A method for preparing high thermal stability frit using glass waste

Abstract

The present invention discloses a method for preparing a high-thermal-stability frit using waste glass, which relates to the technical field of ceramic frits. The method comprises the following steps: reducing and sintering the raw materials to obtain the high-thermal-stability frit; the raw materials include, by weight, 40-60 parts of waste glass powder, 10-20 parts of boron tail powder, 2-8 parts of a fixative, and 1-5 parts of a phosphate mineralizer; the fixative is at least one of zirconium oxide, lanthanum oxide, and tin oxide; and the phosphate mineralizer is aluminum phosphate or magnesium pyrophosphate. The reduction sintering process involves first heating the temperature to 750-850°C in a reducing atmosphere and holding the temperature for 20-30 minutes; then heating the temperature to 1100-1250°C and melting the mixture for 25-50 minutes, and finally quenching the melt. The main raw materials of the present invention are all waste glass, which reduces the cost of the raw materials and produces ceramic frits with high thermal stability.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic frits, and in particular relates to a method for preparing high-thermal stability frits by utilizing glass waste. Background Art

[0002] Using waste glass to prepare ceramic frits can effectively reduce the exploitation of natural mineral resources and achieve resource recycling, which is of great significance to environmental protection and sustainable economic development. However, current methods for treating waste glass are mostly limited to simple decontamination and high-temperature melting and recycling, and there is little research on the resource utilization of high-boron, high-halogen glass.

[0003] Among existing technologies, patent document CN118270980A provides a method for preparing thermally stable frits from waste glass. The core of this method is to precisely adjust the sintering properties of the glass powder by adding feldspar and boric acid as fluxes to ensure that the frit achieves ideal melting properties during the sintering process. In addition, this solution further improves the thermal stability of the frit by carefully adjusting the type and proportion of titanium dioxide, making its performance in high-temperature environments even better. Despite this, this solution still has the problem of high costs during the preparation process.

[0004] Furthermore, existing processes typically involve high-temperature melting, causing halogens to volatilize as either elemental or acidic gases. This not only corrodes equipment but also pollutes the environment. Halogens themselves can serve as functional ingredients, but if they completely evaporate, additional additives must be added, increasing costs. Summary of the Invention

[0005] In order to overcome the above technical problems, the present invention provides a method for preparing a high thermal stability frit using glass waste. The main raw materials of the present invention are all glass waste, the raw material cost is low, and the ceramic frit produced has high thermal stability.

[0006] The present invention solves the above technical problems through the following technical solutions.

[0007] A method for preparing a high thermal stability frit from glass waste comprises the following steps: reducing and sintering the raw materials to obtain a high thermal stability frit;

[0008] The raw materials for the preparation include, by weight: 40 to 60 parts of waste glass powder, 10 to 20 parts of boron tail powder, 2 to 8 parts of a fixing agent, and 1 to 5 parts of a phosphate mineralizer;

[0009] The boron tail powder comprises the following chemical components by mass: 40-45% B2O3, 14-18% K2O, 18-23% Na2O, 6-9% Cl element and 6-9% F element; the contents of F and Cl in the boron tail powder are both calculated in the form of element content;

[0010] The reduction sintering process comprises the following steps: firstly heating the material to 600-750° C. in a reducing atmosphere and keeping the temperature therefor for 20-30 minutes; then heating the material to 900-1050° C. and melting the material for 25-50 minutes; and finally quenching the melt.

[0011] According to some preferred embodiments of the present invention, the preparation raw materials include 40 to 55 parts of waste glass powder, 10 to 15 parts of boron tail powder, 3 to 7 parts of fixing agent and 2 to 5 parts of phosphate mineralizer.

[0012] In the present invention, the waste glass powder comprises the following chemical components in mass percentage: 69-75% SiO2, 2-7% Al2O3, B2O3≥5%, 4-12% alkali metal oxides and 1-6% alkaline earth metal oxides;

[0013] The alkaline earth metal oxide includes at least one of CaO, MgO, BaO and ZnO; and the alkali metal oxide includes at least one of K2O and Na2O.

[0014] Preferably, the waste glass powder comprises 70-75% SiO2, 2-7% Al2O3, 5-11% B2O3, 5-9% NaO, 1-4% K2O, 1-3% BaO, 0-1.5% CaO, 0-1.5% MgO and 0-1.5% ZnO.

