials is made up of lime feldspar, calcium hexaluminate, corundum and uhligite, and wherein, the chemical composition of combined high temperature refractory materials is mainly the Al of 61.44% ~ 62.86% by mass percentage
2o
3, 14.85% ~ 19.30% SiO
2and the CaO of 19.26% ~ 22.29%.
According to one embodiment of present invention, combined high temperature refractory materials by mass percentage can by the lime feldspar (2CaOAl of 28.0% ~ 30.02%
2o
3siO
2, be abbreviated as CAS
2), the calcium hexaluminate (CaO6Al of 49.28% ~ 50.91%
2o
3, be abbreviated as CA
6), the corundum (α-Al of 12.22% ~ 13.09%
2o
3, be abbreviated as A) and 7.61% ~ 8.88% uhligite (CaTiO
3) composition.Therefore, combined high temperature refractory materials according to the present invention also can be called as A-ACS
2-CA
6combined high temperature refractory materials.
Fig. 1 shows the XRD figure of combined high temperature refractory materials according to an exemplary embodiment of the present invention, and Fig. 2 A and Fig. 2 B shows the SEM figure of combined high temperature refractory materials according to an exemplary embodiment of the present invention.
With reference to Fig. 1, Fig. 2 A and Fig. 2 B, combined high temperature refractory materials according to the present invention is by α-Al
2o
3(corundum), CaAl
2si
2o
8(lime feldspar), CaAl
12o
19(calcium hexaluminate) and CaTiO
3(uhligite) forms, wherein, anorthitic fusing point is 1550 DEG C, the fusing point of calcium hexaluminate is 1850 DEG C, the fusing point of corundum is 2050 DEG C, and the fusing point of uhligite is 1975 DEG C, therefore, form all very high according to each phase fusing point of combined high temperature refractory materials of the present invention, the lime feldspar that wherein fusing point is lower is then as Binder Phase.As shown in Figure 2 A and 2 B, in the microtexture of combined high temperature refractory materials, lime feldspar crystal between calcium hexaluminate crystal and corundum crystal, plays the effect of bonding calcium hexaluminate crystal and corundum crystal, to improve the intensity of combined high temperature refractory materials as Binder Phase.
According to one embodiment of present invention, the volume density of combined high temperature refractory materials is 1.75g/cm
3~ 1.92g/cm
3, reheating linear change rate on reheating is-0.4% ~ 0.2%, and compressive strength is 145MPa ~ 190MPa, and refractoriness is 1600 DEG C ~ 1650 DEG C, and thermal conductivity when 800 DEG C is 0.37W/m.k ~ 0.45W/m.k.Therefore, according to combined high temperature refractory materials of the present invention, have that thermal conductivity is low, good stability under high-temperature reductibility atmosphere, alkali resistant erosional competency and slag corrosion resistance ability is good, intensity is high, the life-span is long, energy-saving efficiency is a high feature.
The manufacture method according to combined high temperature refractory materials of the present invention is described in detail below in conjunction with accompanying drawing.
Fig. 4 shows the process flow sheet manufacturing combined high temperature refractory materials according to an exemplary embodiment of the present invention.
With reference to Fig. 4, method according to manufacture combined high temperature refractory materials of the present invention comprises the following steps: (a) by be the aluminum oxide slag of 48% ~ 76% by mass percentage, the white alundum powder of 20% ~ 50% and 2% ~ 6% carbon black pore-forming material to mix and shaping, obtain combined high temperature refractory materials green compact, wherein, aluminum oxide slag is made up of corundum, gehlenite and calcium hexaluminate; B () carries out drying to combined high temperature refractory materials green compact; C () calcines dried combined high temperature refractory materials green compact, obtain combined high temperature refractory materials.
In step (a), the carbon black pore-forming material added plays the effect of pore-creating.Alternatively, refractory materials forming machine can be utilized the raw material mixed to be prepared the combined high temperature refractory materials green compact of desired shape, such as cylindrical (as shown in Figure 3).
