CN109734301B - Decolorizer for removing coloring of super-white high-turbine plate glass by defoaming agent and using method - Google Patents
Decolorizer for removing coloring of super-white high-turbine plate glass by defoaming agent and using method Download PDFInfo
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Abstract
The invention discloses a decolorizer for eliminating coloring of ultra-white high turbine plate glass by a composite defoaming agent and a using method thereof. The decolorizer mainly comprises rubidium oxide and cobalt oxide in a certain ratio, the decolorizer is premixed with a proper amount of glass main material silica sand, then the mixture is integrally mixed with other raw materials and enters a kiln, and the coloring effect is optimized and eliminated by controlling the proper oxidizability of the flame zone space of the kiln.
Description
Technical Field
The invention belongs to the field of ultra-white high turbine plate glass, and particularly relates to a decolorizer for coloring ultra-white high turbine plate glass by adopting a composite defoaming agent in the production process.
Background
The ultra-white high turbine plate glass is widely applied to the fields of buildings, solar energy, electronic display and the like, and the chemistry of the ultra-white high turbine plate glass is mainly SiO270 to 74.0 wt.% of Al2O30 to 2.0wt%, CaO 6 to 10 wt%, MgO 2 to 5wt%, and Na2O is 12 to 15wt%, K20 to 2.0wt% of O and Fe2O3≤120ppm，TiO2Less than or equal to 80ppm, and large-scale batch production is realized by adopting a float process; the main raw materials comprise silica sand, sulfate, carbonate and the like, the raw materials are melted in a special high-temperature melting furnace, and CO of a large amount of gas is released in the melting process2、SO2When the surface of the molten glass is covered by a large amount of gas, if the surface of the molten glass is simply reduced by raising the melting temperature to eliminate bubbles, the effective utilization rate of the fuel is reduced due to the reflection effect of the foam layer on the heating flame at the upper part of the foam layer, the fuel consumption is increased by about 5% -10%, the temperature of the inner surface of the arch top of the melting furnace for melting the glass is raised by 10-20 ℃ due to the heat of the reflected heating flame, the corrosion speed of the melting furnace is increased, and the service life of the melting furnace is seriously influenced.
CN107162403A develops a composite defoaming agent (the main components are n-butyl titanate, titanium dioxide, sodium sulfate, calcium sulfate, ferrocene, aviation kerosene, diesel oil and heavy oil are mixed according to a certain proportion) suitable for glass production, the cracking of the bubble layer on the surface of the glass liquid in different temperature areas of the kiln can be accelerated without increasing the melting temperature of the ultrawhite high turbine plate glass production kiln, the foam layer is basically eliminated, thus not only the fuel cost is not increased, but also the qualification rate of the ultrawhite high turbine plate glass products is ensured, and the service life of the kiln can be prolonged. However, the composite defoaming agent contains the titanium dioxide or the titanium butyl titanate as an essential component, so that the composite defoaming agent is used for improving the qualification rate of the ultra-white high turbine plate glass product and prolonging the service life of a kiln, and titanium ions introduced into the defoaming agent also enable the glass to generate a yellow visual effect, so that the application of the ultra-white high turbine plate glass in the fields of solar cell substrates, electronic display and the like is limited.
Meanwhile, in the manufacturing process of the ultra-white high-turbine plate glass, the silica sand accounts for more than 60 percent of the weight of the whole raw material, although high-purity silica Sand (SiO) with higher cost is adopted2The content is more than or equal to 99.5 percent, and TiO2Content ≤ 80ppm, note: titanium dioxide with valence of +/-4), and a certain amount of TiO2Even if the ultra-high-purity silica sand is adopted, the cost of each ton of silica sand is increased by more than 500 yuan, the cost increase pressure is huge for a production line using hundreds of tons of high-purity silica sand every day, and the introduction of titanium ions cannot be completely avoided, so that the final glass substrate has color visual effects of different degrees.
