CN112194473A - Chrome corundum brick with high erosion resistance and thermal shock resistance prepared by secondary mixed grinding and drying and process thereof - Google Patents

Chrome corundum brick with high erosion resistance and thermal shock resistance prepared by secondary mixed grinding and drying and process thereof Download PDF

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CN112194473A
CN112194473A CN202010602427.4A CN202010602427A CN112194473A CN 112194473 A CN112194473 A CN 112194473A CN 202010602427 A CN202010602427 A CN 202010602427A CN 112194473 A CN112194473 A CN 112194473A
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powder
drying
grinding
granularity
mixing
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CN112194473B (en
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陈松林
王俊涛
吴跃峰
袁林
钱蛇大
俞永平
吴忠阳
张伯南
闫昕
孙旭东
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Ruitai Technology Co ltd
Yixing Ruitai Refractory Material Co ltd
China Building Materials Academy CBMA
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Ruitai Technology Co ltd
Yixing Ruitai Refractory Material Co ltd
China Building Materials Academy CBMA
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Abstract

The invention relates to a method for preparing high erosion resistance and high thermal shock resistance chromium corundum brick by secondary mixed grinding and drying and a process thereof2And (3) coating the pretreated granular material with a chromium sand granular structure with powder. Then modifyingThe granules, the powder and the binding agent are subjected to secondary mixing and grinding, the thermosetting resin is oxidized into gas to escape during sintering after ageing, a coated granule structure with various hole defects is left, and the refractory material with high erosion resistance and high thermal shock resistance is obtained through the air hole defects and zirconium oxide phase change toughening. Compared with the original high-chromium brick, the chromium corundum brick has equivalent erosion resistance, and the water quenching cycle times of the thermal shock resistance at 1100 ℃ are improved to more than 6 times from the original 1-2 times.

Description

Chrome corundum brick with high erosion resistance and thermal shock resistance prepared by secondary mixed grinding and drying and process thereof
Technical Field
The invention relates to a chrome corundum brick with high erosion resistance and high thermal shock resistance prepared by secondary mixed grinding and drying and a process thereof, belonging to the field of inorganic non-metallic material subject high-temperature ceramics and refractory materials.
Background
China is a country with oil shortage, less gas and more coal, the proportion of energy consumption of coal in China is 64 percent in 2015, 74 percent of electric power is from coal, and the proportion of energy consumption is predicted to be over 50 percent even in 2050. The Texaco coal gasification technology with great popularization strength in China is a gasification technology which takes coal water slurry as a raw material and is operated at high temperature (1300-. Because the operating temperature must be higher than the melting point of the coal ash, Fe must be introduced into the coal water slurry2O3CaO, etc. lower the melting point of the fly ash, but this makes the fly ash aggravate the erosion of the lining materialAnd flushing. Over 85wt% high Cr2O3Content of Cr2O3-Al2O3-ZrO2The series material has excellent compatibility with coal slag, and is a key refractory material commonly used in the existing coal water slurry gasification furnace. Although the erosion resistance of the water coal slurry slag of the high-chromium brick is good, the service life of the high-chromium brick in a water coal slurry gasification furnace is still short, and the high-chromium brick can only be operated for about 5000 hours generally, and the fundamental reason is that the thermal shock resistance of the high-chromium brick is extremely poor, and the water quenching circulation is only 1-2 times at 1100 ℃.
Therefore, the improvement of the thermal shock resistance of the high-chromium brick becomes the key for solving the service life of the coal water slurry gasification furnace. Generally, the structure of the refractory material is composed of aggregate, matrix and pores. The powder matrix has more apparent porosity, weaker erosion resistance and stronger thermal shock resistance; on the contrary, the granular aggregate has a compact and complete single crystal or polycrystalline structure, and has strong erosion resistance and weak thermal shock resistance. The method for improving the erosion resistance of the material is to prepare the matrix more compact, and the method for improving the thermal shock resistance of the material is to destroy the particle structure of a complete single crystal or polycrystalline structure, introduce more defects and effectively release the thermal stress when the material is subjected to uneven temperature. Reducing the size of the particulate aggregate reduces thermal stress concentrations in the same volume, but sacrifices the erosion resistance of the material. The invention adopts a method for modifying the particles, and the obtained pseudo particles with the coating structure artificially introduce more structural defects, thereby achieving the effects of reducing the thermal stress concentration in the same volume, improving the thermal shock resistance and not sacrificing the erosion resistance of the material.
