阅读说明：本技术 一种高炉风口表面耐高温陶瓷材料及其制备方法和应用 (High-temperature-resistant ceramic material for surface of blast furnace tuyere and preparation method and application thereof ) 是由 王长宝 邹仲平 苏荣茂 亓福川 陈相成 王延平 张英 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种用于高炉风口表面的耐高温陶瓷材料及其制备方法和应用,所述耐高温陶瓷材料含有粒度为0.1～0.3mm的CaO20～25％,粒度为0.1～0.5mm的CuO15～20％,粒度≤0.088mm的Pr-6O-(11)8～18％,粒度＜60μm的MnO13～20％,粒度为90～120目的SnO-210～18％,粒度＜0.088mm的ZnO8％～15％,粒度为180～200目的活性α-Al-2O-33～8％。该耐高温陶瓷材料具有耐高温、强度高、耐摩擦,抗侵蚀能力强等优点,加上先进的处理工艺,可满足高炉内部使用条件,与未处理的铜质风口小套相比,增强风口小套承受的临界热流强度和抗冲刷能力,从而大大提高了其使用寿命。同时,还可以提高铁水产量,降低风口小套漏水风险,改善高炉炉况,满足高炉稳定顺产作业要求。(The invention discloses a high-temperature-resistant ceramic material for the surface of a blast furnace tuyere and a preparation method and application thereof, wherein the high-temperature-resistant ceramic material contains 0.1-0.3 mm CaO 20-25%, 0.1-0.5 mm CuO 15-20%, and 0.088mm or less Pr 6 O 11 8-18%, MnO 13-20% with granularity less than 60 mu m, and SnO with granularity of 90-120 meshes 2 10-18 percent of ZnO 8-15 percent with granularity less than 0.088mm and active alpha-Al with granularity of 180-200 meshes 2 O 3 3-8%. The high-temperature resistant ceramic material has the advantages of high temperature resistance, high strength, friction resistance, strong erosion resistance and the like, and can meet the use conditions in a blast furnace by adding an advanced treatment process, andcompared with the untreated copper tuyere small sleeve, the critical heat flow strength and the anti-scouring capacity born by the tuyere small sleeve are enhanced, so that the service life of the tuyere small sleeve is greatly prolonged. Meanwhile, the molten iron yield can be increased, the water leakage risk of the tuyere small sleeve is reduced, the furnace condition of the blast furnace is improved, and the stable and downstream operation requirement of the blast furnace is met.)

1. The high-temperature-resistant ceramic material for the surface of the tuyere of the blast furnace is characterized by comprising the following raw material components:

2. the high-temperature resistant ceramic material for the surface of the blast furnace tuyere of claim 1, which comprises the following raw material components:

3. the high-temperature-resistant ceramic material for the surface of the blast furnace tuyere of claim 1, which comprises the following raw material components:

4. the high-temperature-resistant ceramic material for the surface of the blast furnace tuyere of claim 1, which comprises the following raw material components:

5. a preparation method of the high-temperature resistant ceramic material for the surface of the blast furnace tuyere of any one of claims 1 to 4 comprises the following steps:

weighing various materials according to the proportion, putting the materials into a stirrer to be mixed and stirred for 5-8 minutes to obtain a mixed material, adding water into the mixed material, and then mixing and stirring for 5-8 minutes to obtain the high-temperature resistant ceramic material for the surface of the tuyere of the blast furnace.

6. The preparation method according to claim 5, wherein water is added in an amount of 5 to 10% by weight based on the total weight of the mixture.

7. The use of the refractory ceramic material for the surface of a tuyere of a blast furnace as claimed in any one of claims 1 to 4 for protecting a small sleeve of a tuyere of a copper blast furnace.

8. A surface protection treatment method for a blast furnace tuyere small sleeve comprises the following steps:

1) pretreating the surface of the tuyere small sleeve, putting the tuyere small sleeve into a drying box, heating to 450-600 ℃, preserving heat for 8-10 hours to oxidize metal copper on the surface of the tuyere small sleeve to generate copper oxide, and cooling to room temperature;

2) uniformly coating the prepared high-temperature-resistant ceramic material on the surface of the blast-furnace tuyere of any one of claims 1 to 4 on the surface of a pre-treated copper sleeve for 2 to 3mm, putting the tuyere small sleeve into a drying box, heating to 110 to 150 ℃, preserving heat for 24 to 26 hours at the temperature of 2200 to 2400 ℃ in a high-temperature furnace, and naturally cooling to finish the treatment.

9. The surface protection treatment method for the small tuyere sleeve of the blast furnace as claimed in claim 8, wherein in the step 2), the copper sleeve is cooled by water during the heat preservation and natural cooling of the high-temperature furnace.

