CN113943502B - Method for preparing infrared coating paint by utilizing metallurgical solid wastes - Google Patents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a method for preparing an infrared coating by utilizing metallurgical solid wastes, belonging to the field of infrared energy-saving materials. The method for preparing the infrared coating by utilizing the metallurgical solid wastes comprises the following steps: a. uniformly mixing the metallurgical solid waste with iron oxide red; b. sintering the mixed material by stages, and cooling to obtain a roasted material; c. uniformly mixing the roasting material, MgO and transition metal oxide; d. sintering the mixed material again, cooling, and mechanically crushing to obtain infrared coating powder; e. and fully mixing the infrared coating powder, the high-temperature binder and water to obtain the infrared coating paint. The material prepared by the method has the advantages of softening temperature not lower than 1500 ℃, better high-temperature cohesiveness, comprehensive emissivity not lower than 0.87, low-band emissivity (1-5 mu m) not lower than 0.93, excellent comprehensive performance and low production cost, and can effectively solve the problems of poor radiation performance and higher preparation cost of the existing infrared coating under the high-temperature condition.
Description
Technical Field
The invention belongs to the field of infrared energy-saving materials, and relates to a method for preparing an infrared coating by utilizing metallurgical solid wastes.
Background
In recent years, infrared coating paint has a great deal of development in the fields of aviation, building, photocatalysis, energy conservation, environmental protection and the like, and especially, the application of the infrared coating paint in the fields of energy conservation and environmental protection is the main development trend of the infrared coating paint. However, the infrared coating in China has a great difference in product performance compared with the foreign coating. The utilization rate of infrared coating paint in many developed countries reaches 40%, and the radiation coefficient is above 0.9, while the utilization rate of infrared coating paint in industrial furnaces is only 15%, and the infrared radiation coefficient is about 0.8, which greatly limits the utilization rate of industrial furnace energy.
Preparation and Properties of high emissivity Metal oxide coatings (Wang Qian Ping, Guo Xionghua, Zhang Jia Sheng, Liu Li hong)]Material heat treatmentJournal of science 2012,33(02): 137-141) provides a method for preparing high emissivity coating by modifying binder, Cr2O3、MnO2As the main raw material, ZrSiO is used as the auxiliary material4、Fe2O3And MgO and other oxides, respectively preserving heat at 950 ℃, 1100 ℃ and 1250 ℃ for 2h, quenching with water, discharging, and preparing a high-emissivity coating on the surface of the stainless steel by adopting a high-temperature melting method, wherein the normal emissivity of the coating in a 1-22 mu m wave band can reach 0.90.
CN1552779 of 12 month and 8 days in 2004 discloses a micro-nano ultrafine powder high-temperature far-infrared coating, which comprises components of zirconium oxide and Cr2O3Refractory clay, bentonite, titanium dioxide, brown corundum, iron oxide, silicon carbide, PA80 glue or water glass, and carboxymethyl cellulose. The components are weighed according to the proportion and mixed to prepare the viscous suspension fluid. The nanometer superfine treatment is adopted to ensure that the granularity reaches 25-780nm, and a nanometer high-temperature far infrared coating product is obtained, and the emissivity can reach 0.93. Most of the existing methods for preparing the high-emissivity coating adopt pure chemical preparations, so that the raw material cost is high, the process is complex, and the preparation cost and the use cost are high.
CN101302365A of 11/12/2008 discloses a far infrared coating and a preparation method thereof, and the raw materials of the far infrared coating of the method are as follows: 20-60% of vanadium-containing industrial waste residue, 0-10% of sintering agent, 30-60% of binder, 0-2% of dispersing agent, 0-10% of chromium oxide, 0-10% of cobalt oxide, 0-10% of aluminum oxide, 0-10% of manganese dioxide and 0-10% of silicon carbide, can be used for industrial boilers and kilns, and has the advantages of high temperature resistance (over 1250 ℃), excellent high-temperature adhesion performance, easy porcelain forming, energy saving and the like.
The method for preparing the infrared coating provides a method for adopting metallurgical solid wastes as raw materials, effectively reduces the preparation cost, and is necessary for researching an infrared coating with both economy and emissivity in order to improve the green low-carbon development and the energy utilization rate of mining industry.
