Refractory for hydrogen energy glass kiln and preparation method thereof

Abstract

In order to promote hydrogen energy glass kiln faster, it is of great significance to develop a kind of refractory material for hydrogen energy glass kiln. The present application belongs to the field of refractory material preparation, and specifically relates to a kind of refractory material for hydrogen energy glass kiln and a preparation method thereof. The refractory material prepared by the present application can work stably for a long time in a high-temperature environment without significant phase change or decomposition, has good thermal shock resistance, so that the material can withstand frequent temperature changes, exhibits excellent oxidation resistance in a hydrogen combustion environment, prevents the surface of the material from being oxidized and corroded, and has high mechanical strength and wear resistance, greatly improving the reliability and durability of the material in harsh working conditions.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of refractory materials, and particularly relates to a refractory material for a hydrogen energy glass kiln and a preparation method thereof. BACKGROUND

[0002] Glass is mainly made of quartz sand and soda ash as raw materials through high-temperature melting. Glass kiln is a device for melting glass, and there are many types of glass kilns. Hydrogen energy glass kiln is a high-temperature equipment that uses hydrogen as the main fuel, which is used in the melting, refining and homogenizing processes in the glass manufacturing process. Compared with traditional fossil fuels (such as natural gas or heavy oil), hydrogen energy has the advantage of zero carbon emissions, so it is of great significance in achieving the goal of industrial decarbonization. Hydrogen has high calorific value combustion characteristics, and the calorific value of hydrogen is about 142 MJ / kg, which is more than twice that of natural gas, and can provide higher heat output. The combustion products of hydrogen are mainly water vapor, which theoretically does not produce carbon dioxide (CO2), nitrogen oxides (NO x ) and sulfur oxides (SO x ), which helps to reduce environmental pollution. Hydrogen can be directly burned to heat the glass raw materials in the kiln, similar to the use of traditional fuels. Combined with electric heating technology, energy utilization efficiency and temperature control accuracy can be further improved. The advantages of hydrogen energy glass kiln are environmentally friendly, hydrogen combustion does not produce CO2, which meets the global carbon neutralization goal. Compared with traditional fuels, hydrogen combustion produces almost no other harmful gases. The high calorific value of hydrogen means that less fuel is consumed to achieve the same heating effect. Hydrogen combustion is fast, which can quickly raise the temperature of the kiln and shorten the heating time. Hydrogen energy kiln can flexibly adjust operating parameters to adapt to different types and sizes of glass production needs. However, the high temperature and water vapor produced by hydrogen combustion can cause corrosion to the kiln materials, and new refractory materials with high temperature resistance and corrosion resistance need to be developed. Frequent temperature changes can cause cracks or damage to the kiln materials, and the thermal shock resistance of the materials needs to be improved. Therefore, the refractory material for hydrogen energy glass kiln needs to have excellent high temperature stability, thermal shock resistance and oxidation resistance to adapt to the high temperature environment produced by hydrogen combustion and possible rapid temperature changes. Hydrogen energy glass kiln as a new clean energy technology has great potential in achieving industrial decarbonization. In order to promote the hydrogen energy glass kiln faster, it is of great significance to develop a refractory material for hydrogen energy glass kiln. SUMMARY

[0003] In view of the above problems, the application provides a refractory material for a hydrogen energy glass kiln and a preparation method thereof, and the specific preparation method is as follows:

[0004] S1, take 5-12 mL of hydrochloric acid, dilute to 20-33 mL with ethanol, immerse in copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone and ultrasonic for 5-11 min, rinse with ethanol, then immerse in ethanol and ultrasonic for 8-16 min to obtain clean copper foil; all solutions in this step need to be prepared fresh to avoid re-oxidation.

[0005] S2, take 2-3 g of sodium hydroxide and 0.15-0.5 g of ammonium thiosulfate and dissolve in 12-23 mL of deionized water, immerse the copper foil treated in step S1, soak for 8-15 min and then rinse clean to obtain Cu(OH)2 nanowires, then calcine in a muffle furnace at 320-410 ℃ for 1.5-3.1 h to obtain CuO nanowires; the calcination of Cu(OH)2 nanowires in the muffle furnace in this step is to quickly dehydrate and prepare more ductile CuO nanowires.

[0006] S3, dissolve 0.61-0.83 mmol of cobalt nitrate, 0.23-0.44 mmol of cesium chloride, 0.23-0.44 mmol of high rhenium acid ammonium and 0.3-0.5 g of hexamethylene tetramine in 33-45 mL of deionized water, stir for 12-23 min, put in the CuO nanowires prepared in step S2, soak for 12-16 min, then transfer to the reaction kettle together, calcine at 118-148 ℃ for 8-10 h, after cooling, immerse the copper foil with the material in ethanol, ultrasonic stripping for 1 h, centrifugal dry to obtain Re / Co / Cs-LDH@CuO. This material utilizes the one-dimensional structure of copper oxide nanowires, and coats Re, Co and Cs metal nanoparticles on the outer layer of the nanowires. The three metal particles are uniformly attached to the nanowires through hydrothermal reaction, and can improve the toughness and thermal shock resistance of the refractory material as an additive, to ensure that the refractory material will not crack or break in frequent temperature changes.

