High-strength wear-resistant thermal-insulation refractory material for dry quenching and preparation method thereof
By adding additives to silicon carbide refractory materials for dry quenching coke, a low thermal conductivity phase network and solid solution are formed. Combined with phenolic resin coating, the problems of insufficient strength, wear resistance and heat insulation performance of refractory materials for dry quenching coke are solved, and a high-strength and high-wear-resistant refractory material is realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU NUOMING HIGH TEMPERATURE MATERIALS CO LTD
- Filing Date
- 2026-02-12
- Publication Date
- 2026-05-12
AI Technical Summary
Existing silicon carbide refractory materials for dry quenching coke ovens lack sufficient strength, wear resistance, and heat insulation properties during long-term use. The silicon carbide matrix is easily corroded, and boron carbide cannot effectively form a hard skeleton for protection in the environment of dry quenching coke ovens.
By adding additives, which are composed of pretreated carbon black and boron oxide mixed with magnesium powder coated with magnesium fluoride, boron carbide and magnesium oxide are generated. These are combined with mullite powder, alumina and ferric oxide to form a low thermal conductivity phase network and solid solution, promoting dense sintering. Phenolic resin is used to graft and coat with epoxy-containing titanium dioxide to improve the mechanical strength and thermal insulation performance of the material.
It significantly improves the mechanical strength and thermal insulation performance of refractory materials used in dry quenching coke, reduces heat transfer efficiency, enhances resistance to erosion by molten slag and metal, and improves wear resistance.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of refractory materials technology, specifically to a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke and its preparation method. Background Technology
[0002] Refractory materials for dry quenching coke include refractory lining materials for dry quenching coke ovens and other refractory materials used in the dry quenching process. The working environment inside a dry quenching coke oven is harsh, therefore, higher requirements are placed on the strength, wear resistance, and thermal shock resistance of its lining refractory materials.
[0003] Among them, the patent with announcement number CN101580395B and titled "Refractory Material for Dry Quenching Coke" discloses a silicon carbide refractory material for dry quenching coke. Because it contains a large proportion of silicon carbide and β-silicon carbide, which are highly thermally conductive raw materials, its thermal insulation performance needs further improvement. Furthermore, during long-term use, the silicon carbide matrix is easily corroded, leading to a decrease in the strength, wear resistance, and thermal shock resistance of the refractory material for dry quenching coke. Boron carbide, with its high hardness, forms a hard skeleton in the environment of a dry quenching coke oven, effectively resisting the erosion and wear of molten slag and metal, and protecting the silicon carbide matrix from corrosion.
[0004] Therefore, how to add boron carbide and other additives to silicon carbide refractories for dry quenching to obtain refractories with excellent strength, wear resistance and thermal insulation properties requires further research. Summary of the Invention
[0005] To address the aforementioned technical problems, this invention provides a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke and its preparation method.
[0006] The objective of this invention can be achieved through the following technical solutions: A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke comprises the following raw materials in parts by weight: 60-70 parts silicon carbide, 0.5-1 parts ferric oxide, 10-15 parts alumina, 5-7 parts additives, and 8-12 parts mullite powder.
[0007] The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke is prepared by the following steps: Silicon carbide, ferric oxide, alumina, and mullite powder are mixed and stirred for 30-35 minutes. Add additives and continue stirring for 10-15 minutes. The mixture is then pressed into shape and heated and kept at a temperature of 8-12 hours in a protective gas environment. The temperature is then increased and kept at a temperature of 2-3 hours, and the mixture is cooled down. Finally, it is allowed to cool naturally to obtain a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching. Furthermore, the stirring speed is 35-40 rpm for 30-35 min; the stirring speed is 50-60 rpm for 10-15 min; and the pressing pressure is 100-200 MPa. Furthermore, the heating and holding process involves heating to 130-150℃ at a rate of 2-3℃ / min and then holding the temperature; the continued heating and holding process involves heating to 1450-1500℃ at a rate of 3-4℃ / min and then holding the temperature. Furthermore, the temperature is reduced to 750-800℃ at a rate of 4-5℃ / min.
