CN109293347A - A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof - Google Patents

A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof Download PDF

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Publication number
CN109293347A
CN109293347A CN201811190796.6A CN201811190796A CN109293347A CN 109293347 A CN109293347 A CN 109293347A CN 201811190796 A CN201811190796 A CN 201811190796A CN 109293347 A CN109293347 A CN 109293347A
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stemming
tapping hole
hot furnace
mineral hot
environmentally protective
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CN109293347B (en
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潘家和
李亚伟
徐义彪
张志韧
桑绍柏
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Hunan Lida High-New Material Co Ltd
Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Hunan Lida High-New Material Co Ltd
Wuhan University of Science and Engineering WUSE
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Abstract

Present invention relates particularly to a kind of mineral hot furnace tapping hole environmentally protective stemmings and preparation method thereof.Its technical solution is: in elder generation with the alumina of 45~65wt%, the kyanite of 5~15wt%, the quartzy fine powder of 5~15wt%, the andalusite fine powder of 1~3wt%, the alumina powder of 10~30wt%, the montmorillonite micro mist of 0.5~2wt%, the simple substance silica fine powder of 1~2wt%, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the ZrOCl of the polypropylene fibre of the additional 0.05~0.1wt% of raw material, the retarder of 0.05~0.3wt%, 0.5~2wt%2·8H2The aluminium dihydrogen phosphate aqueous solution of O and 8~20wt%, it is wet to grind 15~30 minutes, then mud molding is squeezed to get the environmentally protective stemming of mineral hot furnace tapping hole through mud extruder.The present invention is low in cost and environmental-friendly, and the environmentally protective stemming of prepared mineral hot furnace tapping hole has the characteristics that intensity is high, volume stability is good, flushing resistance is excellent, erosion-resisting characteristics is excellent and can repair tapping hole.

Description

A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof
Technical field
The invention belongs to mineral hot furnace tapping hole technical field of refractory materials.More particularly to a kind of mineral hot furnace tapping hole with green Colour circle protects stemming and preparation method thereof.
Background technique
Mineral hot furnace is a kind of energy using electric arc to produce the electricity of the ferroalloys such as ferrosilicon, manganese iron, ferrochrome and dilval Furnace.Smelting process is continuous charging, and the intermittent ferroalloy that will melt is released from tapping hole.Block the refractory material of mineral hot furnace tapping hole Should have following performance for stemming to meet requirement: (1) plasticity and caking property are good, are easy to get into and fill up Tie Kou Channel；(2) the suitable porosity and pore-size distribution, discharge moisture and gas when being easy to use；(3) high volume stability is good, It can avoid cracking；(4) sintering character is good, intensity is high, resistance to erosion and resistant to corrosion；(5) be open functional, tapping machine drill mouth It is easy；(6) environmental pollution is small；(7) tapping hole can be repaired, effectively prevent reaming.
Differentiation of the mineral hot furnace with stemming Technology origin in Anhydrous stemming for blast furnace is imitated, but the working environment of blast furnace and mineral hot furnace Differ larger, therefore Anhydrous stemming for blast furnace is not suitable for directly using in mineral hot furnace.In recent years, both at home and abroad to mineral hot furnace stemming Formula and performance carried out a certain amount of research work, have developed stemming containing chromium oxide, but current mineral hot furnace big gun containing chromium Still generally existing environmental pollution is big, intensity is lower, volume stability is poor, resistance to erosion erosion performance is poor for mud, can not Efficient software patching The problems such as tapping hole.Since the tapping hole of mineral hot furnace repeated multiple times will be opened and fill daily, if stemming quality exists The above problem, red-hot molten iron and slag liquid, which can generate tapping hole stemming, wash away and corrosion function, and tapping hole is just in use process It will appear reaming, iron mouth caused to shoal, flowing molten iron is unstable, out not clean iron, seriously affects normal production, and finally influence mineral hot furnace Service life and smelt yield.In addition, the use of the stemming containing chromium oxide to humans and animals it is healthy and safe also constitute it is larger It threatens.
Summary of the invention
The present invention is directed to overcome prior art defect, and it is an object of the present invention to provide a kind of mineral hot furnace low in cost and environmental-friendly The preparation method of the environmentally protective stemming of tapping hole, the environmentally protective stemming intensity of mineral hot furnace tapping hole prepared with this method Height, volume stability is good, flushing resistance is excellent, erosion-resisting characteristics is excellent and can repair tapping hole.
