Reusable glass frosting liquid as well as preparation method and application thereof

Abstract

The invention provides reusable glass frosting as well as a preparation method and application thereof, and relates to the technical field of glass frosting, the reusable glass frosting comprises the following components in parts by mass: 20-40 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 40-50 parts of inorganic acid and 10-30 parts of water; the reusable glass frosting liquid is subjected to precipitation treatment after a glass frosting process to obtain a frosting liquid precipitate, the frosting liquid precipitate is used as one of components for preparing the regenerated glass frosting liquid, and the regenerated glass frosting liquid comprises the following components in parts by mass: 2-10 parts of the frosting liquid precipitate, 20-30 parts of fluoride salt, 5-10 parts of inorganic salt and 5-10 parts of solid particles, 30-40 parts of inorganic acid, 2-5 parts of complexing agent and 10-20 parts of water. According to the method, the waste glass frosting liquid is effectively treated, the supernate is converted into the pickling solution, and the precipitate is compounded and reused, so that the total discharge amount and discharge times of the waste liquid are greatly reduced, the recycling of resources is effectively promoted, and the win-win situation of economic benefit and environmental protection is realized.

Description

Technical Field

[0001] The invention relates to the technical field of glass frosting, in particular to a reusable glass frosting liquid and a preparation method and application thereof. Background Art

[0002] At present, the frosting liquid used in the AG (anti-glare) treatment process of mobile phone glass is generally carefully formulated with strong acid as the main ingredient. This special formula ensures the efficient execution of the frosting process and gives the surface of the mobile phone glass an ideal matte effect and anti-fingerprint properties. However, when this production process is successfully completed, the waste liquid generated has become a problem that needs to be solved urgently: the acidic fluorine-containing waste liquid poses a significant pollution threat to the environment due to its high chemical activity and potential bioaccumulation. If these waste liquids are directly discharged into the natural environment without proper treatment, they will not only seriously damage the ecological balance of the water body and affect the survival of aquatic organisms, but may also be amplified step by step through the food chain, and ultimately pose a long-term risk to human health. Therefore, from the perspective of environmental protection, this type of waste liquid cannot be discharged directly.

[0003] In order to meet this challenge, the current response is to put these waste liquids through a series of complex and sophisticated centralized treatment processes. This treatment process aims to effectively remove or reduce the fluoride ion concentration and acidic substances in the waste liquid through chemical reactions, physical separation or biodegradation, so that it meets national or local emission standards. However, this series of treatment steps not only requires advanced technology and equipment support, but also comes with high operating costs, including the purchase of treatment materials, energy consumption, and maintenance and management by professionals, all of which directly increase the cost consumption of the producer and put pressure on the economic benefits of the enterprise.

[0004] More importantly, the current waste liquid treatment mode is often to treat the waste liquid immediately after the production of each tank of medicine is completed. Although this "immediate treatment after production" method ensures the continuity and compliance of the production line, it may lead to inefficient treatment and cost accumulation in actual operation. Therefore, exploring and implementing innovative strategies that can effectively reduce the total amount of waste liquid emissions or the number of emissions is not only of great significance for alleviating environmental pressure and promoting sustainable development, but also an effective way for enterprises to optimize cost structure and improve economic benefits. Through technological innovation, such as developing more efficient recycling systems, optimizing production processes to reduce waste liquid generation, or exploring more economical and environmentally friendly waste liquid treatment technologies, are important directions to achieve this goal. In summary, reducing the discharge or frequency of acidic fluorine-containing waste liquid is particularly urgent and crucial, both for environmental protection and cost control. Summary of the invention

[0005] The purpose of the present invention is to provide a reusable glass frosting liquid and a preparation method and application thereof. By effectively treating the waste liquid of the glass frosting liquid, its supernatant is converted into a pickling liquid, and its precipitate is compounded and reused, which not only greatly reduces the total amount and frequency of waste liquid discharge, but also effectively promotes the recycling of resources, achieving a win-win situation of economic benefits and environmental protection.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a reusable glass frosting liquid, which comprises the following components by weight: 20-40 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 40-50 parts of inorganic acid, and 10-30 parts of water;

[0008] The reusable glass frosting liquid is subjected to a precipitation treatment after a glass frosting process to obtain a frosting liquid precipitate. The frosting liquid precipitate is used as one of the components to prepare a regenerated glass frosting liquid. The regenerated glass frosting liquid comprises the following components by mass: 2-10 parts of frosting liquid precipitate, 20-30 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 30-40 parts of inorganic acid, 2-5 parts of complexing agent, and 10-20 parts of water.