In addition, the composite defoaming agent containing the titanium n-butyl titanate or the titanium dioxide is sprayed into a combustion flame space in the kiln from a molten glass upper space in a foam layer area of the glass kiln to perform a series of physical and chemical reactions, the temperature of the area is 1000-1400 ℃, and the titanium ions after the reactions exist in the glass products in the forms of TiO and Ti due to the influence of the temperature and the redox atmosphere in the kiln2O3、TiO2Finally, the glass products show colors such as yellow, yellow green, orange yellow and amber, and the colors are different in depth, so that the selection of the type of the decolorizer, the proportion of the used amount of the decolorizer and the use method of the decolorizer become unstable, and the whole glass production cannot be stably and continuously carried out directly.
Disclosure of Invention
The invention aims to solve the technical problem that titanium ions introduced into a super-white high-transparency glass raw material and titanium ions introduced by using a composite defoaming agent influence the color of glass, and provides a decolorizer for removing the defoaming agent from coloring super-white high-transparency turbine plate glass and a using method thereof, so that the normal use of the defoaming agent can be ensured, the purpose of reducing the service life of a temperature delay kiln can be achieved, the influence of the defoaming agent and the titanium ions introduced into the raw material on the whole glass color can be treated, and the raw material cost is reduced.
The technical scheme adopted by the invention for solving the problems is as follows:
a decolorizer for removing a defoaming agent to color ultra-white high turbine plate glass is characterized in that the decolorizer mainly comprises rubidium oxide and cobalt oxide, the mass ratio of the cobalt oxide to the rubidium oxide is less than or equal to 1:3, and meanwhile, the requirements that the input quantity ratio of the rubidium oxide to the whole glass raw material is less than or equal to 120ppm, and the input quantity ratio of the cobalt oxide to the whole glass raw material is less than or equal to 90ppm are met.
According to the scheme, the representative composition range of the ultra-white high turbine plate glass is as follows: SiO2270 to 72.0 wt.% of Al2O30.5 to 2.0wt%, CaO 7 to 9wt%, MgO 2 to 5wt%, and Na2O is 13 to 15wt%, K20 to 1.0wt% of O and Fe2O3≤120ppm；TiO2The content is less than or equal to 80 ppm. The ultra-white high turbine plate glass can be prepared from the following raw materials: high-purity silica sand, alumina powder, limestone, dolomite, soda ash, mirabilite, carbon powder and the like, and the representative composition range is realized. Wherein the specification of each raw material is as follows: high purity silica Sand (SiO)2≥98.5wt％，Al2O3≤1.1wt％、Fe2O3≤100ppm；TiO2Less than or equal to 60ppm), alumina powder (Al)2O3≥99.0wt％，Fe2O3Less than or equal to 200 ppm; ) Limestone (CaO 55.00 + -0.5 wt%, Fe)2O3≤80ppm；TiO2Content less than or equal to 80ppm), dolomite (21.00 +/-1.0 wt% of MgO, 32.00 +/-1.0 wt% of CaO, Fe2O3≤80ppm；TiO2Content less than or equal to 80ppm), sodium carbonate (Na)2CO3Not less than 99.5 wt%, Fe2O3≤50ppm；TiO2Content less than or equal to 50ppm), Natrii sulfas (Na)2SO3Not less than 99.0 wt%, Fe2O3≤100ppm；TiO2The content is less than or equal to 50 ppm). Wherein the amount of the carbon powder is 2-3 wt% of the mirabilite.
According to the scheme, the defoaming agent mainly adopts the composite defoaming agent disclosed in CN107162403A and suitable for producing common flat glass. The composite defoaming agent mainly comprises a main component and a solvent component, wherein the main component comprises a defoaming agent consisting of a titanium compound, a foam wall thinning agent consisting of sodium sulfate and calcium sulfate, and a solvent combustion efficiency optimizing agent of glutaric iron; the solvent component contains diesel oil, aviation kerosene, heavy oil or their mixture in any proportion, the flash point of the solvent is greater than or equal to 38 deg.C, and the main component is dissolved in the solvent or suspended in the solvent in the form of solid particles.
According to the scheme, the mass ratio of the content of titanium dioxide to the decolorizer in the glass composition of the ultra-white high turbine plate glass is less than or equal to 1: 1.