According to one embodiment of present invention, the fineness of aluminum oxide slag can be 40 order ~ 60 orders, and the fineness of white alundum powder can be 60 order ~ 80 orders, and the fineness of carbon black pore-forming material can be 300 order ~ 350 orders.
According to the present invention, aluminum oxide slag is made up of corundum, gehlenite and calcium hexaluminate.Preferably, the described aluminum oxide slag aluminum oxide slag that can be high swage bauxite obtain after coal-based direct reduction melts point, in this case, aluminum oxide slag by mass percentage can by the SiO of 20.69% ~ 23.09%
2, the CaO of 23.06% ~ the 31.05% and Al of 41.14% ~ 45.91%
2o
3, 1.55% ~ 1.73% FeO, the MnO of 2.70% ~ 3.01%, the TiO of 2.50% ~ 2.79%
2with 0.37% ~ 0.41 V
2o
5composition.
Specifically, according to one exemplary embodiment of the present invention, when utilize method that coal-based direct reduction melts point is carried out to obtain aluminum oxide slag to high swage bauxite time, carrying out to high swage bauxite the method that coal-based direct reduction melts point can comprise the following steps: by mass percentage by the high-iron bauxite breeze of 74.39% ~ 78.63%, the coal dust of 9.45% ~ 9.98% and 11.39% ~ 16.16% slaked lime mix after manufacture pelletizing; Dried by pelletizing, bake out temperature is 200 DEG C ~ 240 DEG C, and drying time is 3 hours ~ 5 hours; Sent in pushed bat kiln by pelletizing after drying, carry out molten point of reduction when nitrogen protection, nitrogen flow is 5.0L/min ~ 7.0L/min, and the molten point temperature of reduction is 1400 DEG C ~ 1450 DEG C, and the reduction molten point time is 25min ~ 35min; To the pelletizing deironing after molten point of reduction, obtain manufacturing combined high temperature refractory materials according to the present invention aluminum oxide slag used.
In the step manufacturing pelletizing, coal dust plays the effect of reductive agent and fuel, and slaked lime plays slag making and reduces the effect of slag system fusing point, and the reduction being conducive to ferriferous oxide is separated with the effective of slag iron.
In the step that pelletizing is dried, bake out temperature or drying time relevant with the size of pelletizing, when pelletizing size changes, can suitably regulate bake out temperature and drying time, and avoid that bake out temperature is too low or too high and drying time is too short or long, if bake out temperature is too low or drying time is too short, then effectively can not dry pelletizing, if bake out temperature is too high or drying time is long, then moisture evaporation can be caused too fast and pelletizing cracking occurs, and the energy consumption of stoving process is raised.
Pelletizing after drying is carried out when nitrogen protection reducing in the process of molten point, if nitrogen flow is less than 5.0L/min, then can not play the effect of available protecting, if nitrogen flow is greater than 7.0L/min, then can increase cost; If the temperature that reduction is molten point is less than 25min, then the iron that can not effectively reduce in high-iron bauxite lower than the time of 1400 DEG C or molten point of reduction; If the temperature that reduction is molten point is greater than 35min higher than the time of 1450 DEG C or molten point of reduction, then pelletizing can be caused to melt bonding furnace bottom completely, cause unnecessary energy expenditure simultaneously.
Alternatively, can comprise: pelletizing is crushed to 5mm ~ 10mm to the step of the pelletizing deironing after molten point of reduction, the granulated iron of magnetic separation removing more than 0.3mm, obtains the first aluminum oxide slag; By levigate for the first aluminum oxide slag to 40 order ~ 60 orders, carry out low intensity magnetic separation deironing after obtain manufacturing combined high temperature refractory materials aluminum oxide slag used, wherein, the magnetic induction density that low intensity magnetic separation uses is 0.14T ~ 0.16T.Aluminum oxide slag after magnetic separation is separated has extremely low FeO content and higher alumina content, and the weight percentage of FeO can lower than 2.0%, and the weight percentage of aluminum oxide can higher than 41%.But the present invention is not limited thereto, those skilled in the art can adopt other method for removing iron to carry out deironing to the pelletizing after molten point of reduction under the teachings of the present invention.
