Multifunctional glass melting accelerator as well as preparation and application methods thereof
Patent Information
- Application Number
- CN202411410361.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-10
- Publication Date
- 2025-01-10
AI Technical Summary
Existing rare earth raw materials have a single function in glass production and are difficult to meet a variety of needs. Especially in the melting of all-electric furnaces, they are prone to problems such as bubbles, stones, stripes, and crystallization, and the effect is not ideal and difficult to prevent and control.
Using a multifunctional glass melting accelerator, including cerium ammonium nitrate, sodium sulfate and other components such as lanthanum fluoride, cerium oxide, etc., the gas is taken away by low temperatures, forming a gradient clarification pattern to promote low The conversion of valence oxides to high valence states improves the clarification, decolorization and coloring effects of glass, while reducing bubbles and viscosity, enhancing the water resistance and thermal stability of glass.
Significantly accelerates the melting of glass, improves clarification efficiency and appearance quality, reduces linear thermal expansion coefficient, enhances the gloss, brightness and refractive index of glass, and is suitable for a variety of glass types and processing equipment.
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Figure CN119285222A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of glass flux and clarifier. Background Art
[0002] Rare earth raw materials have many applications in ordinary Na2O-CaO-SiO2 glass, such as cerium oxide (CeO2) or cerium oxide in combination with sodium sulfate or sodium nitrate for clarification; erbium oxide (Er2O3) for decolorization; neodymium oxide (Nd2O3), praseodymium oxide (Pr2O3), and samarium oxide (Sm2O3) for coloring, but the functions of these rare earth raw materials are relatively single, and the effects are not significant enough, and it is difficult to meet the various needs in glass production. For example, erbium oxide is a simple physical decolorizer and does not have a fluxing or clarification effect, while cerium oxide generally only has a clarification effect, and the clarification effect is not ideal, especially in the all-electric melting furnace. Because the design and adjustment of the fluxing and clarification raw materials are relatively complicated, it is very easy to cause melt defects related to melting and clarification, such as bubbles, stones, streaks, crystallization, etc.; at other times, there may also be problems such as exposure coloration and microbubble problems, and these problems may occur randomly and are difficult to prevent and control. Summary of the invention
[0003] In order to solve the above-mentioned problems of the prior art, the purpose of the present invention is to provide a new multifunctional glass melting accelerator and its preparation and application method, wherein the multifunctional glass melting accelerator has the function of accelerating glass melting, and at the same time has the functions of improving glass clarification efficiency, strengthening glass homogenization, improving the visual quality of glass appearance such as gloss, brightness, refractive index, improving the water resistance and thermal stability of glass and reducing its linear thermal expansion coefficient.
[0004] The technical solution of the present invention is as follows:
[0005] A multifunctional glass melting accelerator comprises component A, component B, component C and other components containing one or more of the following elements: F element, La element, Ce element, Cl element and O element; wherein component A is ammonium cerium nitrate, and its content is 10 to 20 parts by mass; component B is sodium sulfate, and its content is 5 to 20 parts by mass; component C is a humidifier, and its content is 1 to 10 parts by mass; and the content of other components is 60 to 80 parts by mass.
[0006] In the above formula of the present invention, component A, cerium ammonium nitrate, contains nitrate, ammonium ion (NH 4+) and cerium oxide, which have a low melting point (107-108°C) and can form a primary liquid phase earlier in the glass melting process, accelerating the melting rate of other raw materials. At the same time, the nitrate ion can decompose oxygen, nitrogen and ammonia at low temperature, taking away a large amount of gas produced in the early stage of silicate formation in the glass, improving the clarification efficiency and effect in the later clarification stage. At the same time, the oxygen released by itself can promote the conversion of low-valent cerium to high-valent or promote the conversion of low-valent variable-valent oxides in other raw materials to high-valent, thereby increasing the oxidation potential of the glass liquid. Therefore, the decolorization and coloring effects of the glass can be further improved, making the melting accelerator produce multiple functions; component B sodium sulfate can provide sulfate and sodium ions, among which sulfate is a very effective high-temperature clarifier. After being combined with the nitrate ion with low-temperature clarification effect in component A, a gradient clarification mode can be formed in the glass melting process, greatly improving the clarification effect of the glass liquid. At the same time, the inventors unexpectedly discovered that the above two components and the other components used in combination with one or more of some commonly used humidifiers in the art, such as water, sodium hydroxide aqueous solution, sodium silicate aqueous solution, etc., will produce better effects of promoting melting, improving clarification efficiency, and improving product appearance and mechanical properties.
