Novel compound clarifying agent and preparation method thereof
By preparing a composite clarifying agent containing dolomite, limestone, sodium sulfate, cerium oxide, and chitosan, the problems of high cost and low efficiency of existing clarifying agents are solved, achieving efficient bubble elimination and improved transparency, while meeting environmental protection requirements.
Patent Information
- Application Number
- CN202511851529.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-10
- Publication Date
- 2026-03-03
AI Technical Summary
Existing clarifying agents are costly, pose significant environmental risks, and have limited clarification efficiency, making it difficult to meet the requirements of high transparency and low iron content for photovoltaic glass.
A composite clarifying agent is prepared by low-temperature blending using dolomite, limestone, and sodium sulfate as the base, with the addition of cerium oxide, chitosan, and composite additives. This process synergistically improves bubble removal efficiency and reduces energy consumption.
It achieves a bubble elimination rate of over 98%, increases light transmittance to ≥91.6%, reduces energy consumption by 30%, meets green manufacturing requirements, and has stronger adaptability.
Smart Images
Figure CN121591406A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of inorganic non-metallic material preparation technology, specifically to a novel composite clarifying agent and its preparation method. Background Technology
[0002] In the glass manufacturing process, molten glass often contains a large number of bubbles (mainly composed of O2, N2, CO2, SO2, etc.). If these bubbles cannot be effectively removed, they will seriously affect the transparency, mechanical properties, and appearance quality of glass products. Therefore, clarifying agents need to be added to the batch to promote the merging, growth, and upward displacement of bubbles through physical or chemical action. As a core encapsulation material for photovoltaic modules, the light transmittance of photovoltaic glass directly affects the module efficiency. Currently, mainstream clarifying agents (such as sodium antimonate pyroantimonate and antimony trioxide) have problems such as high cost and significant environmental impact. Developing new environmentally friendly clarifying agents can reduce production costs and enhance product competitiveness.
[0003] Traditional clarifying agents rely on toxic substances such as arsenic and antimony, posing a risk of environmental pollution. The clarification efficiency of a single clarifying agent is limited, necessitating the use of multiple agents to improve effectiveness. The low-iron and high-transmittance requirements of photovoltaic glass place even greater challenges on the performance of clarifying agents. Summary of the Invention
[0004] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a novel composite clarifying agent and its preparation method. Based on dolomite, limestone, and sodium sulfate, cerium oxide and composite additives are added to replace traditional toxic substances. Cerium oxide and other clarifying agents work synergistically to improve bubble removal efficiency and reduce light transmittance loss (target ≥91.6%). A low-temperature blending method is used to avoid the generation of harmful gases from high-temperature decomposition and reduce energy consumption by 30%.
[0005] (II) Technical Solution To achieve the above objectives, the present invention is implemented through the following technical solution: a novel composite clarifying agent, the raw materials of which include, by weight: 20-40 parts dolomite, 20-30 parts limestone, 5-10 parts sodium sulfate, 3-5 parts cerium oxide, 5-10 parts chitosan, 3-5 parts polydimethyldiallylammonium chloride and 3-5 parts composite additives.
[0006] Preferably, the raw materials include, by weight: 30 parts dolomite, 25 parts limestone, 7 parts sodium sulfate, 4 parts cerium oxide, 7 parts chitosan, 4 parts polydimethyldiallyl ammonium chloride, and 4 parts composite additives.
[0007] Preferably, the raw materials include, by weight: 20 parts dolomite, 20 parts limestone, 10 parts sodium sulfate, 5 parts cerium oxide, 10 parts chitosan, 5 parts polydimethyldiallylammonium chloride, and 5 parts composite additives.
[0008] Preferably, the raw materials include, by weight: 40 parts dolomite, 30 parts limestone, 5 parts sodium sulfate, 3 parts cerium oxide, 5 parts chitosan, 3 parts polydimethyldiallyl ammonium chloride, and 3 parts composite additives.
[0009] Preferably, the composite additive is any combination of two or more of sodium nitrate, sodium sulfate, sodium chloride, or tin oxide.
[0010] Preferably, the chitosan is attapulgite-loaded chitosan.