Disclosure of Invention
The invention prepares ZrO by mixing and grinding large-particle chromium sand aggregate, submicron zirconia micro powder and thermosetting resin at one time, drying, heating and thermosetting2Powder coated pretreated granules of chrome sand grain structure (see figure 1). Then the modified particle material, powder material and binding agent are mixed and ground for the second time, after the material ageing, forming and secondary drying, the thermosetting resin is oxidized and ablated to escape and leave micropores, microporous holes and coating particle structures of zirconia (as shown in figure 2), and the coating particle structures pass through the pore defects and the phase change of the zirconiaThe toughening mechanism relieves the heat stress concentration, and the refractory material with high erosion resistance and high thermal shock resistance is obtained.
The technical characteristics of the secondary mixing grinding and drying process have 4 aspects: (1) ZrO coating around chromium sand particles by using thermosetting resin2The powder is prepared by heating thermosetting resin to obtain high strength, so that the chromium sand and the coating powder are formed into a compact pseudo particle. Compared with other physical adsorption methods, the chromium sand and nano zirconia pseudo particles can bear high mechanical grinding force of secondary mixing grinding without ZrO2The powder falls off to destroy the coating structure. The thermosetting resin acts as a binder during primary mixing and milling. (2) The fine powder is strongly premixed and added with a trace amount of additive, the additive comprises a dispersing agent and a mineralizing agent, and the dispersing agent has the functions of ensuring that the flowing property of the fine powder is good, reducing the delta potential and reducing or eliminating the electrostatic repulsion force of compression molding; the mineralizer has the functions of reducing the sintering temperature, promoting the sintering of the material, enabling the particles and the matrix to be combined more tightly and the matrix to be more compact, and improving the strength, the wear resistance, the slag penetration resistance and the erosion resistance of the refractory material. (3) The aluminum sol is used as a bonding agent to carry out secondary mixing and grinding on the granules and the powder, because the aluminum sol has better wettability on the resin-bonded pseudo granules than that of phosphate, and the influence of phosphate decomposition during the sintering of aluminum dihydrogen phosphate is avoided. (4) In the sintering process of the refractory material, the thermosetting resin in the pseudo particles is oxidized and ablated to escape and leave fine air holes, so that a micro-structure with the particles wrapped by the micro-holes is formed, a buffer space is provided for the particles when the particles expand with heat and contract with cold, and the concentration of thermal stress is reduced. The granule material is modified to achieve the effect of toughening and improve the thermal shock resistance of the material. The thermosetting resin plays a role of a pore-forming agent when the material is sintered after secondary mixing, grinding and drying.
The formula and the preparation process of the invention are as follows:
1. and (3) carrying out primary mixing and grinding and drying on large granules with the granularity of more than 1mm to obtain the pretreated granules A. The formula and treatment method of the pretreated granular material A are as follows:
(1) 10-23 wt% of chromium sand with the granularity of 6-4 mm;
(2) 5-10 wt% of chromium sand with the granularity of 4-2 mm;
(3) 16-25 wt% of chromium sand with the granularity of 2-1 mm;
(4) 3-8 wt% of zirconia powder with the particle size of 0.1-0.5 mu m;
(5) a thermosetting resin, plus + 1-2 wt%.
Sequentially mixing the three granular materials (1), (2) and (3), adding (5) thermosetting resin and 1-2 wt%, and then adding (4) powder; mixing and grinding for 5-10 minutes; drying the mixture for 3 to 5 hours at 220 to 260 ℃. Preparing the pretreated granule material A with a zirconia-coated chromium sand granule structure.
