Method for preparing orange fluorescent ceramic by adding rare earth Y type zeolite cracking catalyst tailings

Abstract

The invention aims to provide a method for preparing orange fluorescent ceramic by adding rare earth Y type zeolite cracking catalyst tailings, and belongs to the technical field of luminescent materials.The method comprises the steps that firstly, magnesium oxide, fumed silica, aluminum hydroxide, europium oxide and yttrium oxide are weighed, water is added, ball milling is conducted, and precursor fluorescent powder is obtained after drying; preparing luminescent powder containing precursor fluorescent powder, frit, aluminum hydroxide, potassium feldspar, pyrophyllite and strontium carbonate; and weighing the luminescent powder and the rare earth Y-type zeolite cracking catalyst tailings, adding water, carrying out ball milling, drying, carrying out compression molding, and sintering at a high temperature to obtain the orange fluorescent ceramic. The technical process is simple, industrial production is facilitated, the excitation spectrum, the emission spectrum and the fluorescence color of the orange fluorescent ceramic can be regulated and controlled through the content of the rare earth Y-type zeolite cracking catalyst tailings, and the method can also be used as a recycling technology of the rare earth Y-type zeolite cracking catalyst tailings.

Description

TECHNICAL FIELD

[0001] The application relates to a method for preparing orange-red fluorescent ceramics by adding tailings of a rare earth Y-type zeolite cracking catalyst, and belongs to the technical field of luminescent materials. BACKGROUND

[0002] In the field of light emitting display, two kinds of light emitting combination modes can realize white light display: one is composed of blue light and yellow light, and the other is composed of red light, green light and blue light. In the current commercial application white light, the white light generated by the combination of blue light and yellow light has low saturation, and under the illumination of the white light, red or yellow objects appear relatively dark, blurred and colorless. Therefore, the white light display effect composed of red light, green light and blue light is particularly important, and the related research on the europium atom luminescent material doped with red light emitting europium atoms is concerned.

[0003] The europium atom luminescence corresponds to the jump between corresponding atomic energy levels, 5 D0→ 7 F J (J=0, 1, 2, 3, 4), and the standard red light corresponds to 5 D0→ 7 F2, that is, the electron returns from the excited state 5 D0 to the ground state 7 F2 level, and the excess energy is generated in the form of red light emission. Chinese invention patent 201911021449.5 discloses a preparation method of a europium-containing photoemission fluorescent powder material, which is applied to a ceramic surface and used for preparing a red light emitting glazed ceramic. The luminescence effect of europium atoms in the luminescent material, the peak position and peak intensity of the luminescence spectrum are influenced by the chemical environment of europium atoms, and the corresponding energy level transition type and probability also change. When the chemical environment around the europium atom is relatively complex, the luminescence peak is high, the background noise of the luminescence spectrum is wide, the fine spectral structure of the luminescence peak is covered, the europium atom spectrum becomes complex, and the color control of the luminescence is also relatively difficult. The CaLa2ZnO5:Eu 3+ (Eu 3+: 10 mol.%) luminescent materials (V.R. Bandi, et al., J. Alloy. Compd. 512 (2012) 264-269) emit orange-red light, the process characteristics of sol-gel method make the chemical environment of europium atoms more uniform, and the crystallinity of the luminescent material is also relatively high, which can better regulate the chemical environment around the europium atoms, and then prepare orange-red luminescent materials. In the traditional solid-phase sintering method, the solubility of europium ions in the luminescent material is low, the concentration is not easy to control, and europium ion aggregates are easily formed, so that the specific structure and color of the luminescent material containing europium ions are not easy to control. Chinese invention patent 201910118982.7 discloses a preparation method of europium-doped borophosphate orange-red fluorescent powder, that is, the orange-red fluorescent powder is prepared by mixing and then solid-phase reaction, which specifically includes multiple sintering-cooling-grinding processes and a long process of high-temperature holding time.

