CN105272315B - A kind of porous zirconium calcium aluminate and preparation method thereof - Google Patents
A kind of porous zirconium calcium aluminate and preparation method thereof Download PDFInfo
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- CN105272315B CN105272315B CN201510783878.1A CN201510783878A CN105272315B CN 105272315 B CN105272315 B CN 105272315B CN 201510783878 A CN201510783878 A CN 201510783878A CN 105272315 B CN105272315 B CN 105272315B
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Abstract
The present invention relates to a kind of porous zirconium calcium aluminate and preparation method thereof.Its technical scheme is：Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio carry out dispensing for 7 ︰, 3 ︰ 1, be put in ball mill with water as medium wet grinding 1 ~ 10 hour, slurry be filtered dry, be dried, obtain final product mixture block.Mixture block is milled to into the powder body that granularity is 1 ~ 100 μm again, then addition accounts for the water of the 1 ~ 10wt% of powder body in powder body, is mixed, be pressed into base, stand 24 hours.Then will insert in high temperature furnace and be incubated 2 ~ 8 hours under the conditions of 1000 ~ 1800 DEG C in 110 DEG C of dryings 24 hours, cooling is crushed or is finely ground to desired particle size, obtains final product porous zirconium calcium aluminate.Present invention process is simple, the porous zirconium calcium aluminate of preparation has gelling property, as the bonding agent and raw material that prepare high-temperature ceramicss and refractory material, energy consumption when product drying or heat treatment can be significantly reduced, moreover it is possible to improve the thermal shock resistance energy and elevated temperature strength of refractory material.
Description
Technical field
The invention belongs to high-temperature ceramicss and technical field of refractory materials.More particularly to a kind of porous zirconium calcium aluminate and its preparation
Method.
Background technology
Pouring fireproof material is most common and a large amount of unshape refractories for using.It is by aggregate, fine powder and bonding agent
The compound for not having adhesion of composition.Generally formed with casting and constructing after siccative delivery, with water or other liquid mixing.Aluminic acid
Calcium cement is current most popular castable bonding agent, and it is calcined as raw material Jing with aluminium oxide or Alumina with Calcium Carbonate
Or electric smelting and be obtained, also useful high red bauxite and limestone are that raw material Jing meltings are obtained high ferro aluminous cement, also useful oxidation
Aluminum or Alumina are obtained aluminous cement containing magnesium aluminate spinel for raw material with dolomite.
The pouring fireproof material that cement is combined can be divided into ordinary cement castable, Low Cement Castable by the addition of cement
With ultra-low cement deposit material.Cement is most widely used castable bonding agent, compared with other bonding agent, its advantage it
One can be the short time（6~24h）Interior acquisition high intensity.But in castable refractory cement have the shortcomings that can bring in terms of three：
If 1. cement amount is big, the required water yield is also big, the high energy consumption after product drying or heat treatment.
2. hydras amount present in castable is big, the middle temperature of Jing（538～982 DEG C）After process, as hydras are dehydrated,
Intensity declines big.
3. the calcium oxide that cement is brought into is more, affects the high-temperature behavior of material.
Disadvantage mentioned above has significantly impacted consumption of the cement in refractory material, especially makes under high temperature severe rugged environment
The existing trend replaced by other bonding agent of cement in refractory material, such as hydrated alumina, aluminum Ludox etc..
The content of the invention
It is contemplated that overcoming the defect of prior art, it is therefore an objective to provide a kind of system of the porous zirconium calcium aluminate of process is simple
Preparation Method, the porous zirconium calcium aluminate material prepared with the method have gelling property, used as preparing high-temperature ceramicss and refractory material
Bonding agent and raw material, the addition of water can not only be significantly reduced during use, moreover it is possible to improve the thermal shock resistance of refractory material
Energy and elevated temperature strength.
For achieving the above object, the technical solution used in the present invention is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio matched somebody with somebody for 7 ︰, 3 ︰ 1
Material, places in ball mill with water as medium wet grinding 1 ~ 10 hour, is then filtered dry slurry, is dried 24 little under the conditions of 110 DEG C
When, obtain final product mixture block.
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for described
The water of 1 ~ 10wt% of powder body, mixes, is pressed into base, stands 24 hours naturally.
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace in 1000 ~ 1800 DEG C of conditions
Lower insulation 2 ~ 8 hours, cooling are crushed or are finely ground into desired particle size, obtain final product porous zirconium calcium aluminate.
The CaCO of the limestone3Content >=93wt%, granularity be 1 ~ 500 μm.
The Al (OH) of the aluminium hydroxide3Content >=98wt%, granularity are 1 ~ 500 μm.
The Zr (OH) of the zirconium hydroxide4Content >=98wt%, granularity are 1 ~ 500 μm.
Ball-milling medium in the ball mill is tungsten-carbide ball.