[0008] The preparation method of the auxiliary agent includes the following steps: Step (1): After vacuum drying of carbon black, ultrasonic dispersion is performed to obtain pretreated carbon black; after vacuum drying of boron oxide, pretreated boron oxide is obtained; in a protective gas, magnesium powder, polytetrafluoroethylene and ball milling media are mixed and ball-milled to obtain pretreated magnesium powder; in a protective gas, pretreated carbon black, pretreated boron oxide and pretreated magnesium powder are mixed and stirred to obtain mixed powder. Step (2): After ultrasonically dispersing titanium dioxide powder and anhydrous ethanol, undecenoic acid is added, heated and stirred, and post-processed to obtain product 1; after ultrasonically dispersing product 1 and anhydrous ethanol, oxidant is added, heated and stirred, and post-processed to obtain epoxy-containing titanium dioxide. Step (3): In a protective gas atmosphere, the mixed powder and rosin solution are mixed and stirred, then added to the phenolic resin solution, ground, and then titanium dioxide dispersion containing epoxy groups and DMP-30 are added. The mixture is heated and stirred, and the additive is obtained after post-treatment.
[0009] Furthermore, the preparation method of the auxiliary agent includes the following specific steps: Step (1): Vacuum dry carbon black for 4-4.5 h to obtain pretreated carbon black; vacuum dry boron oxide for 8-8.5 h to obtain pretreated boron oxide; in a protective gas, mix magnesium powder, polytetrafluoroethylene and ball milling media and ball milling for 1.5-2.1 h to obtain pretreated magnesium powder; in a protective gas, mix and stir pretreated carbon black, pretreated boron oxide and pretreated magnesium powder for 1-1.5 h to obtain mixed powder; Furthermore, the vacuum drying temperature for carbon black is 115-120℃; the vacuum drying temperature for boron oxide is 180-200℃. Furthermore, the ratio of the total mass of magnesium powder and polytetrafluoroethylene (PTFE) to the mass of the milling media is 1:20-25; the ratio of magnesium powder to PTFE is 70-75g:25-30g; the milling media are PTFE balls; the milling is performed at a speed of 100-120 rpm, and then the speed is increased to 150-200 rpm; the milling time ratio at 100-120 rpm and 150-200 rpm is 1:2. Furthermore, the ratio of pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder is 15-17g: 58-59g: 63-65g; In step (1), magnesium fluoride is coated onto the surface of magnesium powder by controlling the rotation speed of the ball milling of magnesium powder and polytetrafluoroethylene in a protective gas and adjusting the ball milling time at different rotation speeds. Step (2): Mix titanium dioxide powder and anhydrous ethanol and ultrasonically disperse for 30-40 min, add undecenoic acid, heat to 60-65℃, stir for 2-2.5 h, centrifuge, wash, and vacuum dry at 50-60℃ for 4-5 h to obtain product 1; mix product 1 and anhydrous ethanol and ultrasonically disperse for 20-30 min, add oxidant, stir at 50-55℃ for 3-3.5 h, filter, wash, and dry to obtain epoxy-containing titanium dioxide; Furthermore, the ratio of titanium dioxide powder, anhydrous ethanol, and undecenoic acid is 10-12g: 55-65mL: 0.5-1g; Furthermore, the ratio of product 1, anhydrous ethanol, and oxidant is 13-15g:70-80mL:8-10mL; the oxidant is a 40-45% m-chlorobenzoic acid solution. In step (2), undecenoic acid is used to modify the surface of titanium dioxide to obtain titanium dioxide containing terminal alkenyl groups, i.e., product 1; the alkenyl groups in product 1 are oxidized to epoxy groups to obtain titanium dioxide containing epoxy groups. Step (3): In a protective gas atmosphere, mix the powder and rosin solution and stir for 20-30 min, then add to the phenolic resin solution and grind for 5-6 h. Add the titanium dioxide dispersion containing epoxy groups and DMP-30, heat to 150-155℃, reflux and stir for 1.5-2 h, cool to room temperature, centrifuge, wash with ethanol, and vacuum dry for 12-13 h to obtain the additive; Furthermore, the ratio of the mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:1.5-2mL:10-15mL:8-10mL:15-20mg; Furthermore, the rosin solution is obtained by mixing and stirring rosin and anhydrous ethanol at a ratio of 1g:10-15mL; the phenolic resin solution is obtained by mixing phenolic resin and anhydrous ethanol at a ratio of 5-10g:100mL, stirring at 60-70℃ for 20-30min, and then cooling; the epoxy-containing titanium dioxide dispersion is obtained by ultrasonically dispersing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 10-12g:60-70mL. Furthermore, the grinding speed is 200-300 rpm; the vacuum drying temperature is 70-80℃; In step (3), the rosin solution is first used to pre-wet and mix the mixed powder, and then the phenolic resin solution is added for grinding. Under the catalysis of DMP-30, the phenolic resin reacts with the epoxy-containing titanium dioxide to obtain the mixed powder coated with phenolic resin (grafted with titanium dioxide), which is the additive.