2. And meanwhile, strongly premixing the fine powder to prepare premixed powder B. The formula and the premixing method of the premixed powder B are as follows:
(6) 10-20 wt% of chromium sand powder with the particle size less than or equal to 88 mu m;
(7) 5-15 wt% of chromium green powder with the particle size less than or equal to 5 mu m;
(8) alpha-Al with particle size of 2-1 mu m2O310-18 wt% of powder;
(9) dextrin powder, plus + 0.5-1 wt%;
(10) high-dispersion hydroxypropyl methyl cellulose, plus, + 0.05-0.1 wt%
Mixing the above three powders (6), (7) and (8), adding (9) dextrin powder and 0.5-1 wt% and adding (10) high-dispersion hydroxypropyl methyl cellulose and 0.05-0.1 wt%, and strongly premixing at high speed for 10-20 minutes. To prepare premixed powder B.
3. Secondary mixing and grinding
(11) 5-10 wt% of chromium sand with the granularity of 1-0 mm;
(12) 2-5 wt% of mullite with the granularity of 1-0 mm;
(13) aluminum sol with the pH value of 3.5-4.0 and the particle size of colloidal particles of 10-20 nanometers, and + 3-5 wt%.
Sequentially adding pretreated particle material A, (11) 5-10 wt% of chromium sand with the granularity of 1-0 mm, (12) 2-5 wt% of mullite with the granularity of 1-0 mm, and (13) 3-5 wt% of alumina sol with the pH value of 3.5-4.0 and the particle size of colloidal particles of 10-20 nanometers, mixing and grinding for 1-2 minutes, and then adding premixed powder material B. And (3) strongly mixing and grinding for 10-20 minutes.
4. Ageing mixture
After the secondary mixing and grinding, ageing the mixture for 24-48 hours.
5. Shaping of
And (5) performing pressure forming according to the required drawing.
6. Secondary drying
And naturally drying the formed biscuit for 24 hours, and then drying the biscuit for 12 to 36 hours at the temperature of more than or equal to 150 ℃.
7. Firing into
And after drying, firing at 1550-1650 ℃ for 5-8 hours.
The invention has the advantages that: compared with the original high-chromium brick, the chrome corundum brick with high erosion resistance and high thermal shock resistance prepared by secondary mixed grinding and drying has equivalent erosion resistance; but compared with the high-chromium brick which is only subjected to water quenching circulation for 1-2 times at 1100 ℃, the circulation frequency is more than 5 times, the thermal shock resistance is obviously improved, the service life of the high-chromium brick applied to the coal water slurry gasification furnace is prolonged to more than 10000 hours, and the service life is prolonged by more than one time compared with the service life of the original high-chromium brick which is 5000 hours. Due to the excellent erosion resistance and thermal shock resistance, the material is suitable for a coal water slurry gasification furnace, a plasma melting furnace, an ultrahigh temperature gasification furnace and the like.
Drawings
FIG. 1 shows ZrO produced by primary mulling, drying and thermosetting2The powder-coated chromium sand particles are structurally schematic, wherein 1 is chromium sand, 2 is zirconium oxide and 3 is resin.
Fig. 2 is a schematic view of the structure of the microporous holes and zirconia-coated chromium sand particles formed after secondary mixing, grinding, drying, forming and firing, wherein 1 is chromium sand, 2 is zirconia, and 4 is pores.
Detailed Description
Example one
1. The pre-treated granules A1 were prepared by primary mixing and drying of large granules having a particle size of 1mm or more. The weight percentage formulation and treatment method of the pretreated granular material A1 are as follows:
(1) 10wt% of chromium sand with the granularity of 6-4 mm;
(2) 10wt% of chromium sand with the granularity of 4-2 mm;
(3) 25wt% of chromium sand with the granularity of 2-1 mm;
(4) 8wt% of zirconia powder with the granularity of 0.1-0.5 mu m;
(5) thermosetting resin, plus, +2 wt%.
Sequentially mixing the three granular materials (1), (2) and (3), adding (5) thermosetting resin and 2wt%, and then adding (4) powder; mixing and grinding for 5 minutes; dried at 220 ℃ for 5 hours. The pretreated granule A1 having a zirconia-coated chromium sand granule structure was obtained.
2. At the same time, the fine powder was subjected to intensive premixing to obtain premixed powder B1. The formula and premixing method of premixed powder B1 are as follows:
(6) 20wt% of chromium sand powder with the granularity less than or equal to 88 mu m;
(7) 5wt% of chromium green powder with the granularity less than or equal to 5 mu m;
(8) alpha-Al with particle size of 2-1 mu m2O3Powder, 10 wt%;
(9) dextrin powder, plus, +0.5 wt%;
(10) high-dispersion hydroxypropyl methylcellulose, plus, +0.05wt%
Mixing the above powders (6), (7) and (8), adding (9) dextrin powder +0.5wt% and (10) high-dispersion hydroxypropyl methylcellulose +0.05wt%, and strongly premixing at high speed for 20 min. A premix powder B1 was obtained.