The decolorizer of the invention is applied to the aspect of removing the coloring of the ultra-white high turbine plate glass, and the specific use method is as follows:
(1) weighing high-purity silica sand, alumina powder, limestone, dolomite, sodium carbonate and mirabilite as raw materials according to the representative composition range of the ultra-white high-turbine plate glass, and preparing a decolorizer according to the proportion of the decolorizer to the whole glass raw materials;
(2) premixing a decolorizer and silica sand, then assimilating aluminum powder, limestone, dolomite, soda ash and mirabilite, integrally mixing, feeding into a kiln by a feeder, heating by space flame in the kiln, passing through a batching melting area (100-1300 ℃), a bubble area (1300-1450 ℃), a high-temperature area (1450-1500 ℃), a cooling area (1450-1200 ℃), and controlling O in space gas in each area in the kiln2The volume percentage content ensures that the defoaming agent is atomized by air and then sprayed into the kiln from a defoaming area to achieve the purpose of eliminating a bubble layer, simultaneously is beneficial to the fact that more than 95 percent of titanium ions in the kiln can be finally converted into plus-4 value, and the titanium ions are stably stored in a glass product in the form of titanium dioxide to achieve the matching with the type, the using amount and the using condition of the stable decolorizer.
According to the scheme, in order to ensure that the decolorizer is uniformly distributed in the ingredients, the decolorizer and part of silica sand are premixed, the decolorizer accounts for 1-4 per mill of the weight of the premixed silica sand during premixing, and the mixing time is 2-5 minutes.
According to the scheme, the final existing form of titanium ions in the glass is ensuredAnd the matching of a defoaming agent, namely, a material mixing and melting area O in the glass kiln2The volume percentage content is 0.5 percent to 2 percent, and the bubble layer area O23-4% of volume percentage content, high temperature zone O25-6% volume percentage, cooling zone O2The volume percentage content is 6-10%.
The main technical conception of the invention is as follows: in order to ensure the stable and high-efficiency production of the super-white glass, firstly, the condition degree of the redox atmosphere of each subarea in the kiln is controlled to promote titanium ions to exist in the glass (more than 95 percent exists in a valence-4 form) in a sustainable and stable form or a combined form, and then the type and the using amount of a decolorizer which can form a decolorization effect with the titanium ions existing in the stable form and can be matched with the atmosphere condition in the kiln and the using mode are searched, so that the stable production and stable decolorization of the glass are realized.
Compared with the prior art, the invention has the beneficial effects that:
the decolorizer for removing the coloring of the super-white high turbine plate glass by the defoaming agent and the use method thereof can ensure the normal use of the defoaming agent, achieve the purpose of reducing the temperature and delaying the service life of a kiln, treat the influence of titanium ions introduced into the defoaming agent and raw materials on the integral coloring of the glass and reduce the cost of the raw materials.
Drawings
FIG. 1 is a chart of experimental chroma drop distribution.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
In the following examples, the color index of glass (CIE1976LAB, L is a lightness index because the lightness of glass is in a direct relationship with the transmittance, and the values of the color indexes a and b are of interest in view of the fact that the transmittance of ultra-white high-turbine glass is slightly changed) measured using a spectrophotometer satisfies
Preference is given to
The color of the ultra-white high turbine plate glass meets the requirement.
Examples 1 to 8
The ultra-white high turbine plate glasses used in examples 1-8 had a chemical composition of: SiO2260.0 wt% of Al2O31.5 wt%, MgO 4.0 wt%, CaO 8.0 wt%, Na2O is 14.0 wt%, Fe2O3Is 90ppm, TiO2Was 50 ppm.
In examples 1 to 8, high-purity silica sand, alumina powder, limestone, dolomite, soda ash and mirabilite were selected according to the above glass chemical composition, and the total amount of glass raw materials was 1kg, wherein the amount of carbon powder was 2.8 wt% of mirabilite. The specification of each raw material is as follows: high purity silica Sand (SiO)2≥98.5wt％，Al2O3≤1.1wt％、Fe2O3≤100ppm；TiO2Less than or equal to 60ppm), alumina powder (Al)2O3≥99.0wt％，Fe2O3Less than or equal to 200 ppm; ) Limestone (CaO 55.00 + -0.5 wt%, Fe)2O3≤80ppm；TiO2Content less than or equal to 80ppm), dolomite (21.00 +/-1.0 wt% of MgO, 32.00 +/-1.0 wt% of CaO, Fe2O3≤80ppm；TiO2Content less than or equal to 80ppm), sodium carbonate (Na)2CO3Not less than 99.5 wt%, Fe2O3≤50ppm；TiO2Content less than or equal to 50ppm), Natrii sulfas (Na)2SO3Not less than 99.0 wt%, Fe2O3≤100ppm；TiO2The content is less than or equal to 50 ppm).