[0007] S4, 5-7 g of Re / Co / Cs-LDH@CuO prepared in step S3, 33-41 g of aluminum oxide, 5-8 g of silicon dioxide, 11-13 g of zirconium oxide, 4-6 g of mullite, 17-23 g of silicon carbide, 6-8 g of cerium dioxide, 7-11 g of titanium oxide, 2-5 g of ethylenediaminetetraacetic acid, and 8-13 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) are added to a ball milling tank for ball milling for 35-45 min; the uniformly ball-milled powder is transferred to a high-speed mixer for uniform mixing, 120-150 mL of a polyvinyl alcohol solution, 50-80 mL of ethylene glycol, and 300-450 mL of methanol are added, and stirring is continued for 30 min to form a suspension; the suspension is then subjected to spray drying by a spray dryer, with the inlet temperature set to 135 °C and the outlet temperature set to 160 °C, to obtain a granular material; in this step, the aluminum oxide (Al2O3) serves as a matrix material, providing good mechanical strength and high-temperature stability; the silicon dioxide (SiO2) enhances the structural stability and corrosion resistance of the material; the zirconium oxide (ZrO2) improves the thermal shock resistance and toughness of the material; the mullite (3Al2O3·2SiO2) provides excellent high-temperature performance and creep resistance; the silicon carbide (SiC) increases the thermal conductivity and wear resistance; the cerium dioxide can promote densification and improve the microstructure; the P123 has good surface activity due to its amphiphilic structure, can reduce the surface tension of the liquid, and has solubilizing and dispersing effects; in addition, the use of the spray drying method in this step to prepare the granular material can control the size of the generated particles, and the formed particles are usually spherical or approximately spherical, with good flowability; the spray drying method used in this step has the characteristics of speed, efficiency, high quality, and flexibility, and the granular material is easy to shape in subsequent processes.

[0008] S5, the granulated material from step S4 is placed in a mold, and compression is performed at a pressure of 100-700 MPa, with a holding time of 15-34 min, to form the desired shape; then pre-sintering is performed at about 800-1000 °C to remove organic matter and initially solidify; sintering is performed in an argon-hydrogen mixed gas containing 5% hydrogen for 2-3 h, with a sintering temperature of 1600-1800 °C, to densify the material and form a stable crystal structure, and then cooling is performed at a rate of 5 °C / min to room temperature, to obtain a refractory material for a hydrogen energy glass kiln. The cold isostatic pressing used in this step ensures higher density and uniformity; the mold is made of a flexible mold made of rubber or elastic plastic, ensuring uniform transmission of pressure; the cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop. -1

[0009] ​Preferably: in the step S2, 2 g of sodium hydroxide and 0.15 g of ammonium thiosulfate are weighed and dissolved in 12 mL of deionized water, the copper foil treated in step S1 is immersed, taken out and rinsed clean after 8 min of soaking, Cu(OH)2nanowires are obtained, and then calcination is performed in a muffle furnace at 320 ℃ for 1.5 h, and CuO nanowires are obtained.

[0010] Preferably: in the step S2, 3 g of sodium hydroxide and 0.5 g of ammonium thiosulfate are weighed and dissolved in 23 mL of deionized water, the copper foil treated in step S1 is immersed, taken out and rinsed clean after 15 min of soaking, Cu(OH)2nanowires are obtained, and then calcination is performed in a muffle furnace at 410 ℃ for 3.1 h, and CuO nanowires are obtained.

[0011] Preferably: in the step S3, 0.61 mmol of cobalt nitrate, 0.23 mmol of cesium chloride, 0.23 mmol of ammonium perrhenate and 0.3 g of hexamethylenetetramine are dissolved in 33 mL of deionized water, stirred for 12 min, and then transferred to the reaction kettle together with the CuO nanowires prepared in step S2, calcined at 118 ℃ for 8 h, and then the copper foil with the material is taken out, immersed in ethanol, ultrasonically peeled for 1 h, and centrifuged and dried, and Re / Co / Cs-LDH@CuO is obtained.

[0012] Preferably: in the step S3, 0.83 mmol of cobalt nitrate, 0.44 mmol of cesium chloride, 0.44 mmol of ammonium perrhenate and 0.5 g of hexamethylenetetramine are dissolved in 45 mL of deionized water, stirred for 23 min, and then transferred to the reaction kettle together with the CuO nanowires prepared in step S2, calcined at 148 ℃ for 10 h, and then the copper foil with the material is taken out, immersed in ethanol, ultrasonically peeled for 1 h, and centrifuged and dried, and Re / Co / Cs-LDH@CuO is obtained.

[0013] Preferably: In step S4, 5 g of Re / Co / Cs-LDH@CuO prepared in step S3, 33 g of aluminum oxide, 5 g of silicon dioxide, 11 g of zirconium oxide, 4 g of mullite, 17 g of silicon carbide, 6 g of cerium dioxide, 7 g of titanium oxide, 2 g of ethylenediaminetetraacetic acid, and 8 g of polyethylene oxide-polypropylene oxide-polyethylene oxide are added to a ball mill and ball-milled for 35 min. The powder after uniform ball milling is transferred to a high-speed mixer for uniform mixing, and 120 mL of polyvinyl alcohol solution, 50 mL of ethylene glycol, and 300 mL of methanol are added. The mixture is stirred for another 30 min to form a suspension. The suspension is then spray-dried using a spray dryer with an inlet air temperature of 135 ℃ and an outlet air temperature of 160 ℃ to obtain granular material.

[0014] Preferably: In step S4, 7 g of Re / Co / Cs-LDH@CuO prepared in step S3, 41 g of aluminum oxide, 8 g of silicon dioxide, 13 g of zirconium oxide, 6 g of mullite, 23 g of silicon carbide, 8 g of cerium dioxide, 11 g of titanium oxide, 5 g of ethylenediaminetetraacetic acid, and 13 g of polyethylene oxide-polypropylene oxide-polyethylene oxide are added to a ball mill and ball-milled for 45 min. The powder after uniform ball milling is transferred to a high-speed mixer for uniform mixing, and 150 mL of polyvinyl alcohol solution, 80 mL of ethylene glycol, and 450 mL of methanol are added. The mixture is stirred for another 30 min to form a suspension. The suspension is then spray-dried using a spray dryer with an inlet air temperature of 135 ℃ and an outlet air temperature of 160 ℃ to obtain granular material.