[0007] The above other components of the present invention may exist in the form of independent compounds or in combination, such as lanthanum fluoride containing F and La elements and cerium fluoride containing F and Ce elements, etc., or may exist in the form of complex salts, such as metal salts containing three or more of the elements at the same time.
[0008] Preferably, the other components are selected from one or more of lanthanum fluoride, cerium fluoride, cerium chloride, cerium oxide, and lanthanum oxide.
[0009] In this preferred embodiment, in addition to the nitrate, sulfate, ammonium ion, sodium ion and cerium element contained in components A and B, the other components further appropriately introduce fluorine, chlorine, lanthanum and oxygen elements.
[0010] Among them, the addition of fluorine element can further reduce the transition temperature of α-tridymite to α-cristobalite, significantly increase the volume expansion rate, make the SiO2 structure loose during the melting process, and then accelerate the reaction rate of SiO2 with other components. At the same time, it is easy to form a low-temperature eutectic with carbonates, such as Na2CO3·CaF2, so that the batch material produces a liquid phase at a lower temperature, which greatly accelerates the formation process of silicates. The introduction of 0.5% fluorine in the batch material can accelerate the glass formation rate by more than double, the melting capacity is increased by 15%, and the liquid phase appearance temperature is reduced by about 200°C. At the same time, it can increase the thermal permeability of the batch material during melting, reduce the melt viscosity and surface tension, and about 40% of the fluorine in the fluoride will volatilize, which can destroy the gas balance in the bubbles, reduce the partial pressure of other gases in the bubbles, and make the bubbles grow rapidly and escape.
[0011] The chlorine element not only has a good fluxing effect, but can also escape in molecular form, which enhances the glass clarification effect and is conducive to the rapid growth and escape of bubbles.
[0012] Lanthanum element can form lanthanum oxide during melting, which can reduce the viscosity of high-temperature melt and facilitate the rapid escape of bubbles. At the same time, it can easily react with acid to improve the water resistance of glass, reduce the linear thermal expansion coefficient of glass, improve the thermal stability of glass, and improve the lighting performance of glass. Lanthanum can also be dissolved in glass in large quantities to increase its refractive index, reduce the dispersion rate, increase the hardness of glass, increase its softening temperature and chemical stability, and effectively prevent the erosion of water and acid on the glass surface. It plays an important role in improving the weathering of flat glass and the water resistance of container glass.
[0013] Oxygen can further promote the production of some oxides with significant fluxing and clarifying effects, such as cerium oxide and lanthanum oxide. Among them, cerium oxide is a high-temperature clarifier with ultraviolet cutoff ability, which can prevent food and medicine from deteriorating in bottles. In the physical decolorization of selenium cobalt, its discoloration degree is lower than that of arsenic oxide and antimony oxide glass when exposed to sunlight; at the same time, it has strong oxidizing properties and is an excellent chemical decolorizer, which can improve the efficiency and effect of physical decolorization. Both cerium oxide and lanthanum oxide have high refractive index and low dispersion characteristics, which can increase the refractive index of glass, reduce dispersion, and obtain the visual quality of glass crystal texture.