[0015] In the present invention, the particle size of the waste glass powder is 300-500 mesh.

[0016] According to some preferred embodiments of the present invention, the boron tail powder includes the following chemical components in parts by mass: 42-44% B2O3, 15.5-17% K2O, 19-22% Na2O, 6.5-8% Cl element and 6.5-8% F element.

[0017] For example, the boron tail powder includes the following chemical components in mass percentage: 43.03% B2O3, 16.19% K2O, 20.07Na2O, 7.22% Cl element, 7.72% F element, 2.96% SiO2, 0.41% Ti2O and 0.38% BaO.

[0018] In the present invention, the particle size of the boron tail powder is 300-500 mesh.

[0019] In the present invention, the fixing agent is at least one of zirconium oxide, lanthanum oxide, and tin oxide. The fixing agent can form stable MO-Cl / F bonds with the halogen ions in the boron tail powder, inhibiting halogen volatilization even under high-temperature sintering environments exceeding 1000°C. Halogens, due to their strong bonding ability, form chemical bonds with the molecules, enhancing thermal stability.

[0020] In the present invention, the D50 of the fixing agent is 20-50 μm, preferably 30-40 μm.

[0021] In the present invention, the phosphate mineralizer is aluminum phosphate (AlPO4) or magnesium pyrophosphate (Mg2P2O7). The aluminum phosphate decomposes at high temperature to produce P2O5 which can react with B2O3 to form [PO4] 3- -[BO3] 3- Mixed network enhances the stability of glass phase. Compared with aluminum phosphate, magnesium pyrophosphate has higher activity in releasing P2O5 and is more likely to form glass phase with B2O3. However, it should be noted that excessive addition of phosphate mineralizer may cause emulsion. In addition, [PO4] 3- It easily reacts with free halogens to form thermally stable chlorophosphate and fluorapatite analogues, reducing high-temperature volatilization.

[0022] According to some preferred embodiments of the present invention, the reduction sintering process is: first, heating to 600-650°C in a reducing atmosphere and keeping warm for 25-30 minutes; then heating to 900-1000°C and melting for 40-50 minutes; and finally, quenching the melt.

[0023] In the present invention, the volume ratio of CO:N2 in the reducing atmosphere is 1:3~6, preferably 1:4~5.

[0024] In the present invention, the heating rate is 5-8°C / min.

[0025] In the present invention, after the insulation is completed, nitrogen is introduced and then the temperature is increased, so that the melting process is carried out in a nitrogen atmosphere.

[0026] In the present invention, the halogen retention rate of the high thermal stability frit is: Cl element ≥ 70%, preferably 70-75%.

[0027] In the present invention, the halogen retention rate of the high thermal stability frit is: F element ≥ 69%, preferably 69-77%.

[0028] The halogen retention rate in the present invention is a key indicator for measuring the efficiency of fixing fluorine and chlorine, and is calculated based on the mass percentage of the halogen content in the raw materials and products.

[0029] In the present invention, the high thermal stability frit is rapidly cooled from 350° C. to 0° C., and the thermal shock resistance thereof is tested to be ≥30 times through repeated cycle testing.

[0030] On the basis of conforming to the common sense in this field, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention uses waste glass powder and boron tail powder as the main raw materials, eliminating the need for the addition of high-purity quartz sand or flux, thereby significantly reducing raw material costs. During the preparation process, the chlorine and fluorine in the boron tail powder are directly converted into stable compounds through the synergistic effect of a fixative and a phosphate mineralizer, significantly improving the high-temperature resistance and thermal shock resistance of the frit. Furthermore, this process achieves resource utilization of halogens and effectively avoids environmental pollution.

[0033] 2. The present invention adopts a two-stage reduction-melting sintering process. The reduction and heat preservation stage in the low-temperature stage promotes the formation of a low-temperature eutectic phase between Na2O / K2O and B2O3; at the same time, it prevents equipment corrosion and solves the halogen element pollution problem in the recycling process of high-halogen glass waste.