[0015] Preferably: In step S5, the granulated material from step S4 is placed in a mold, pressed at a pressure of 100 MPa for 15 minutes to form the desired shape; then pre-fired at approximately 800 °C to remove organic matter and pre-solidify; sintered in an argon-hydrogen mixture containing 5% hydrogen for 2 hours at a sintering temperature of 1600 °C to densify the material and form a stable crystal structure, and then sintered at 5 °C for 5 minutes. -1 By cooling the material to room temperature at a certain rate, a refractory material for hydrogen-powered glass furnaces can be obtained.

[0016] Preferably: In step S5, the granulated material from step S4 is placed in a mold, pressed at a pressure of 700 MPa for 34 min to form the desired shape; then pre-fired at approximately 1000°C to remove organic matter and pre-solidify; sintered in an argon-hydrogen mixture containing 5% hydrogen for 3 h at a sintering temperature of 1800°C to densify the material and form a stable crystal structure, and then sintered at 5°C for 5 min. -1The cooling rate is 10-20℃ / min, and the cooling is stopped at 1000-1200℃.

[0017] Advantages of the present application:

[0018] 1. The refractory material prepared by the present application can work stably for a long time in high temperature environment without significant phase change or decomposition.

[0019] 2. The refractory material prepared by the present application has good thermal shock resistance, so that the material can withstand frequent temperature changes.

[0020] 3. The refractory material prepared by the present application exhibits excellent oxidation resistance in hydrogen combustion environment, preventing the material surface from being oxidized and eroded.

[0021] 4. The refractory material prepared by the present application has high mechanical strength and wear resistance, greatly improving the reliability and durability of the material in harsh working conditions

[0022] 5. The preparation process of the present application is simple, and the product is low in price. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0024] Figure 1 Scanning electron microscope image of Cu(OH)2 nanowires prepared by the present application.

[0025] Figure 2 Scanning electron microscope image of CuO nanowires prepared by the present application.

[0026] Figure 3 Scanning electron microscope image of Re / Co / Cs-LDH@CuO prepared by Example 2 of the present application.

[0027] Figure 4 Scanning electron microscope image of Re / Cs-LDH@CuO prepared by Comparative Example 1 of the present application.

[0028] Figure 5 Scanning electron microscope image of Re / Co-LDH@CuO prepared by Comparative Example 2 of the present application.

[0029] Figure 6 Scanning electron microscope image of Co / Cs-LDH@CuO prepared by Comparative Example 3 of the present application. DETAILED DESCRIPTION

[0030] In order to make the technical problems, technical solutions and beneficial effects of the present patent more clear, the present patent will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present patent and do not limit the present patent. Example 1

[0031] S1, take 5 mL of hydrochloric acid, dilute to 20 mL with ethanol, immerse in copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone for 5 min, rinse with ethanol, then immerse in ethanol for 8 min, and clean copper foil can be obtained; all solutions in this step need to be prepared fresh to avoid re-oxidation.

[0032] S2, weigh 2 g of sodium hydroxide and 0.15 g of ammonium thiosulfate into 12 mL of deionized water, immerse the copper foil treated in step S1, soak for 8 min and then rinse clean, and Cu(OH)2 nanowires can be obtained, then calcine in a muffle furnace at 320 ℃ for 1.5 h, and CuO nanowires can be obtained; the calcination of Cu(OH)2 nanowires in the muffle furnace in this step is to quickly dehydrate and prepare more ductile CuO nanowires.

[0033] S3, dissolve 0.61 mmol of cobalt nitrate, 0.23 mmol of cesium chloride, 0.23 mmol of ammonium perrhenate and 0.3 g of hexamethylenetetramine in 33 mL of deionized water, stir for 12 min, put into the CuO nanowires prepared in step S2, soak for 12 min, then transfer to the reaction kettle together, calcine at 118 ℃ for 8 h, after cooling, immerse the copper foil with the material into ethanol, ultrasonic stripping for 1 h, centrifugal dry, and Re / Co / Cs-LDH@CuO can be obtained. This material utilizes the one-dimensional structure of copper oxide nanowires, and Re, Co and Cs metal nanoparticles are coated on the outer layer of the nanowires. The three kinds of metal particles are uniformly attached to the nanowires through hydrothermal reaction, and as an additive of refractory material, it can improve the toughness and thermal shock resistance of the refractory material to ensure that the refractory material will not crack or break in frequent temperature changes.

[0034] S4, 5 g of Re / Co / Cs-LDH@CuO prepared in step S3, 33 g of aluminum oxide, 5 g of silicon dioxide, 11 g of zirconium oxide, 4 g of mullite, 17 g of silicon carbide, 6 g of cerium dioxide, 7 g of titanium oxide, 2 g of ethylenediaminetetraacetic acid and 8 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) were added to a ball milling tank and ball milled for 35 min; the uniformly ball milled powder was transferred to a high-speed mixer and uniformly mixed, 120 mL of a polyvinyl alcohol solution, 50 mL of ethylene glycol and 300 mL of methanol were added, and stirring was continued for 30 min to form a suspension; then the suspension was sprayed dried by a spray dryer, the inlet temperature was set to 135 DEG C and the outlet temperature was set to 160 DEG C, and a granular material was obtained; in this step, aluminum oxide (Al2O3) is used as a matrix material to provide good mechanical strength and high temperature stability; silicon dioxide (SiO2) is used as a structural stability and corrosion resistance enhancer; zirconium oxide (ZrO2) is used to improve the thermal shock resistance and toughness of the material; mullite (3Al2O3 2SiO2) provides excellent high temperature performance and creep resistance; silicon carbide (SiC) increases thermal conductivity and wear resistance; cerium dioxide can promote densification and improve the microstructure; P123 has good surface activity as an amphiphilic structure, can reduce the surface tension of the liquid, has solubilizing and dispersing effects; in addition, the granular material prepared by the spray drying method in this step can control the size of the generated particles, and the formed particles are usually spherical or approximately spherical, and have good flowability; the spray drying method used in this step has the characteristics of rapidness, efficiency, high quality and flexibility, and the granular material is easy to form.