[0014] At the same time, oxygen can have a direct impact on the redox balance of glass throughout the glass melting process. For example, changing the redox atmosphere of the batch material and reducing the Fe 2+ / Fe 3+ , improve the effect of chemical decolorization and physical decolorization efficiency of glass; promote the redox reaction of variable valence ions in the glass, accelerate the clarification process of the glass, and promote the floating and escape of bubbles; under the conditions of flame kiln glass melting, it can make the flame burn more fully, enhance the oxidizing atmosphere of the furnace gas, weaken the coloring ability of variable valence coloring ions in the glass, and improve the whiteness and brightness of the glass; the oxygen partial pressure has a direct impact on the activity of oxygen and oxygen ions in the high-temperature melt of the glass, and has a direct impact on the reaction of various media (such as refractory materials, electrodes, etc.) during the glass melting, clarification, homogenization, coloring, decolorization and melting process.
[0015] Preferably, the other components are selected from lanthanum fluoride and cerium oxide.
[0016] Preferably, the other components are selected from lanthanum fluoride, cerium fluoride and cerium chloride.
[0017] Preferably, the other components are selected from cerium oxide and lanthanum oxide.
[0018] Preferably, the multifunctional glass melting accelerator comprises 15 parts by mass of the component A, 15 parts by mass of the component B, 5 parts by mass of the component C, 35 parts by mass of lanthanum fluoride and 30 parts by mass of cerium oxide.
[0019] Preferably, the multifunctional glass melting accelerator comprises 15 parts by mass of the component A, 10 parts by mass of the component B, 5 parts by mass of the component C, 35 parts by mass of lanthanum fluoride, 25 parts by mass of cerium fluoride and 10 parts by mass of cerium chloride.
[0020] Preferably, the multifunctional glass melting accelerator comprises 15 parts by mass of the component A, 15 parts by mass of the component B, 5 parts by mass of the component C, 40 parts by mass of cerium oxide and 25 parts by mass of lanthanum oxide.
[0021] The present invention further discloses a preparation method of the multifunctional glass melting accelerator, which comprises the steps of uniformly mixing the component A, the component B, the component C and other components and then granulating the components.
[0022] The present invention further discloses an application method of the above multifunctional glass melting accelerator, which comprises adding the multifunctional glass melting accelerator to other glass raw materials, mixing all the raw materials uniformly and then performing heat melting to obtain glass products, wherein the heat melting process comprises: heating to 1200-1400°C at a heating rate of 5-10°C / min, keeping warm for 30-60min, and then heating to 1500-1550°C at a heating rate of 5-10°C / min, and keeping warm for 120-150min; the addition amount of the multifunctional glass melting accelerator is 0.5-2.0wt% of all the raw materials.
[0023] Preferably, the other glass raw materials are raw materials for obtaining one or more glasses selected from photovoltaic glass, high-white rolled glass, vessel glass, cosmetic glass, bottle glass, milky white or jade-like glass, art glass and decorative glass.
[0024] Preferably, the other glass raw materials contain SiO2: 72.5wt%, Al2O3: 1.5wt%, CaO: 8.0wt%, MgO: 1.5wt%, BaO: 1.0wt% and Na2O: 14.5wt%.
[0025] The present invention has the following beneficial effects:
[0026] The multifunctional glass melting accelerator of the present invention is suitable for various types of glass such as photovoltaic glass, high-white rolled glass, utensil glass, cosmetic glass, bottle glass, milky white / imitation jade glass, art glass, decorative glass, etc. At the same time, it is suitable for various processing equipment such as all-oxygen kilns, natural gas kilns, all-electric melting kilns, electric crucible kilns, etc. during processing, and is easy to prepare and has wide applicability;
[0027] The multifunctional glass melting accelerator of the present invention has the functions of accelerating glass melting, clarification, homogenization, improving glass water resistance and thermal stability, reducing linear thermal expansion coefficient, and improving glass appearance visual quality, such as glass gloss, brightness, refractive index and other optical properties. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 The figure is a comparison of the changing trend of the average number of bubbles during melting between Examples 1-3 and the traditional formulation.
[0029] Figure 2 The figure is a comparison of the variation trend of the average bubble diameter during melting between Examples 1-3 and the traditional formulation. DETAILED DESCRIPTION
[0030] The technical scheme of the present invention will be further described below in conjunction with the embodiments and drawings of the present invention. The embodiments described below are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.