[0034] 3. The high thermal stability frit prepared by the present invention has excellent thermal shock resistance, and its thermal shock resistance number is ≥30 times, and in some preferred embodiments can reach 32 to 36 times. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The present invention is a flow chart of preparing high thermal stability frit using glass waste materials. DETAILED DESCRIPTION

[0036] To facilitate understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0037] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0038] The "ranges" disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the particular range. Ranges defined in this manner can be inclusive or exclusive of the end values ​​and can be combined in any manner, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values ​​listed are 1 and 2, and if the maximum range values ​​listed are 3, 4, and 5, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this disclosure, unless otherwise indicated, the numerical range "ab" is an abbreviation for any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed herein, and "0-5" is merely an abbreviation for these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0039] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0040] Unless otherwise specified, all technical features and optional technical features of the present invention can be combined with each other to form a new technical solution.

[0041] Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, preferably sequentially. For example, "the method includes steps (a) and (b)" indicates that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, "the method may further include step (c)" indicates that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0042] Unless otherwise specified, the terms "include" and "comprising" used in the present invention may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0043] Unless otherwise specified, the term "or" is inclusive in this disclosure. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, the condition "A or B" is satisfied if any of the following conditions are met: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0044] The raw material information used in the following examples is as follows:

[0045] Waste glass powder and boron tail powder come from medical waste glass;

[0046] Waste glass powder is made from waste glass, that is, it is made by removing impurities, crushing, cleaning, drying and grinding the waste glass; waste glass mainly refers to discarded injection bottles;

[0047] Chemical composition of waste glass powder: 70.3% SiO2, 6.2% Al2O3, 8.3% B2O3, 7.9% NaO, 1.6% K2O, 2.3% BaO, 1.1% CaO, 0.67% MgO, 0.56% ZnO and the remainder impurities;

[0048] Boron tail powder comes from culture dishes, micromanipulation dishes and their covers;

[0049] The chemical composition of boron tail powder is: 43.03% B2O3, 16.19% K2O, 20.07% Na2O, 7.22% Cl element, 7.72% F element, 2.96% SiO2, 0.41% Ti2O, 0.38% BaO and the remaining impurities.

[0050] The various components in the raw materials of the present invention are measured by chemical analysis methods, and the testing methods refer to conventional standards in the field, such as GB / T 16537-2010, GB / T 4734-2022, GB / T 3050-2000 and GB / T 14506.12-2010.

[0051] The following process converts the above glass waste into high thermal stability frit. Figure 1 .

[0052] Example 1

[0053] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0054] The raw materials for preparation are 50 parts of waste glass powder, 15 parts of boron tail powder, 6 parts of fixative (zirconium oxide, D50 = 32 μm) and 4 parts of phosphate mineralizer (aluminum phosphate);

[0055] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept for 25 minutes; then the temperature was raised to 950°C and melted for 45 minutes, and finally the melt was quenched in water. The heating rate of this process was 5°C / min.

[0056] Halogen retention rate: 74.2% Cl, 72.8% F.

[0057] Example 2

[0058] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0059] The raw materials for preparation are 55 parts of waste glass powder, 10 parts of boron tail powder, 4.5 parts of fixative (2.4 parts of lanthanum oxide and 2.1 parts of zirconium oxide, fixative D50 = 40 μm) and 5 parts of phosphate mineralizer (aluminum phosphate);

[0060] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept for 25 minutes; then the temperature was raised to 950°C and melted for 45 minutes, and finally the melt was quenched in water. The heating rate of this process was 5°C / min.

[0061] Halogen retention rate: 71.5% Cl, 73.7% F.

[0062] Example 3

[0063] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0064] The raw materials for preparation are 50 parts of waste glass powder, 15 parts of boron tail powder, 7 parts of fixative (3 parts of lanthanum oxide and 4 parts of tin oxide, fixative D50 = 37 μm) and 3.5 parts of phosphate mineralizer (aluminum phosphate);

[0065] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept warm for 25 minutes; nitrogen was introduced, and the temperature was raised to 950°C and melted for 45 minutes. Finally, the melt was quenched in water. The heating rate of this process was 5°C / min.

[0066] Halogen retention rate: 72.1% Cl, 76.7% F.

[0067] Example 4

[0068] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0069] The raw materials for preparation are 44 parts of waste glass powder, 12 parts of boron tail powder, 6 parts of fixative (zirconium oxide, D50 = 32 μm) and 3 parts of phosphate mineralizer (magnesium pyrophosphate);

[0070] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept warm for 25 minutes; nitrogen was introduced, and the temperature was raised to 950°C and melted for 45 minutes. Finally, the melt was quenched in water. The heating rate of this process was 5°C / min.

[0071] Halogen retention rate: 73.7% Cl, 70.0% F.