Disclosure of Invention
The invention aims to solve the technical problems of poor radiation performance and high preparation cost of the existing infrared coating under high temperature conditions.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for preparing the infrared coating by utilizing the metallurgical solid wastes comprises the following steps:
a. uniformly mixing metallurgical solid waste and iron oxide red according to the mass ratio of 100: 30-35 to obtain a mixed material A;
b. sintering the mixed material A, heating to 600-800 ℃, preserving heat for 3-4h, then heating to 1000-1200 ℃, preserving heat for 1-2h, and cooling to room temperature along with the furnace after sintering to obtain a sintering material;
c. uniformly mixing the roasted material, MgO and transition metal oxide according to the mass ratio of 100: 8-10: 4-5 to obtain a mixed material B;
d. sintering the mixed material B, heating to 1300-;
e. and fully mixing the infrared coating powder, the high-temperature binder and water to obtain the infrared coating paint.
In the step a, the metallurgical solid waste is high-temperature carbide slag solid waste in a vanadium-titanium smelting process, and the metallurgical solid waste comprises the following chemical components in percentage by mass: 10-15% of Ti, 10-20% of TiC and Al2O3 15-25%，SiO220-30 percent of CaO, 23-35 percent of CaO and inevitable impurities.
Further, the granularity of the metallurgical solid waste is-200 meshes and accounts for more than or equal to 70 percent.
In the step a, the iron oxide red is cold-rolled and acid-washed iron scale, and the chemical composition of the iron oxide red is 95-98% of Fe by mass2O3And inevitable impurities.
Further, the granularity of the iron oxide red is-200 meshes.
In the step c, the particle size of the roasting material is more than or equal to 70 percent when the particle size is-200 meshes.
In the step c, the transition metal oxide is CuO, CoO or Cr2O3、MnO2、ZrO2At least one of them.
In the step d, the granularity of the infrared coating powder after mechanical crushing is-300 meshes.
In the step e, the high-temperature binder is water glass, and the modulus is 2.0-2.5.
Furthermore, the addition amount of the high-temperature binder is 5-10% of the mass of the infrared radiation coating powder.
The invention has the beneficial effects that: firstly, TiC in metallurgical solid waste reacts with oxygen in the air at the temperature of 600-800 ℃ to generate TiO2And TiO 22Fe of CaO and red iron oxide2O3The perovskite composite oxide is prepared by adopting a high-temperature sintering process at the temperature of 1000-1200 ℃, so that the infrared radiation performance of the material can be greatly improved; secondly, through Al in solid waste2O3、SiO2MgO is synthesized into cordierite (Mg) in 1300-1400 ℃ high-temperature melting state2All4Si5O18) And then the transition metal oxide is used for modifying the cordierite so that the cordierite has stronger corresponding characteristics of infrared radiation.
The preparation method of the invention utilizes high-temperature carbide slag in the vanadium-titanium smelting process and active ingredients in iron oxide red to mix transition metal oxide, prepares miscellaneous cordierite and perovskite composite oxide by adopting a step-by-step and staged high-temperature sintering process, and simultaneously prepares miscellaneous cordierite-perovskite crystal, namely infrared coating paint, by combining the control and coordination of a high-temperature binder, wherein the crystal material has good heat resistance and high incidence, the softening temperature is not lower than 1500 ℃, the high-temperature cohesiveness is good, the comprehensive emissivity is not lower than 0.87, the low-band emissivity (1-5 mu m) is not lower than 0.93, and the comprehensive performance is excellent.
Detailed Description
The technical solution of the present invention can be specifically implemented as follows.
The method for preparing the infrared coating by utilizing the metallurgical solid wastes comprises the following steps:
a. uniformly mixing metallurgical solid waste and iron oxide red according to the mass ratio of 100: 30-35 to obtain a mixed material A;
b. sintering the mixed material A, heating to 600-plus-one temperature of 800 ℃, preserving heat for 3-4h, then heating to 1000-plus-one temperature of 1200 ℃, preserving heat for 1-2h, and cooling to room temperature along with the furnace after sintering to obtain a sintering material;
c. uniformly mixing the roasted material, MgO and transition metal oxide according to the mass ratio of 100: 8-10: 4-5 to obtain a mixed material B;
d. sintering the mixed material B, heating to 1300-;
e. and fully mixing the infrared coating powder, the high-temperature binder and water to obtain the infrared coating paint.
In the step a, the metallurgical solid waste is high-temperature carbide slag solid waste in a vanadium-titanium smelting process, and the metallurgical solid waste comprises the following chemical components in percentage by mass: 10-15% of Ti, 10-20% of TiC and Al2O3 15-25%，SiO220-30% of CaO, 23-35% of CaO and inevitable impurities, wherein the proportion of the metallurgical solid waste with the granularity of-200 meshes is more than or equal to 70%.