[0035] S5, the granulated material in step S4 was placed in a mold, and the pressure was set to 100 MPa for pressing, and the pressure holding time was 15 min to form the required shape; then pre-sintering was performed at about 800 DEG C to remove organic matter and preliminary solidification; sintering was performed in an argon-hydrogen mixed gas containing 5% hydrogen for 2 h, and the sintering temperature was 1600 DEG C, so that the material was densified and a stable crystal structure was formed, and then cooled to room temperature at a rate of 5 DEG C / min -1 to obtain a refractory material for a hydrogen energy glass kiln. The cold isostatic pressing forming used in this step ensures higher density and uniformity; the mold is made of flexible rubber or elastic plastic to ensure uniform transmission of pressure; the cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop.

[0036] Figure 1 Scanning electron microscope image of Cu(OH)2 nanowires prepared in the present application. Figure 2The scanning electron microscope image of the CuO nanowire prepared in the application. As can be seen from the figure, the Cu(OH)2 nanowire is quickly dehydrated in the muffle furnace to become a curved CuO nanowire, which, as a skeleton, greatly improves the toughness of the refractory material after attaching Re / Co / Cs-LDH. Example 2

[0037] S1, take 12 mL of hydrochloric acid, dilute with ethanol to 33 mL, immerse the copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone and ultrasonic for 11 min, rinse with ethanol, then immerse in ethanol and ultrasonic for 16 min, to obtain clean copper foil; all solutions in this step need to be prepared on site to avoid re-oxidation.

[0038] S2, weigh 3 g of sodium hydroxide and 0.5 g of ammonium thiosulfate into 23 mL of deionized water, immerse the copper foil treated in step S1, soak for 15 min, then take out and rinse clean, to obtain Cu(OH)2 nanowire, then calcine in a muffle furnace at 410 ℃ for 3.1 h, to obtain CuO nanowire; the calcination of Cu(OH)2 nanowire in the muffle furnace in this step is to quickly dehydrate and prepare more tough CuO nanowire.

[0039] S3, dissolve 0.83 mmol of cobalt nitrate, 0.44 mmol of cesium chloride, 0.44 mmol of rhenium ammonium sulfate and 0.5 g of hexamethylenetetramine in 45 mL of deionized water, stir for 23 min, put into the CuO nanowire prepared in step S2, soak for 16 min, then transfer to the reaction kettle together, calcine at 148 ℃ for 10 h, after cooling, take out the copper foil with material and immerse in ethanol, ultrasonic stripping for 1 h, centrifugal dry, to obtain Re / Co / Cs-LDH@CuO. This material utilizes the one-dimensional structure of copper oxide nanowire, and coats Re, Co and Cs metal nanoparticles on the outer layer of the nanowire. The three kinds of metal particles are uniformly attached to the nanowire through hydrothermal reaction, which can improve the toughness and thermal shock resistance of the refractory material as an additive of the refractory material, to ensure that the refractory material will not crack or break in frequent temperature changes.

[0040] S4, 7 g of Re / Co / Cs-LDH@CuO prepared in step S3, 41 g of aluminum oxide, 8 g of silicon dioxide, 13 g of zirconium oxide, 6 g of mullite, 23 g of silicon carbide, 8 g of cerium dioxide, 11 g of titanium oxide, 5 g of ethylenediaminetetraacetic acid and 13 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) were added into a ball milling tank and ball milled for 45 min; the uniformly ball milled powder was transferred into a high-speed mixer and uniformly mixed, 150 mL of polyvinyl alcohol solution, 80 mL of ethylene glycol and 450 mL of methanol were added, and stirring was continued for 30 min to form a suspension; then the suspension was sprayed dried by a spray dryer, the inlet temperature was set to 135 °C and the outlet temperature was set to 160 °C, and a granular material was obtained; in this step, aluminum oxide (Al2O3) was used as a matrix material to provide good mechanical strength and high temperature stability; silicon dioxide (SiO2) was used as a structural stability and corrosion resistance enhancer; zirconium oxide (ZrO2) was used to improve the thermal shock resistance and toughness of the material; mullite (3Al2O3·2SiO2) provided excellent high temperature performance and creep resistance; silicon carbide (SiC) increased the thermal conductivity and wear resistance; cerium dioxide could promote densification and improve the microstructure; P123 had good surface activity as an amphiphilic structure, could reduce the surface tension of the liquid, and had solubilizing and dispersing effects; in addition, the granular material prepared by spray drying in this step could control the size of the generated particles, and the formed particles were usually spherical or approximately spherical, with good flowability; the spray drying method used in this step had the characteristics of rapidness, efficiency, high quality and flexibility, and the granular material was easy to form a subsequent shape.

[0041] S5, the granulated material in step S4 was placed into a mold, and was pressed at a pressure of 700 MPa for 34 min to form a desired shape; then pre-sintering was performed at about 1000 °C to remove organic matter and preliminarily solidify; sintering was performed in an argon-hydrogen mixed gas containing 5% hydrogen for 3 h at a sintering temperature of 1800 °C to densify the material and form a stable crystal structure, and then cooling was performed at a rate of 5 °C / min to room temperature, and a refractory material for a hydrogen energy glass kiln was obtained. The cold isostatic pressing forming used in this step ensures higher density and uniformity; the mold is a flexible mold made of rubber or elastic plastic to ensure uniform transmission of pressure; the cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop. -1 The cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop.

[0042] Comparative Example 1: Except that 0.83 mmol of cobalt nitrate was not added in step S3, the other steps were the same as those in Example 2.

[0043] Comparative Example 2: The remaining steps are the same as Example 2, except that 0.44 mmol of cesium chloride is not added in step S3.

[0044] Comparative Example 3: The remaining steps are the same as Example 2, except that 0.44 mmol of ammonium perrhenate is not added in step S3.