In the step (b) manufacturing combined high temperature refractory materials, after forming combined high temperature refractory materials green compact, drying is carried out to combined high temperature refractory materials green compact, alternatively, carry out drying to combined high temperature refractory materials green compact can comprise the following steps: by green compact seasoning 12 hours ~ 24 hours; Then green compact are dried in the drying kiln of 50 DEG C ~ 200 DEG C.But the present invention is not limited thereto, those skilled in the art can adopt other drying means be suitable for carry out drying to combined high temperature refractory materials green compact under the teachings of the present invention.
In the step (c) manufacturing combined high temperature refractory materials, dried combined high temperature refractory materials green compact are calcined.800 DEG C ~ 1000 DEG C calcinings 2 ~ 3 hours can be included in, 1100 DEG C ~ 1200 DEG C calcinings 3 ~ 4 hours, then 1400 DEG C ~ 1500 DEG C calcinings 4 hours ~ 6 hours to the step that combined high temperature refractory materials green compact are calcined.If calcining temperature is too low or calcination time is too short, then can not ensure the thermal conductivity of combined high temperature refractory materials, stability, alkali resistant erosional competency, slag corrosion resistance ability and intensity etc.If calcining temperature is too high or calcination time is long, then can cause unnecessary energy consumption.
Below in conjunction with concrete exemplary embodiment, the manufacture method according to combined high temperature refractory materials of the present invention is described.
Example 1
Be prepared into after the high-iron bauxite breeze of 78.63%, the coal dust of 9.98% and the slaked lime of 11.39% are mixed by weight percentage and be of a size of
pelletizing, then sent into by pelletizing in net belt type continuous drying case and dry, bake out temperature is 200 DEG C, and drying time is 3 hours.Sent into by pelletizing in hyperchannel high-temperature electric heat pushed bat kiln after oven dry, carry out molten point of reduction when nitrogen protection, nitrogen flow is 5.0L/min, and the molten point temperature of reduction is 1400 DEG C, and the reduction molten point time is 35min.After molten point of reduction terminates by pelletizing air cooling to room temperature, utilize jaw crusher that cooled pelletizing is crushed to 5mm ~ 10mm, magnetic separation removes large-sized granulated iron, obtains aluminum oxide slag.Again aluminum oxide slag is carried out slight ore grinding, grinding fineness is 50 orders, and further low intensity magnetic separation deironing after ore grinding, low intensity magnetic separation magnetic induction density is 0.16T.Aluminum oxide slag after deironing is by mass percentage by the FeO of 1.73%, the SiO of 23.09%
2, the CaO of 23.06%, the Al of 45.91%
2o
3, the MnO of 3.01%, the TiO of 2.79%
2with 0.41% V
2o
5composition.
By the aluminum oxide slag of 78% by mass percentage, the white alundum powder of 20% and 2% carbon black pore-forming material mix and utilize refractory materials forming machine to prepare combined high temperature refractory materials green compact, wherein, the fineness of aluminum oxide slag is 50 orders, the fineness of white alundum powder is 60 orders, and the fineness of carbon black pore-forming material is 300 orders.The at room temperature seasoning of wet green after shaping after 12 hours, then dries 5 hours with the drying kiln of 150 DEG C.Then be sent in hyperthermia tunnel Kiln by the combined high temperature refractory materials green compact of having dried and calcine, calcinating system is: be incubated 3 hours at 900 DEG C, is incubated 4 hours at 1100 DEG C, and 1400 DEG C are incubated 6 hours.After calcining terminates, in stove, the mode of slow cooling is cooled to room temperature, finally obtains combined high temperature refractory materials.