[0004] Silicate materials composed of siloxane tetrahedra can make metal ions have a good uniform distribution in the material. Magnesiosilicate, such as forsterite and protoenstatite, can be used as a doped carrier of europium ions, and as a luminescent material using europium ions to replace magnesium ions to occupy the octahedral position. This structure has inversion symmetry, which can improve the luminescent intensity, but the fine structure of the europium ion luminescence spectrum cannot be regulated. In the preparation process of rare earth Y-type zeolite cracking catalyst with Y-molecular sieve as the carrier, the rare earth ions in the chemical reaction solution first undergo ion exchange with sodium elements in the Y-molecular sieve, and then the pH value of the reaction solution is increased to make the rare earth ions in the reaction solution precipitate. Part of the precipitation occurs in the pores inside the molecular sieve to form a chemically modified Y-molecular sieve catalyst, while the rare earth elements in the solution precipitate in the solution. Finally, the precipitates in the solution and the molecular sieve catalyst are separated, dried, and then the by-product produced in the preparation process of the rare earth Y-type zeolite cracking catalyst, that is, the tailings of the rare earth Y-type zeolite cracking catalyst, is prepared. In the solid-phase reaction process, that is, the process of forming the siloxane tetrahedral network structure, there is no report on the interaction between europium ions, rare earth element ions and magnesium silicate crystalline phases generated in situ during the reaction. There is also no report on the related research on the fine structure of the europium ion luminescence spectrum in this structure. SUMMARY

[0005] The purpose of the present application is to provide a method for preparing orange-red fluorescent ceramic by adding rare earth Y-type zeolite cracking catalyst tailings: Step 1, the precursor fluorescent powder material is prepared by mixing magnesium oxide, fumed silica, aluminum hydroxide, europium oxide and yttrium oxide in a mass ratio of 11.43:8.57:8.57:1.76:1.20, adding water to a water-to-material ratio of 2:1, and then ball milling the mixture in a rapid ball mill for 15 minutes, and drying the obtained slurry at 120℃ for 2 hours; Step 2, the luminescent powder material is prepared by mixing the precursor fluorescent powder material prepared in Step 1, frit, aluminum hydroxide, potassium feldspar, pyrophyllite and strontium carbonate in a mass ratio of 0.72:2.90:0.36:0.58:0.29:0.14, and then mixing; Step 3, the luminescent ceramic powder material is prepared by mixing the luminescent powder material prepared in Step 2 and the tailings of the rare earth Y-type zeolite cracking catalyst in a mass ratio of 5:1, 5:2 or 5:4, adding water to a water-to-material ratio of 2:1, and then ball milling the mixture in a rapid ball mill for 15 minutes, and drying the obtained slurry at 120℃ for 2 hours; Step 4, the luminescent ceramic powder material prepared in Step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green ceramic body under a pressure of 200 MPa for 1 minute, the green ceramic body is dried at 120℃ for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700℃ at a rate of 7℃ per minute, then heated to 1000℃ at a rate of 5℃ per minute, and then heated to 1050℃ at a rate of 3℃ per minute, held at 1050℃ for 15 minutes, and then cooled with the furnace, to prepare an orange-red fluorescent ceramic.

[0006] The chemical composition of the frit in step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO and 0.311% PbO or 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, 0.0213% PbO. The rare earth Y-type zeolite cracking catalyst tailings in step 3 are rare earth Y-type zeolite cracking catalyst tailings generated in the preparation process of the rare earth Y-type zeolite cracking catalyst, and the chemical composition is 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3 and 0.0099% PbO.

[0007] The beneficial effects of the present application are: 1. The process is simple, the raw material cost is low, the sintering temperature is low, the sintering time is short, and it is conducive to industrialized production. 2. The addition amount of europium element is low, the proportion can be as low as 0.39%, and the content of rare earth Y-type zeolite cracking catalyst tailings is high, the proportion can be as high as 44%, which is helpful for the development and application of bulk chemical tailings utilization technology. 3、The tailings of the rare earth Y-type zeolite cracking catalyst are added in the technical scheme, the types and contents of different valence chemical elements in the material are regulated, the number of non-bonding oxygen in the silicon-oxygen link network of the orange-red fluorescent ceramic is gradually reduced, the coordination state of the trivalent metal ions, including europium ions, is changed in the process of changing the bonding mode of the silicon-oxygen bond. By changing the content of the tailings of the rare earth Y-type zeolite cracking catalyst, the absorption range of the europium atom excitation spectrum is regulated, the excitation spectrum of the ultraviolet excitation light source of the light-emitting display device is matched, the fine structure of the luminescence spectrum and the luminescence intensity of different luminescence peaks can also be regulated, and then the luminescence color can be regulated. BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 X-ray diffraction spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 1, 2 and 3, respectively.

[0009] Figure 2 Excitation spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 1, 2 and 3, respectively.

[0010] Figure 3 Fluorescence emission spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 1, 2 and 3, respectively.

[0011] Figure 4 Raman spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 1, 2 and 3, respectively.