[0011] This invention also provides a method for preparing a novel composite clarifying agent, specifically including the following steps: S1. Ingredient preparation: Weigh the required weight parts of dolomite, limestone, sodium sulfate, cerium oxide, chitosan, polydimethyldiallyl ammonium chloride and composite additives using a weighing device, and set them aside for later use. S2. Multi-component solution mixing: Dolomite, limestone, sodium sulfate and cerium oxide are dissolved in deionized water to form aqueous solutions of each component. Chitosan, polydimethyldiallylammonium chloride and composite additives are then added to the deionized water to prepare a composite base solution. Under a stirring speed of 100-120 r / min, the aqueous solutions of each component are added to the composite base solution in proportion for gradient mixing. The mixing time is 30-60 min. S3. Let the mixture stand for 30-60 minutes to allow the components to react fully and stabilize. Then filter the mixture through a 100-mesh sieve to ensure uniform particle size. S4. Drying and pulverizing: The matured mixture is vacuum dried at 55°C to constant weight, and then pulverized to below 100 mesh to obtain the final composite clarifying agent powder.
[0012] Preferably, the chitosan attapulgite loading process specifically includes the following steps: T1. Calcine the attapulgite at 700℃ for 4 hours, cool it down and add it to a 1mol / L hydrochloric acid aqueous solution. The concentration of attapulgite is 0.5g / mL. Stir at 90℃ for 4 hours, centrifuge and wash with water until neutral. T2. Add the acid-activated attapulgite to a 10% oxalic acid aqueous solution at a concentration of 0.5 g / mL, stir at room temperature for 2 hours, let stand for 5 hours, centrifuge, wash with water until neutral, and dry at 120℃. T3. Mix 10wt% oxalic acid aqueous solution and 1wt% acetic acid aqueous solution at a volume ratio of 4:1, add 3% chitosan by mass of the solution, stir at 50-60 rpm, heat to 50℃ and keep warm until the chitosan is completely dissolved to obtain a light yellow viscous chitosan sol. T4. Dilute the chitosan sol with 2.5 times its volume of water, heat to 50°C and stir for 1 hour, cool to room temperature, add acid-activated attapulgite at a concentration of 5 g / mL, stir for 5 hours, centrifuge, filter, and vacuum dry at 55°C to constant weight to obtain attapulgite-loaded chitosan.
[0013] (III) Beneficial Effects This invention provides a novel composite clarifying agent and its preparation method. Compared with the prior art, it has the following advantages: (1) This novel composite clarifying agent and its preparation method utilize the synergistic effect of cerium oxide and sodium nitrate to generate oxygen, the synergistic effect of sodium sulfate and sodium chloride to generate chlorine, and the reaction of tin oxide and water vapor to generate hydrogen, forming a multi-gas synergistic effect that causes bubbles in the molten glass to rapidly merge, grow, and float to the surface for discharge. When continuously applied at a high temperature of 1550-1610℃ for 72-100 hours, the bubble elimination rate reaches over 98%, which is 15%-20% higher than that of traditional clarifying agents.
[0014] (2) This novel composite clarifying agent and its preparation method, by eliminating highly toxic white arsenic (As2O3) and fluorine-containing compounds, adopts non-toxic and harmless components such as cerium oxide and tin oxide, which meets the requirements of modern green manufacturing. At the same time, the addition of chitosan and polydimethyldiallylammonium chloride improves biocompatibility and safety. The clarification temperature range of the composite clarifying agent of this invention is 1200-1450℃, which is wider than the 1300-1400℃ range of traditional clarifying agents, and has stronger adaptability. Attached Figure Description
[0015] Figure 1 This is a flowchart of the preparation method of the present invention. Detailed Implementation
[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0017] Please see Figure 1 The present invention provides three technical solutions: a novel composite clarifying agent and its preparation method, specifically including the following embodiments: Example 1: A novel composite clarifying agent, the raw materials of which include by weight: 30 parts dolomite, 25 parts limestone, 7 parts sodium sulfate, 4 parts cerium oxide, 7 parts chitosan, 4 parts polydimethyldiallylammonium chloride and 4 parts composite additives, the composite additives being a composition of sodium nitrate, sodium sulfate, sodium chloride and tin oxide, and the chitosan being attapulgite-loaded chitosan.