[0010] This invention discloses a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke and its preparation method. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke is obtained by mixing silicon carbide, ferric oxide, alumina, additives, and mullite powder, pressing them into shape, and then sintering them in a protective gas.
[0011] The beneficial effects of this invention are: 1. The additives used in this invention are prepared by mixing dried and pretreated carbon black and boron oxide with magnesium powder coated with magnesium fluoride after pretreatment to obtain a mixed powder. Titanium dioxide is then modified with undecenoic acid and oxidized with an oxidant to obtain epoxy-containing titanium dioxide. The mixed powder, rosin solution, phenolic resin solution, and epoxy-containing titanium dioxide dispersion are then mixed. Grafting of phenolic resin with epoxy-containing titanium dioxide is promoted through grinding and heating catalysis. A mixed powder coated with phenolic resin (grafted with titanium dioxide) is obtained through a liquid-phase grinding and coating process. In this invention, mullite powder is dispersed in a silicon carbide matrix to form a low thermal conductivity phase network. Alumina and ferric oxide form a solid solution with mullite at high temperature, promoting dense sintering. Ferric oxide stabilizes the low thermal conductivity glass phase, reducing heat transfer efficiency and ensuring that the thermal insulation performance of the dry-quenched refractory material meets the application requirements.
[0012] 2. In the additives of this invention, polytetrafluoroethylene and magnesium powder are ball-milled in a protective gas environment. This method avoids the use of corrosive and safety-risk reagents such as hydrofluoric acid and ammonium fluoride. The preparation method is simple and environmentally friendly. A magnesium fluoride coating layer is formed on the surface of the magnesium powder. This magnesium fluoride coating layer, together with the subsequent phenolic resin coating layer grafted with titanium dioxide, synergistically protects the magnesium powder, allowing it to react with carbon black and boron oxide during the inert gas and heated sintering process to generate boron carbide and magnesium oxide. The generated boron carbide enables the refractory material to resist slag and metal corrosion, improving the wear resistance, mechanical strength, and other properties of the refractory material.
