CN110282971A - A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon - Google Patents

A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon Download PDF

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CN110282971A
CN110282971A CN201910632409.8A CN201910632409A CN110282971A CN 110282971 A CN110282971 A CN 110282971A CN 201910632409 A CN201910632409 A CN 201910632409A CN 110282971 A CN110282971 A CN 110282971A
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carbon
low
zro
zirconium
refractory
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黄军同
胡智辉
李喜宝
闫明格
熊庆明
陈智
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Nanchang Hangkong University
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Nanchang Hangkong University
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Abstract

The invention discloses a kind of zirconium carbon refractories and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon, first prepared nitrate absolute alcohol solution is mixed with phenolic resin, the flakey carbon of 0.1~6wt% is poured into again and is wherein stirred, it pours the mixture into three-roll grinder and carries out differential recirculation gas stripper 1-20 times, it collects to obtain the resin based mixtures of micro-nano graphite flake from discharge roller, resin based mixtures are heated into 5~30min in 40 DEG C~90 DEG C water-baths, by ZrO2Resin based mixtures after particle and heating are put into 3~15min of mixing in kneading machine, are eventually adding ZrO2Fine powder and antioxidant continue 4~15min of mixing and are made pug, ageing mixture 1~for 24 hours, and adobe is then made, and in dry kiln baking-curing at 140~300 DEG C of temperature, baking time is 7~36h, then buried at 1300~1600 DEG C carbon handle 2~12h to get.The zirconium carbon refractory of low-carbon Ultra-low carbon of the present invention can be in holding/raising ZrO2Being greatly lowered for carbon content is realized on the basis of-C refractory material comprehensive performance.

Description

A kind of continuous casting immersion outlet the zirconium carbon refractory of low-carbon Ultra-low carbon and its preparation Method
Technical field
The present invention relates to technical field of refractory materials, and in particular to a kind of zirconium of continuous casting immersion outlet low-carbon Ultra-low carbon Carbon refractory and preparation method thereof.
Background technique
Submersed nozzle is under the molten steel face being immersed in the mouth of a river in crystallizer, as the pipeline of casting, be molten steel therefrom Between packet enter crystallizer channel.It also changes while protecting steel stream, preventing secondary oxidation of steel, promote inclusion floating Become flow regime of the molten steel in crystallizer, meanwhile, and slab quality can be improved, prevent the effects of slag, to raising steel Quality and the production capacity of continuous casting play an important role.Due to the presence of the molten glass layers of steel surface inside mold, this is molten Melt glassy layer and contains CaO, SiO2、Na2O、K2O etc. understands the Al in Eroded submersed nozzle material2O3、SiO2, C, for a long time Operation the corrosion resistance of submersed nozzle material can be had an impact.Therefore, it is contacted in submersed nozzle with molten glass layers Position mostly uses greatly strong ZrO corrosion-resistant to molten glass layers2Material.
Carbon materials have good heat-resisting quantity, chemical stability and heat-resistant knocking stability, especially and molten metal The interfacial tension of iron liquid greatly without it is wetted the features such as, be widely used in the industrial carbon containing refractory of smelting iron and steel, energy Enough significantly improve its slag corrosion resistance and thermal shock resistance.The carbon raw of existing domestic and international Large Steel station-service carbon containing refractory makes With it is most be crystalline flake graphite, traditional carbon containing refractory is since containing higher carbon content, (carbon of general 10-20wt% contains Amount) lead to the serious problems such as inoxidizability is poor, mechanical strength is low.Secondly, high heat conductance caused by high-carbon content will lead to it is huge The generation of heat loss, the cooling of molten steel, the deformation of converter steel sheel, cause the waste of the energy and disturbing for steel casting process Disorderly, thus the carbon content of carbon containing refractory must be decreased to low-level appropriate (carbon graphite of < 5wt%, it is ideal < 3wt%).In general, submersed nozzle improves corrosion resistance by improving zirconia content.On the other hand, oxidation is improved The content of zirconium will lead to ZrO2The thermal expansion coefficient and thermal conductivity of-C material rise, and therefore, zirconia content and graphite are kept to contain The balance of amount is critically important.However, if only simply in existing ZrO2Carbon content is reduced in-C refractory material, can be made Continuous phase or continuity degree decline cannot be formed by obtaining carbon, certainly will lead to ZrO2- C refractory material heat-resistant knocking stability can be invaded with resistance to Lose degradation.Therefore, ZrO is reduced using a kind of suitable method2Its high temperature is kept in-C refractory material while carbon content Stability especially corrosion resistance is to prepare high performance ZrO2The key of-C refractory material.