[0012] Figure 5 Colorimetric values of fluorescence of fluorescent ceramics: (a), (b) and (c) are colorimetric values of fluorescent ceramics prepared by examples 1, 4 and comparative example 1, respectively.

[0013] Figure 6 Scanning electron microscope graph of orange-red fluorescent ceramics prepared by example 4.

[0014] Figure 7 X-ray diffraction spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 4, 5 and 6, respectively.

[0015] Figure 8 Excitation spectra of orange-red fluorescent ceramics: (a), (b) and (c) are spectra of orange-red fluorescent ceramics prepared by examples 4, 5 and 6, respectively.

[0016] Figure 9 The fluorescence emission spectra of the orange-red fluorescent ceramics are shown in (a), (b), and (c), which are the spectra of the orange-red fluorescent ceramics prepared in Examples 4, 5, and 6, respectively.

[0017] Figure 10 The Raman spectra of the orange-red fluorescent ceramics are shown in (a), (b), and (c), which are the spectra of the orange-red fluorescent ceramics prepared in Examples 4, 5, and 6, respectively.

[0018] Figure 11 X-ray diffraction patterns of fluorescent ceramics emitting near-red fluorescence: (a), (b) and (c) are the spectra of fluorescent ceramics emitting near-red fluorescence prepared according to Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively.

[0019] Figure 12 Excitation spectra of near-red fluorescent ceramics: (a), (b) and (c) are the spectra of near-red fluorescent ceramics prepared according to Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively.

[0020] Figure 13 Fluorescence emission spectra of fluorescent ceramics emitting near-red fluorescence: (a), (b) and (c) are the spectra of fluorescent ceramics emitting near-red fluorescence prepared according to Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively.

[0021] Figure 14 Raman spectra of near-red fluorescent ceramics: (a), (b) and (c) are the spectra of near-red fluorescent ceramics prepared according to Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively. Detailed Implementation Example 1

[0022] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in Step 2 and the rare earth Y-type zeolite cracking catalyst tailings are mixed in a mass ratio of 5:1, and water is added to make the ratio of water to material 2:1, and then the mixture containing water is ball milled in a rapid ball mill for 15 minutes, and then the obtained slurry is dried at 120°C for 2 hours to prepare a luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in Step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute, and then the green body is dried at 120°C for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700°C at a rate of 7°C per minute, then heated to 1000°C at a rate of 5°C per minute, and then heated to 1050°C at a rate of 3°C per minute, and then kept at 1050°C for 15 minutes and then cooled with the furnace to prepare an orange-red fluorescent ceramic.

[0023] The chemical composition of the frit mentioned in Step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO, and 0.311% PbO. The rare earth Y-type zeolite cracking catalyst tailings mentioned in Step 3 have a chemical composition of 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0024] According to the chemical composition of the luminescent powder prepared in Step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations as 0.40. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in Step 4 is as follows: Figure 1As shown in (a), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 2 As shown in (a), there is absorption between 300 nm and 400 nm, which can effectively match the excitation spectrum of the ultraviolet excitation source for light-emitting display devices. The emission spectrum (excitation wavelength of 285 nm during testing) is as follows. Figure 3 As shown in (a), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 52% and 58%, respectively. The Raman spectra are shown below. Figure 4 As shown in (a), it is located at 700 cm. -1 The changes in the nearby absorption peaks indicate changes in the network structure of silicon-oxygen and metal ion-oxygen bonds. The chromaticity values ​​of the light are as follows: Figure 5 As shown in (a), the chromaticity value (x, y) of the light is (0.55, 0.45), the color temperature is 2115 K, and it appears orange-red between the coordinates of pure red light (0.67, 0.33) and pure yellow light (0.51, 0.49). Example 2

[0025] Step 1: Prepare the ingredients according to the mass ratio, so that the ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide is 11.43:8.57:8.57:1.76:1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in step 2 and the rare earth Y-type zeolite cracking catalyst tailings were mixed in a mass ratio of 5:2, water was added to make the ratio of water to material 2:1, and then the mixture containing water was ball milled in a rapid ball mill for 15 minutes, and then the obtained slurry was dried at 120°C for 2 hours to prepare the luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in step 3 was sieved through an 80-mesh sieve, and the undersize material was pressed into a green body at 200 MPa for 1 minute, and then the green body was dried at 120°C for 2 hours, and finally it was placed in a muffle furnace, heated from room temperature to 700°C at a rate of 7°C per minute, then heated to 1000°C at a rate of 5°C per minute, and then heated to 1050°C at a rate of 3°C per minute, and then kept at 1050°C for 15 minutes and then cooled in the furnace to prepare an orange-red fluorescent ceramic.