In the step a, the iron oxide red is cold-rolled and acid-washed iron scale, and the chemical composition of the iron oxide red is 95-98% of Fe by mass2O3And inevitable impurities, wherein the granularity of the iron oxide red is-200 meshes.
The method adopts TiC in solid waste to react with oxygen in the air at the temperature of 600-800 ℃ to generate TiO2While CaO in the solid waste and the generated TiO2Can synthesize CaTiO at the high temperature of 1000-3A crystal; meanwhile, ferric iron ions of the iron oxide red are used for replacing B-site ions in the crystal at high temperature to form the perovskite composite oxide. The perovskite composite oxide has a unique crystal structure, particularly a crystal defect structure and performance formed after doping, the introduction of impurities causes the distortion of crystal lattices, the vibration absorption of the crystal lattices is enhanced, and the infrared radiation performance of the material, particularly the short wave band (1-5 mu m), can be greatly improved.
In the step c, the particle size of the roasting material is more than or equal to 70 percent when the particle size is-200 meshes.
In the step c, the transition metal oxide is CuO, CoO or Cr2O3、MnO2、ZrO2At least one of them.
And Al in the solid waste component2O3、SiO2Can be synthesized into cordierite (Mg) with additional MgO under the high temperature condition of 1300-1400 DEG C2All4Si5O18) The transition metal oxide is added to replace metal elements in cordierite, and the cordierite is modified under the high-temperature condition, so that impurities are reasonably added into the original crystal structure, the symmetry becomes worse, the dipole moment change is larger when the crystal lattice vibrates, and the corresponding characteristic of stronger infrared radiation is realized. In addition, cordierite has the advantages of good thermal stability and small thermal expansion coefficient, and is used as a framework of chemical compositions of infrared radiation materials.
In the step d, the granularity of the infrared coating powder after mechanical crushing is-300 meshes.
The modulus of water glass is an important parameter of water glass, the larger the modulus of water glass is, the more insoluble solid water glass is in water, n is 1, the solid water glass can be dissolved by warm water at normal time, when n is increased, the solid water glass can be dissolved by hot water, and when n is more than 3, the solid water glass can be dissolved by steam with the pressure of more than 4 atmospheres. The larger the water glass modulus is, the more the silicon oxide content is, the water glass viscosity is increased, and the water glass is easy to decompose and harden, and the binding power is increased. Therefore, in the step e, the high-temperature binder is preferably water glass, and the modulus is 2.0-2.5. The invention adopts the water glass with the modulus of 2.0-2.5, is for industrial large-scale preparation, the mixing by hot water is beneficial to large-scale preparation, the modulus is too low to be decomposed and hardened, the high-temperature caking property can be reduced, and the range of 2.0-2.5 is determined after tests. The medium silica component of the water glass further promotes the formation of heterocordierite-perovskite crystals at high temperatures in the furnace.
Furthermore, the addition amount of the high-temperature binder is 5-10% of the mass of the infrared radiation coating powder.
The technical solutions and effects of the present invention will be further described below by practical examples.
Examples
The invention provides a group of examples for preparing infrared coating paint by adopting the method, and the chemical components of the solid waste high-temperature carbide slag adopted in the examples are based on the qualityThe weight percentage is as follows: 14.6 percent of Ti, 17.2 percent of TiC and Al2O3 18.7%，SiO222.1 percent, CaO 26.4 percent and inevitable impurities.
The specific experimental steps for preparing the infrared coating by utilizing the metallurgical solid wastes are as follows:
a. crushing 200g of solid waste high-temperature carbide slag until the proportion of-200 meshes is more than or equal to 70%, and uniformly mixing the crushed solid waste and iron oxide red according to the mass ratio of 100: 30 to obtain a mixed material A, wherein the total amount is 460 g;
b. placing the mixed material A into a muffle furnace, sintering at the high temperature of 700 ℃ for 4h, then heating to 1100 ℃ for sintering for 2h, and cooling to room temperature along with the furnace to obtain a roasting material;
c. crushing the roasted material B to the proportion of more than or equal to 70 percent of 200 meshes, and then mixing the crushed roasted material B with MgO and MnO2Mixing according to the mass ratio of 100: 10: 5, and fully mixing to obtain a mixed material B, wherein the total mass is 529 g;
d. placing the mixed material B in a muffle furnace, sintering for 2h at 1300 ℃, cooling to room temperature, and mechanically crushing to-300 meshes to obtain infrared coating powder;
e. mixing 90% of infrared coating powder and 10% of 2.3 modulus water glass according to the mass percentage, and adding hot water for stirring to obtain the infrared coating paint.