Summary of the invention
Problem to be solved by this invention is: provide continuous casting immersion outlet low-carbon Ultra-low carbon zirconium carbon refractory and ZrO can be greatly lowered in preparation method2The carbon content and thermal conductivity of-C refractory material, and the carbon containing ZrO of low-carbon can be improved2- C is resistance to The thermal shock resistance and resistance to slag of fiery material are conducive to the hair of the clean steels such as mild steel, ultra-low-carbon steel production and Secondary Refining Technology Exhibition.
The present invention in order to solve the above problem provided by technical solution are as follows: a kind of continuous casting immersion outlet low-carbon Ultra-low carbon Zirconium carbon refractory, component percentage are as follows: ZrO2Gather materials the phenolic resin knot of 85~98.5wt%, 1~7wt% Mixture, the carbon raw of 0.1~6wt%, the nitrate compound of 0~1wt%, 0.1~3.5wt% composite antioxidant； The carbon raw is one or both of crystalline flake graphite, expanded graphite mixture；The nitrate compound is nothing One of water nickel nitrate, anhydrous nitric acid iron, anhydrous nitric acid cobalt are two or more.
Preferably, the ZrO2Gather materials for electric-melting zirconia, zircon, CaO partially stabilized zirconium oxide, the part MgO it is steady Fixed zirconium oxide, Y2O3One kind of partially stabilized zirconium oxide and several, main component ZrO2, wherein ZrO2Content 99wt% or more, ZrO285~98.5wt% of the total ingredient of the Zhan that gathers materials, wherein the 15 of the total ingredient of the Zhan of 5~3mm of granularity~ 25~35wt% of the total ingredient of 25wt%, the Zhan of 3~1mm of granularity, the 15~25wt%, ZrO of the total ingredient of granularity≤1mm Zhan2 15~25wt% of the total ingredient of granularity≤0.074mm of fine powder, Zhan.
Preferably, the antioxidant be one of metal Al powder, Si powder, boride or several, partial size≤ 0.074mm。
Preferably, the boride is B4C or BN or ZrB2Or CaB6。
A kind of preparation method of the zirconium carbon refractory of continuous casting immersion outlet low-carbon Ultra-low carbon, the method includes with Lower step,
(1) nitrate compound of 0~1wt% is first configured to mass percent concentration is 1~30wt% without watery wine Smart solution；
(2) nitrate alcoholic solution prepared in (1) is poured into stir in the phenolic resin binder of 1~7wt% and is mixed 1~20min is closed, then the carbonaceous material of 0.1~6wt% is poured into and is wherein stirred 2~25min of mixing, is formed evenly dispersed Mixture；
(3) mixture in (2) is then added to three-roll grinder from feed roller and carries out the removing of three roller differentials, circulation stripping After 1~20 time, collects to obtain graphite from discharge roller and remove the micro-nano graphite flake to be formed and be dispersed in containing nitrate Mixture in resin；The rotating ratio of three roller rates in three-roll grinder is N3 (feed roller): N2 (breast roll): N1 (discharging Roller) within 1:1.5:3~1:3:9, the gap between each roll shaft is 0.01~0.2mm；
(4) viscosity of the resin based mixtures obtained for collection in reduction (3) is to increase mobility, by it 40 DEG C~90 The heating of 5~30min is carried out in DEG C water-bath；
(5) composite antioxidant of 15~25wt% of powdered zirconium oxide, 0.1~3.5wt% are uniformly mixed, are mixed Fine powder；
(6) by the ZrO of the total 85~98.5wt% of ingredient of Zhan2ZrO in gathering materials2Resin base in particle and (4) after heating is mixed It closes object and is put into mixing 3~15min, the ZrO being eventually adding in (5) in kneading machine (edge runner-wet mill)2Fine powder and compound anti-oxidation dosage form At mixed powder continue 4~15min of mixing pug be made, then ageing mixture 1~for 24 hours；
(7) pug being stranded is added to be pressed in mold using combined type friction press and adobe is made；
(8) molding adobe is placed in baking-curing in tunnel drying oven, 140~300 DEG C of baking temperature, baking time For 5~36h；
(9) adobe being cured is buried at 1300~1600 DEG C and is handled under carbon or other non-oxygen atmospheres, handle 2~12h, Obtain the ultralow carbon refractory of low-carbon of the present invention.