[0013] 3. The magnesium oxide generated in this invention can react with titanium dioxide to form high-melting-point magnesium titanate, which serves as a heterogeneous nucleation site, lowers the nucleation energy barrier, promotes sintering neck growth and pore closure, and enhances the mechanical strength of refractory materials. Magnesium titanate has strong chemical inertness and does not easily react with slag in dry quenching coke ovens, preventing slag phase penetration. This solves the problem that magnesium oxide obtained from the reaction of carbon black, boron oxide and magnesium powder cannot be effectively removed, and realizes diversified utilization of the product. Detailed Implementation
[0014] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0015] Example 1 The preparation method of the additive includes the following steps: Step (1): Carbon black (supplier: Tianjin Huarun Chemical Technology Co., Ltd., model: YJ-2) was vacuum dried at 115℃ for 4h to obtain pretreated carbon black; boron oxide (supplier: Aladdin, item number: B108406) was vacuum dried at 180℃ for 8h to obtain pretreated boron oxide; magnesium powder (supplier: Aladdin, item number: M305513), polytetrafluoroethylene (supplier: Aladdin, item number: P434338), and ball milling media were mixed in nitrogen and ball milled at 100rpm for 0.5h, then ball milled at 150rpm for 1h, and cooled in a nitrogen atmosphere to obtain pretreated magnesium powder; in nitrogen, pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder were mixed and stirred for 1h, and ground through a 200-mesh sieve to obtain mixed powder; The ratio of the total mass of magnesium powder and polytetrafluoroethylene to the mass of the milling media is 1:20; the ratio of magnesium powder to polytetrafluoroethylene is 70g:30g; the milling media are polytetrafluoroethylene balls (supplier: Jiangsu Linwei New Material Co., Ltd., diameter 5mm); the ratio of pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder is 15g:58g:63g. Step (2): Titanium dioxide powder (supplier: Aladdin, item number: T294738) and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 30 min. Undecenoic acid was added, heated to 60℃, stirred for 2 h, centrifuged at 1000 rpm for 15 min, washed three times with 95% ethanol, and vacuum dried at 50℃ for 4 h to obtain product 1. Product 1 and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 20 min. Oxidizing agent was added, stirred at 50℃ for 3 h, filtered, washed three times with ethanol, and vacuum dried at 60℃ for 4 h to obtain epoxy-containing titanium dioxide. The ratio of titanium dioxide powder, anhydrous ethanol, and undecenoic acid is 10g:55mL:0.5g; the ratio of product 1, anhydrous ethanol, and oxidant is 13g:70mL:8mL; the oxidant is a 40% m-chlorobenzoic acid solution. Step (3): In nitrogen, mix the powder and rosin solution for 20 min, then add it to the phenolic resin solution and grind it at 200 rpm for 5 h. Add the epoxy-containing titanium dioxide dispersion and DMP-30, heat to 150℃, reflux and stir for 1.5 h, cool to room temperature, centrifuge at 1000 rpm for 20 min, wash three times with 95% ethanol, and vacuum dry at 70℃ for 12 h to obtain the additive. The ratio of mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:1.5mL:10mL:8mL:15mg. The rosin solution is obtained by mixing rosin (supplier: Aladdin, item number: G331394) and anhydrous ethanol at a ratio of 1g:10mL. The phenolic resin solution is obtained by mixing phenolic resin (supplier: Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., active ingredient content 99%) and anhydrous ethanol at a ratio of 5g:100mL, stirring at 60℃ for 20min, and then cooling. The epoxy-containing titanium dioxide dispersion is obtained by mixing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 10g:60mL and ultrasonically dispersing at 80W for 30min.
[0016] Example 2 The preparation method of the additive includes the following steps: Step (1): Carbon black (supplier: Tianjin Huarun Chemical Technology Co., Ltd., model: YJ-2) was vacuum dried at 118℃ for 4.3h to obtain pretreated carbon black; boron oxide (supplier: Aladdin, item number: B108406) was vacuum dried at 190℃ for 8.3h to obtain pretreated boron oxide; magnesium powder (supplier: Aladdin, item number: M305513), polytetrafluoroethylene (supplier: Aladdin, item number: P434338), and ball milling media were mixed in nitrogen and ball milled at 110rpm for 0.6h, then ball milled at 170rpm for 1.2h, and cooled in a nitrogen atmosphere to obtain pretreated magnesium powder; in nitrogen, pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder were mixed and stirred for 1.3h, and ground through a 200-mesh sieve to obtain mixed powder; The ratio of the total mass of magnesium powder and polytetrafluoroethylene to the mass of the milling media is 1:23; the ratio of magnesium powder to polytetrafluoroethylene is 73g:27g; the milling media are polytetrafluoroethylene balls (supplier: Jiangsu Linwei New Material Co., Ltd., diameter 5mm); the ratio of pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder is 16g:58.5g:64g. Step (2): Titanium dioxide powder (supplier: Aladdin, item number: T294738) and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 35 min. Undecenoic acid was added, heated to 63℃, stirred for 2.3 h, centrifuged at 1000 rpm for 15 min, washed three times with 95% ethanol, and vacuum dried at 55℃ for 4.5 h to obtain product 1. Product 1 and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 25 min. Oxidizing agent was added, stirred at 53℃ for 3.3 h, filtered, washed three times with ethanol, and vacuum dried at 60℃ for 4 h to obtain epoxy-containing titanium dioxide. The ratio of titanium dioxide powder, anhydrous ethanol, and undecenoic acid is 11g:60mL:0.8g; the ratio of product 1, anhydrous ethanol, and oxidant is 14g:75mL:9mL; the oxidant is a 43% m-chlorobenzoic acid solution. Step (3): In nitrogen, mix the powder and rosin solution and stir for 23 min, then add to the phenolic resin solution and grind at 250 rpm for 5.5 h. Add the epoxy-containing titanium dioxide dispersion and DMP-30, heat to 153℃, reflux and stir for 1.8 h, cool to room temperature, centrifuge at 1000 rpm for 20 min, wash three times with 95% ethanol, and vacuum dry at 75℃ for 12.5 h to obtain the additive. The ratio of mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:1.8mL:13mL:9mL:18mg. The rosin solution is obtained by mixing rosin (supplier: Aladdin, product number: G331394) and anhydrous ethanol at a ratio of 1g:13mL. The phenolic resin solution is obtained by mixing phenolic resin (supplier: Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., effective ingredient content 99%) and anhydrous ethanol at a ratio of 8g:100mL, stirring at 65℃ for 25min, and then cooling. The epoxy-containing titanium dioxide dispersion is obtained by mixing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 11g:65mL and ultrasonically dispersing at 80W for 30min.
[0017] Example 3 The preparation method of the additive includes the following steps: Step (1): Carbon black (supplier: Tianjin Huarun Chemical Technology Co., Ltd., model: YJ-2) was vacuum dried at 120℃ for 4.5h to obtain pretreated carbon black; boron oxide (supplier: Aladdin, item number: B108406) was vacuum dried at 200℃ for 8.5h to obtain pretreated boron oxide; magnesium powder (supplier: Aladdin, item number: M305513), polytetrafluoroethylene (supplier: Aladdin, item number: P434338), and ball milling media were mixed in nitrogen and ball milled at 120rpm for 0.7h, then ball milled at 200rpm for 1.4h, and cooled in a nitrogen atmosphere to obtain pretreated magnesium powder; in nitrogen, pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder were mixed and stirred for 1.5h, and ground through a 200-mesh sieve to obtain mixed powder; The ratio of the total mass of magnesium powder and polytetrafluoroethylene to the mass of the milling media is 1:5; the ratio of magnesium powder to polytetrafluoroethylene is 75g:25g; the milling media are polytetrafluoroethylene balls (supplier: Jiangsu Linwei New Material Co., Ltd., diameter 5mm); the ratio of pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder is 17g:59g:65g. Step (2): Titanium dioxide powder (supplier: Aladdin, item number: T294738) and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 40 min. Undecenoic acid was added, heated to 65℃, stirred for 2.5 h, centrifuged at 1000 rpm for 15 min, washed three times with 95% ethanol, and vacuum dried at 60℃ for 5 h to obtain product 1. Product 1 and anhydrous ethanol were mixed and ultrasonically dispersed at 100W for 30 min. Oxidizing agent was added, stirred at 55℃ for 3.5 h, filtered, washed three times with ethanol, and vacuum dried at 60℃ for 4 h to obtain epoxy-containing titanium dioxide. The ratio of titanium dioxide powder, anhydrous ethanol, and undecenoic acid is 12g:65mL:1g; the ratio of product 1, anhydrous ethanol, and oxidant is 15g:80mL:10mL; the oxidant is a 45% m-chlorobenzoic acid solution. Step (3): In nitrogen, mix the powder and rosin solution for 30 min, then add it to the phenolic resin solution and grind it at 300 rpm for 6 h. Add the epoxy-containing titanium dioxide dispersion and DMP-30, heat to 155℃, reflux and stir for 2 h, cool to room temperature, centrifuge at 1000 rpm for 20 min, wash three times with 95% ethanol, and vacuum dry at 80℃ for 13 h to obtain the additive. The ratio of mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:2mL:15mL:10mL:20mg. The rosin solution is obtained by mixing rosin (supplier: Aladdin, product number: G331394) and anhydrous ethanol at a ratio of 1g:15mL. The phenolic resin solution is obtained by mixing phenolic resin (supplier: Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., effective ingredient content 99%) and anhydrous ethanol at a ratio of 10g:100mL, stirring at 70℃ for 30min, and then cooling. The epoxy-containing titanium dioxide dispersion is obtained by mixing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 12g:70mL and ultrasonically dispersing at 80W for 30min.