3. Secondary mixing and grinding
(11) 10wt% of chromium sand with the granularity of 1-0 mm;
(12) 2wt% of mullite with the granularity of 1-0 mm;
(13) the pH value is 3.5, the particle size of the colloidal particle is 10-20 nanometers, and plus 3 wt%.
Sequentially adding pretreated particle material A1, (11) 10wt% of chrome sand with the granularity of 1-0 mm, (12) 2wt% of mullite with the granularity of 1-0 mm, (13) adding 3wt% of aluminum sol with the pH value of 3.5 and the particle size of colloidal particles of 10-20 nanometers, mixing and grinding for 2 minutes, and then adding premixed powder material B1. And (5) strongly mixing and grinding for 10 minutes.
4. Ageing mixture
After the secondary mixing and grinding, the material is aged for 24 hours.
5. Shaping of
And (5) performing pressure forming according to the required drawing.
6. Secondary drying
The shaped biscuit was dried naturally for 24 hours and then dried at 150 ℃ for 12 hours.
7. Firing into
After drying, the mixture was fired at 1550 ℃ for 8 hours.
Compared with the original high-chromium brick, the chromium corundum brick with high erosion resistance and high thermal shock resistance prepared in the embodiment I has equivalent erosion resistance, and the water quenching cycle times of the thermal shock resistance at 1100 ℃ are improved to 7 times from the original 1-2 times. The water-coal-slurry gasification furnace is applied to a water-coal-slurry gasification furnace of Hua certain company, is replaced after being actually used for 10200 hours, and can be used for 1 month according to the conjecture of the length of the replaced residual brick. The service life of the brick is 10200 hours, which is more than doubled compared with the average service life of 5000 hours of the original high chrome brick.
Example two
1. The pre-treated granules A2 were prepared by primary mixing and drying of large granules having a particle size of 1mm or more. The formula and treatment method of the pretreated granular material A2 are as follows:
(1) 17wt% of chromium sand with the granularity of 6-4 mm;
(2) 7wt% of chromium sand with the granularity of 4-2 mm;
(3) 20wt% of chromium sand with the granularity of 2-1 mm;
(4) 6wt% of zirconia powder with the granularity of 0.1-0.5 mu m;
(5) thermosetting resin, plus, +1.5 wt%.
Sequentially mixing the three granular materials (1), (2) and (3), adding (5) thermosetting resin and 1.5wt%, and then adding (4) powder; mixing and grinding for 10 minutes; dried at 260 ℃ for 3 hours. The pretreated granule A2 having a zirconia-coated chromium sand granule structure was obtained.
2. At the same time, the fine powder was subjected to intensive premixing to obtain premixed powder B2. The formula and premixing method of premixed powder B2 are as follows:
(6) 15wt% of chromium sand powder with the granularity less than or equal to 88 mu m;
(7) 10wt% of chromium green powder with the granularity less than or equal to 5 mu m;
(8) alpha-Al with particle size of 2-1 mu m2O3Powder, 13 wt%;
(9) dextrin powder, plus, +0.8 wt%;
(10) high-dispersion hydroxypropyl methylcellulose, plus, +0.08wt%
Mixing the above powders (6), (7) and (8), adding (9) dextrin powder +0.8wt% and (10) high-dispersion hydroxypropyl methylcellulose +0.08wt%, and strongly premixing at high speed for 15 min. A premix powder B2 was obtained.
3. Secondary mixing and grinding
(11) 8wt% of chromium sand with the granularity of 1-0 mm;
(12) 4wt% of mullite with the granularity of 1-0 mm;
(13) the pH value is 3.5, the particle size of the colloidal particle is 10-20 nanometers, and plus 4 wt%.