Compared with prior art, the invention has the advantages that the present invention is with ZrO2, carbon raw, antioxidant as starting Raw material, phenolic resin are bonding agent, and nitrate compound is catalyst, and it is good to grind removing acquisition crystallization effect by three roller differentials And large specific surface area, the micro-nano graphite flake that is dispersed in phenolic resin, it is carbon containing to apply it to high-performance low-carbon ZrO2In-C refractory material, production cost can be effectively reduced；Micro-nano graphite flake after removing may be uniformly dispersed in phenol More effective in urea formaldehyde and then in entire refractory material, uniform distribution can give full play to excellent properties of graphite and whole Body carbon content can be greatly reduced；In-situ preparation carbon nanotube and carbon fiber in heat treatment process, can effectively improve ZrO2- Heat-resistant knocking stability, resistance to slag and the resistance to flaking of C refractory material；Therefore, the continuous casting immersion outlet prepared by the present invention With low-carbon Ultra-low carbon ZrO2- C carbon refractory can be greatly lowered and contain on the basis of keeping or improving the comprehensive performance of material The carbon content and thermal conductivity of carbon refractory have significant effect to energy-saving and emission-reduction, and to China's Refining Clean Steel in ASEA-SKF technology and The development of high temperature industry has important impetus and practical application value.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, whereby to the present invention how application technology hand Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon.First by 0~1wt% Nitrate compound be configured to the absolute alcohol solution that mass percent concentration is 1~30wt%, then by prepared nitric acid Salt alcoholic solution pours into and is stirred 1~20min in the phenolic resin of 1~7wt%, then the carbonaceous material of 0.1~6wt% is poured into It is wherein stirred 2~25min of mixing, forms evenly dispersed mixture；The grinding of three rollers is added from feed roller in mixture again Machine carries out three roller differential recirculation gas strippers, after recirculation gas stripper 1~20 time, collects to obtain resin based mixtures from discharge roller, to reduce The viscosity of obtained resin based mixtures is collected to increase mobility, it is carried out to 5~30min's in 40 DEG C~90 DEG C water-baths Heating, is then mixed to get mixing fine powders for the composite antioxidant of 15~25wt% of powdered zirconium oxide, 0.1~3.5wt%.It will The ZrO of the total 85~98.5wt% of ingredient of Zhan2ZrO in gathering materials2It is (wet that resin based mixtures after particle and heating are put into kneading machine Mill) 3~15min of middle mixing, it is eventually adding mixed ZrO2The mixed powder that fine powder and composite antioxidant are formed continues to mix Pug is made in 4~15min of refining, then ageing mixture 1~for 24 hours.The pug being stranded is added in mold and uses combined type friction press It is pressed and adobe is made, and molding adobe is placed in baking-curing in tunnel drying oven, baking temperature 140~ 300 DEG C, baking time is 7~36h, then buries the adobe being cured under carbon or other non-oxygen atmospheres at 1300~1600 DEG C Processing handles 2~6h to get the zirconium carbon refractory of low-carbon Ultra-low carbon of the present invention is arrived.
The ZrO2Gather materials the oxidation partially stabilized for electric-melting zirconia, zircon, CaO partially stabilized zirconium oxide, MgO Zirconium, Y2O3One kind of partially stabilized zirconium oxide and several, main component ZrO2, wherein ZrO2Content 99wt% or more, ZrO285~98.5wt% of the total ingredient of the Zhan that gathers materials, wherein 15~25wt% of the total ingredient of the Zhan of 5~3mm of granularity, granularity 3~ 15~the 25wt%, ZrO of the total ingredient of 25~35wt% of the total ingredient of the Zhan of 1mm, granularity≤1mm Zhan2The granularity of fine powder≤ 15~25wt% of the total ingredient of 0.074mm, Zhan.
The carbon raw is one or two kinds of mixtures of crystalline flake graphite, expanded graphite；Granularity be greater than 0.045mm and Less than 5mm.
The nitrate compound be anhydrous nitric acid nickel, anhydrous nitric acid iron, anhydrous nitric acid cobalt it is one or two kinds of with On.
The antioxidant is metal Al powder, Si powder, boride (B4C or BN or ZrB2Or CaB6) one or several kinds, Partial size≤0.074mm.
The phenolic resin is one of thermoplastic liquid phenolic resin, heat curing type liquid phenolic resin.