[0018] Example 4 A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke comprises the following raw materials in parts by weight: 60 parts silicon carbide, 0.5 parts ferric oxide, 10 parts alumina, 5 parts of the additives obtained in Example 1, and 8 parts mullite powder.
[0019] The preparation method of a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke includes the following steps: Silicon carbide (supplier: Anyang Henghao Metallurgical Refractory Co., Ltd., 200 mesh), ferric oxide (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), alumina (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), and mullite powder (supplier: Lingshou County Zhongxin Mineral Products Processing Plant, 200 mesh) were mixed and stirred at 35 rpm for 30 min. The additives obtained in Example 1 were added, and stirring was continued at 50 rpm for 10 min. The mixture was pressed into shape under a pressure of 100 MPa. In nitrogen, the mixture was heated to 130°C at a rate of 2°C / min and held for 8 h. The temperature was then increased to 1450°C at a rate of 3°C / min and held for 2 h. The temperature was then decreased to 750°C at a rate of 4°C / min and then allowed to cool naturally to obtain a high-strength, wear-resistant, and heat-insulating dry quenching refractory material.
[0020] Example 5 A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke comprises the following raw materials in parts by weight: 65 parts silicon carbide, 0.8 parts ferric oxide, 13 parts alumina, 6 parts of the additives obtained in Example 2, and 10 parts mullite powder.
[0021] The preparation method of a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke includes the following steps: Silicon carbide (supplier: Anyang Henghao Metallurgical Refractory Co., Ltd., 200 mesh), ferric oxide (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), alumina (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), and mullite powder (supplier: Lingshou County Zhongxin Mineral Products Processing Plant, 200 mesh) were mixed and stirred at 37 rpm for 33 min. The additives obtained in Example 2 were added, and stirring was continued at 55 rpm for 13 min. The mixture was pressed into shape under a pressure of 150 MPa. In nitrogen, the mixture was heated to 140°C at a rate of 2.5°C / min and held for 10 h. The temperature was then increased to 1480°C at a rate of 3.5°C / min and held for 2.5 h. The temperature was then decreased to 780°C at a rate of 4.5°C / min and then allowed to cool naturally to obtain a high-strength, wear-resistant, and heat-insulating dry quenching refractory material.
[0022] Example 6 A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke comprises the following raw materials in parts by weight: 70 parts silicon carbide, 1 part ferric oxide, 15 parts alumina, 7 parts of the additives obtained in Example 3, and 12 parts mullite powder.
[0023] The preparation method of a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke includes the following steps: Silicon carbide (supplier: Anyang Henghao Metallurgical Refractory Co., Ltd., 200 mesh), ferric oxide (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), alumina (supplier: Kairui New Materials (Beijing) Technology Co., Ltd., 200 mesh), and mullite powder (supplier: Lingshou County Zhongxin Mineral Products Processing Plant, 200 mesh) were mixed and stirred at 40 rpm for 35 min. The additives obtained in Example 3 were added, and stirring was continued at 60 rpm for 15 min. The mixture was pressed into shape under a pressure of 200 MPa. In nitrogen, the mixture was heated to 150°C at a rate of 3°C / min and held for 12 h. The temperature was then increased to 1500°C at a rate of 4°C / min and held for 3 h. The temperature was then decreased to 800°C at a rate of 5°C / min and then allowed to cool naturally to obtain a high-strength, wear-resistant, and heat-insulating dry quenching refractory material.