Sequentially adding pretreated particle material A2, (11) 8wt% of chrome sand with the granularity of 1-0 mm, (12) 4wt% of mullite with the granularity of 1-0 mm, (13) adding 4wt% of aluminum sol with the pH value of 3.5 and the particle size of colloidal particles of 10-20 nanometers, mixing and grinding for 2 minutes, and then adding premixed powder material B2. And (5) strongly mixing and grinding for 15 minutes.
4. Ageing mixture
After the secondary mixing and grinding, the material is aged for 24 hours.
5. Shaping of
And (5) performing pressure forming according to the required drawing.
6. Secondary drying
The formed biscuit is naturally dried for 24 hours and then dried for 24 hours at the temperature of more than or equal to 150 ℃.
7. Firing into
After drying, the mixture was fired at 1590 ℃ for 7 hours.
Compared with the original high-chromium brick, the chromium corundum brick with high erosion resistance and high thermal shock resistance prepared in the second embodiment has equivalent erosion resistance, and the water quenching cycle times of the thermal shock resistance at 1100 ℃ are improved to 6 times from the original 1-2 times. The water-coal-slurry gasification furnace is applied to a water-coal-slurry gasification furnace of Hua certain company, is replaced after being actually used for 10200 hours, and can be used for 1 month according to the conjecture of the length of the replaced residual brick. The service life of the brick is 10200 hours, which is more than doubled compared with the average service life of 5000 hours of the original high chrome brick.
EXAMPLE III
1. The pre-treated granules A3 were prepared by primary mixing and drying of large granules having a particle size of 1mm or more. The formula and treatment method of the pretreated granular material A3 are as follows:
(1) 23wt% of chromium sand with the granularity of 6-4 mm;
(2) 5wt% of chromium sand with the granularity of 4-2 mm;
(3) 16wt% of chromium sand with the granularity of 2-1 mm;
(4) 3wt% of zirconia powder with the granularity of 0.1-0.5 mu m;
(5) thermosetting resin, plus, +1 wt%.
Sequentially mixing the three granular materials (1), (2) and (3), adding (5) thermosetting resin and 1wt%, and then adding (4) powder; mixing and grinding for 5 minutes; dried at 260 ℃ for 3 hours. The pretreated granule A3 having a zirconia-coated chromium sand granule structure was obtained.
2. At the same time, the fine powder was subjected to intensive premixing to obtain premixed powder B3. The formula and premixing method of premixed powder B3 are as follows:
(6) 10wt% of chromium sand powder with the granularity less than or equal to 88 mu m;
(7) 15wt% of chromium green powder with the granularity less than or equal to 5 mu m;
(8) alpha-Al with particle size of 2-1 mu m2O3Powder, 18 wt%;
(9) dextrin powder, plus, +1 wt%;
(10) high-dispersion hydroxypropyl methylcellulose, plus, +0.1wt%
Mixing the above powders (6), (7) and (8), adding (9) dextrin powder +1wt% and (10) high-dispersion hydroxypropyl methylcellulose +0.1wt%, and strongly premixing at high speed for 10 min. A premix powder B3 was obtained.
3. Secondary mixing and grinding
(11) 5wt% of chromium sand with the granularity of 1-0 mm;
(12) 5wt% of mullite with the granularity of 1-0 mm;
(13) the pH value is 4.0, the particle size of the colloidal particle is 10-20 nanometers, and plus 5 wt%.
Sequentially adding pretreated particle material A3, (11) 5wt% of chromium sand with the granularity of 1-0 mm, (12) 5wt% of mullite with the granularity of 1-0 mm, (13) 5wt% of aluminum sol with the pH value of 4.0 and the particle size of colloidal particles of 10-20 nanometers, mixing and grinding for 1 minute, and then adding premixed powder material B3. And (5) strongly mixing and grinding for 20 minutes.
4. Ageing mixture
After the secondary mixing and grinding, the material is aged for 48 hours.
5. Shaping of
And (5) performing pressure forming according to the required drawing.
6. Secondary drying
The formed biscuit is naturally dried for 24 hours and then dried for 36 hours at the temperature of more than or equal to 150 ℃.
7. Firing into
After drying, the mixture was fired at 1650 ℃ for 5 hours.