To achieve the above object, the technical solution adopted by the present invention is that: first alumina, 5~15wt% with 45~65wt% Kyanite, the quartzy fine powder of 5~15wt%, the andalusite fine powder of 1~3wt%, the alumina powder of 10~30wt%, 0.5 The montmorillonite micro mist of~2wt%, the simple substance silica fine powder of 1~2wt%, the amorphous graphite micro mist of 0.5~1wt% and 1~2wt% Ti3SiC2Fine powder is raw material, then the slow setting of the polypropylene fibre of the additional 0.05~0.1wt% of raw material, 0.05~0.3wt% Agent, 0.5~2wt% ZrOCl2·8H2The aluminium dihydrogen phosphate aqueous solution of O and 8~20wt%, it is wet to grind 15~30 minutes, then pass through Mud extruder squeezes mud molding to get the environmentally protective stemming of mineral hot furnace tapping hole.
The grain composition of the alumina is: partial size is that 5~3mm accounts for the 15~30wt% of alumina, and partial size is less than 3mm and big 15~the 30wt% of alumina is accounted in being equal to 1mm, partial size, which is less than 1mm and is more than or equal to 0.1mm, accounts for the 50~60wt% of alumina.
The grain composition of the kyanite is: partial size is that 3~1mm accounts for the 50~60wt% of kyanite, and partial size is less than 1mm And be more than or equal to 0.5mm and account for the 15~30wt% of kyanite, partial size, which is less than 0.5mm and is more than or equal to 0.1mm, accounts for the aquamaine 15~30wt% of stone.
The C content ﹥ 80wt% of the amorphous graphite micro mist；5 μm of the partial size ﹤ of the amorphous graphite micro mist.
The length of the polypropylene fibre is 2~4mm, and the diameter of polypropylene fibre is 10~20 μm.
The retarder is one or more of sodium tripolyphosphate, calgon and citric acid.
The density of the aluminium dihydrogen phosphate aqueous solution is 1.48~1.58g/cm3。
Due to the adoption of the above technical scheme, the present invention has following good effect compared with prior art:
Mineral hot furnace tapping hole prepared by the present invention is Trend of Chrome-free refractory material with environmentally protective stemming (hereinafter referred to as stemming), It is free from environmental pollution, potential threat not will cause to the health of humans and animals, it is environmentally protective.
The primary raw material of stemming prepared by the present invention is alumina, and raw material is not necessarily to add price height compared with horn of plenty and cheaply High chromium oxide fine powder, therefore low production cost.The retarder that the present invention uses has good moistening effect, and is added to illiteracy De- stone micro mist, making stemming, service performance and operating characteristics do not decline in the long-term storage process.The present invention uses aluminium dihydrogen phosphate Solution is bonding agent, in addition ZrOCl2·8H2O and water act on, and impart the higher early strength of stemming.Simple substance in the present invention Silicon reacts at high temperature with amorphous graphite micro mist can be formed in situ erosion resistant SiC whisker, reinforcement material matrix and aggregate In conjunction with so that stemming has high intensity, resistance to erosion and erosion-resisting characteristics excellent.
Ti is also added into stemming prepared by the present invention3SiC2Fine powder, Ti in use process3SiC2Aoxidize the TiO formed2And SiO2The biggish electrodeposition substance of viscosity can be formed with other oxides in Tie Kouchu, self dimension can be carried out to the tapping hole to become larger Shield and reparation, prevent reaming, can effectively improve the service life of mineral hot furnace.
Under the high temperature conditions, the kyanite in the present invention can be converted into mullite and quartzy phase, alumina powder meeting and stone English reaction generates mullite, effectively facilitates solid phase reaction and sintering process, while mullite is formed and quartz crystal conversion causes Expansion can effectively improve sample compactness, make prepared stemming intensity with higher.
In use, the polypropylene fibre in the present invention, which is melted in stemming, forms small network stomata, opens water Gas channel mitigates internal stress, prevents from bursting；Andalusite will be slow mullitization under high temperature simultaneously, offset the receipts that sintering generates Contracting, ZrOCl2·8H2O is decomposed into zirconium oxide and is uniformly distributed in material internal, improves stemming overall volume stability and thermal shock resistance Energy.The micro crystal graphite micro mist being added in stemming is nonwetting with molten iron, and erosion-resisting characteristics is excellent.
Mineral hot furnace tapping hole prepared by the present invention is with environmentally protective stemming through detecting: 200 DEG C × for 24 hours bulk density be 2.87~2.97g/cm3, 1400 DEG C × 4h bulk density is 2.82~2.92g/cm3；200 DEG C × for 24 hours flexural strength be 14~ 20Mpa, 1400 DEG C × 4h flexural strength are 16~22Mpa；Be highly resistant to molten iron to stemming wash away and to corrode 18~24 small When.