[0024] Comparative Example 1 Compared with Example 6, Product 1 in the preparation of the additives was replaced with Product 1-1, and the rest was exactly the same as in Example 9, to obtain a dry quenching refractory material; Specifically, titanium dioxide powder (supplier: Aladdin, item number: T294738), anhydrous ethanol, and deionized water were mixed and ultrasonically dispersed at 100W for 40 min. KH560 was added, heated to 65℃, stirred for 2.5 h, centrifuged at 1000 rpm for 15 min, washed three times with deionized water, and vacuum dried at 60℃ for 5 h to obtain product 1-1. The ratio of titanium dioxide powder, anhydrous ethanol, deionized water, and KH560 was 12 g: 45 mL: 20 mL: 1 g.
[0025] Comparative Example 2 Compared with Example 6, the additive used was replaced with additive-1, and the rest was exactly the same as in Example 6, to obtain a dry quenching refractory material; Specifically: In nitrogen, the mixed powder and rosin solution were mixed and stirred for 30 min, then phenolic resin solution, epoxy-containing titanium dioxide dispersion and DMP-30 were added, and the mixture was ground at 300 rpm for 6 h, heated to 155 °C and stirred for 2 h, cooled to room temperature, centrifuged at 1000 rpm for 20 min, washed three times with 95% ethanol, and vacuum dried at 80 °C for 13 h to obtain additive-1; The ratio of mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:2mL:15mL:10mL:20mg. The rosin solution is obtained by mixing rosin (supplier: Aladdin, item number: G331394) and anhydrous ethanol at a ratio of 1g:15mL. The phenolic resin solution is obtained by mixing phenolic resin (supplier: Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., effective ingredient content 99%) and anhydrous ethanol at a ratio of 10g:100mL, stirring at 70℃ for 30min, and then cooling. The epoxy-containing titanium dioxide dispersion is obtained by ultrasonically dispersing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 12g:70mL at a power of 80W.
[0026] Comparative Example 3 Compared with Example 6, the additive used was replaced with additive-2, and everything else was exactly the same as in Example 6, to obtain a dry quenching refractory material; Specifically: In nitrogen atmosphere, the mixed powder, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 were mixed and stirred for 30 min, ground at 300 rpm for 6 h, heated to 155 °C, stirred for 2 h, cooled to room temperature, centrifuged at 1000 rpm for 20 min, washed three times with 95% ethanol (v / v), and vacuum dried at 80 °C for 13 h to obtain additive-2. The ratio of mixed powder, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:17mL:10mL:20mg; the rosin solution is obtained by mixing rosin (supplier: Aladdin, item number: G331394) and anhydrous ethanol at a ratio of 1g:15mL; the phenolic resin solution is obtained by mixing phenolic resin (supplier: Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., effective ingredient content 99%) and anhydrous ethanol at a ratio of 10g:100mL, stirring at 70℃ for 30min, and then cooling; the epoxy-containing titanium dioxide dispersion is obtained by ultrasonically dispersing epoxy-containing titanium dioxide and anhydrous ethanol at a ratio of 12g:70mL at a power of 80W.
[0027] The following is a further performance test of the dry quenching refractory material prepared according to the present invention, and the test results are shown below.
[0028] Room temperature compressive strength test: The test was conducted in accordance with GB / T 5072-2023 "Test Method for Room Temperature Compressive Strength of Refractory Materials".
[0029] High-temperature flexural strength test: The high-temperature flexural strength test at 1450℃ was conducted in accordance with GB / T 3002-2017 "Test Method for High-Temperature Flexural Strength of Refractory Materials".
[0030] Abrasion resistance test: The test was conducted according to GB / T 18301-2012 "Test Method for Abrasion Resistance of Refractory Materials at Room Temperature", and the abrasion amount (cm) was recorded. 3 ).
[0031] The results are recorded in Table 1; Table 1: Test Results According to the data in Table 1, the refractory material for dry quenching coke of the present invention has high room temperature compressive strength and high temperature flexural strength, as well as low wear.
[0032] Comparing Example 6 with Comparative Example 1, it can be seen that replacing Product 1 in the preparation of the additives with Product 1-1 shows that the dry quenching refractory material prepared by using Product 1 in this invention has higher room temperature compressive strength and high temperature flexural strength, as well as lower wear.