[0026] The chemical composition of the frit mentioned in step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO, and 0.311% PbO. The chemical composition of the rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 is 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0027] According to the chemical composition of the luminescent powder prepared in step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations as 0.29. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in step 4 is as follows: Figure 1As shown in (b), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. Scanning electron microscope images of the sample are shown below. Figure 6 As shown, the grains are small and distributed within the glass phase. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 2 As shown in (b), there is strong absorption between 300 nm and 400 nm, which can effectively match the excitation spectrum of the ultraviolet excitation source for light-emitting display devices. The emission spectrum (excitation wavelength of 285 nm during testing) is as follows. Figure 3 As shown in (b), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 128% and 186%, respectively. The Raman spectra are shown below. Figure 4 As shown in (b), it is located at 700 cm. -1 The nearby absorption peaks become stronger, revealing a finer structure, indicating changes in the network structure of silicon-oxygen and metal ions bonded to oxygen. The chromaticity values ​​(x, y) of the light are (0.60, 0.40), and the color temperature is 1710 K. It appears orange-red between the coordinates (0.67, 0.33) of pure red light and the coordinates (0.51, 0.49) of pure yellow light. Example 3

[0028] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in step 2 and the rare earth Y-type zeolite cracking catalyst tailings are mixed in a mass ratio of 5:4, and water is added to make the ratio of water to material 2:1, and then the mixture containing water is ball milled in a rapid ball mill for 15 minutes, and then the obtained slurry is dried at 120℃ for 2 hours to prepare a luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute, and then the green body is dried at 120℃ for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700℃ at a rate of 7℃ per minute, then heated to 1000℃ at a rate of 5℃ per minute, and then heated to 1050℃ at a rate of 3℃ per minute, and then kept at 1050℃ for 15 minutes and then cooled with the furnace to prepare an orange-red fluorescent ceramic.

[0029] The chemical composition of the frit mentioned in step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO, and 0.311% PbO. The rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 have a chemical composition of 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0030] According to the chemical composition of the luminescent powder prepared in step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations as 0.15. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in step 4 is as follows: Figure 1As shown in (c), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 2 As shown in (c), there is strong absorption between 300 nm and 400 nm, which can effectively match the excitation spectrum of the ultraviolet excitation source for light-emitting display devices. The emission spectrum (excitation wavelength of 285 nm during testing) is as follows. Figure 3 As shown in (c), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 206% and 104%, respectively. The Raman spectra are shown below. Figure 4 As shown in (c), it is located at 700 cm. -1 The nearby absorption peaks become stronger, and the refined structure becomes more pronounced, indicating changes in the network structure of silicon-oxygen and metal ions bonded to oxygen. The chromaticity values ​​(x, y) of the light are (0.60, 0.40), and the color temperature is 1709 K. It appears orange-red between the coordinates (0.67, 0.33) of pure red light and the coordinates (0.51, 0.49) of pure yellow light. Example 4

[0031] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in step 2 and the rare earth Y-type zeolite cracking catalyst tailings are mixed in a mass ratio of 5:1, and water is added to make the ratio of water to material 2:1, and then the mixture containing water is ball milled in a rapid ball mill for 15 minutes, and then the obtained slurry is dried at 120°C for 2 hours to prepare a luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute, and then the green body is dried at 120°C for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700°C at a rate of 7°C per minute, then heated to 1000°C at a rate of 5°C per minute, and then heated to 1050°C at a rate of 3°C per minute, and then kept at 1050°C for 15 minutes and then cooled with the furnace to prepare an orange-red fluorescent ceramic.

[0032] The chemical composition of the frit mentioned in step 2 is 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, 0.0213% PbO. The chemical composition of the rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 is 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0033] According to the chemical composition of the luminescent powder prepared in step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations, which is 0.56. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in step 4 is as follows: Figure 7As shown in (a), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 8 As shown in (a), there is a small amount of absorption between 300 nm and 400 nm, which can effectively match the excitation spectrum of the ultraviolet excitation source of the light-emitting display device. The emission spectrum (excitation wavelength of 285 nm during testing) is as follows. Figure 9 As shown in (a), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 187% and 493%, respectively. The Raman spectra are shown below. Figure 10 As shown in (a), it is located at 700 cm -1 The nearby absorption peaks become stronger, and the refined structure is more pronounced, indicating changes in the network structure of silicon-oxygen and metal ion-oxygen bonds. The chromaticity values ​​of the light are as follows: Figure 5 As shown in (b), the chromaticity value (x, y) of the light is (0.61, 0.39), the color temperature is 1727 K, and it appears orange-red between the coordinates of pure red light (0.67, 0.33) and pure yellow light (0.51, 0.49). Example 5