Therefore, the present invention is low in cost and environmental-friendly, and prepared mineral hot furnace tapping hole has with environmentally protective stemming The characteristics of intensity is high, volume stability is good, flushing resistance is excellent, erosion-resisting characteristics is excellent and can repair tapping hole.
Specific embodiment
The invention will be further described With reference to embodiment, not to the limitation of its protection scope:
It is first that material Unify legislation involved in present embodiment is as follows to avoid repeating, in specific embodiment not It repeats again:
The grain composition of the alumina is: partial size is that 5~3mm accounts for the 15~30wt% of alumina, and partial size is less than 3mm and big 15~the 30wt% of alumina is accounted in being equal to 1mm, partial size, which is less than 1mm and is more than or equal to 0.1mm, accounts for the 50~60wt% of alumina.
The grain composition of the kyanite is: partial size is that 3~1mm accounts for the 50~60wt% of kyanite, and partial size is less than 1mm And be more than or equal to 0.5mm and account for the 15~30wt% of kyanite, partial size, which is less than 0.5mm and is more than or equal to 0.1mm, accounts for the aquamaine 15~30wt% of stone.
The C content ﹥ 80wt% of the amorphous graphite micro mist；5 μm of the partial size ﹤ of the amorphous graphite micro mist.
The length of the polypropylene fibre is 2~4mm, and the diameter of polypropylene fibre is 10~20 μm.
The retarder is one or more of sodium tripolyphosphate, calgon and citric acid.
The density of the aluminium dihydrogen phosphate aqueous solution is 1.48~1.58g/cm3。
Embodiment 1
A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof.Preparation method described in the present embodiment is:
First with the alumina of 45~55wt%, the kyanite of 5~10wt%, 10~15wt% quartzy fine powder, 1~3wt% Andalusite fine powder, the alumina powder of 20~30wt%, the montmorillonite micro mist of 0.5~2wt%, the elemental silicon of 1~2wt% it is thin Powder, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional raw material 0.05~ The polypropylene fibre of 0.1wt%, the retarder of 0.05~0.3wt%, 0.5~2wt% ZrOCl2·8H2O and 8~16wt% Aluminium dihydrogen phosphate aqueous solution, it is wet to grind 15~25 minutes, it is green to get mineral hot furnace tapping hole then to squeeze mud molding through mud extruder Environmentally friendly stemming.
Mineral hot furnace tapping hole obtained by the present embodiment 1 is with environmentally protective stemming through detecting: 200 DEG C × bulk density for 24 hours 2.87~2.92g/cm3, 1400 DEG C × 4h bulk density, 2.82~2.86g/cm3；200 DEG C × 14~16Mpa of flexural strength for 24 hours, 1400 DEG C × 4h flexural strength, 16~18Mpa；It is highly resistant to molten iron washing away and corroding 18~20 hours to stemming.
Embodiment 2
A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof.Preparation method described in the present embodiment is:
First with the alumina of 48~58wt%, the kyanite of 7~12wt%, the quartzy fine powder of 8~13wt%, 1~3wt% Andalusite fine powder, the alumina powder of 17~27wt%, the montmorillonite micro mist of 0.5~2wt%, the elemental silicon of 1~2wt% are thin Powder, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional raw material 0.05~ The polypropylene fibre of 0.1wt%, the retarder of 0.05~0.3wt%, 0.5~2wt% ZrOCl2·8H2O and 10~18wt% Aluminium dihydrogen phosphate aqueous solution, it is wet to grind 17~27 minutes, it is green to get mineral hot furnace tapping hole then to squeeze mud molding through mud extruder Environmentally friendly stemming.
Mineral hot furnace tapping hole obtained by the present embodiment 2 is with environmentally protective stemming through detecting: 200 DEG C × bulk density for 24 hours 2.88~2.93g/cm3, 1400 DEG C × 4h bulk density, 2.83~2.876g/cm3；200 DEG C × for 24 hours flexural strength 15~ 17Mpa, 1400 DEG C × 4h flexural strength, 17~19Mpa；It is highly resistant to molten iron washing away and corroding 19~21 hours to stemming.
Embodiment 3:
A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof.Preparation method described in the present embodiment is:
First with the alumina of 51~61wt%, the kyanite of 9~14wt%, the quartzy fine powder of 6~11wt%, 1~3wt% Andalusite fine powder, the alumina powder of 14~24wt%, the montmorillonite micro mist of 0.5~2wt%, the elemental silicon of 1~2wt% are thin Powder, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional raw material 0.05~ The polypropylene fibre of 0.1wt%, the retarder of 0.05~0.3wt%, 0.5~2wt% ZrOCl2·8H2O and 12~20wt% Aluminium dihydrogen phosphate aqueous solution, it is wet to grind 19~29 minutes, it is green to get mineral hot furnace tapping hole then to squeeze mud molding through mud extruder Environmentally friendly stemming.