[0072] Example 5

[0073] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0074] The raw materials for preparation are 50 parts of waste glass powder, 15 parts of boron tail powder, 6 parts of fixative (zirconium oxide, D50 = 32 μm) and 4 parts of phosphate mineralizer (aluminum phosphate);

[0075] After ball milling the above-prepared raw materials, the temperature was raised to 650°C in a reducing atmosphere with a CO:N2 volume ratio of 1:3 and kept for 30 minutes; nitrogen was introduced, and the temperature was raised to 900°C and melted for 50 minutes. Finally, the melt was quenched in water. The heating rate of this process was 8°C / min.

[0076] Halogen retention rate: 70.6% Cl, 69.2% F.

[0077] Example 6

[0078] The method for preparing high thermal stability frit using glass waste in this embodiment is as follows:

[0079] The raw materials for preparation are 50 parts of waste glass powder, 15 parts of boron tail powder, 6 parts of fixative (zirconium oxide, D50 = 32 μm) and 4 parts of phosphate mineralizer (aluminum phosphate);

[0080] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept warm for 30 minutes; nitrogen was introduced, and the temperature was raised to 1100°C and melted for 20 minutes. Finally, the melt was quenched in water. The heating rate of this process was 10°C / min.

[0081] Halogen retention rate: 67.2% Cl, 63.7% F.

[0082] Comparative Example 1

[0083] The method for preparing high thermal stability frit using glass waste in this comparative example is as follows:

[0084] The raw materials for preparation are 54 parts of waste glass powder, 13 parts of boron tail powder and 4.8 parts of phosphate mineralizer (aluminum phosphate);

[0085] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:4 and kept warm for 30 minutes; nitrogen was introduced, and the temperature was raised to 950°C and melted for 40 minutes. Finally, the melt was quenched in water. The heating rate of this process was 5°C / min.

[0086] Without adding a fixative, the halogen is almost completely volatilized; in addition, compared with the toughening effect brought by ZrO2 in Example 1, the strength of the frit prepared by this comparative example method is poor.

[0087] Halogen retention rate: 7.2% Cl, 1.6% F.

[0088] Comparative Example 2

[0089] The method for preparing high thermal stability frit using glass waste in this comparative example is as follows:

[0090] The raw materials for preparation are 50 parts of waste glass powder, 13 parts of boron tail powder and 7 parts of fixative (zirconia, D50=32μm);

[0091] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept warm for 25 minutes; nitrogen was introduced, and the temperature was raised to 950°C and melted for 40 minutes. Finally, the melt was quenched in water. The heating rate of this process was 5°C / min.

[0092] In this comparative example, the [BO3] unit cannot form a mixed network with [PO4], and a stable glass phase cannot be obtained. The frit finally obtained is prone to thermal shock cracking.

[0093] Halogen retention rate: 12.3% Cl, 5.8% F.

[0094] Comparative Example 3

[0095] The difference between this comparative example and Example 1 is:

[0096] The method for preparing high thermal stability frit using glass waste in this comparative example is as follows:

[0097] The raw materials for preparation are 52 parts of waste glass powder, 11.7 parts of boron tail powder, 15 parts of fixative (zirconium oxide, D50 = 32 μm) and 7 parts of phosphate mineralizer (aluminum phosphate);

[0098] After ball milling the above-prepared raw materials, the temperature was raised to 600°C in a reducing atmosphere with a CO:N2 volume ratio of 1:5 and kept warm for 20 minutes; nitrogen was introduced, and the temperature was raised to 950°C and melted for 40 minutes. Finally, the melt was quenched in water. The heating rate of this process was 5°C / min.

[0099] In this comparative example, excessive addition of zirconium oxide resulted in high melt viscosity, hindering the flow of the glass phase. The resulting frit was porous and exhibited reduced thermal shock resistance. Furthermore, excessive addition of aluminophosphate resulted in an excess of P₂O₅, which reacted with B₂O₃ to form a phosphorus-rich phase, which is incompatible with the silicate glass phase and leads to phase separation.

[0100] Halogen retention rate: 62.6Cl%, 58.9F%.