The combined high temperature refractory materials that this example obtains by weight percentage by 28.0% lime feldspar (CaAl
2si
2o
8), the calcium hexaluminate (CaAl of 50.91%
12o
19), the corundum (α-Al of 12.22%
2o
3) and 8.88% uhligite (CaTiO
3) composition.In combined high temperature refractory materials by mass percentage by 60.02% Al
2o
3, 18.85% SiO
2, the CaO of 18.82%, the TiO of 2.31%
2composition, wherein, the crystalline structure of calcium hexaluminate is sheet regular hexagon, and sheet thickness is 1 μm, and grain-size is 8 μm, and the grain-size of granular corundum is 3 μm ~ 8 μm, and lime feldspar is present between calcium hexaluminate and corundum mainly as Binder Phase.The volume density of this combined high temperature refractory materials is 1.75g/cm
3, reheating linear change rate on reheating is-0.4%, and compressive strength is 145MPa, and refractoriness is 1630 DEG C, and the thermal conductivity of 800 DEG C is 0.37W/m.k.
Example 2
Be prepared into after the high-iron bauxite breeze of 76.51%, the coal dust of 9.72% and the slaked lime of 13.78% are mixed by weight percentage and be of a size of
pelletizing, then sent into by pelletizing in net belt type continuous drying case and dry, bake out temperature is 220 DEG C, and drying time is 4 hours.Sent into by pelletizing in hyperchannel high-temperature electric heat pushed bat kiln after oven dry, carry out molten point of reduction when nitrogen protection, nitrogen flow is 6.0L/min, and the molten point temperature of reduction is 1425 DEG C, and the reduction molten point time is 30min.After molten point of reduction terminates by pelletizing air cooling to room temperature, utilize jaw crusher that cooled pelletizing is crushed to 5mm ~ 10mm, magnetic separation removes large-sized granulated iron, obtains aluminum oxide slag.Again aluminum oxide slag is carried out slight ore grinding, grinding fineness is 40 orders, and further low intensity magnetic separation deironing after ore grinding, low intensity magnetic separation magnetic induction density is 0.15T.Aluminum oxide slag after deironing is by mass percentage by the FeO of 1.63%, the SiO of 21.82%
2, the CaO of 27.28%, the Al of 43.39%
2o
3, the MnO of 2.85%, the TiO of 2.64%
2with 0.39% V
2o
5composition.
By by mass percentage 66% aluminum oxide slag, the white alundum powder of 30% and the carbon black pore-forming material of 4% mix and utilize refractory materials forming machine to prepare combined high temperature refractory materials green compact, wherein, the fineness of aluminum oxide slag is 40 orders, the fineness of white alundum powder is 70 orders, and the fineness of carbon black pore-forming material is 325 orders.Wet base at room temperature seasoning after shaping after 16 hours, then dries 5 hours with the drying kiln of 200 DEG C.Then be sent in hyperthermia tunnel Kiln by the combined high temperature refractory materials green compact of having dried and calcine, calcinating system is: be incubated 3 hours at 900 DEG C, is incubated 4 hours at 1100 DEG C, and 1400 DEG C are incubated 5 hours.After calcining terminates, in stove, the mode of slow cooling is cooled to room temperature, finally obtains combined high temperature refractory materials.
Combined high temperature refractory materials by weight percentage by 29.44% lime feldspar (CaAl
2si
2o
8), the calcium hexaluminate (CaAl of 50.18%
12o
19), the corundum (α-Al of 12.85%
2o
3) and 7.43% uhligite (CaTiO
3) composition.In combined high temperature refractory materials by mass percentage by 60.76% Al
2o
3, 16.49% SiO
2, the CaO of 21.62%, the TiO of 2.13%
2composition, wherein, the crystalline structure of calcium hexaluminate is sheet regular hexagon, and sheet thickness is 1 μm, and grain-size is 9 μm, and the grain-size of granular corundum is 4 ~ 9 μm, and lime feldspar is present between calcium hexaluminate and corundum mainly as Binder Phase.The volume density of this combined high temperature refractory materials is 1.83g/cm
3, reheating linear change rate on reheating is 0.2%, and compressive strength is 168MPa, and refractoriness is 1650 DEG C, and the thermal conductivity of 800 DEG C is 0.41W/m.k.