Technical Field

The invention belongs to the field of high-temperature-resistant ceramics for a blast furnace tuyere in the steel industry, and particularly relates to a high-temperature-resistant ceramic material for the surface of the blast furnace tuyere as well as a preparation method and a use method thereof.

Background

A key spare part in the production of pig iron smelted by a blast furnace is an air supply tuyere, the working environment of the blast furnace tuyere is severe, the tuyere is positioned in a high-temperature hearth above 2000 ℃, the tuyere bears radiation and convection thermal shock of a high-temperature region, the front end of the tuyere is washed by liquid iron slag at about 1500 ℃ and hot materials in high-speed circulating motion, hot air at 900-13000 ℃ passes through the tuyere, and the tuyere is simultaneously subjected to strong oxidation and infiltration of trace elements in a combustion circulating region and is also subjected to high-speed abrasion of materials under the conditions of pulverized coal injection and semi-coke injection, and the tuyere breakage is aggravated by adverse factors. The blast furnace tuyere is equipment which continuously works and cannot be overhauled and replaced in use, and once the blast furnace tuyere is damaged, the blast furnace tuyere needs to be temporarily stopped and replaced, so that the adverse effects on the yield, the quality, the coke ratio and the like of pig iron are brought. The service life of the tuyere is low, the spare part cost is increased, the coke consumption is increased, the damping down rate of the blast furnace is increased, and the economic loss is large.

At present, blast furnace tuyere small sleeves are divided into copper and refractory materials in China, but the refractory material tuyere small sleeves need to change a blowing process, so most of the tuyere small sleeves are still copper sleeves, and two forms of cavity water cooling and spiral water cooling are adopted. In the use process, the head of the tuyere extends into the blast furnace, and the liquid iron slag is contacted with the front end of the tuyere, so that the local heat flow intensity of the tuyere exceeds the critical heat flow intensity which can be borne by the tuyere material, the temperature of a copper wall rises to exceed the melting point of copper, and the tuyere is burnt through. Or the furnace condition is not smooth, the suspension of the blast furnace is frequent, and the slag and the iron are not completely discharged, so that the tuyere small sleeve is frequently washed by the iron liquid to be damaged. At present, the average service life of the tuyere small sleeve is only about 6 months, and the tuyere small sleeve becomes one of restrictive factors for further improving the yield and optimizing various economic and technical indexes of a blast furnace.

Disclosure of Invention

Aiming at the problems existing at present, the invention aims to carry out surface treatment on the copper blast furnace tuyere small sleeve, provide a high-quality high-temperature-resistant ceramic material and an advanced treatment process, protect the surface of the copper small sleeve, and enhance the critical heat flow strength and the anti-scouring capability born by the tuyere small sleeve, thereby prolonging the service life of the tuyere small sleeve. Meanwhile, the molten iron yield can be increased, the water leakage risk of the tuyere small sleeve is reduced, the furnace condition of the blast furnace is improved, and the stable and downstream operation requirement of the blast furnace is met.

In order to solve the technical problems, the invention adopts the technical scheme that:

with CaO, CuO, Pr₆O₁₁、MnO、SnO₂ZnO as main material, active alpha-Al₂O₃The material is used as a bonding agent and is used as the surface material of the tuyere small sleeve.

The blast furnace tuyere surface high-temperature resistant ceramic material comprises the following raw material components:

preferably, the high-temperature resistant ceramic material comprises the following raw material components:

further preferably, the high-temperature resistant ceramic material comprises the following raw material components:

further preferably, the high-temperature resistant ceramic material comprises the following raw material components:

the high-quality high-temperature-resistant ceramic material provided by the invention has the advantages of high temperature resistance, high strength, friction resistance, strong erosion resistance and the like, and compared with an untreated copper tuyere small sleeve, the service life is greatly prolonged.

In the invention, CuO is used as a substrate transition layer, the coating-copper substrate and the coating structure and the thermal stress distribution are adjusted, the CaO melting point is as high as 2572 ℃, the ionic crystal is rich in elasticity, and the refractoriness and the high-temperature thermal stability of the coating can be improved. ZnO will react with Al₂O₃Generating zinc spinel with a chemical formula of ZnAl₂O₄And Pr of₆O₁₁The praseodymium-neodymium enrichment material is added into octahedral gahnite, so that the activity and stability of an isometric crystal system can be improved. MnO is used as cubic system powder and can be crossed with octahedral crystals, so that the wear resistance of the material is improved. SnO₂Hexagonal or orthorhombic powder, and improves the strength and the corrosion resistance of the material. Meanwhile, various materials can be mutually blended to form solid solution, and the method has important significance for improving various properties of the materials.