[0101] Comparative Example 4

[0102] The difference between this comparative example and Example 1 is:

[0103] The method for preparing high thermal stability frit using glass waste in this comparative example is as follows:

[0104] The raw materials for preparation are 50 parts of waste glass powder, 13.6 parts of boron tail powder, 5.2 parts of fixative (zirconium oxide, D50 = 32 μm) and 3.8 parts of phosphate mineralizer (aluminum phosphate);

[0105] After ball milling the raw materials prepared above, the temperature was raised to 600°C and kept at this temperature for 20 minutes; the temperature was then raised to 950°C and melted for 40 minutes, and finally the melt was quenched in water. The heating rate of this process was 5°C / min.

[0106] In the preparation process of this embodiment, no reducing gas was introduced. The oxidizing atmosphere in the system caused the halogen to react and generate the corresponding acid, which volatilized. In addition, a large amount of alkali metal oxide was lost, and the melt fluidity was poor.

[0107] Halogen retention rate: 19.8% Cl, 4.5% F.

[0108] Test Case

[0109] The high thermal stability frits prepared in the above examples and comparative examples were tested for thermal shock resistance. The test method was to take 10 high thermal stability frits from each example or comparative example as samples, place the 10 samples in a 350°C high-temperature furnace for 10 minutes, then quickly quench in ice water, and repeat the cycle until the sample surface cracks. The results in Table 1 below are the average of the results of the 10 samples.

[0110] .

[0111] Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in the present invention can be purchased from the market or prepared by existing methods. The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A method for preparing high thermal stability frit using glass waste, characterized in that: The following steps are involved: The prepared raw materials are reduced and sintered to obtain a frit with high thermal stability; The preparation raw materials include, by weight: 40 to 60 parts of waste glass powder, 10 to 20 parts of boron tail powder, 2 to 8 parts of fixing agent and 1 to 5 parts of phosphate mineralizer; The fixing agent is at least one of zirconium oxide, lanthanum oxide and tin oxide; The phosphate mineralizer is aluminum phosphate or magnesium pyrophosphate; The boron tail powder comprises the following chemical components by mass: 40-45% B2O3, 14-18% K2O, 18-23% Na2O, 6-9% Cl element and 6-9% F element; The reduction sintering process comprises the following steps: firstly heating the material to 600-750° C. in a reducing atmosphere and keeping the temperature therefor for 20-30 minutes; then heating the material to 900-1050° C. and melting the material for 25-50 minutes; and finally quenching the melt.

2. The method for preparing high thermal stability frit using glass waste according to claim 1, wherein: The preparation raw materials include, by mass, 40 to 55 parts of waste glass powder, 10 to 15 parts of boron tail powder, 3 to 7 parts of fixing agent and 2 to 5 parts of phosphate mineralizer.

3. The method for preparing high thermal stability frit using glass waste according to claim 2, wherein: The waste glass powder includes the following chemical components in mass percentage: 69-75% SiO2, 2-7% Al2O3, B2O3≥5%, 4-12% alkali metal oxides and 1-6% alkaline earth metal oxides.

4. The method for preparing high thermal stability frit using glass waste according to claim 2, wherein: The boron tail powder includes the following chemical components in parts by mass: 42-44% B2O3, 15.5-17% K2O, 19-22% Na2O, 6.5-8% Cl element and 6.5-8% F element.

5. The method for preparing high thermal stability frit using glass waste according to claim 1, wherein: The reduction sintering process comprises the following steps: firstly heating the material to 600-650° C. in a reducing atmosphere and maintaining the temperature for 25-30 minutes; then heating the material to 900-1000° C. and melting the material for 40-50 minutes; and finally quenching the melt.

6. The method for preparing high thermal stability frit using glass waste according to claim 5, wherein: Meet at least one of the following conditions a to c: a. The reducing atmosphere CO: N2 volume ratio 1: 3 to 6; b. The heating rate is 5~8℃ / min; c. After the insulation is completed, nitrogen is introduced and then the temperature is raised so that the melting process is carried out in a nitrogen atmosphere.

7. The method for preparing high thermal stability frit using glass waste according to claim 5, wherein: The volume ratio of CO:N2 in the reducing atmosphere is 1:4-5.

8. The method for preparing high thermal stability frit using glass waste according to claim 1, wherein: Satisfy at least one of the following conditions a~b: a. Halogen retention rate of the high thermal stability frit: Cl element ≥ 70%; b. Halogen retention rate of the high thermal stability frit: F element ≥ 69%.

9. The method for preparing a high thermal stability frit using glass waste according to any one of claims 1 to 8, wherein: The high thermal stability frit has a thermal shock resistance of ≥30 times.

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