[0045] Figure 3 Scanning electron microscope image of Re / Co / Cs-LDH@CuO prepared for Example 2 of the present application. Figure 4 Scanning electron microscope image of Re / Cs-LDH@CuO prepared for Comparative Example 1 of the present application. Figure 5 Scanning electron microscope image of Re / Co-LDH@CuO prepared for Comparative Example 2 of the present application. Figure 6 Scanning electron microscope image of Co / Cs-LDH@CuO prepared for Comparative Example 3 of the present application. As can be seen from the figure, under the same conditions, different metal elements attached will make the nanowires of different thickness and have different apparent morphologies. When the outer layer of the nanowires is coated with Re, Co and Cs metal nanoparticles at the same time, there is a synergistic effect between the three metal elements. As can be seen from the observed morphology, the apparent area of Re / Co / Cs-LDH@CuO is larger, and in the subsequent preparation of refractory materials, it is better fused with other raw materials, has higher anti-expansion effect, and thus can improve the toughness and thermal shock resistance of the refractory material, so as to ensure that the refractory material will not crack in frequent temperature changes. The addition of Re / Co / Cs-LDH@CuO helps to improve the high-temperature strength and anti-creep property of the material, and can enhance the density of the material, thereby improving the load softening temperature. Example 3

[0046] S1, take 8 mL of hydrochloric acid, dilute with ethanol to 27 mL, immerse the copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone and ultrasonic for 9 min, rinse with ethanol, then immerse in ethanol and ultrasonic for 14 min, to obtain clean copper foil; all solutions in this step need to be prepared immediately before use to avoid re-oxidation.

[0047] S2, weigh 3 g of sodium hydroxide and 0.22 g of ammonium thiosulfate into 20 mL of deionized water, immerse the copper foil treated in step S1, soak for 9 min, then take out and rinse clean, to obtain Cu(OH)2 nanowires, then calcine in a muffle furnace at 405 ℃ for 1.9 h, to obtain CuO nanowires; in this step, the Cu(OH)2 nanowires are calcined in a muffle furnace to quickly dehydrate and prepare more ductile CuO nanowires.

[0048] S3. Dissolve 0.77 mmol of cobalt nitrate, 0.28 mmol of cesium chloride, 0.33 mmol of ammonium perrhenate, and 0.4 g of hexamethylenetetramine in 39 mL of deionized water and stir for 18 min. Add the CuO nanowires prepared in step S2 and soak for 15 min. Then transfer them together to a reaction vessel and calcine at 138 °C for 9 h. After cooling, remove the copper foil with the material growth and immerse it in ethanol. Perform ultrasonic peeling for 1 h, centrifuge and dry to obtain Re / Co / Cs-LDH@CuO. This material utilizes the one-dimensional structure of copper oxide nanowires, with Re, Co, and Cs metal nanoparticles coated on the outer layer of the nanowires. The three metal particles are uniformly attached to the nanowires through a hydrothermal reaction. As an additive for refractory materials, it can improve the toughness and thermal shock resistance of refractory materials, ensuring that the refractory materials will not crack or break under frequent temperature changes.

[0049] S4. Add 6 g of Re / Co / Cs-LDH@CuO prepared in step S3, 39 g of alumina, 7 g of silicon dioxide, 12 g of zirconium oxide, 5 g of mullite, 19 g of silicon carbide, 7 g of cerium dioxide, 8 g of titanium oxide, 4 g of ethylenediaminetetraacetic acid, and 11 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) to a ball mill jar and ball mill for 38 min. Transfer the homogenized powder to a high-speed mixer and mix evenly. Add 140 mL of polyvinyl alcohol solution, 70 mL of ethylene glycol, and 400 mL of methanol, and continue stirring for 30 min to form a suspension. Then, spray dry the suspension using a spray dryer with an inlet air temperature of 135 ℃ and an outlet air temperature of 160 ℃. At ℃, granular materials can be obtained. In this step, alumina (Al2O3) serves as the matrix material, providing good mechanical strength and high-temperature stability; silicon dioxide (SiO2) enhances the structural stability and corrosion resistance of the material; zirconium oxide (ZrO2) improves the thermal shock resistance and toughness of the material; mullite (3Al2O3·2SiO2) provides excellent high-temperature performance and creep resistance; silicon carbide (SiC) increases thermal conductivity and wear resistance; cerium dioxide can promote densification and improve the microstructure; P123, as an amphiphilic structure, has good surface activity, can reduce the surface tension of liquids, and has solubilizing and dispersing effects; in addition, the spray drying method used in this step can control the particle size, and the formed particles are usually spherical or nearly spherical with good flowability; the spray drying method used in this step is fast, efficient, high-quality, and flexible, producing granular materials that are easy to form in subsequent molding.

[0050] S5, the material after granulation in step S4 is put into a mold, and the pressure is set to 500 MPa for pressing, the pressure maintaining time is 19 min, and the required shape is formed; then pre-sintering is performed at about 900°C to remove the organic matter and preliminarily solidify; sintering is performed in argon-hydrogen mixed gas containing 5% hydrogen for 3 h, the sintering temperature is 1700°C, the material is densified and a stable crystal structure is formed, then cooling is performed to room temperature at a rate of 5°C / min -1 The refractory material for hydrogen energy glass kiln is obtained. Cold isostatic pressing is used in this step to ensure higher density and uniformity; the mold is a flexible mold made of rubber or elastic plastic to ensure uniform transmission of pressure; the cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop.

[0051] Comparative Example 4: Except that 0.28 mmol of cesium chloride is not added in step S3, the other steps are the same as those in Example 3.

[0052] Comparative Example 5: Except that 0.77 mmol of cobalt nitrate is not added in step S3, the other steps are the same as those in Example 3.

[0053] Comparative Example 6: Except that 0.33 mmol of ammonium perrhenate is not added in step S3, the other steps are the same as those in Example 3.