The invention also provides a preparation method of the high-temperature-resistant ceramic material on the surface of the blast furnace tuyere, which comprises the following steps:

weighing various materials according to the proportion, putting the materials into a stirrer to be mixed and stirred for 5-8 minutes to obtain a mixed material, adding water into the mixed material, and then mixing and stirring for 5-8 minutes to obtain the high-temperature resistant ceramic material for the surface of the tuyere of the blast furnace.

Preferably, water is added according to 5 to 10 percent of the total weight of the mixed materials.

The invention also provides application of the high-temperature-resistant ceramic material on the surface of the blast furnace tuyere in the protection of the copper blast furnace tuyere small sleeve.

The invention also provides a surface protection treatment method for the blast furnace tuyere small sleeve, which specifically comprises the following steps:

1) pretreating the surface of the tuyere small sleeve, putting the tuyere small sleeve into a drying box, heating to 450-600 ℃, preserving heat for 8-10 hours to oxidize metal copper on the surface of the tuyere small sleeve to generate copper oxide, and cooling to room temperature;

2) uniformly coating the high-temperature-resistant ceramic material on the surface of any blast furnace tuyere onto the surface of a pre-treated copper sleeve for 2-3 mm, then putting the tuyere small sleeve into a drying box, heating to 110-150 ℃, preserving heat for 24-26 hours, then preserving heat for 24-26 hours at the temperature of 2200-2400 ℃ in a high-temperature furnace, and naturally cooling to finish the treatment.

Preferably, in the step 2), the copper sleeve is cooled by water in the processes of heat preservation and natural cooling of the high-temperature furnace so as to prevent the copper sleeve from melting.

The invention has positive and effective effects

1. Compared with untreated copper sleeves, the tuyere small sleeve after surface treatment has the advantages that the critical heat flow strength and the anti-scouring capacity are enhanced, and the average service life of the tuyere small sleeve is prolonged from about 6 months to about 18 months.

2. Compared with untreated copper sleeves, the tuyere small sleeve after surface treatment can reduce the damping down times of the blast furnace and improve the yield of molten iron.

3. Compared with an untreated copper sleeve, the tuyere small sleeve after surface treatment can reduce the water leakage risk of the tuyere small sleeve, improve the furnace condition of the blast furnace and meet the requirement of stable and smooth operation of the blast furnace.

4. The high-temperature resistant ceramic material meets the internal working conditions of the blast furnace, and has the following main physical and chemical indexes:

Detailed Description

Example 1

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the surface of the tuyere small sleeve is pretreated, the tuyere small sleeve is placed in a drying box and heated to 450 ℃, the temperature is kept for 8 hours, the copper on the surface of the tuyere small sleeve is oxidized to generate copper oxide, and then the tuyere small sleeve is cooled to room temperature. Weighing the materials according to the proportion in the table 1, putting the materials into a stirrer, mixing and stirring for 5-8 minutes, and adding water (the added water amount is 5-10% of the total weight of the materials), mixing and stirring for 5-8 minutes. And uniformly coating the mixed material on the surface of a pre-treated copper sleeve by 2-3 mm, putting the tuyere small sleeve into a drying box, heating to 110 ℃, preserving heat for 24 hours at the temperature of 2200 ℃ in a high-temperature furnace (cooling the copper sleeve by water), and naturally cooling to put the copper sleeve into use. The main physical and chemical indexes are as follows:

example 2

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

example 3

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

example 4

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

example 5

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

example 6

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

example 7

A high-temperature resistant ceramic material for the surface of a blast furnace tuyere has the following raw material formula shown in a table 1:

the preparation and treatment process of the high-temperature ceramic material is the same as that of the embodiment 1, and the main physical and chemical indexes are as follows:

table 1 examples 1 to 7 raw material formulation table

Unit: weight percent (%)

Raw materials	Particle size distribution	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
									CaO	0.1～0.3mm	25	22	22	20	21	23	24
CuO	0.1～0.5mm	17	19	17	15	18	16	20
									Pr6O11	≤0.088mm	12	10	14	18	13	16	12
MnO	＜60μm	16	15	16	20	17	18	15
									SnO2	90-120 mesh	15	12	13	16	14	11	10
ZnO	＜0.088mm	10	14	12	8	13	9	14
									α-Al2O3	180 to 200 mesh	5	8	6	3	4	7	5

The embodiment shows that the refractoriness of the high-temperature ceramic material is higher than 2600 ℃, the high-temperature condition in the blast furnace is met, the compressive strength is higher than or equal to 53MPa, the impact of furnace burden can be effectively resisted, the Mohs hardness is higher than or equal to 6.2, the wear resistance is high, the contact frequency of liquid slag and iron can be prevented to reach 16 times or more than 16 times, and the melting loss rate of the tuyere small sleeve is greatly reduced. And the high-temperature ceramic material and the copper sleeve have high bonding strength (more than or equal to 40MPa), are firmly bonded, and can greatly prolong the service life of the tuyere small sleeve.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.