[0034] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in step 2 and the rare earth Y-type zeolite cracking catalyst tailings are mixed in a mass ratio of 5:2, water is added to make the ratio of water to material 2:1, and then the mixture containing water is ball milled in a rapid ball mill for 15 minutes, and the obtained slurry is dried at 120℃ for 2 hours to prepare the luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute, the green body is dried at 120℃ for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700℃ at a rate of 7℃ per minute, then heated to 1000℃ at a rate of 5℃ per minute, and then heated to 1050℃ at a rate of 3℃ per minute, and then kept at 1050℃ for 15 minutes and cooled in the furnace to prepare an orange-red fluorescent ceramic.

[0035] The chemical composition of the frit mentioned in step 2 is 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, 0.0213% PbO. The chemical composition of the rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 is 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0036] According to the chemical composition of the luminescent powder prepared in step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations, which is 0.41. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in step 4 is shown in Figure 2. Figure 7As shown in (b), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 8 As shown in (b), there is strong absorption in the 300 nm to 400 nm range, which can effectively match the excitation spectrum of the ultraviolet excitation source for light-emitting display devices. The emission spectrum (excitation wavelength of 285 nm during testing) is attached. Figure 9 As shown in (b), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 206% and 469%, respectively. The Raman spectra are shown below. Figure 10 As shown in (b), it is located at 700 cm. -1 The nearby absorption peaks become stronger, and the refined structure is significant, indicating changes in the network structure of silicon-oxygen and metal ions bonded to oxygen. The chromaticity values ​​(x, y) of the light are (0.60, 0.40), and the color temperature is 1710 K. It appears orange-red between the coordinates (0.67, 0.33) of pure red light and the coordinates (0.51, 0.49) of pure yellow light. Example 6

[0037] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.14. After mixing, the luminescent powder is prepared. Step 3, the luminescent powder prepared in step 2 and the rare earth Y-type zeolite cracking catalyst tailings are mixed in a mass ratio of 5:4, and water is added to make the ratio of water to material 2:1, and then the mixture containing water is ball milled in a rapid ball mill for 15 minutes, and then the obtained slurry is dried at 120℃ for 2 hours to prepare the luminescent ceramic powder; Step 4, the luminescent ceramic powder prepared in step 3 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute, and then the green body is dried at 120℃ for 2 hours, and finally placed in a muffle furnace, heated from room temperature to 700℃ at a rate of 7℃ per minute, then heated to 1000℃ at a rate of 5℃ per minute, and then heated to 1050℃ at a rate of 3℃ per minute, and then kept at 1050℃ for 15 minutes and then cooled with the furnace to prepare an orange-red fluorescent ceramic.

[0038] The chemical composition of the frit mentioned in step 2 is 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, 0.0213% PbO. The chemical composition of the rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 is 0.644% Na2O, 0.0824% MgO, 23.7% Al2O3, 62% SiO2, 0.0202% P2O5, 0.396% SO3, 0.909% Cl, 0.519% K2O, 0.428% CaO, 0.116% TiO2, 0.819% Fe2O3, 0.004% CuO, 0.0193% ZnO, 0.0071% Ga2O3, 0.0047% Rb2O, 0.0094% SrO, 0.0025% Y2O3, 0.0122% ZrO2, 0.078% BaO, 1.91% La2O3, 7.78% CeO2, 0.464% Sm2O3, and 0.0099% PbO.

[0039] According to the chemical composition of the luminescent powder prepared in step 3, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations, which is 0.23. The X-ray diffraction (XRD) spectrum of the orange-red fluorescent ceramic prepared in step 4 is shown in Figure 2. Figure 7As shown in (c), the high-intensity main XRD diffraction peaks belong to the enstatite phase (protoenstatite, MgSiO3, JCPDS No. 74-2017), and no diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is as follows. Figure 8 As shown in (c), there is strong absorption in the 300 nm to 400 nm range, which can effectively match the excitation spectrum of the ultraviolet excitation source for light-emitting display devices. The emission spectrum (excitation wavelength of 285 nm during testing) is attached. Figure 9 As shown in (c), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 289% and 555%, respectively. The Raman spectra are shown below. Figure 10 As shown in (c), it is located at 700 cm. -1 The nearby absorption peaks become stronger, and the refined structure is significant, indicating changes in the network structure of silicon-oxygen and metal ions bonded to oxygen. The chromaticity values ​​(x, y) of the light are (0.59, 0.41), and the color temperature is 1728 K. It appears orange-red between the coordinates (0.67, 0.33) of pure red light and the coordinates (0.51, 0.49) of pure yellow light. Comparative Example 1