[0054] The Load-softening temperature (LST) of a refractory material is the temperature at which the material starts to deform and exhibit plastic flow under a certain load. This parameter is an important indicator for assessing the high-temperature strength and creep resistance of a refractory material, and is crucial for predicting its performance in actual use. The present invention can significantly improve the load-softening temperature of the material through reasonable component design, microstructure optimization, and sintering process control. The load-softening temperature reflects the stability of the material under the combined action of high temperature and stress. High-temperature strength: The higher the load-softening temperature, the better the mechanical strength of the material at high temperature. Creep resistance: This temperature also indirectly reflects the ability of the material to resist long-term creep. Service life: A high load-softening temperature means that the material can maintain its shape and function at a higher temperature, thereby extending its service life. The test standard used in the present invention is the Chinese national standard: GB / T 7321. The sample is prepared into a standard size cylinder (diameter: 40 mm ± 0.5 mm height: 40 mm ± 0.5 mm), the test sample is placed in a special test equipment, and a load of 0.2 MPa is applied, the sample is heated at a constant rate (such as 5°C / min), while monitoring its deformation. When the compression deformation of the test sample reaches 0.6%, the temperature at this time is recorded as the load-softening temperature. The compressive strength at room temperature of a refractory material is the ability of the material to resist compression load without failure at room temperature. This parameter is one of the important indicators for evaluating the mechanical properties of a refractory material, and is crucial for predicting its performance in actual use. Compressive strength at room temperature refers to the maximum stress that a material can withstand under axial compression load at room temperature. Mechanical strength: reflects the material's resistance to damage when under compression. Structural stability: high compressive strength means that the material can maintain good structural stability in high-temperature furnace lining, kiln, etc. Test standard: Chinese national standard GB / T 3001. Prepare a cylinder of standard size (diameter 40 mm ± 0.5 mm, height 40 mm ± 0.5 mm) according to the standard, ensure that the end surface of the test sample is smooth and free of obvious defects. Dry the test sample in an oven at 110°C ± ℃ to a constant weight. Place the dried test sample between the upper and lower compression plates of a universal testing machine, ensuring that the test sample axis is perpendicular to the compression plates. Apply axial compression load at a constant rate (such as 0.5 MPa / s) until the test sample fails. To rule out accidents, each sample is tested 5 times. Test the load-softening temperature and compressive strength at room temperature of the refractory material prepared in the present invention for hydrogen energy glass kiln.

[0055] Table 1, Load-softening temperature and compressive strength at room temperature test results

[0056]

[0057] Table 1 is the load softening temperature and normal temperature compressive strength of the refractory material for hydrogen energy glass kiln prepared by the present application. By comparison, it is found that the load softening temperature and normal temperature compressive strength of the refractory material prepared in Examples 2 and 3 are better than those of Comparative Examples 4-6, indicating that the three metal elements Re, Co and Cs involved in the additive Re / Co / Cs-LDH@CuO are indispensable. Combined with the scanning diagram analysis, it is known that the three elements Re, Co and Cs in Re / Co / Cs-LDH@CuO have a certain synergistic effect, are attached around the CuO nanowires, and can play a role in adjusting the structure of the material, greatly improving the mechanical properties of the material. Example 4

[0058] S1, take 9 mL of hydrochloric acid, dilute with ethanol to 22 mL, immerse in copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone and ultrasonic for 9 min, rinse with ethanol, then immerse in ethanol and ultrasonic for 13 min, to obtain clean copper foil; all solutions in this step need to be prepared fresh to avoid re-oxidation.

[0059] S2, weigh 3 g of sodium hydroxide and 0.33 g of ammonium thiosulfate into 19 mL of deionized water, immerse the copper foil treated in step S1, soak for 11 min and then rinse clean, to obtain Cu(OH)2 nanowires, then calcine in a muffle furnace at 360 ℃ for 1.9 h, to obtain CuO nanowires; the calcination of Cu(OH)2 nanowires in the muffle furnace in this step is to quickly dehydrate and prepare more ductile CuO nanowires.

[0060] S3, dissolve 0.73 mmol of cobalt nitrate, 0.35 mmol of cesium chloride, 0.36 mmol of ammonium perrhenate and 0.4 g of hexamethylenetetramine in 38 mL of deionized water, stir for 19 min, put into the CuO nanowires prepared in step S2, soak for 14 min, then transfer to the reaction kettle together, calcine at 128 ℃ for 8-10 h, after cooling, immerse the copper foil with the material into ethanol, ultrasonic stripping for 1 h, centrifugal dry, to obtain Re / Co / Cs-LDH@CuO. This material utilizes the one-dimensional structure of copper oxide nanowires, coats Re, Co and Cs metal nanoparticles on the outer layer of the nanowires, and the three metal particles are uniformly attached to the nanowires through hydrothermal reaction, which can improve the toughness and thermal shock resistance of the refractory material as an additive, to ensure that the refractory material will not crack or break in frequent temperature changes.

[0061] S4, 5.9 g of Re / Co / Cs-LDH@CuO prepared in step S3, 37 g of aluminum oxide, 7 g of silicon dioxide, 12 g of zirconium oxide, 5 g of mullite, 18 g of silicon carbide, 7 g of cerium dioxide, 8 g of titanium oxide, 3 g of ethylenediaminetetraacetic acid and 11 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) were added into a ball milling tank and ball milled for 37 min; the uniformly ball milled powder was transferred into a high-speed mixer and uniformly mixed, 133 mL of polyvinyl alcohol solution, 70 mL of ethylene glycol and 390 mL of methanol were added, and stirring was continued for 30 min to form a suspension; then the suspension was sprayed dried by a spray dryer, the inlet temperature was set to 135 ℃ and the outlet temperature was set to 160 ℃, and a granular material was obtained; in this step, aluminum oxide (Al2O3) was used as a matrix material to provide good mechanical strength and high temperature stability; silicon dioxide (SiO2) was used as a structural stability and corrosion resistance enhancer; zirconium oxide (ZrO2) was used to improve the thermal shock resistance and toughness of the material; mullite (3Al2O3·2SiO2) provided excellent high temperature performance and creep resistance; silicon carbide (SiC) increased the thermal conductivity and wear resistance; cerium dioxide could promote densification and improve the microstructure; P123 had good surface activity as an amphiphilic structure, could reduce the surface tension of the liquid, and had solubilizing and dispersing effects; in addition, the granular material prepared by spray drying in this step could control the size of the generated particles, and the formed particles were usually spherical or approximately spherical, with good flowability; the spray drying method used in this step had the characteristics of rapidness, efficiency, high quality and flexibility, and the granular material was easy to form a subsequent shape.