[0009] Further, on the basis of the above technical solution, the complexing agent includes one or more of ethylenediaminetetraacetate, diethylenetriaminepentacarboxylate, sodium nitrilotriacetate, and sodium ethylenediaminetetramethylenephosphate.

[0010] Further, on the basis of the above technical solution, the fluoride salt is one or more of ammonium fluoride, ammonium bifluoride, sodium fluoride, magnesium fluoride, and calcium fluoride, preferably ammonium bifluoride.

[0011] Further, based on the above technical solution, the inorganic salt is one or more of sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, and ammonium sulfate, preferably ammonium chloride and ammonium sulfate.

[0012] Furthermore, based on the above technical solution, the solid particles include one or more of sodium fluorosilicate, potassium fluorosilicate, bentonite, and ammonium fluorosilicate.

[0013] Furthermore, based on the above technical solution, the inorganic acid includes hydrochloric acid or sulfuric acid.

[0014] The present invention also provides a method for preparing the reusable glass frosting liquid as described above, comprising the following steps:

[0015] Fluoride salt, inorganic salt, solid particles, inorganic acid and water are placed in a container in proportion, stirred, and then the container is sealed and heated in a 55-65°C water bath for 60-72 hours. During the heating process, the container is opened and stirred once every 4-6 hours, and the container is sealed after the stirring is completed. After the water bath heating is completed, a reusable glass frosting liquid is obtained.

[0016] The present invention also provides the above-mentioned reusable glass frosting liquid or the use of the reusable glass frosting liquid prepared by the above-mentioned preparation method of the reusable glass frosting liquid, which can be used to prepare regenerated glass frosting liquid and regenerated pickling liquid.

[0017] Further, based on the above technical solution, the method for preparing the regenerated glass frosting liquid comprises the following steps:

[0018] A1: frosting the glass with reusable frosting liquid and then precipitating it to obtain a frosting liquid precipitate;

[0019] A2: first add a complexing agent to the frosting liquid precipitate and mix for 1-2 hours, then add fluoride salt, inorganic salt, solid particles, inorganic acid and water and stir, then seal the container and heat in a 55-65° C. water bath for 60-72 hours; during the heating process, open the container seal and stir once every 4-6 hours, and seal the container after stirring; after the water bath heating is completed, obtain the regenerated glass frosting liquid.

[0020] Further, based on the above technical solution, the preparation method of the regenerated pickling solution comprises the following steps:

[0021] B1: the reusable glass frosting liquid is precipitated after frosting the glass to obtain a frosting liquid supernatant;

[0022] B2: adding a chelating agent to the supernatant of the frosting liquid to perform precipitation, and filtering to obtain a filtrate;

[0023] B3: diluting the filtrate to obtain a regenerated acid wash solution;

[0024] Wherein, the chelating agent includes one or more of sodium metasilicate, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid;

[0025] The added amount of the chelating agent is 0.01-0.05% of the total mass of the supernatant of the frosting liquid.

[0026] The present invention provides a reusable glass frosting liquid and a preparation method and application thereof, and the beneficial effects are as follows:

[0027] 1. The present invention effectively utilizes the waste liquid after frosting treatment, and prepares the regenerated glass frosting liquid through compounding of the frosting liquid precipitate. After precise component analysis and formula adjustment, the effective components in the precipitate are reactivated and combined. It has been verified that it can be reused up to 3 times, and the treatment effect after each use can be maintained at a high level, thereby greatly extending the service life of the frosting liquid and reducing the consumption of new raw materials.