[0040] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Pass the precursor phosphor powder obtained in Step 1 through an 80-mesh sieve. Press the sieved material under 200 MPa for 1 minute to form a ceramic green body. Dry the ceramic green body at 120°C for 2 hours. Finally, place it in a muffle furnace and heat it from room temperature to 700°C at a rate of 7°C per minute, then to 1000°C at a rate of 5°C per minute, and then to 1050°C at a rate of 3°C per minute. Hold it at 1050°C for 15 minutes and then cool it with the furnace to obtain a fluorescent ceramic that emits near-red fluorescence.

[0041] Based on the chemical composition of the luminescent powder prepared in step 1, the value of unbonded oxygen can be calculated to be 2.81 from the molar numbers of anions, trivalent, tetravalent, and pentavalent cations. The X-ray diffraction (XRD) pattern of the near-red fluorescent ceramic prepared in step 2 is attached. Figure 11 As shown in (a), the main high-intensity XRD diffraction peaks belong to the forsterite phase (Mg2SiO4, JCPDS No. 78-1371), along with some impurity phases: protoenstatite (MgSiO3, JCPDS No. 74-2017), enstatite (MgSiO3, JCPDS No. 19-0768), and magnesium oxide (MgO, JCPDS No. 30-0794). No diffraction peaks of europium-related phases were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength was 614 nm during testing; the emission intensity values ​​on the vertical axis were magnified 10 times for clearer visualization) is shown below. Figure 12 As shown in (a), there is almost no absorption in the 300 nm to 400 nm range, which cannot effectively match the excitation spectrum of the ultraviolet excitation source for the light-emitting display device. The emission spectrum (excitation wavelength of 285 nm during testing) is attached. Figure 13 As shown in (a), the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 29% and 389%, respectively. The Raman spectra are shown below. Figure 14 As shown in (a), it is located at 700 cm -1 The weak absorption peaks and indistinct refined structure in the vicinity indicate that the changes in the network structure of silicon-oxygen and metal ion-oxygen bonds are not significant. The chromaticity values ​​of the light are as follows: Figure 5 As shown in (c), the chromaticity value (x, y) of the light is (0.65, 0.35), the color temperature is 2541K, which is close to the coordinate value (0.67, 0.33) of pure red light, and it appears to be pure red. Comparative Example 2

[0042] Step 1, the precursor phosphor powder was prepared by mixing the magnesium oxide, fumed silica, aluminum hydroxide, europium oxide and yttrium oxide in a mass ratio of 11.43:8.57:8.57:1.76:1.20, and then adding water to make the ratio of water to material 2:1, and then ball milling the mixture in a rapid ball mill for 15 minutes, and then drying the slurry at 120°C for 2 hours; Step 2, the luminescent powder was prepared by mixing the precursor phosphor powder prepared in step 1, frit, aluminum hydroxide, potassium feldspar, pyrophyllite and strontium carbonate in a mass ratio of 0.72:2.90:0.36:0.58:0.29:0.14; Step 3, the luminescent ceramic powder prepared in step 2 was sieved through an 80-mesh sieve, and the undersize material was pressed into a green body at 200 MPa for 1 minute, and then the green body was dried at 120°C for 2 hours, and then placed in a muffle furnace, and the temperature was raised from room temperature to 700°C at a rate of 7°C per minute, then to 1000°C at a rate of 5°C per minute, and then to 1050°C at a rate of 3°C per minute, and then held at 1050°C for 15 minutes, and then cooled in the furnace, to obtain a near-red fluorescent luminescent ceramic.

[0043] The chemical composition of the frit mentioned in step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO and 0.311% PbO.