[0062] S5, the granulated material in step S4 was placed into a mold, and compression was performed at a pressure of 600 MPa, with a pressure holding time of 17 min, to form a desired shape; then pre-sintering was performed at about 900 ℃ to remove organic matter and preliminarily solidify; sintering was performed in an argon-hydrogen mixed gas containing 5% hydrogen for 2 h, with a sintering temperature of 1700 ℃, to densify the material and form a stable crystal structure, and then cooling was performed at a rate of 5 ℃ / min to room temperature, to obtain a refractory material for a hydrogen energy glass kiln. The cold isostatic pressing forming used in this step ensures higher density and uniformity; the mold is a flexible mold made of rubber or elastic plastic, which ensures that the pressure can be uniformly transmitted; the cooling rate is controlled to avoid cracks or deformation caused by sudden temperature drop. -1

[0063] Comparative Example 7: Except that 3 g of ethylenediaminetetraacetic acid was not added in step S4, the other steps were the same as those in Example 4.

[0064] ​Comparative Example 8: Except that 11 g of polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) was not added in step S4, the other steps were the same as those in Example 4.

[0065] Comparative Example 9: Except that Re / Co / Cs-LDH@CuO was not added in step S4, the other steps were the same as those in Example 4.

[0066] Table 2 is the abrasion loss of the refractory material for hydrogen energy glass kiln prepared by the present application on a Taber abrasion tester with a grinding wheel rotating 1000 times. The heating permanent line change (1450℃×2h) / % is 0.1, and the detection of thermal shock resistance is as follows: the refractory material is treated at 1450℃ for 2h to measure the bending strength P1, then after being kept at 1100℃ for 20min, it is rapidly cooled in 20℃ cold water, and the above process is repeated for 30 times, and the bending strength is P2. Through the comparison of the test data in Table 1, it can be seen that the addition of ethylenediaminetetraacetic acid, Re / Co / Cs-LDH@CuO and polyethylene oxide-polypropylene oxide-polyethylene oxide (P123) has a positive effect on improving the thermal shock resistance of the refractory material prepared by the present application. Especially, Re / Co / Cs-LDH@CuO has a great influence on improving the mechanical properties of the material. In Comparative Example 9, Re / Co / Cs-LDH@CuO is not added, and the mechanical properties of the prepared refractory material are very poor.

[0067]

[0068] Table 2

[0069]

[0070] The above-described examples only describe the preparation process of the present application, and do not limit the scope of the present application. Without departing from the design spirit of the present application, various modifications and improvements to the technical solutions of the present application made by those skilled in the art shall fall within the protection scope determined by the claims of the present application.​

Claims

1. A refractory material for a hydrogen glass furnace, characterized by: The specific preparation steps are as follows: S1, take 5-12 mL of hydrochloric acid, dilute to 20-33 mL with ethanol, immerse in copper foil, soak until the solution turns yellow, take out the copper foil, rinse with ethanol, then immerse in acetone and ultrasonic for 5-11 min, rinse with ethanol, then immerse in ethanol and ultrasonic for 8-16 min, to obtain clean copper foil; S2, weigh 2-3 g of sodium hydroxide and 0.15-0.5 g of ammonium thiosulfate into 12-23 mL of deionized water, immerse the copper foil treated in step S1, soak for 8-15 min, then take out and rinse clean, to obtain Cu(OH)2 nanowires, then calcine in a muffle furnace at 320-410 ℃ for 1.5-3.1 h, to obtain CuO nanowires; S3, dissolve 0.61-0.83 mmol of cobalt nitrate, 0.23-0.44 mmol of cesium chloride, 0.23-0.44 mmol of high rhenium acid ammonium and 0.3-0.5 g of hexamethylene tetramine in 33-45 mL of deionized water, stir for 12-23 min, put into the CuO nanowires prepared in step S2, soak for 12-16 min, then transfer to the reaction kettle together, calcine at 118-148 ℃ for 8-10 h, after cooling, immerse the copper foil with material into ethanol, ultrasonic for 1 h, centrifugal dry, to obtain Re / Co / Cs-LDH@CuO; S4, put 5-7 g of Re / Co / Cs-LDH@CuO prepared in step S3, 33-41 g of aluminum oxide, 5-8 g of silicon dioxide, 11-13 g of zirconium oxide, 4-6 g of mullite, 17-23 g of silicon carbide, 6-8 g of cerium dioxide, 7-11 g of titanium oxide, 2-5 g of ethylenediaminetetraacetic acid and 8-13 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 into a ball mill jar, ball mill for 35-45 min; the uniformly ball-milled powder is transferred to a high-speed mixer and uniformly mixed, 120-150 mL of polyvinyl alcohol solution, 50-80 mL of ethylene glycol and 300-450 mL of methanol are added, and stirring is continued for 30 min to form a suspension; then the suspension is sprayed and dried by a spray dryer, the inlet temperature is set to 135 ℃, and the outlet temperature is set to 160 ℃, to obtain a granular material; S5, the material after granulation in step S4 is put into a mold, and pressing is performed at a pressure of 100-700 MPa, and the pressure holding time is 15-34 min, to form a required shape; then pre-sintering is performed at 800-1000 ℃ to remove organic matter and preliminarily solidify; sintering is performed in argon-hydrogen mixed gas containing 5% hydrogen for 2-3 h, the sintering temperature is 1600-1800 ℃, to densify the material and form a stable crystal structure, and then cooling is performed at a rate of 5 ℃ min -1 to room temperature, to obtain a refractory material for a hydrogen energy glass kiln.