[0028] 2. The present invention converts the supernatant of the frosting liquid in the waste liquid after frosting treatment into a regenerated pickling liquid for further pickling treatment, which can fully meet the requirements of the glass product pickling process in terms of performance, thereby realizing the recycling of resources and avoiding the environmental pollution that may be caused by direct discharge.

[0029] 3. The present invention adds a specific type of complexing agent to the regenerated glass frosting liquid. This complexing agent has a high degree of selectivity and complexing ability, can accurately identify and effectively bind metal ions in the precipitate, and effectively break the original chemical bonding state of these ions by forming a stable complex structure. This process not only helps to release more originally bound active ions from the precipitate, making the active ingredients in the regenerated frosting liquid more abundant, and the reaction more rapid and thorough; at the same time, the use of the complexing agent can also effectively reduce the adverse effects of impurities on the performance of the frosting liquid, improve the clarity and uniformity of the regenerated frosting liquid, and reduce its unnecessary corrosiveness, thereby ensuring that a better frosting effect and higher production efficiency can be demonstrated in practical applications.

[0030] 4. The present invention adds a chelating agent to the supernatant of the frosting solution. The chelating agent, by virtue of its unique chemical properties, can react efficiently and stably with the metal ions in the solution to form a tightly structured complex. The formed complex is separated from the solution by precipitation and filtration operations, and the obtained filtrate exhibits a lower metal salt content. The treated filtrate not only greatly reduces the concentration of metal salts, but also has a purer chemical composition, significantly reduces the number of metal ions that may be free in the pickling solution, and effectively weakens the many adverse effects that these metal ions may have on the pickling process, such as slowing down the pickling rate, affecting the pickling uniformity, and possible surface contamination. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1A schematic diagram of a process for frosting a group of glasses A using the reusable glass frosting liquid provided in Example 1 of the present invention and preparing a regenerated glass frosting liquid A and a regenerated pickling liquid A;

[0033] Figure 2 A schematic diagram of a process of frosting group B glass with the regenerated glass frosting liquid A provided in Example 2 of the present invention and preparing the regenerated glass frosting liquid B and the regenerated pickling liquid B;

[0034] Figure 3 A schematic diagram of the process of frosting group C glass with the regenerated glass frosting liquid B provided in Example 3 of the present invention and preparing the regenerated glass frosting liquid C and the regenerated pickling liquid C;

[0035] Figure 4 A schematic diagram of the process of frosting a group of glass D with the regenerated glass frosting liquid C provided in Example 4 of the present invention and preparing the regenerated glass frosting liquid D and the regenerated pickling liquid D;

[0036] Figure 5 A schematic diagram of the process of frosting group E glass with the regenerated glass frosting liquid D provided in Example 5 of the present invention and preparing the regenerated glass frosting liquid E and the regenerated pickling liquid E. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0038] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0039] According to a first aspect of the present invention, a reusable glass frosting solution is provided, which comprises the following components by weight: 20-40 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 40-50 parts of inorganic acid, and 10-30 parts of water;

[0040] The reusable glass frosting liquid is subjected to a precipitation treatment after a glass frosting process to obtain a frosting liquid precipitate. The frosting liquid precipitate is used as one of the components to prepare a regenerated glass frosting liquid. The regenerated glass frosting liquid comprises the following components by mass: 2-10 parts of frosting liquid precipitate, 20-30 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 30-40 parts of inorganic acid, 2-5 parts of complexing agent, and 10-20 parts of water.

[0041] Specifically, the frosting liquid precipitate is obtained by precipitation after a fine glass frosting process. The composition is extremely complex, including not only inorganic salts such as fluorosilicates and fluorides, but also residues that are not completely converted in the raw materials and foreign impurities introduced during the treatment process. During the precipitation and separation process, these precipitates may undergo changes in physical or chemical properties due to changes in environmental conditions (such as temperature fluctuations, improper pH adjustment, etc.), and thus lose some of their original activity. This reduction in activity will significantly affect the reaction rate when these precipitates are subsequently used to prepare regenerated glass frosting liquid, making the kinetic characteristics of the regeneration process slow, which is not conducive to efficient production.