Example 3
Be prepared into after the high-iron bauxite breeze of 74.39%, the coal dust of 9.45% and the slaked lime of 11.39% are mixed by weight percentage and be of a size of
pelletizing, then sent into by pelletizing in net belt type continuous drying case and dry, bake out temperature is 240 DEG C, and drying time is 3 hours.Sent into by pelletizing in hyperchannel high-temperature electric heat pushed bat kiln after oven dry, carry out molten point of reduction when nitrogen protection, nitrogen flow is 7.0L/min, and the molten point temperature of reduction is 1450 DEG C, and the reduction molten point time is 25min.After molten point of reduction terminates by pelletizing air cooling to room temperature, utilize jaw crusher that cooled pelletizing is crushed to 5mm ~ 10mm, magnetic separation removes large-sized granulated iron, obtains aluminum oxide slag.Again aluminum oxide slag is carried out slight ore grinding, grinding fineness is 60 orders, and further low intensity magnetic separation deironing after ore grinding, low intensity magnetic separation magnetic induction density is 0.14T.Aluminum oxide slag after deironing is by mass percentage by the FeO of 1.55%, the SiO of 20.69%
2, the CaO of 31.05%, the Al of 41.14%
2o
3, the MnO of 2.70%, the TiO of 2.50%
2with 0.37% V
2o
5composition.
By by mass percentage 54% aluminum oxide slag, the white alundum powder of 40% and the carbon black pore-forming material of 6% mix and utilize refractory materials forming machine to prepare combined high temperature refractory materials green compact, wherein, the fineness of aluminum oxide slag is 60 orders, the fineness of white alundum powder is 80 orders, and the fineness of carbon black pore-forming material is 350 orders.Wet base at room temperature seasoning after shaping after 22 hours, then dries 4 hours with the drying kiln of 200 DEG C.Then be sent in hyperthermia tunnel Kiln by the combined high temperature refractory materials green compact of having dried and calcine, calcinating system is: be incubated 3 hours at 900 DEG C, is incubated 4 hours at 1100 DEG C, and 1500 DEG C are incubated 4 hours.After calcining terminates, in stove, the mode of slow cooling is cooled to room temperature, finally obtains combined high temperature refractory materials.
Combined high temperature refractory materials by weight percentage by 30.02% lime feldspar (CaAl
2si
2o
8), the calcium hexaluminate (CaAl of 49.28%
12o
19), the corundum (α-Al of 13.09%
2o
3) and 7.61% uhligite (CaTiO
3) composition.In combined high temperature refractory materials by mass percentage by 62.09% Al
2o
3, 14.67% SiO
2, the CaO of 22.02%, the TiO of 1.22%
2composition, wherein, the crystalline structure of calcium hexaluminate is sheet regular hexagon, and sheet thickness is 1 μm, and grain-size is 10 μm, and the grain-size of granular corundum is 5 ~ 10 μm, and lime feldspar is present between calcium hexaluminate and corundum mainly as Binder Phase.The volume density of this combined high temperature refractory materials is 1.92g/cm
3, reheating linear change rate on reheating is-0.1%, and compressive strength is 190MPa, and refractoriness is 1610 DEG C, and the thermal conductivity of 800 DEG C is 0.45W/m.k.
Can be found out by above-mentioned example 1-3, the aluminum oxide slag of high-iron bauxite after coal-based direct reduction can be utilized to manufacture combined high temperature refractory materials according to the present invention, the combined high temperature refractory materials produced can overcome the problems such as high, the slag corrosion resistance ability of thermal conductivity that current kiln corundum fire brick series exists, life-span be short.