[0018] This invention also provides a method for preparing a novel composite clarifying agent, specifically including the following steps: S1. Ingredient preparation: Weigh the required weight parts of dolomite, limestone, sodium sulfate, cerium oxide, chitosan, polydimethyldiallyl ammonium chloride and composite additives using a weighing device, and set them aside for later use. S2. Multi-component solution mixing: Dolomite, limestone, sodium sulfate and cerium oxide are dissolved in deionized water to form aqueous solutions of each component. Chitosan, polydimethyldiallylammonium chloride and composite additives are then added to the deionized water to prepare a composite base solution. The aqueous solutions of each component are added to the composite base solution in proportion under a stirring speed of 110 r / min for gradient mixing for 45 min. S3. Let the mixture stand for 45 minutes to allow the components to react fully and stabilize. Then filter it through a 100-mesh sieve to ensure uniform particle size. S4. Drying and pulverizing: The matured mixture is vacuum dried at 55°C to constant weight, and then pulverized to below 100 mesh to obtain the final composite clarifying agent powder.
[0019] Example 2: A novel composite clarifying agent, the raw materials of which include, by weight: 20 parts dolomite, 20 parts limestone, 10 parts sodium sulfate, 5 parts cerium oxide, 10 parts chitosan, 5 parts polydimethyldiallylammonium chloride and 5 parts composite additive, wherein the composite additive is a combination of sodium nitrate and sodium sulfate, and the chitosan is attapulgite-loaded chitosan.
[0020] This invention also provides a method for preparing a novel composite clarifying agent, specifically including the following steps: S1. Ingredient preparation: Weigh the required weight parts of dolomite, limestone, sodium sulfate, cerium oxide, chitosan, polydimethyldiallyl ammonium chloride and composite additives using a weighing device, and set them aside for later use. S2. Multi-component solution mixing: Dolomite, limestone, sodium sulfate and cerium oxide are dissolved in deionized water to form aqueous solutions of each component. Chitosan, polydimethyldiallylammonium chloride and composite additives are then added to the deionized water to prepare a composite base solution. The aqueous solutions of each component are added to the composite base solution in proportion under a stirring speed of 100 r / min for gradient mixing for 30 min. S3. Let the mixture stand for 30 minutes to allow the components to react fully and stabilize. Then filter it through a 100-mesh sieve to ensure uniform particle size. S4. Drying and pulverizing: The matured mixture is vacuum dried at 55°C to constant weight, and then pulverized to below 100 mesh to obtain the final composite clarifying agent powder.
[0021] Example 3: A novel composite clarifying agent, the raw materials of which include, by weight: 40 parts dolomite, 30 parts limestone, 5 parts sodium sulfate, 3 parts cerium oxide, 5 parts chitosan, 3 parts polydimethyldiallylammonium chloride and 3 parts composite additive, wherein the composite additive is a composition of sodium nitrate, sodium chloride and tin oxide, and the chitosan is chitosan loaded with attapulgite.
[0022] This invention also provides a method for preparing a novel composite clarifying agent, specifically including the following steps: S1. Ingredient preparation: Weigh the required weight parts of dolomite, limestone, sodium sulfate, cerium oxide, chitosan, polydimethyldiallyl ammonium chloride and composite additives using a weighing device, and set them aside for later use. S2. Multi-component solution mixing: Dolomite, limestone, sodium sulfate and cerium oxide are dissolved in deionized water to form aqueous solutions of each component. Chitosan, polydimethyldiallylammonium chloride and composite additives are then added to the deionized water to prepare a composite base solution. The aqueous solutions of each component are added to the composite base solution in proportion under a stirring speed of 120 r / min for gradient mixing for 60 min. S3. Let the mixture stand for 60 minutes to allow the components to react fully and stabilize. Then filter it through a 100-mesh sieve to ensure uniform particle size. S4. Drying and pulverizing: The matured mixture is vacuum dried at 55°C to constant weight, and then pulverized to below 100 mesh to obtain the final composite clarifying agent powder.