[0033] Comparing Example 6 with Comparative Example 2, it can be seen that replacing the additive with Additive-1 shows that the dry quenching refractory material prepared by the present invention has higher room temperature compressive strength and high temperature flexural strength, and lower wear.
[0034] Comparing Example 6 with Comparative Example 3, it can be seen that replacing the additive with Additive-2 shows that the dry quenching refractory material prepared by the present invention has higher room temperature compressive strength and high temperature flexural strength, and lower wear.
[0035] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.
Claims
1. A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke, characterized in that: The raw materials include the following parts by weight: 60-70 parts silicon carbide, 0.5-1 parts ferric oxide, 10-15 parts alumina, 5-7 parts additives, and 8-12 parts mullite powder.
2. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke as described in claim 1, characterized in that: The preparation method of the auxiliary agent includes the following steps: Step (1): After vacuum drying of carbon black, ultrasonic dispersion is performed to obtain pretreated carbon black; after vacuum drying of boron oxide, pretreated boron oxide is obtained; in a protective gas environment, magnesium powder, polytetrafluoroethylene and ball milling media are mixed and ball-milled to obtain pretreated magnesium powder. In a protective gas atmosphere, pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder are mixed and stirred to obtain a mixed powder. Step (2): After ultrasonically dispersing titanium dioxide powder and anhydrous ethanol, undecenoic acid is added, heated and stirred, and post-processed to obtain product 1; after ultrasonically dispersing product 1 and anhydrous ethanol, oxidant is added, heated and stirred, and post-processed to obtain epoxy-containing titanium dioxide. Step (3): In a protective gas atmosphere, the mixed powder and rosin solution are mixed and stirred, then added to the phenolic resin solution, ground, and then titanium dioxide dispersion containing epoxy groups and DMP-30 are added. The mixture is heated and stirred, and the additive is obtained after post-treatment.
3. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke as described in claim 2, characterized in that: In step (1), the ratio of the total mass of magnesium powder and polytetrafluoroethylene to the mass of the milling media is 1:20-25; the milling media is polytetrafluoroethylene balls.
4. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (1), the ratio of magnesium powder to polytetrafluoroethylene is 70-75g: 25-30g; the ratio of pretreated carbon black, pretreated boron oxide, and pretreated magnesium powder is 15-17g: 58-59g: 63-65g.
5. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (2), the ratio of titanium dioxide powder, anhydrous ethanol, and undecenoic acid is 10-12g: 55-65mL: 0.5-1g.
6. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (2), the ratio of product 1, anhydrous ethanol, and oxidant is 13-15g: 70-80mL: 8-10mL.
7. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (3), the ratio of the mixed powder, rosin solution, phenolic resin solution, epoxy-containing titanium dioxide dispersion, and DMP-30 is 1g:1.5-2mL:10-15mL:8-10mL:15-20mg.
8. The high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (3), the rosin solution is obtained by mixing rosin and anhydrous ethanol at a ratio of 1g:10-15mL; the phenolic resin solution is obtained by mixing phenolic resin and anhydrous ethanol at a ratio of 5-10g:100mL, stirring at 60-70℃ for 20-30min, and then cooling.
9. A high-strength, wear-resistant, and heat-insulating refractory material for dry quenching coke according to claim 2, characterized in that: In step (3), the epoxy-containing titanium dioxide dispersion is obtained by ultrasonically dispersing epoxy-containing titanium dioxide and anhydrous ethanol in a ratio of 10-12g:60-70mL.
10. A method for preparing a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching as described in any one of claims 1-9, characterized in that: Includes the following steps: Silicon carbide, ferric oxide, alumina, and mullite powder are mixed and stirred for 30-35 minutes. Add additives and continue stirring for 10-15 minutes. The mixture is then pressed into shape and heated and kept at a constant temperature for 8-12 hours in a protective gas environment. The temperature is then increased and kept at a constant temperature for 2-3 hours, followed by cooling. The mixture is then allowed to cool naturally to obtain a high-strength, wear-resistant, and heat-insulating refractory material for dry quenching.