The ratio between three roller rates of the three-roll grinder are 1:1.5:3~1:3:9, the gap 0.01 between three rollers~ 0.2mm。
Testing result shows the preparation-obtained low-carbon Ultra-low carbon ZrO of the present embodiment2- C refractory material, carbon content are 5% or so.The low-carbon Ultra-low carbon ZrO of the preparation containing present embodiment2The compressive resistance of-C refractory material, thermal shock resistance are stablized Property, flexural strength and antioxygenic property be improved, at 1600 DEG C and bury and carry out slag corrosion resistance experiment under carbon atmosphere, without obviously invading Erosion or phenomenon of osmosis.Therefore, the low-carbon Ultra-low carbon ZrO of the invention2- C refractory material can keep or improve carbon containing refractory Comprehensive performance on the basis of, the carbon content and thermal conductivity of carbon containing refractory is greatly lowered, has to energy-saving and emission-reduction significant Effect, and to the development of China's Refining Clean Steel in ASEA-SKF technology and high temperature industry have important impetus and practical application value.
Embodiment 1
A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon.First by 6wt%'s Crystalline flake graphite, which pours into the heat curing type liquid phenolic resin of 7wt%, is stirred 10min, then mixture is added three from feed roller Three roller differential recirculation gas strippers of roller mill progress (rotating ratio of three roller rates in three-roll grinder is N3 (feed roller): N2 (in Heart roller): N1 (discharge roller) 1:2:4, gap between feed roller and breast roll are 0.08mm, between breast roll and discharge roller between Gap is 0.02mm, after recirculation gas stripper 15 times, collects to obtain graphite from discharge roller and removes the micro-nano graphite flake to be formed and uniformly divide The mixture being dispersed in resin, and it is carried out to the heating of 25min in 40 DEG C of water-baths to increase its mobility, then by electric smelting The Si powder of Al, 1wt% of powdered zirconium oxide 15wt% (granularity≤0.074mm), 1wt% are mixed to get mixing fine powders.Zhan is total (wherein the 20wt% of the total ingredient of the Zhan of 5~3mm of granularity, the Zhan of 3~1mm of granularity are total for the electric-melting zirconia particle of ingredient 70wt% The 15wt% of the total ingredient of the 35wt% of ingredient, granularity≤1mm Zhan) and heating after resin based mixtures be put into kneading machine mix 10min is refined, the mixed powder that mixed electric-melting zirconia fine powder and composite antioxidant are formed is eventually adding and continues to be kneaded 5min Pug is made, then ageing mixture 8h.The pug being stranded is added in mold, system is pressed using combined type friction press Baking-curing in tunnel drying oven is placed at adobe, and molding adobe, 180 DEG C of baking temperature, baking time 8h, so The adobe being cured is buried to carbon processing at 1350 DEG C afterwards, handles 10h to get the zirconium carbon fire proofed wood of low-carbon of the present invention is arrived Material.
A kind of preparation-obtained continuous casting immersion outlet low-carbon ZrO2The performance of-C carbon refractory product is as follows: body Product density 3.9g/cm3, apparent porosity 15.6%, cold crushing strength 42.8MPa, high temperature break resistant intensity (1400 DEG C of * 3h) 9.4MPa；Scouring experiment, no obvious erosion and phenomenon of osmosis are carried out under the conditions of 1600 DEG C of * 3h bury carbon.
Embodiment 2
A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon.First by 0.2wt% Anhydrous nitric acid nickel be configured to mass percent concentration be 5wt% absolute alcohol solution, prepared nitrate alcohol is molten Liquid, which pours into the thermoplastic liquid phenolic resin of 3wt%, is stirred 10min, then by the expanded graphite of 1wt% pour into wherein into Row is stirred 15min, forms evenly dispersed mixture；Three-roll grinder is added from feed roller in mixture again and carries out three rollers Differential recirculation gas stripper, the rotating ratio of three roller rates in three-roll grinder are N3 (feed roller): N2 (breast roll): N1 (discharge roller) 1:3:8, the gap between feed roller and breast roll are 0.1mm, and the gap between breast roll and discharge roller is 0.01mm, circulation stripping After 10 times, collects to obtain graphite from discharge roller and remove the mixing that the micro-nano graphite flake to be formed is dispersed in resin Object, and it is carried out to the heating of 20min in 60 DEG C of water-baths to increase its mobility, the then zirconium oxide that MgO is partially stabilized The Si powder of fine powder 25.4wt% (granularity≤0.074mm) and 0.4wt% is mixed to get mixing fine powders.By the total ingredient 70wt%'s of Zhan MgO partially stabilized zirconia particles be (the total ingredient of the wherein total ingredient 16wt% of the Zhan of 5~3mm of granularity, the Zhan of 3~1mm of granularity The 24wt% of the total ingredient of 30wt%, granularity≤1mm Zhan) and heating after resin based mixtures be put into kneading machine (edge runner-wet mill) It is kneaded 5min, is eventually adding mixed ZrO2The mixed powder that fine powder and composite antioxidant are formed continues mixing 15min and is made Pug, then ageing mixture is for 24 hours.The pug being stranded is added to be pressed in mold using combined type friction press, brick is made Base, and molding adobe is placed in baking-curing in tunnel drying oven, 200 DEG C of baking temperature, baking time 30h, then By the adobe being cured, argon atmosphere is handled at 1400 DEG C, and it is resistance to get the zirconium carbon to Ultra-low carbon of the present invention to handle 6h Fiery material.