[0023] In this embodiment of the invention, the chitosan attapulgite loading process specifically includes the following steps: T1. Calcine the attapulgite at 700℃ for 4 hours, cool it down and add it to a 1mol / L hydrochloric acid aqueous solution. The concentration of attapulgite is 0.5g / mL. Stir at 90℃ for 4 hours, centrifuge and wash with water until neutral. T2. Add the acid-activated attapulgite to a 10% oxalic acid aqueous solution at a concentration of 0.5 g / mL, stir at room temperature for 2 hours, let stand for 5 hours, centrifuge, wash with water until neutral, and dry at 120℃. T3. Mix 10wt% oxalic acid aqueous solution and 1wt% acetic acid aqueous solution at a volume ratio of 4:1, add 3% chitosan by mass of the solution, stir at 55 rpm, heat to 50℃ and keep warm until the chitosan is completely dissolved to obtain a light yellow viscous chitosan sol. T4. Dilute the chitosan sol with 2.5 times its volume of water, heat to 50°C and stir for 1 hour, cool to room temperature, add acid-activated attapulgite at a concentration of 5 g / mL, stir for 5 hours, centrifuge, filter, and vacuum dry at 55°C to constant weight to obtain attapulgite-loaded chitosan.
[0024] Bubble control: Optimize the oxygen release rate at high temperatures, reduce the "starry sky" microbubble defect, and improve the glass transmittance to ≥91.5%.
[0025] Performance comparison: Compared with cerium oxide clarifier alone, the bubble density is reduced by 60% and the glass whiteness is increased by 15%.
[0026] The main technical specifications of this invention are as follows: Light transmittance: Target value: ≥92%, the current mainstream level is 91%-91.5%.
[0027] Improvement path: by reducing iron content (Fe2O3≤0.02%) and optimizing the efficiency of clarifying agent in decomposing gases.
[0028] Bubble defect rate: Target value: ≤0.1% (bubble diameter <0.1mm).
[0029] Key control: Composite clarifying agents (such as sodium pyroantimonate + cerium oxide) can improve the bubble elimination rate to 99.2%.
[0030] Target melting temperature: ≤1500℃ (traditional processes require 1550-1600℃), and energy savings of approximately 8% can be achieved for every 50℃ reduction.
[0031] Technical solution: Use a low-temperature decomposition clarifying agent (such as sodium pyroantimonate, which has a decomposition temperature of 800-1000℃).
[0032] Economic indicators and cost percentage: Clarifying agent accounts for 5.1%-6% of the total cost of photovoltaic glass (sodium pyroantimonate system).
[0033] Cost reduction target: Reduce costs to 4%-5% through composite formulations (such as antimony-cerium composites). Antimony emission reduction: Current antimony addition levels are 0.2%-0.4%, necessitating the development of low-antimony (≤0.1%) or non-antimony alternatives. Gas release temperature range: 800-1450℃ (composite clarifying agent needs to cover the entire process).
[0034] Insulation time: 4-8 hours (5 hours or more for cerium oxide). Traditional antimony trioxide accounts for 5.1%-9.92% of the total cost of photovoltaic glass, of which: Raw material costs account for approximately 10%, with a consumption rate of 0.2%-0.25% (2-2.5 kg / ton of glass).
[0035] Sodium pyroantimonate: accounts for about 6% of the cost, with an addition amount of 0.2%-0.4%. Because it exists directly in the form of pentavalent antimony, the process efficiency is higher.
[0036] Cost reduction effect of composite clarifying agent: Using a composite formula of sodium sulfate + sodium nitrate + antimony oxide + cerium oxide can reduce the amount of antimony used to 0.2%, resulting in a 10%-30% reduction in cost per ton. Energy cost optimization: Low-temperature clarifying agents such as sodium pyroantimonate can reduce the melting temperature by 30-50℃, corresponding to an 8% reduction in energy consumption. Energy costs account for 38%-40% of the total cost of photovoltaic glass, demonstrating significant energy-saving potential.
[0037] In summary, this invention utilizes the synergistic effect of cerium oxide and sodium nitrate to generate oxygen, the synergistic effect of sodium sulfate and sodium chloride to generate chlorine, and the reaction of tin oxide and water vapor to generate hydrogen, forming a multi-gas synergistic effect that causes bubbles in the molten glass to rapidly merge, grow, and float to the surface for discharge. When continuously applied at a high temperature of 1550-1610℃ for 72-100 hours, the bubble elimination rate reaches over 98%, which is 15%-20% higher than traditional clarifying agents. By eliminating highly toxic white arsenic (As₂O₃) and fluorine-containing compounds, and using non-toxic and harmless components such as cerium oxide and tin oxide, it meets the requirements of modern green manufacturing. Furthermore, the addition of chitosan and polydimethyldiallylammonium chloride improves biocompatibility and safety. The clarifying temperature range of this composite clarifying agent is 1200-1450℃, which is wider than the 1300-1400℃ range of traditional clarifying agents, making it more adaptable.