[0044] According to the chemical composition of the luminescent powder prepared in step 2, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent and pentavalent cations, which is 0.56. The X-ray diffraction (XRD) spectrum of the near-red fluorescent luminescent ceramic prepared in step 3 is shown in Figure (b), and the main XRD diffraction peaks with high intensity belong to the original protoenstatite phase (MgSiO Figure 11 (b), and the main XRD diffraction peaks with high intensity belong to the original protoenstatite phase (MgSiO 3，The diffraction patterns of europium-related phases were as follows: (JCPDS No. 74-2017) and magnesium oxide (MgO, JCPDS No. 30-0794), along with some impurity phases: forsterite (Mg2SiO4, JCPDS No. 78-1371) and enstatite (MgSiO3, JCPDS No. 19-0768). No diffraction peaks were detected for europium-related phases, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (emission wavelength at 614 nm during testing) is shown below. Figure 12 As shown in (b), there is almost no absorption in the 300 nm to 400 nm range, which cannot effectively match the ultraviolet excitation spectrum of the ultraviolet excitation source for the light-emitting display device. The emission spectrum (excitation wavelength of 285 nm during testing) is attached. Figure 13 As shown in (b), the emission spectrum (the excitation wavelength during the test was 285 nm; to make the spectrum clearer, the emission intensity values ​​on the vertical axis were magnified 10 times), and the emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 29% and 389%, respectively. The Raman spectra are shown below. Figure 14 As shown in (b), it is located at 700 cm. -1 The weak absorption peaks and indistinct fine structure indicate that the changes in the network structure of silicon-oxygen and metal ion-oxygen bonds are not significant. The chromaticity values ​​(x, y) of the light are (0.59, 0.41), and the color temperature is 1719 K, which is close to the coordinates (0.67, 0.33) of pure red light, indicating a near-red hue. Comparative Example 3

[0045] Step 1: Prepare the materials according to the mass ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide as 11.43: 8.57: 8.57: 1.76: 1.20. Then add water to make the water-to-material ratio 2:1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2, the precursor phosphor powder prepared in step 1 is mixed according to the mass ratio of 0.72:2.90:0.36:0.58:0.29:0.14 to prepare the luminescent powder; Step 3, the luminescent ceramic powder prepared in step 2 is sieved through an 80-mesh sieve, and the undersize material is pressed into a green body at 200 MPa for 1 minute. The green body is dried at 120°C for 2 hours, and then placed in a muffle furnace. The temperature is raised at a rate of 7°C per minute from room temperature to 700°C, then at a rate of 5°C per minute to 1000°C, and then at a rate of 3°C per minute to 1050°C. After holding at 1050°C for 15 minutes, the furnace is cooled down to prepare a near-red fluorescent luminescent ceramic.

[0046] The chemical composition of the frit mentioned in step 2 is 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, and 0.0213% PbO.

[0047] According to the chemical composition of the luminescent powder prepared in step 2, the number of non-bonding oxygen can be calculated from the number of anions, trivalent, tetravalent, and pentavalent cations, which is 0.78. The X-ray diffraction (XRD) spectrum of the near-red fluorescent luminescent ceramic prepared in step 3 is shown in FIG. 4. Figure 11 (c), the main XRD diffraction peaks with high intensity belong to the protoenstatite phase (MgSiO 3， JCPDS No. 74-2017) and the magnesium oxide phase (MgO, JCPDS No. 30-0794), as well as some impurity phases: the forsterite phase (Mg2SiO4, JCPDS No. 78-1371) and the enstatite phase (MgSiO3, JCPDS No. 19-0768). No diffraction peaks related to europium elements were detected, indicating that europium ions have been doped into the luminescent ceramic lattice. The excitation spectrum (the emission wavelength is 614 nm during testing; the emission intensity value is magnified by 10 times to make the spectrum clearer) is shown in FIG. 5. Figure 12As shown in (c), there is a small amount of absorption between 300 nm and 400 nm, which cannot effectively match the excitation spectrum of the ultraviolet excitation source of the light-emitting display device. The emission spectrum (excitation wavelength of 285 nm during testing) is attached. Figure 13 As shown in (c), the emission spectrum (the excitation wavelength during the test was 285 nm; to make the spectrum clearer, the emission intensity value on the vertical axis was magnified by 2.5 times), emission peak ( 5 D0→ 7 The integral area of ​​F0 and the emission peak ( 5 D0→ 7 The integral area of ​​F2) and the emission peak ( 5 D0→ 7 The ratio A of the integral area of ​​F1) 01 and A 21 The percentages are 26% and 429%, respectively. The Raman spectra are shown below. Figure 14 As shown in (c), it is located at 700 cm. -1 The nearby absorption peaks are weak, and the refined structure is not obvious, indicating that the changes in the network structure of silicon-oxygen and metal ion-oxygen bonding are not significant. The chromaticity value (x, y) of the light is (0.65, 0.35), and the color temperature is 2427 K, which is close to the coordinate value (0.67, 0.33) of pure red light, showing a near-red hue.