Mineral hot furnace tapping hole obtained by the present embodiment 3 is with environmentally protective stemming through detecting: 200 DEG C × bulk density for 24 hours 2.90~2.94g/cm3, 1400 DEG C × 4h bulk density, 2.85~2.89g/cm3；200 DEG C × 16~18Mpa of flexural strength for 24 hours, 1400 DEG C × 4h flexural strength, 18~20Mpa；It is highly resistant to molten iron washing away and corroding 20~22 hours to stemming.
Embodiment 4
A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof.Preparation method described in the present embodiment is:
First with the alumina of 54~64wt%, the kyanite of 10~15wt%, 5~10wt% quartzy fine powder, 1~3wt% Andalusite fine powder, the alumina powder of 11~21wt%, the montmorillonite micro mist of 0.5~2wt%, the elemental silicon of 1~2wt% it is thin Powder, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional raw material 0.05~ The polypropylene fibre of 0.1wt%, the retarder of 0.05~0.3wt%, 0.5~2wt% ZrOCl2·8H2O and 9~17wt% Aluminium dihydrogen phosphate aqueous solution, it is wet to grind 20~30 minutes, it is green to get mineral hot furnace tapping hole then to squeeze mud molding through mud extruder Environmentally friendly stemming.
Mineral hot furnace tapping hole obtained by the present embodiment 4 is with environmentally protective stemming through detecting: 200 DEG C × bulk density for 24 hours 2.92~2.96g/cm3, 1400 DEG C × 4h bulk density, 2.86~2.90g/cm3；200 DEG C × 17~19Mpa of flexural strength for 24 hours, 1400 DEG C × 4h flexural strength, 19~21Mpa；It is highly resistant to molten iron washing away and corroding 21~23 hours to stemming.
Embodiment 5
A kind of mineral hot furnace tapping hole environmentally protective stemming and preparation method thereof.Preparation method described in the present embodiment is:
First with the alumina of 55~65wt%, the kyanite of 8~13wt%, the quartzy fine powder of 7~9wt%, 1~3wt% Andalusite fine powder, the alumina powder of 10~20wt%, the montmorillonite micro mist of 0.5~2wt%, the elemental silicon of 1~2wt% are thin Powder, the amorphous graphite micro mist of 0.5~1wt% and the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional raw material 0.05~ The polypropylene fibre of 0.1wt%, the retarder of 0.05~0.3wt%, 0.5~2wt% ZrOCl2·8H2O and 11~19wt% Aluminium dihydrogen phosphate aqueous solution, it is wet to grind 18~28 minutes, it is green to get mineral hot furnace tapping hole then to squeeze mud molding through mud extruder Environmentally friendly stemming.
Mineral hot furnace tapping hole obtained by the present embodiment 5 is with environmentally protective stemming through detecting: 200 DEG C × bulk density for 24 hours 2.93~2.97g/cm3, 1400 DEG C × 4h bulk density, 2.88~2.92g/cm3；200 DEG C × 18~20Mpa of flexural strength for 24 hours, 1400 DEG C × 4h flexural strength, 20~22Mpa；It is highly resistant to molten iron washing away and corroding 22~24 hours to stemming.
Present embodiment has following good effect compared with prior art:
The mineral hot furnace tapping hole of present embodiment preparation is Trend of Chrome-free with environmentally protective stemming (hereinafter referred to as stemming) Refractory material, it is free from environmental pollution, potential threat not will cause to the health of humans and animals, it is environmentally protective.
The primary raw material of the stemming of present embodiment preparation is alumina, and raw material is not necessarily to add compared with horn of plenty and cheaply Add expensive chromium oxide fine powder, therefore low production cost.The retarder that present embodiment uses has good guarantor Wet effect, and it is added to montmorillonite micro mist, making stemming, service performance and operating characteristics do not decline in the long-term storage process.This tool Body embodiment uses phosphate dihydrogen aluminum solution for bonding agent, in addition ZrOCl2·8H2O and water act on, and it is higher to impart stemming Early strength.Elemental silicon in present embodiment reacts at high temperature with amorphous graphite micro mist can be formed in situ resistant to corrosion SiC whisker, the combination of reinforcement material matrix and aggregate so that stemming have high intensity and excellent resistance to erosion aggressivity Energy.