[0038] Furthermore, any content not described in detail in this specification is existing technology known to those skilled in the art.
[0039] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0040] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A novel composite clarifying agent, characterized in that: Its raw materials, by weight, include: 20-40 parts dolomite, 20-30 parts limestone, 5-10 parts sodium sulfate, 3-5 parts cerium oxide, 5-10 parts chitosan, 3-5 parts polydimethyldiallylammonium chloride, and 3-5 parts composite additives.
2. The novel composite clarifying agent according to claim 1, characterized in that: Its raw materials, by weight, include: 30 parts dolomite, 25 parts limestone, 7 parts sodium sulfate, 4 parts cerium oxide, 7 parts chitosan, 4 parts polydimethyldiallyl ammonium chloride, and 4 parts composite additives.
3. The novel composite clarifying agent according to claim 1, characterized in that: Its raw materials, by weight, include: 20 parts dolomite, 20 parts limestone, 10 parts sodium sulfate, 5 parts cerium oxide, 10 parts chitosan, 5 parts polydimethyldiallylammonium chloride, and 5 parts composite additives.
4. The novel composite clarifying agent according to claim 1, characterized in that: Its raw materials, by weight, include: 40 parts dolomite, 30 parts limestone, 5 parts sodium sulfate, 3 parts cerium oxide, 5 parts chitosan, 3 parts polydimethyldiallyl ammonium chloride, and 3 parts composite additives.
5. A novel composite clarifying agent according to any one of claims 1-4, characterized in that: The composite additive is any combination of two or more of sodium nitrate, sodium sulfate, sodium chloride, or tin oxide.
6. A novel composite clarifying agent according to any one of claims 1-4, characterized in that: The chitosan used is attapulgite-loaded chitosan.
7. A method for preparing the novel composite clarifying agent according to any one of claims 1-4, characterized in that: Specifically, the following steps are included: S1. Ingredient preparation: Weigh the required weight parts of dolomite, limestone, sodium sulfate, cerium oxide, chitosan, polydimethyldiallyl ammonium chloride and composite additives using a weighing device, and set them aside for later use. S2. Multi-component solution mixing: Dolomite, limestone, sodium sulfate and cerium oxide are dissolved in deionized water to form aqueous solutions of each component. Chitosan, polydimethyldiallylammonium chloride and composite additives are then added to the deionized water to prepare a composite base solution. Under a stirring speed of 100-120 r / min, the aqueous solutions of each component are added to the composite base solution in proportion for gradient mixing. The mixing time is 30-60 min. S3. Let the mixture stand for 30-60 minutes to allow the components to react fully and stabilize. Then filter the mixture through a 100-mesh sieve to ensure uniform particle size. S4. Drying and pulverizing: The matured mixture is vacuum dried at 55°C to constant weight, and then pulverized to below 100 mesh to obtain the final composite clarifying agent powder.
8. The method for preparing a novel composite clarifying agent according to claim 7, characterized in that: The chitosan attapulgite loading process specifically includes the following steps: T1. Calcine the attapulgite at 700℃ for 4 hours, cool it down and add it to a 1mol / L hydrochloric acid aqueous solution. The concentration of attapulgite is 0.5g / mL. Stir at 90℃ for 4 hours, centrifuge and wash with water until neutral. T2. Add the acid-activated attapulgite to a 10% oxalic acid aqueous solution at a concentration of 0.5 g / mL, stir at room temperature for 2 hours, let stand for 5 hours, centrifuge, wash with water until neutral, and dry at 120℃. T3. Mix 10wt% oxalic acid aqueous solution and 1wt% acetic acid aqueous solution at a volume ratio of 4:1, add 3% chitosan by mass of the solution, stir at 50-60 rpm, heat to 50℃ and keep warm until the chitosan is completely dissolved to obtain a light yellow viscous chitosan sol. T4. Dilute the chitosan sol with 2.5 times its volume of water, heat to 50°C and stir for 1 hour, cool to room temperature, add acid-activated attapulgite at a concentration of 5 g / mL, stir for 5 hours, centrifuge, filter, and vacuum dry at 55°C to constant weight to obtain attapulgite-loaded chitosan.