In examples 1 to 8, the defoaming agent was a mixture of n-butyl titanate and aviation kerosene at a mass ratio of 1: 15. In the case of the amount of the glass raw material used of 1kg, the specific amount of n-butyl titanate used in the defoaming agent was 0.05 g.
The specific amounts and compositions of the colorants in examples 1-8 are detailed in Table 1.
The process for preparing ultra-white high turbine plate glass using the decolorizer described in examples 1 to 8 was as follows:
according to the chemical composition of the glass and the dosage of the decolorizer and the defoamer, the decolorizer and the defoamer are firstly mixedAfter silica sand is premixed, the silica sand is integrally mixed with alumina powder, limestone, dolomite, soda ash, mirabilite and carbon powder and then enters a kiln, the mixture is heated by space flame in the kiln, and the mixture passes through a material mixing and melting region (100-; wherein O in the space gas of each area in the kiln is controlled2Volume percentage of ingredient melting zone O21-1.5 percent of volume percentage content, and a bubble layer region O23-4% of volume percentage content, high temperature zone O25-6% volume percentage, cooling zone O2The volume percentage content is 7-8%; and atomizing the defoaming agent by using air, and spraying the atomized defoaming agent into the kiln from the defoaming area. The specific properties are detailed in table 1.
TABLE 1
Remarking:
example 2
Based on the chemical composition and test results of example 1, the test production was carried out on a 550 ton/day ultra-white high-transmittance float glass line of a company using high purity silica sand (SiO2 ≥ 98.5 wt%, Al) as the main raw material2O3≤1.1wt％、Fe2O3≤100ppm；TiO2Less than or equal to 60ppm), alumina powder (Al)2O3≥99.0wt％，Fe2O3Less than or equal to 200 ppm; ) Limestone (CaO 55.00 + -0.5 wt%, Fe)2O3≤80ppm；TiO2Content less than or equal to 80ppm), dolomite (21.00 +/-1.0 wt% of MgO, 32.00 +/-1.0 wt% of CaO, Fe2O3≤80ppm；TiO2The content is less than or equal to 80ppm), soda ash (Na)2CO3Not less than 99.5 wt%, Fe2O3≤50ppm；TiO2Content less than or equal to 50ppm), Natrii sulfas (Na)2SO3Not less than 99.0 wt%, Fe2O3≤100ppm；TiO2The content is less than or equal to 50 ppm); in consideration of the production cost, titanium ion raw materials which can generate glass coloring to a certain extent are adopted;
the specific dosage of each raw material is as follows: 325 tons of high-purity silica sand; 2.5 tons of alumina powder; 90 tons of dolomite; 16 tons of limestone; 102 tons of soda ash; 5 tons of mirabilite; 0.14 ton of carbon powder;
in order to reduce the bubble defect of glass, properly reduce the highest melting temperature and prolong the service life of a kiln, a defoaming agent is used in a flame gun area 3 in front of a production line, the main components of the defoaming agent are 99 wt% of n-butyl titanate, 1 wt% of sodium sulfate and a solvent made of aviation kerosene, the dosage of the solvent is 15 times of the total mass of the n-butyl titanate and the sodium sulfate, the main components of the defoaming agent are sprayed into the kiln after mixing, the dosage of the main components of the defoaming agent is 25 kg/day, and the dosage of the solvent is 250 kg/day;
the overall preparation process was similar to that of examples 1 to 8, and the final glass product, without addition of the decolorizer of the present invention, was visually observed to be yellowish in color, and measured to have a transmittance of 90.8% for a 3mm glass plate, a color index of-0.013, b of 0.25, and a pour point value of 4.64.