[0042] The slowdown in reaction rate is not only directly related to the extension of the preparation cycle of the regenerated frosting liquid, but may also have a profound impact on the frosting effect, which is manifested as uneven thickness of the frosting layer, increased surface roughness, or failure to achieve the expected matte effect, thus affecting the overall quality and market competitiveness of the product. In addition, the impurities remaining in the precipitate and those chemical components that have not completely reacted will play the role of "interference factors" in the regenerated frosting liquid. They may interfere with the normal chemical reaction path of the frosting liquid, resulting in a decrease in the clarity of the regenerated frosting liquid, impaired uniformity, and even increased corrosiveness, placing an additional burden on production equipment, while also limiting the applicability of the frosting liquid in specific application scenarios.

[0043] In view of this, the present invention innovatively proposes to add a specific type of complexing agent to the regenerated glass frosting liquid. This complexing agent has a high degree of selectivity and complexing ability, can accurately identify and effectively bind metal ions in the precipitate, and effectively break the original chemical bonding state of these ions by forming a stable complex structure. This process not only helps to release more originally bound active ions from the precipitate, making the active ingredients in the regenerated frosting liquid more abundant, and the reaction more rapid and thorough; at the same time, the use of the complexing agent can also effectively reduce the adverse effects of impurities on the performance of the frosting liquid, improve the clarity and uniformity of the regenerated frosting liquid, and reduce its unnecessary corrosiveness, thereby ensuring that a better frosting effect and higher production efficiency can be demonstrated in practical applications.

[0044] Furthermore, the present invention limits the amount of the complexing agent to be 2-5 parts, such as 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, etc., because if the amount of the complexing agent added is too much, its strong complexing ability may cause unnecessary interference to the newly added fluoride salts, inorganic salts and other substances, and may destroy the balance of these chemical components, resulting in a decrease in the performance of the frosting liquid, and even affecting the quality and performance of the final product. If the amount added is too little, the bound active ions in the precipitate will not be fully released.

[0045] As an optional embodiment of the present invention, the complexing agent includes one or more of ethylenediaminetetraacetate, diethylenetriaminepentacarboxylate, sodium nitrilotriacetate, and sodium ethylenediaminetetramethylenephosphate.

[0046] As an optional embodiment of the present invention, the fluoride salt is one or more of ammonium fluoride, ammonium bifluoride, sodium fluoride, magnesium fluoride and calcium fluoride, preferably ammonium bifluoride.

[0047] As an optional embodiment of the present invention, the inorganic salt is one or more of sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, and ammonium sulfate, preferably ammonium chloride and ammonium sulfate.

[0048] As an optional embodiment of the present invention, the solid particles include one or more of sodium fluorosilicate, potassium fluorosilicate, bentonite, and ammonium fluorosilicate.

[0049] As an optional embodiment of the present invention, the inorganic acid includes hydrochloric acid or sulfuric acid.

[0050] According to a second aspect of the present invention, a method for preparing a reusable glass frosting liquid is provided, comprising the following steps:

[0051] Fluoride salt, inorganic salt, solid particles, inorganic acid and water are placed in a container in proportion, stirred, and then the container is sealed and heated in a 55-65°C water bath for 60-72 hours. During the heating process, the container is opened and stirred once every 4-6 hours, and the container is sealed after the stirring is completed. After the water bath heating is completed, a reusable glass frosting liquid is obtained.

[0052] According to a third aspect of the present invention, there is provided an application of the reusable glass frosting liquid as described above or the reusable glass frosting liquid prepared by the preparation method of the reusable glass frosting liquid as described above, which can be used to prepare regenerated glass frosting liquid and regenerated pickling liquid.