The infrared coating powder and the coating prepared in the examples are detected as follows:
1. the infrared coating powder prepared by the embodiment is detected by a melting point tester and an emissivity tester, and the result is as follows: the softening temperature is more than 1500 ℃, the average emissivity in a 1-22 mu m wave band is 0.89, and the emissivity in a 1-5 mu m short wave band is 0.93.
2. The infrared coating paint prepared in the example is coated on the surface of a substrate, and then the detection is carried out:
(1) coating the infrared coating on the bottom of a 1L beaker filled with 500ml of water, and then carrying out flame heating on the bottom of the beaker;
(2) coating the infrared coating on 1 polished 300mm × 300mm refractory brick, placing the refractory brick in a muffle furnace, heating the refractory brick to 1000 ℃ from normal temperature, cooling the refractory brick along with the furnace, repeating the process for 25 times, and observing the appearance of the coating.
Meanwhile, the invention prepares the coating according to the coating formula and the preparation method in patents CN101302365A and CN1552779, and the experiments (1) and (2) are carried out in the same way, and comparative analysis is carried out as a comparative example, and the experimental results are shown in Table 1.
TABLE 1 Infrared coating paint test results
As can be seen from table 1, the beaker coated with the infrared coating paint prepared in the embodiment of the present invention has a time required for heating water to boiling that is 24.7% faster than that of the uncoated beaker and 9.3% faster than that of the shortest CN 101302365A-sample 2 used in the comparative example, and thus, the infrared coating paint prepared by the method of the present invention has excellent energy saving and consumption reduction properties; after the infrared coating paint disclosed by the embodiment of the invention is subjected to 25 thermal shock experiments, the high-temperature cohesiveness is good, the heat-resistant temperature is more than 1500 ℃, the emissivity is 0.87, and the comprehensive performance is superior to that of similar products.
Claims (8)
1. The method for preparing the infrared coating by utilizing the metallurgical solid waste is characterized by comprising the following steps of:
a. uniformly mixing metallurgical solid waste and iron oxide red according to the mass ratio of 100: 30-35 to obtain a mixed material A;
b. sintering the mixed material A, heating to 600-plus-one temperature of 800 ℃, preserving heat for 3-4h, then heating to 1000-plus-one temperature of 1200 ℃, preserving heat for 1-2h, and cooling to room temperature along with the furnace after sintering to obtain a sintering material;
c. uniformly mixing the roasted material, MgO and transition metal oxide according to the mass ratio of 100: 8-10: 4-5 to obtain a mixed material B;
d. sintering the mixed material B, heating to 1300-1400 ℃, preserving heat for 0.5-3h, cooling to room temperature after sintering, and obtaining infrared coating powder after mechanical crushing;
e. fully mixing the infrared coating powder, the high-temperature binder and water to obtain an infrared coating paint;
in the step a, the metallurgical solid waste is high-temperature carbide slag solid waste in a vanadium-titanium smelting process, and the metallurgical solid waste comprises the following chemical components in percentage by mass: 10-15% of Ti, 10-20% of TiC and Al2O3 15-25%，SiO220-30%, CaO 23-35%, and inevitable impurities;
in step c, the transition metal oxide is CuO, CoO, Cr2O3、MnO2、ZrO2At least one of them.
2. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 1, is characterized in that: the granularity of the metallurgical solid waste is-200 meshes and the proportion is more than or equal to 70 percent.
3. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 1, is characterized in that: in the step a, the iron oxide red is cold-rolled and acid-washed iron scale, and the chemical composition of the iron oxide red is 95-98% of Fe by mass2O3And inevitable impurities.
4. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 3, is characterized in that: the granularity of the iron oxide red is-200 meshes.
5. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 1, is characterized in that: in the step c, the particle size of the roasting material is more than or equal to 70 percent when the particle size is-200 meshes.
6. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 1, is characterized in that: in the step d, the granularity of the infrared coating powder after mechanical crushing is-300 meshes.
7. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 1, is characterized in that: in the step e, the high-temperature binder is water glass, and the modulus is 2.0-2.5.
8. The method for preparing the infrared coating paint by utilizing the metallurgical solid waste, according to claim 7, is characterized in that: the addition amount of the high-temperature binder is 5-10% of the mass of the infrared coating powder.
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