Simultaneously, according to combined high temperature refractory materials of the present invention, by selecting suitable raw material and controlling calcining temperature and time, combined high temperature refractory materials is had, and thermal conductivity is low, good stability under high-temperature reductibility atmosphere, alkali resistant erosional competency and slag corrosion resistance ability is good, intensity is high, the life-span is long, energy-saving efficiency is high feature.
In addition, according to combined high temperature refractory materials manufacture method of the present invention, the aluminum oxide slag obtained after can effectively utilizing high-iron bauxite direct-reduction to melt point, is manufactured combined high temperature refractory materials, can be realized the comprehensive utilization of aluminium in high-iron bauxite.
Although describe some embodiments of the present invention with reference to the accompanying drawings, it should be appreciated by those skilled in the art that when not departing from by the principle of the present invention of claim and its scope of equivalents thereof and spirit, can modify to these embodiments.
Claims (10)
1. a combined high temperature refractory materials, it is characterized in that, described combined high temperature refractory materials is made up of lime feldspar, calcium hexaluminate, corundum and uhligite, and wherein, the chemical composition of described combined high temperature refractory materials is mainly the Al of 61.44% ~ 62.86% by mass percentage
2o
3, 14.85% ~ 19.30% SiO
2with 19.26% ~ 22.29% CaO.
2. combined high temperature refractory materials according to claim 1, it is characterized in that, with the total weight of described combined high temperature refractory materials, described combined high temperature refractory materials by 28.0% ~ 30.02% lime feldspar, the calcium hexaluminate of 49.28% ~ 50.91%, the corundum of 12.22% ~ 13.09% and 7.61% ~ 8.88% uhligite form.
3. combined high temperature refractory materials according to claim 1, is characterized in that, the volume density of described combined high temperature refractory materials is 1.75g/cm
3~ 1.92g/cm
3, reheating linear change rate on reheating is-0.4% ~ 0.2%, and compressive strength is 145MPa ~ 190MPa, and refractoriness is 1600 DEG C ~ 1650 DEG C, and the thermal conductivity 800 DEG C time is 0.37W/mk ~ 0.45W/mk.
4. manufacture a method for combined high temperature refractory materials, it is characterized in that, said method comprising the steps of:
(a) by be the aluminum oxide slag of 48% ~ 76% by mass percentage, the white alundum powder of 20% ~ 50% and 2% ~ 6% carbon black pore-forming material to mix and shaping, obtain combined high temperature refractory materials green compact;
B () carries out drying to combined high temperature refractory materials green compact;
C () calcines dried combined high temperature refractory materials green compact, obtain described combined high temperature refractory materials,
Wherein, aluminum oxide slag is made up of corundum, gehlenite and calcium hexaluminate,
Wherein, described combined high temperature refractory materials is made up of lime feldspar, calcium hexaluminate, corundum and uhligite, and wherein, the chemical composition of described combined high temperature refractory materials is mainly the Al of 61.44% ~ 62.86% by mass percentage
2o
3, 14.85% ~ 19.30% SiO
2with 19.26% ~ 22.29% CaO.
5. method according to claim 4, is characterized in that, described aluminum oxide slag by mass percentage by 20.69% ~ 23.09% SiO
2, the CaO of 23.06% ~ the 31.05% and Al of 41.14% ~ 45.91%
2o
3, 1.55% ~ 1.73% FeO, the MnO of 2.70% ~ 3.01%, the TiO of 2.50% ~ 2.79%
2with 0.37% ~ 0.41% V
2o
5composition,
Wherein, the fineness of aluminum oxide slag is 40 ~ 60 orders, and the fineness of white alundum powder is 60 order ~ 80 orders, and the fineness of carbon black pore-forming material is 300 order ~ 350 orders.
6. the method according to claim 4 or 5, is characterized in that, by carrying out coal-based direct reduction molten point of aluminum oxide slag obtained in described step (a) to high-iron bauxite.