There is following good effect compared with prior art due to adopting above-mentioned technical proposal, the present invention：
The present invention makes three kinds of raw material mix homogeneously by carrying out wet grinding to limestone, aluminium hydroxide and zirconium hydroxide,
In high temperature sintering process, due to raw material decomposition and leave pore in the original location so that the product of generation be zirconium calcium aluminate be porous
Structure, preparation process is simple.Obtained porous zirconium calcium aluminate：The porosity >=20wt%；Zirconium aluminic acid calcium content >=90wt%.
Porous zirconium calcium aluminate prepared by the present invention is when using as pouring material binding agent, due to its surface area it is larger, it is active
Height, the speed for participating in hydration reaction and being transformed into gel are significantly improved, and so as to the water consumption for substantially reducing castable, product is done
Energy consumption during dry or heat treatment is low, and medium temperature intensity decline degree is little.
When porous zirconium calcium aluminate prepared by the present invention is as Binder Materials bonding agent, the generation of calcium zirconate under high temperature can be improved
The elevated temperature strength of castable（The fusing point of calcium zirconate is more than 2200 DEG C）.Meanwhile, using zirconium calcium aluminate castable at high temperature
Have corundum phase（Al2O3）Generate, the high-temperature behavior to improving material is also beneficial.When castable is tied using zirconium calcium aluminate
During mixture, wherein zirconic presence can improve the toughness of material, and then the thermal shock resistance energy of material is improved.
Therefore, present invention process is simple, and prepared porous zirconium calcium aluminate material has gelling property, crushes or is finely ground into
Desired particle size, is the high-quality raw material for preparing high-temperature ceramicss and refractory material.Compared with aluminate cement, in the bar of same amount
The addition of water can be significantly reduced under part, energy consumption when product drying or heat treatment can be substantially reduced；The use of zirconium calcium aluminate is also
The thermal shock resistance energy and elevated temperature strength of refractory material casting material can be improved.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, not the restriction to its protection domain.
To avoid repeating, first will be the technical parameter Unify legislation involved by this specific embodiment as follows, in embodiment not
Repeat again：
The CaCO of the limestone3Content >=93wt%, granularity be 1 ~ 500 μm.
The Al (OH) of the aluminium hydroxide3Content >=98wt%, granularity are 1 ~ 500 μm.
The Zr (OH) of the zirconium hydroxide4Content >=98wt%, granularity are 1 ~ 500 μm.
Ball-milling medium in the ball mill is tungsten-carbide ball.
Embodiment 1
A kind of porous zirconium calcium aluminate and preparation method thereof.The preparation method of the present embodiment is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio matched somebody with somebody for 7 ︰, 3 ︰ 1
Material, places in ball mill with water as medium wet grinding 1 ~ 3 hour, is then filtered dry slurry, is dried 24 little under the conditions of 110 DEG C
When, obtain final product mixture block.
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for described
The water of 1 ~ 3wt% of powder body, mixes, is pressed into base, stands 24 hours naturally.
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace in 1000 ~ 1200 DEG C of conditions
Lower insulation 5 ~ 8 hours, cooling are crushed or are finely ground into desired particle size, obtain final product porous zirconium calcium aluminate.
Porous zirconium calcium aluminate manufactured in the present embodiment：The porosity >=20wt%；Zirconium aluminic acid calcium content >=90wt%.
Embodiment 2
A kind of porous zirconium calcium aluminate and preparation method thereof.The preparation method of the present embodiment is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio matched somebody with somebody for 7 ︰, 3 ︰ 1
Material, places in ball mill with water as medium wet grinding 3 ~ 5 hours, is then filtered dry slurry, is dried 24 little under the conditions of 110 DEG C
When, obtain final product mixture block.
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for described
The water of 3 ~ 5wt% of powder body, mixes, is pressed into base, stands 24 hours naturally.
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace in 1200 ~ 1400 DEG C of conditions
Lower insulation 4 ~ 7 hours, cooling are crushed or are finely ground into desired particle size, obtain final product porous zirconium calcium aluminate.
Porous zirconium calcium aluminate manufactured in the present embodiment：The porosity >=20wt%；Zirconium aluminic acid calcium content >=90wt%.
Embodiment 4
A kind of porous zirconium calcium aluminate and preparation method thereof.The preparation method of the present embodiment is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio matched somebody with somebody for 7 ︰, 3 ︰ 1
Material, places in ball mill with water as medium wet grinding 5 ~ 8 hours, is then filtered dry slurry, is dried 24 little under the conditions of 110 DEG C
When, obtain final product mixture block.
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for described
The water of 5 ~ 8wt% of powder body, mixes, is pressed into base, stands 24 hours naturally.
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace in 1400 ~ 1600 DEG C of conditions
Lower insulation 3 ~ 6 hours, cooling are crushed or are finely ground into desired particle size, obtain final product porous zirconium calcium aluminate.
Porous zirconium calcium aluminate manufactured in the present embodiment：The porosity >=20wt%；Zirconium aluminic acid calcium content >=90wt%.
Embodiment 4
A kind of porous zirconium calcium aluminate and preparation method thereof.The preparation method of the present embodiment is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio matched somebody with somebody for 7 ︰, 3 ︰ 1
Material, places in ball mill with water as medium wet grinding 8 ~ 10 hours, is then filtered dry slurry, is dried 24 little under the conditions of 110 DEG C
When, obtain final product mixture block.