[0031] The humidifier used in the following examples is any one of water, sodium hydroxide aqueous solution (concentration such as 32 wt %), sodium silicate aqueous solution (modulus such as 2.5), etc., which is commonly used in the glass industry.
[0032] In the following examples, the traditional formula for comparison with the multifunctional glass melting accelerator is: 25 parts by mass of sodium nitrate, 30 parts by mass of sodium sulfate and 45 parts by mass of cerium oxide (the added amounts and other glass raw materials are the same as in Example 1).
[0033] Example 1
[0034] 15 parts by mass of ammonium cerium nitrate, 35 parts by mass of lanthanum fluoride, 15 parts by mass of sodium sulfate, 30 parts by mass of cerium oxide and 5 parts by mass of a humidifier are fully mixed and granulated to obtain a multifunctional glass melting accelerator;
[0035] Glass raw materials are prepared according to the raw material formula of SiO2: 72.5wt%, Al2O3: 1.5wt%, CaO: 8.0wt%, MgO: 1.5wt%, BaO: 1.0wt%, Na2O: 14.5wt% and 1.0wt% of the obtained multifunctional glass melting accelerator. The specific raw material preparation method is quartz sand: 120.01 parts by mass, aluminum hydroxide 3.83 parts by mass, calcite 17.24 parts by mass, dolomite 12.36 parts by mass, barium carbonate 3.19 parts by mass, soda ash 41.39 parts by mass, sodium nitrate 1.98 parts by mass and 1.65 parts by mass of the obtained multifunctional glass melting accelerator;
[0036] The multifunctional glass melting accelerator is added to other glass raw materials, all the raw materials are mixed evenly and added into a corundum crucible, the temperature is increased to 1350°C at a heating rate of 10°C / min, and the temperature is kept for 30 minutes, and then the temperature is increased to 1500°C at a heating rate of 10°C / min, and the temperature is kept for 120 minutes to obtain a glass product.
[0037] Example 2
[0038] The glass product was prepared according to the process of Example 1, except that the formula of the multifunctional glass melting accelerator was changed to: 15 parts by mass of ammonium cerium nitrate, 35 parts by mass of lanthanum fluoride, 25 parts by mass of cerium fluoride, 10 parts by mass of sodium sulfate, 10 parts by mass of cerium chloride and 5 parts by mass of humidifier.
[0039] Example 3
[0040] The glass product was prepared according to the process of Example 1, except that the formula of the multifunctional glass melting accelerator was changed to: 15 parts by mass of ammonium cerium nitrate, 15 parts by mass of sodium sulfate, 40 parts by mass of cerium oxide, 25 parts by mass of lanthanum oxide and 5 parts by mass of humidifier.
[0041] The changes of bubbles in the melting of Examples 1-3 and the traditional formula glass were observed by using the GWC-ii-1700 glass high temperature video melting experimental system. The results are shown in the attached figure. Figure 1 , 2 shown.
[0042] From the attached Figure 1 It can be seen from the change in the number of bubbles with the melting time that, as time goes on, the average number of bubbles in the formula with the addition of the multifunctional glass melting accelerator is always less than the number of bubbles produced by the traditional formula, indicating that more bubbles are clarified and removed in Examples 1-3 per unit time, while fewer bubbles remain in the glass liquid.
[0043] From the attached Figure 2 From the variation of the average bubble diameter with melting time, it can be seen that the bubbles in different formulations tend to increase with time, and the average diameter of the bubbles in the formulation with the addition of the multifunctional glass melting accelerator is always significantly larger than that in the traditional formulation. According to the clarification mechanism, larger bubbles are more conducive to their floating and escaping, indicating that the bubbles in Examples 1-3 are more likely to overflow faster.