Claims

1. A method for preparing orange-red fluorescent ceramics by adding rare earth Y-type zeolite cracking catalyst tailings, characterized in that: Step 1: Prepare the ingredients according to the mass ratio, so that the ratio of magnesium oxide: fumed silica: aluminum hydroxide: europium oxide: yttrium oxide is 11.43:8.57:8.57:1.76:1.

20. Then add water to make the water-to-material ratio 2:

1. Then ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then dry the resulting slurry at 120°C for 2 hours to prepare the precursor phosphor powder. Step 2: Prepare the materials according to the mass ratio so that the ratio of the precursor phosphor powder obtained in Step 1: frit: aluminum hydroxide: potassium feldspar: pyrophyllite: strontium carbonate is 0.72:2.90:0.36:0.58:0.29:0.

14. After mixing, the luminescent powder is prepared. Step 3: Prepare the materials according to the mass ratio, so that the mass ratio of the luminescent powder prepared in Step 2 to the tailings of the rare earth Y-type zeolite cracking catalyst is 5:1, 5:2 or 5:

4. Then add water to make the water-to-material ratio 2:

1. Then, ball mill the water-containing mixture in a high-speed ball mill for 15 minutes. Then, dry the resulting slurry at 120°C for 2 hours to prepare the luminescent ceramic powder. Step 4: Pass the luminescent ceramic powder obtained in Step 3 through an 80-mesh sieve. Press the sieved material under 200 MPa for 1 minute to form a ceramic green body. Dry the ceramic green body at 120°C for 2 hours. Finally, place it in a muffle furnace and heat it from room temperature to 700°C at a rate of 7°C per minute, then to 1000°C at a rate of 5°C per minute, and then to 1050°C at a rate of 3°C per minute. Hold it at 1050°C for 15 minutes and then cool it with the furnace to obtain orange-red fluorescent ceramic.

2. The method for preparing orange-red fluorescent ceramics by adding rare earth Y-type zeolite cracking catalyst tailings as described in claim 1, characterized in that... The chemical composition of the fused block described in step 2 is 8.46% B2O, 2.07% Na2O, 0.124% MgO, 8.71% Al2O3, 57.2% SiO2, 0.0534% P2O5, 0.061% SO3, 0.0631% Cl, 3.1% K2O, 8.08% CaO, 0.0897% Fe2O3, 0.003% CuO, 5.02% ZnO, 0.0096% Rb2O, 1.83% SrO, 0.0285% ZrO2, 0.024% I, 4.72% BaO, and 0.311% PbO.

3. The method for preparing orange-red fluorescent ceramics by adding rare earth Y-type zeolite cracking catalyst tailings as described in claim 1, characterized in that... The chemical composition of the fused block described in step 2 is 3.05% Na2O, 1.15% MgO, 17.4% Al2O3, 48% SiO2, 0.0549% P2O5, 0.0702% SO3, 0.0358% Cl, 2.21% K2O, 11.2% CaO, 0.127% Fe2O3, 6.46% ZnO, 0.0173% Rb2O, 0.0707% SrO, 0.0005% Y2O3, 0.0754% ZrO2, 0.0282% I, 10.1% BaO, and 0.0213% PbO.

4. The method for preparing orange-red fluorescent ceramics by adding rare earth Y-type zeolite cracking catalyst tailings as described in claim 1, characterized in that... The rare earth Y-type zeolite cracking catalyst tailings mentioned in step 3 are by-product tailings generated during the preparation of rare earth Y-type zeolite cracking catalysts.

5. The method for preparing orange-red fluorescent ceramics by adding rare earth Y-type zeolite cracking catalyst tailings as described in claim 1, characterized in that... The rare earth Y-type zeolite cracking catalyst tailings described in step 3 have the following chemical composition: 0.644% Na₂O, 0.0824% MgO, 23.7% Al₂O₃, 62% SiO₂, 0.0202% P₂O₅, 0.396% SO₃, 0.909% Cl, 0.519% K₂O, 0.428% CaO, 0.116% TiO₂, 0.819% Fe₂O₃, 0.004% CuO, and 0.0193% CaO. ZnO, 0.0071%Ga2O3, 0.0047%Rb2O, 0.0094%SrO, 0.0025%Y2O3, 0.0122%ZrO2, 0.078%BaO, 1.91%La2O3, 7.78%CeO2, 0.464%Sm2O3 and 0.0099%PbO.

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