Ti is also added into the stemming of present embodiment preparation3SiC2Fine powder, Ti in use process3SiC2Aoxidize shape At TiO2And SiO2Can be with other oxides formation biggish electrodeposition substance of viscosity in Tie Kouchu, it can be to the tapping hole to become larger Self and reparation are carried out, reaming is prevented, the service life of mineral hot furnace can be effectively improved.
Under the high temperature conditions, the kyanite in present embodiment can be converted into mullite and quartzy phase, and aluminium oxide is micro- Powder can generate mullite with quartz reaction, effectively facilitate solid phase reaction and sintering process, while mullite is formed and quartz crystal Expansion caused by conversion can effectively improve sample compactness, make prepared stemming intensity with higher.
In use, the polypropylene fibre in present embodiment, which is melted in stemming, forms small network gas Aqueous vapor channel is opened in hole, is mitigated internal stress, is prevented from bursting；Andalusite will be slow mullitization under high temperature simultaneously, offset sintering The contraction of generation, ZrOCl2·8H2O is decomposed into zirconium oxide and is uniformly distributed in material internal, improve stemming overall volume stability and Thermal shock resistance.The micro crystal graphite micro mist being added in stemming is nonwetting with molten iron, and erosion-resisting characteristics is excellent.
Mineral hot furnace tapping hole prepared by present embodiment is with environmentally protective stemming through detecting: 200 DEG C × volume for 24 hours Density is 2.87~2.97g/cm3, 1400 DEG C × 4h bulk density is 2.82~2.92g/cm3；200 DEG C × for 24 hours flexural strength be 14~20Mpa, 1400 DEG C × 4h flexural strength are 16~22Mpa；Be highly resistant to molten iron to stemming wash away and corrode 18~ 24 hours.
Therefore, present embodiment is low in cost and environmental-friendly, and prepared mineral hot furnace tapping hole is with environmentally protective Stemming is high with intensity, volume stability is good, flushing resistance is excellent, erosion-resisting characteristics is excellent and can repair the spy of tapping hole Point.

Claims (8)

1. a kind of preparation method of the environmentally protective stemming of mineral hot furnace tapping hole, it is characterised in that: first with the alum of 45~65wt% The oxygen of soil, the andalusite fine powder of the quartzy fine powder of the kyanite of 5~15wt%, 5~15wt%, 1~3wt%, 10~30wt% Change the amorphous graphite micro mist of aluminium micro mist, the montmorillonite micro mist of 0.5~2wt%, the simple substance silica fine powder of 1~2wt%, 0.5~1wt% With the Ti of 1~2wt%3SiC2Fine powder is raw material, then the additional 0.05~0.1wt% of raw material polypropylene fibre, 0.05~ The ZrOCl of the retarder of 0.3wt%, 0.5~2wt%2·8H2The aluminium dihydrogen phosphate aqueous solution of O and 8~20wt%, it is wet grind 15~ 30 minutes, mud molding then was squeezed to get the environmentally protective stemming of mineral hot furnace tapping hole through mud extruder.
2. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described The grain composition of alumina is: partial size is that 5~3mm accounts for the 15~30wt% of alumina, and partial size is less than 3mm and accounts for more than or equal to 1mm 15~the 30wt% of alumina, partial size, which is less than 1mm and is more than or equal to 0.1mm, accounts for the 50~60wt% of alumina.
3. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described The grain composition of kyanite is: partial size is that 3~1mm accounts for the 50~60wt% of kyanite, and partial size is less than 1mm and is more than or equal to 0.5mm accounts for the 15~30wt% of kyanite, partial size be less than 0.5mm and be more than or equal to 0.1mm account for the kyanite 15~ 30wt%.
4. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described 5 μm of C content the ﹥ 80wt%, partial size ﹤ of amorphous graphite micro mist.
5. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described The length of polypropylene fibre is 2~4mm, and the diameter of polypropylene fibre is 10~20 μm.
6. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described Retarder be one or more of sodium tripolyphosphate, calgon and citric acid.
7. the preparation method of the environmentally protective stemming of mineral hot furnace tapping hole according to claim 1, it is characterised in that described Aluminium dihydrogen phosphate aqueous solution density be 1.48~1.58g/cm3。
8. a kind of environmentally protective stemming of mineral hot furnace tapping hole, it is characterised in that the environmentally protective stemming of the mineral hot furnace tapping hole Be any one of according to claim 1~7 described in prepared by preparation method of the mineral hot furnace tapping hole with environmentally protective stemming The environmentally protective stemming of mineral hot furnace tapping hole.
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