A kind of preparation-obtained continuous casting immersion outlet Ultra-low carbon ZrO2The performance of-C carbon refractory product is as follows: Bulk density 4.1g/cm3, apparent porosity 16.8%, cold crushing strength 45.2MPa, high temperature break resistant intensity (1400 DEG C of * 3h) 10.3MPa；Scouring experiment, no obvious erosion and phenomenon of osmosis are carried out under the conditions of 1600 DEG C of * 3h bury carbon.
Embodiment 3
A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon.First by 0.1wt% Anhydrous nitric acid iron and 0.1wt% anhydrous nitric acid cobalt be configured to mass percent concentration be 10wt% absolute alcohol solution, Prepared nitrate alcoholic solution is poured into the thermoplastic liquid phenolic resin of 5.8wt% and be stirred 12min, then will The expanded graphite of 4wt%, which pours into, is wherein stirred mixing 18min, forms evenly dispersed mixture；Again by mixture from into Expect that roller is added three-roll grinder and carries out three roller differential recirculation gas strippers, the rotating ratio of three roller rates in three-roll grinder be N3 (into Expect roller): N2 (breast roll): N1 (discharge roller) 1:3:9, gap between feed roller and breast roll are 0.06mm, breast roll with go out Expect that the gap between roller is 0.02mm, after recirculation gas stripper 20 times, collects to obtain graphite from discharge roller and remove the micro-nano stone to be formed Black thin slice is dispersed in the mixture in resin, and it is carried out the heating of 10min in 80 DEG C of water-baths to increase its flowing Property, then by the antioxidant of powdered zirconium oxide 20wt% (granularity≤0.074mm) and 1wt% (0.25wt%Al powder, 0.5wt%Si powder and 0.25wt%B4C powder) it is mixed to get mixing fine powders.By the partially stabilized oxygen of the CaO of the total ingredient 70wt% of Zhan Change zirconium particle (28wt% of the total ingredient of the wherein total ingredient 22wt% of the Zhan of 5~3mm of granularity, the Zhan of 3~1mm of granularity, granularity≤ The 20wt% of the total ingredient of the Zhan of 1mm) and heating after resin based mixtures be put into kneading machine (edge runner-wet mill) and be kneaded 8min, finally Mixed ZrO is added2The mixed powder that fine powder and composite antioxidant are formed continues mixing 12min and pug is made, then ageing mixture 18h.The pug being stranded is added to be pressed in mold using combined type friction press, adobe is made, and molding Adobe is placed in baking-curing in tunnel drying oven, and 300 DEG C of baking temperature, baking time 12h, the adobe that then will be cured Carbon processing is buried at 1600 DEG C, handles 4h to get the zirconium carbon refractory of low-carbon of the present invention is arrived.
A kind of preparation-obtained continuous casting immersion outlet low-carbon ZrO2The performance of-C carbon refractory product is as follows: body Product density 3.7g/cm3, apparent porosity 14.7%, cold crushing strength 38.6MPa, high temperature break resistant intensity (1400 DEG C of * 3h) 7.9MPa；Scouring experiment, no obvious erosion and phenomenon of osmosis are carried out under the conditions of 1600 DEG C of * 3h bury carbon.
Only highly preferred embodiment of the present invention is described above, but is not to be construed as limiting the scope of the invention.This Invention is not only limited to above embodiments, and specific structure is allowed to vary.All protection models in independent claims of the present invention Interior made various change is enclosed to all fall in the scope of protection of the present invention.