Compared with the original high-chromium brick, the chromium corundum brick with high erosion resistance and high thermal shock resistance prepared in the third embodiment has equivalent erosion resistance, and the water quenching cycle times of the thermal shock resistance at 1100 ℃ are improved to 6 times from the original 1-2 times. The water-coal-slurry gasification furnace is applied to a water-coal-slurry gasification furnace of Hua certain company, is replaced after being actually used for 10200 hours, and can be continuously used for about half a month according to the conjecture of the length of the replaced residual bricks. The service life of the brick is 10200 hours, which is more than doubled compared with the average service life of 5000 hours of the original high chrome brick.

Claims (1)

1. The invention relates to a chrome corundum brick with high erosion resistance and high thermal shock resistance prepared by secondary mixed grinding and drying and a process thereof, which is characterized in that the formula and the preparation process of the secondary mixed grinding process are as follows:
1. and (3) carrying out primary mixing and grinding and drying on large granules with the granularity of more than 1mm to obtain the pretreated granules A. The formula and treatment method of the pretreated granular material A are as follows:
(1) 10-23 wt% of chromium sand with the granularity of 6-4 mm;
(2) 5-10 wt% of chromium sand with the granularity of 4-2 mm;
(3) 16-25 wt% of chromium sand with the granularity of 2-1 mm.
(4) 3-8 wt% of zirconia powder with the particle size of 0.1-0.5 mu m;
(5) a thermosetting resin, plus + 1-2 wt%.
Sequentially mixing the three granular materials (1), (2) and (3), adding (5) thermosetting resin and 0.5-1 wt%, and then adding (4) powder; mixing and grinding for 5-10 minutes; drying for 3-5 hours at 220-260 ℃ to obtain the pretreated granule A with the zirconia-coated chromium sand granule structure, mixing and grinding the thermosetting resin for the first time and drying the thermosetting resin to be used as a bonding agent, drying and sintering the thermosetting resin for the second time, and oxidizing and ablating the thermosetting resin to escape and leave micropores during sintering to form the pore-forming agent.
2. And (3) strongly premixing the fine powder to prepare premixed powder B. The formula and the premixing method of the premixed powder B are as follows:
(6) 10-20 wt% of chromium sand powder with the particle size less than or equal to 88 mu m;
(7) 5-15 wt% of chromium green powder with the particle size less than or equal to 5 mu m;
(8) alpha-Al with particle size of 2-1 mu m2O310-18 wt% of powder;
(9) dextrin powder, and 0.5-1 wt% of the total weight of the paste powder.
(10) High-dispersion hydroxypropyl methyl cellulose, plus, + 0.05-0.1 wt%
Mixing the above three powders (6), (7) and (8), adding (9) dextrin powder and 0.5-1 wt% and adding (10) high-dispersion hydroxypropyl methyl cellulose and 0.05-0.1 wt%, and strongly premixing at high speed for 10-20 minutes. To prepare premixed powder B.
3. Secondary mixing and grinding
(11) 5-10 wt% of chromium sand with the granularity of 1-0 mm;
(12) 2-5 wt% of mullite with the granularity of 1-0 mm;
(13) aluminum sol with the pH value of 3.5-4.0 and the particle size of colloidal particles of 10-20 nanometers, and + 3-5 wt%.
Sequentially adding pretreated particle material A, (11) 5-10 wt% of chromium sand with the granularity of 1-0 mm, (12) 2-5 wt% of mullite with the granularity of 1-0 mm, and (13) 3-5 wt% of alumina sol with the pH value of 3.5-4.0 and the particle size of colloidal particles of 10-20 nanometers, mixing and grinding for 1-2 minutes, and then adding premixed powder material B. And (3) strongly mixing and grinding for 10-20 minutes.
4. Ageing mixture
After the secondary mixing and grinding, ageing the mixture for 24-48 hours.
5. Shaping of
And (5) performing pressure forming according to the required drawing.
6. Secondary drying
And naturally drying the formed biscuit for 24 hours, and then drying the biscuit for 12 to 36 hours at the temperature of more than or equal to 150 ℃.
7. Firing into
And after drying, firing at 1550-1650 ℃ for 5-8 hours.
CN202010602427.4A 2020-06-30 2020-06-30 Chrome corundum brick with high erosion resistance and thermal shock resistance prepared by secondary mixed grinding and drying and process thereof Active CN112194473B (en)

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