Then, referring to the above preparation method, a decolorizer composed of cobalt oxide and rubidium oxide (the mass ratio of cobalt oxide to rubidium oxide is 1:7) was added, and 200g of the decolorizer and 80kg of silica sand were premixed for 3 minutes while keeping the other conditions unchanged. As about 1300 tons of glass liquid exist in the glass kiln with about 550 tons/day of the whole batch, the glass liquid is melted by continuously adding ingredients to form new glass liquid, the original glass liquid is diluted and convectively mixed, the color gradually becomes lighter after 2 days, and the color can not be seen after one week. The prepared 3mm glass plate has the advantages that the transmittance is 90.9 percent, the chroma index a is-0.013, the chroma index b is 0.17 and the falling point value is 0.80; the problem of titanium ion coloring is solved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (4)
1. A method for removing defoaming agent to color ultra-white high turbine plate glass by using a decolorizer is characterized in that the decolorizer consists of rubidium oxide and cobalt oxide, and the mass ratio of the cobalt oxide to the rubidium oxide is 1: 5-1: 8;
meanwhile, the ratio of the rubidium oxide in the decolorizer to the whole raw material input amount of the glass is less than or equal to 60 ppm;
the mass ratio of the titanium dioxide content to the decolorizer in the glass composition of the ultra-white high turbine plate glass is less than or equal to 1: 1.
2. The method according to claim 1, characterized in that the representative composition range of the ultra-white high turbine plate glass is: SiO2270 to 72.0 wt.% of Al2O30.5 to 2.0wt%, CaO 7 to 9wt%, MgO 2 to 5wt%, and Na2O is 13 to 15wt%, K20 to 1.0wt% of O and Fe2O3≤120ppm，TiO2The content is less than or equal to 50 ppm.
3. Use of the method according to claim 2 for de-tinting of ultra-white high turbine plate glass, characterized in that the method is used in particular as follows:
(1) weighing high-purity silica sand, alumina powder, limestone, dolomite, soda ash and mirabilite as raw materials according to the representative composition range of the ultra-white high-turbine plate glass, and preparing a decolorizer according to the proportion of the decolorizer to the whole glass raw materials;
(2) premixing a decolorizer and silica sand, then integrally mixing the decolorizer with alumina powder, limestone, dolomite, soda ash, mirabilite and carbon powder, then feeding the mixture into a kiln by a feeder, heating the mixture in the kiln by space flame, and cooling the mixture to room temperature after the mixture passes through a batching melting zone of 100-1300 ℃, a bubble layer zone of 1300-1450 ℃, a high temperature zone of 1450-1500 ℃ and a cooling zone of 1450-1200 ℃ to obtain ultra-white high turbine plate glass; wherein O in the space gas of each area in the kiln is controlled2Volume percent, melting of the ingredientsRegion O20.5-2% of volume percentage content, and a bubble layer area O2The volume percentage content is 3% -4%, and the high temperature zone O25-6% volume percentage, cooling zone O2The volume percentage content is 6% -10%; and atomizing the defoaming agent by using air and spraying the defoaming agent into the kiln from the defoaming area.
4. The use according to claim 3, characterized in that the decolorizer is premixed with a portion of the silica sand, the decolorizer accounting for 1 to 4 per mill of the premixed silica sand during the premixing, and the mixing time being 2 to 5 minutes.
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| CN113735452B (en) * | 2021-09-27 | 2022-12-30 | 湖北烁砺新材料科技有限公司 | High-strength refractory fiber and preparation method thereof |
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| CN106587607A (en) * | 2016-12-10 | 2017-04-26 | 温州雏鹰科技有限公司 | Ultraviolet-proof glass for vehicle windows |
| CN107162407A (en) * | 2017-04-14 | 2017-09-15 | 中建材（宜兴）新能源有限公司 | A kind of ultra-thin photovoltaic rolled glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106587607A (en) * | 2016-12-10 | 2017-04-26 | 温州雏鹰科技有限公司 | Ultraviolet-proof glass for vehicle windows |
| CN107162407A (en) * | 2017-04-14 | 2017-09-15 | 中建材（宜兴）新能源有限公司 | A kind of ultra-thin photovoltaic rolled glass |
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