7. method according to claim 6, is characterized in that, carries out molten point of coal-based direct reduction comprise the following steps high-iron bauxite:
By mass percentage by the high-iron bauxite breeze of 74.39% ~ 78.63%, the coal dust of 9.45% ~ 9.98% and 11.39% ~ 16.16% slaked lime mixing after manufacture pelletizing;
Dried by pelletizing, bake out temperature is 200 DEG C ~ 240 DEG C, and drying time is 3 hours ~ 5 hours;
Sent in pushed bat kiln by pelletizing after drying, carry out molten point of reduction when nitrogen protection, nitrogen flow is 5.0L/min ~ 7.0L/min, and the molten point temperature of reduction is 1400 DEG C ~ 1450 DEG C, and the reduction molten point time is 25min ~ 35min;
To the pelletizing deironing after molten point of reduction, obtain the aluminum oxide slag described in step (a).
8. method according to claim 7, is characterized in that, comprises the step of the pelletizing deironing after molten point of reduction:
Pelletizing is crushed to 5mm ~ 10mm, and the granulated iron of magnetic separation removing more than 0.3mm, obtains the first aluminum oxide slag;
By levigate for the first aluminum oxide slag to 40 order ~ 60 orders, carry out low intensity magnetic separation deironing after obtain the aluminum oxide slag described in step (a), wherein, low intensity magnetic separation use magnetic induction density be 0.14T ~ 0.16T.
9. method according to claim 4, is characterized in that, carries out dry step comprise combined high temperature refractory materials green compact:
By green compact seasoning 12 hours ~ 24 hours;
Then green compact are dried in the drying kiln of 50 DEG C ~ 200 DEG C.
10. method according to claim 4, it is characterized in that, 800 DEG C ~ 1000 DEG C calcinings 2 ~ 3 hours are included in the step that combined high temperature refractory materials green compact are calcined, calcine 3 ~ 4 hours for 1100 DEG C ~ 1200 DEG C, then 1400 DEG C ~ 1500 DEG C calcinings 4 hours ~ 6 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107056313A (en) * | 2017-06-30 | 2017-08-18 | 张静芬 | A kind of cement rotary kiln stove castable refractory |
| CN107324838A (en) * | 2017-07-26 | 2017-11-07 | 合肥铭佑高温技术有限公司 | A kind of high-temperature refractory and preparation method thereof |
| CN111410543A (en) * | 2020-04-24 | 2020-07-14 | 朔州西廊煤炭科技有限公司 | Method for preparing functional ceramic engineering material combustion-supporting catalyst by utilizing coal solid waste or bauxite solid waste |
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| CN101928153A (en) * | 2010-09-01 | 2010-12-29 | 中国地质大学（北京） | Calcium hexaluminate and corundum composite porous light heat insulation refractory material and preparation method thereof |
| CN102531555A (en) * | 2012-03-15 | 2012-07-04 | 福州大学 | Calcium hexaaluminate/corundum composite synthesized in situ with aluminium factory sludge and oyster shells |
| CN103420684A (en) * | 2012-07-25 | 2013-12-04 | 田玉明 | Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof |
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| CN101928153A (en) * | 2010-09-01 | 2010-12-29 | 中国地质大学（北京） | Calcium hexaluminate and corundum composite porous light heat insulation refractory material and preparation method thereof |
| CN102531555A (en) * | 2012-03-15 | 2012-07-04 | 福州大学 | Calcium hexaaluminate/corundum composite synthesized in situ with aluminium factory sludge and oyster shells |
| CN103420684A (en) * | 2012-07-25 | 2013-12-04 | 田玉明 | Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056313A (en) * | 2017-06-30 | 2017-08-18 | 张静芬 | A kind of cement rotary kiln stove castable refractory |
| CN107324838A (en) * | 2017-07-26 | 2017-11-07 | 合肥铭佑高温技术有限公司 | A kind of high-temperature refractory and preparation method thereof |
| CN111410543A (en) * | 2020-04-24 | 2020-07-14 | 朔州西廊煤炭科技有限公司 | Method for preparing functional ceramic engineering material combustion-supporting catalyst by utilizing coal solid waste or bauxite solid waste |
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