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for described
The water of 8 ~ 10wt% of powder body, mixes, is pressed into base, stands 24 hours naturally.
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace in 1600 ~ 1800 DEG C of conditions
Lower insulation 2 ~ 5 hours, cooling are crushed or are finely ground into desired particle size, obtain final product porous zirconium calcium aluminate.
Porous zirconium calcium aluminate manufactured in the present embodiment：The porosity >=20wt%；Zirconium aluminic acid calcium content >=90wt%.
This specific embodiment has following good effect compared with prior art：
This specific embodiment mixes three kinds of raw materials by carrying out wet grinding to limestone, aluminium hydroxide and zirconium hydroxide
Close uniform, in high temperature sintering process, due to raw material decomposition and leave pore in the original location so that the product of generation is zirconium aluminic acid
Calcium is loose structure, preparation process is simple.Obtained porous zirconium calcium aluminate：The porosity >=20wt%；Zirconium aluminic acid calcium content >=
90wt%。
Porous zirconium calcium aluminate prepared by this specific embodiment is when using as pouring material binding agent, due to its surface area compared with
Greatly, activity is high, and the speed for participating in hydration reaction and being transformed into gel is significantly improved, and uses water so as to substantially reduce castable
Amount, energy consumption when product drying or heat treatment are low, and medium temperature intensity decline degree is little.
When porous zirconium calcium aluminate prepared by this specific embodiment is as Binder Materials bonding agent, the life of calcium zirconate under high temperature
Into the elevated temperature strength that can improve castable（The fusing point of calcium zirconate is more than 2200 DEG C）.Meanwhile, using the castable of zirconium calcium aluminate
Corundum phase is had at high temperature（Al2O3）Generate, the high-temperature behavior to improving material is also beneficial.When castable adopts zirconium aluminum
When sour calcium makees bonding agent, wherein zirconic presence can improve the toughness of material, and then the thermal shock resistance energy of material is improved.
Therefore, this specific embodiment process is simple, prepared porous zirconium calcium aluminate material have gelling property, crush
Or desired particle size is finely ground into, it is the high-quality raw material for preparing high-temperature ceramicss and refractory material.Compared with aluminate cement, identical
The addition of water can be significantly reduced under conditions of consumption, energy consumption when product drying or heat treatment can be substantially reduced；Zirconium calcium aluminate
Use can also improve the thermal shock resistance energy and elevated temperature strength of refractory material casting material.
Claims (6)
1. a kind of preparation method of porous zirconium calcium aluminate, it is characterised in that the preparation method is：
1）Limestone, aluminium hydroxide and zirconium hydroxide are pressed into CaO ︰ Al first2O3︰ ZrO2Mol ratio carry out dispensing for 7 ︰, 3 ︰ 1, then
It is put in ball mill with water as medium wet grinding 1 ~ 10 hour, then slurry is filtered dry, be dried 24 hours under the conditions of 110 DEG C, i.e.,
Obtain mixture block；
2）The mixture block is milled to into the powder body that granularity is 1 ~ 100 μm, is then added in the powder body and is accounted for the powder body 1
The water of ~ 10wt%, mixes, is pressed into base, stands 24 hours naturally；
3）Base substrate after standing is dried 24 hours under the conditions of 110 DEG C, is inserted in high temperature furnace and is protected under the conditions of 1000 ~ 1800 DEG C
Temperature 2 ~ 8 hours, cooling are crushed or fine grinding, obtain final product porous zirconium calcium aluminate.
2. the preparation method of porous zirconium calcium aluminate according to claim 1, it is characterised in that the CaCO of the limestone3Contain
Amount >=93wt%, granularity are 1 ~ 500 μm.
3. the preparation method of porous zirconium calcium aluminate according to claim 1, it is characterised in that the Al (OH) of the aluminium hydroxide3
Content >=98wt%, granularity are 1 ~ 500 μm.
4. the preparation method of porous zirconium calcium aluminate according to claim 1, it is characterised in that the Zr (OH) of the zirconium hydroxide4
Content >=98wt%, granularity are 1 ~ 500 μm.
5. the preparation method of porous zirconium calcium aluminate according to claim 1, it is characterised in that the ball milling in the ball mill is situated between
Matter is tungsten-carbide ball.
6. a kind of porous zirconium calcium aluminate, it is characterised in that the porous zirconium calcium aluminate is according to any one of claim 1 ~ 5
Porous zirconium calcium aluminate prepared by the preparation method of described porous zirconium calcium aluminate.
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| CN109851260B (en) * | 2019-01-18 | 2021-09-03 | 武汉科技大学 | Calcium aluminate cement containing carbon and preparation method thereof |
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| CN101665367A (en) * | 2009-10-20 | 2010-03-10 | 瑞泰科技股份有限公司 | Thermal shock resistant corundum-magnesium aluminum spinel pouring material |
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