2. A refractory material for a hydrogen glass furnace according to claim 1, characterized in that: In step S2, weigh 2 g of sodium hydroxide and 0.15 g of ammonium thiosulfate into 12 mL of deionized water, immerse the copper foil treated in step S1, soak for 8 min, then take out and rinse clean, to obtain Cu(OH)2 nanowires, then calcine in a muffle furnace at 320 ℃ for 1.5 h, to obtain CuO nanowires.

3. A refractory material for a hydrogen glass furnace according to claim 1 or 2, characterized in that: In the step S2, 3 g of sodium hydroxide and 0.5 g of ammonium thiosulfate are dissolved in 23 mL of deionized water, and the copper foil treated in the step S1 is immersed, soaked for 15 min, and then taken out and washed clean to obtain Cu(OH)2 nanowires, which are then calcined in a muffle furnace at 410°C for 3.1 h to obtain CuO nanowires.

4. A refractory material for a hydrogen glass furnace as claimed in claim 1, wherein: In the step S3, 0.61 mmol of cobalt nitrate, 0.23 mmol of cesium chloride, 0.23 mmol of ammonium perrhenate, and 0.3 g of hexamethylenetetramine are dissolved in 33 mL of deionized water, stirred for 12 min, and then transferred into the reaction kettle together with the CuO nanowires prepared in the step S2, soaked for 12 min, and then calcined at 118°C for 8 h. After cooling, the copper foil with the material is immersed in ethanol, ultrasonically peeled for 1 h, and then centrifuged and dried to obtain Re / Co / Cs-LDH@CuO.

5. A refractory material for a hydrogen glass furnace according to claim 1 or 4, characterized in that: In the step S3, 0.83 mmol of cobalt nitrate, 0.44 mmol of cesium chloride, 0.44 mmol of ammonium perrhenate, and 0.5 g of hexamethylenetetramine are dissolved in 45 mL of deionized water, stirred for 23 min, and then transferred into the reaction kettle together with the CuO nanowires prepared in the step S2, soaked for 16 min, and then calcined at 148°C for 10 h. After cooling, the copper foil with the material is immersed in ethanol, ultrasonically peeled for 1 h, and then centrifuged and dried to obtain Re / Co / Cs-LDH@CuO.

6. A refractory material for a hydrogen glass furnace as claimed in claim 1, wherein: In the step S4, 5 g of Re / Co / Cs-LDH@CuO prepared in the step S3, 33 g of aluminum oxide, 5 g of silicon dioxide, 11 g of zirconium oxide, 4 g of mullite, 17 g of silicon carbide, 6 g of cerium dioxide, 7 g of titanium oxide, 2 g of ethylenediaminetetraacetic acid, and 8 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 are added into a ball milling tank and ball milled for 35 min. The uniformly ball milled powder is transferred into a high-speed mixer and uniformly mixed, 120 mL of polyvinyl alcohol solution, 50 mL of ethylene glycol, and 300 mL of methanol are added, and stirring is continued for 30 min to form a suspension. The suspension is then sprayed and dried by a spray dryer, with the inlet temperature set to 135°C and the outlet temperature set to 160°C, to obtain a granular material.

7. A refractory material for a hydrogen glass furnace according to claim 1 or 6, characterized in that: In the step S4, 7 g of Re / Co / Cs-LDH@CuO prepared in the step S3, 41 g of aluminum oxide, 8 g of silicon dioxide, 13 g of zirconium oxide, 6 g of mullite, 23 g of silicon carbide, 8 g of cerium dioxide, 11 g of titanium oxide, 5 g of ethylenediaminetetraacetic acid and 13 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 are added into a ball milling tank for ball milling for 45 min; the uniformly ball-milled powder is transferred into a high-speed mixer for uniform mixing, 150 mL of polyvinyl alcohol solution, 80 mL of ethylene glycol and 450 mL of methanol are added, and stirring is continued for 30 min to form a suspension; then the suspension is subjected to spray drying through a spray dryer, the inlet air temperature is set to 135 DEG C, the outlet air temperature is set to 160 DEG C, and a granular material can be obtained.

8. A refractory material for a hydrogen glass furnace as claimed in claim 1, wherein: The material after granulation in step S4 is put into a mold in the step S5, and the pressure is set to 100 MPa for pressing, and the pressure holding time is 15 min, to form the required shape; then pre-sintering is carried out at 800 ℃ to remove the organic matter and preliminarily solidify; sintering is carried out in argon-hydrogen mixed gas containing 5% hydrogen for 2 h, and the sintering temperature is 1600 ℃, so that the material is densified and a stable crystal structure is formed, and then cooling is carried out at a rate of 5 ℃ / min -1 to room temperature, so that the refractory material for hydrogen energy glass kiln is obtained.

9. A refractory material for a hydrogen glass furnace as claimed in claim 1, wherein: The material after granulation in step S4 is put into a mold in step S5, and pressing is performed at a pressure of 700 MPa, and the pressure holding time is 34 min, to form a required shape; then pre-sintering is performed at 1000℃ to remove organic matter and preliminarily solidify; sintering is performed in argon-hydrogen mixed gas containing 5% hydrogen for 3 h, and the sintering temperature is 1800℃, to densify the material and form a stable crystal structure, and then cooling is performed at a rate of 5℃ / min to room temperature, to obtain a refractory material for a hydrogen energy glass kiln. -1 The refractory material for a hydrogen energy glass kiln is obtained.

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