Claims (5)

1. a kind of zirconium carbon refractory of continuous casting immersion outlet low-carbon Ultra-low carbon, it is characterised in that: component percentage by weight Number is calculated as: ZrO2Gather materials 85~98.5wt%, the phenolic resin binder of 1~7wt%, the carbon raw of 0.1~6wt%, 0~ The composite antioxidant of the nitrate compound of 1wt%, 0.1~3.5wt%；The carbon raw is crystalline flake graphite, expansion One or both of graphite mixture；The nitrate compound is anhydrous nitric acid nickel, anhydrous nitric acid iron, anhydrous nitric acid cobalt One of or it is two or more.
2. a kind of zirconium carbon carbon refractory of continuous casting immersion outlet according to claim 1 low-carbon Ultra-low carbon, special Sign is: the ZrO2Gather materials the oxidation partially stabilized for electric-melting zirconia, zircon, CaO partially stabilized zirconium oxide, MgO Zirconium, Y2O3One kind of partially stabilized zirconium oxide and several, main component ZrO2, wherein ZrO2Content 99wt% or more, ZrO285~98.5wt% of the total ingredient of the Zhan that gathers materials, wherein 15~25wt% of the total ingredient of the Zhan of 5~3mm of granularity, granularity 3~ 15~the 25wt%, ZrO of the total ingredient of 25~35wt% of the total ingredient of the Zhan of 1mm, granularity≤1mm Zhan2The granularity of fine powder≤ 15~25wt% of the total ingredient of 0.074mm, Zhan.
3. a kind of zirconium carbon refractory of continuous casting immersion outlet low-carbon Ultra-low carbon according to claim 1, feature Be: the antioxidant is one of metal Al powder, Si powder, boride or several, partial size≤0.074mm.
4. a kind of zirconium carbon refractory of continuous casting immersion outlet low-carbon Ultra-low carbon according to claim 3, feature Be: the boride is B4C or BN or ZrB2Or CaB6。
5. a kind of preparation side of the zirconium carbon refractory of continuous casting immersion outlet low-carbon Ultra-low carbon as described in claim 1 Method, it is characterised in that: it the described method comprises the following steps,
(1) first by the nitrate compound of 0~1wt% be configured to mass percent concentration be 1~30wt% absolute alcohol it is molten Liquid；
(2) nitrate alcoholic solution prepared in (1) is poured into the phenolic resin binder of 1~7wt% and is stirred 1~ 20min, then the carbonaceous material of 0.1~6wt% is poured into and is wherein stirred 2~25min of mixing, form evenly dispersed mixing Object；
(3) mixture in (2) is then added to three-roll grinder from feed roller and carries out the removing of three roller differentials, recirculation gas stripper 1 After~20 times, collects to obtain graphite from discharge roller and remove the micro-nano graphite flake to be formed and be dispersed in the resin containing nitrate In mixture；The rotating ratio of three roller rates in three-roll grinder is N3 (feed roller): N2 (breast roll): N1 (discharge roller) exists Within 1:1.5:3~1:3:9, the gap between each roll shaft is 0.01~0.2mm；
(4) viscosity of the resin based mixtures obtained for collection in reduction (3) is to increase mobility, by it in 40 DEG C~90 DEG C water The heating of 5~30min is carried out in bath；
(5) composite antioxidant of 15~25wt% of powdered zirconium oxide, 0.1~3.5wt% are uniformly mixed, it is thin obtains mixing Powder；
(6) by the ZrO of the total 85~98.5wt% of ingredient of Zhan2ZrO in gathering materials2Resin based mixtures in particle and (4) after heating It is put into kneading machine (edge runner-wet mill) and is kneaded 3~15min, the ZrO being eventually adding in (5)2What fine powder and composite antioxidant were formed Mixed powder continues 4~15min of mixing and pug is made, then ageing mixture 1~for 24 hours；
(7) pug being stranded is added to be pressed in mold using combined type friction press and adobe is made；
(8) molding adobe is placed in baking-curing in tunnel drying oven, 140~300 DEG C of baking temperature, baking time 5 ~36h；
(9) adobe being cured is buried at 1300~1600 DEG C and is handled under carbon or other non-oxygen atmospheres, handle 2~12h to get To the ultralow carbon refractory of low-carbon of the present invention.
CN201910632409.8A 2019-07-13 2019-07-13 A kind of zirconium carbon refractory and preparation method thereof of continuous casting immersion outlet low-carbon Ultra-low carbon Pending CN110282971A (en)

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