[0044] Furthermore, by attaching Figure 1 , 2It can also be seen that in Example 2, the direct addition of cerium oxide in Example 1 is replaced by cerium fluoride and cerium chloride, which not only reduces the amount of sodium sulfate used, but also produces cerium oxide due to oxidation during the melting process, and at the same time increases the content of fluorine and further introduces chlorine, so that the obtained multifunctional glass melting accelerator has better accelerated melting and clarification effects than Example 1. (It is manifested in that the bubbles remaining per unit time are less and the bubble diameter is larger).
[0045] Furthermore, by attaching Figure 1 , 2 It can also be seen that, although Example 3 increases the amount of cerium oxide, introduces lanthanum oxide, and reduces lanthanum fluoride relative to Example 1, its effect of accelerating melting and clarification is not as good as that of Example 1 or Example 2 (now that more bubbles remain per unit time and the bubble diameter is smaller), but it is still significantly improved compared to the traditional formula.
[0046] It should be noted that the above is only a preferred embodiment of the present invention, which should not limit the protection scope of the technical solution of the present invention. Any modification of the technical solution recorded in the above embodiments and equivalent replacement of technical features by ordinary technicians in the field within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A multifunctional glass melting accelerator, comprising component A, component B, component C and other components containing one or more of the following elements: F element, La element, Ce element, Cl element, O element; wherein: The component A is ammonium cerium nitrate, and its content is 10-20 parts by mass; the component B is sodium sulfate, and its content is 5-20 parts by mass; the component C is a humidifier, and its content is 1-10 parts by mass; and the content of the other components is 60-80 parts by mass.
2. The multifunctional glass melting accelerator according to claim 1, characterized in that: The other components are selected from one or more of lanthanum fluoride, cerium fluoride, cerium chloride, cerium oxide, and lanthanum oxide.
3. The multifunctional glass melting accelerator according to claim 1, characterized in that: The other components are selected from lanthanum fluoride and cerium oxide; or the other components are selected from lanthanum fluoride, cerium fluoride and cerium chloride; or the other components are selected from cerium oxide and lanthanum oxide.
4. The multifunctional glass melting accelerator according to claim 1, characterized in that: The composition comprises 15 parts by mass of the component A, 15 parts by mass of the component B, 5 parts by mass of the component C, 35 parts by mass of lanthanum fluoride and 30 parts by mass of cerium oxide.
5. The multifunctional glass melting accelerator according to claim 1, characterized in that: The composition comprises 15 parts by mass of the component A, 10 parts by mass of the component B, 5 parts by mass of the component C, 35 parts by mass of lanthanum fluoride, 25 parts by mass of cerium fluoride and 10 parts by mass of cerium chloride.
6. The multifunctional glass melting accelerator according to claim 1, characterized in that: The composition comprises 15 parts by mass of the component A, 15 parts by mass of the component B, 5 parts by mass of the component C, 40 parts by mass of cerium oxide and 25 parts by mass of lanthanum oxide.
7. A method for preparing the multifunctional glass melting accelerator according to any one of claims 1 to 6, comprising: The component A, component B, component C and other components are uniformly mixed and then granulated.
8. The method for applying the multifunctional glass melting accelerator according to any one of claims 1 to 6, which comprises adding the multifunctional glass melting accelerator to other glass raw materials, mixing all the raw materials uniformly and then performing heat melting to obtain a glass product, wherein: The hot melting process includes: heating to 1200-1400°C at a heating rate of 5-10°C / min, keeping warm for 30-60 minutes, then heating to 1500-1550°C at a heating rate of 5-10°C / min, and keeping warm for 120-150 minutes; the addition amount of the multifunctional glass melting accelerator is 0.5-2.0wt% of all raw materials.
9. The application method according to claim 8, characterized in that: The other glass raw materials are raw materials for obtaining one or more glasses selected from photovoltaic glass, high-white rolled glass, vessel glass, cosmetic glass, bottle glass, milky white or jade-like glass, art glass and decorative glass.
10. The application method according to claim 8, characterized in that: The other glass raw materials contain SiO2: 72.5wt%, Al2O3: 1.5wt%, CaO: 8.0wt%, MgO: 1.5wt%, BaO: 1.0wt% and Na2O: 14.5wt%.