[0053] As an optional embodiment of the present invention, the method for regenerating glass frosting liquid comprises the following steps:

[0054] A1: The reusable glass frosting liquid is subjected to precipitation after glass frosting to obtain a frosting liquid precipitate;

[0055] A2: first add a complexing agent to the frosting liquid precipitate and mix for 1-2 hours, then add fluoride salt, inorganic salt, solid particles, inorganic acid and water and stir, then seal the container and heat in a 55-65° C. water bath for 60-72 hours; during the heating process, open the container seal and stir once every 4-6 hours, and seal the container after stirring; after the water bath heating is completed, obtain the regenerated glass frosting liquid.

[0056] Specifically, the complexing agents provided by the present invention are all known for their high chemical stability and selective complexing ability. These complexing agents exhibit unique properties in solution, that is, they tend to combine with metal ions in the precipitate to form an extremely stable complex structure. In the preparation process of the regenerated frosting solution, in order to avoid unnecessary reactions between these complexing agents and newly added fluoride salts, inorganic salts and other substances, thereby interfering with the overall performance and expected effect of the frosting solution, the present invention firstly mixes and contacts these complexing agents with the frosting solution precipitate to ensure that the complexing agents have enough time to fully react with the metal ions in the precipitate to release more active ions. By accurately controlling the reaction conditions such as the ratio of the complexing agent to the frosting solution precipitate and the mixing time, the complexing agent can preferentially and effectively lock the metal ions in the precipitate to form a stable complex. After the complexing agent reacts with the precipitate, necessary additives such as fluoride salts and inorganic salts are added in sequence. The advantage of doing so is that, on the one hand, it can ensure that the complexing agent does not interfere with the normal function of the newly added chemical components, and on the other hand, it can ensure the uniform distribution and effective function of the components in the frosting liquid, thereby preparing a regenerated frosting liquid with more stable performance and more ideal effect. This pretreatment strategy not only improves the preparation efficiency of the frosting liquid, but also significantly optimizes its application performance, providing new ideas and methods for the innovation and development of the frosting process.

[0057] As an optional embodiment of the present invention, the method for preparing the regenerated pickling solution comprises the following steps:

[0058] B1: the reusable glass frosting liquid is precipitated after frosting the glass to obtain a frosting liquid supernatant;

[0059] B2: adding a chelating agent to the supernatant of the frosting liquid to perform precipitation, and filtering to obtain a filtrate;

[0060] B3: diluting the filtrate to obtain a regenerated acid wash solution.

[0061] As an optional embodiment of the present invention, the chelating agent includes one or more of sodium metasilicate, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid.

[0062] Specifically, the frosting liquid supernatant contains F - , H+ , Cl - 、SO4 2- NH4 + And other other metal ions, the supernatant of the frosting liquid can be diluted and stirred evenly and used as a regenerated pickling liquid for pickling, but the supernatant of the frosting liquid also contains metal salts such as fluoride salts, chloride salts, sulfates, silicates, etc. The purpose of pickling is to remove impurities such as grease on the surface of the workpiece, and at the same time form a dense passivation film on the surface of the workpiece to protect it from further oxidation. However, the presence of metal salts may interfere with this process, resulting in an incomplete or unstable passivation film. These metal salts may compete with oxides or other impurities on the surface of the workpiece, thereby affecting the pickling rate. This competitive reaction may cause the pickling solution to have uneven cleanliness on the surface of the workpiece.

[0063] In view of this, the present invention creatively adds a chelating agent to the supernatant of the frosting solution. The chelating agent, by virtue of its unique chemical properties, can react efficiently and stably with the metal ions in the solution to form a tightly structured complex. The formed complex is separated from the solution by precipitation and filtration operations, and the obtained filtrate exhibits a lower metal salt content. The treated filtrate not only greatly reduces the concentration of metal salts, but also has a purer chemical composition, significantly reduces the number of metal ions that may be free in the pickling solution, and effectively weakens the many adverse effects that these metal ions may have on the pickling process, such as slowing down the pickling rate, affecting the pickling uniformity, and possible surface contamination.

[0064] As an optional embodiment of the present invention, the added amount of the chelating agent is 0.01-0.05% (such as 0.02%, 0.03%, 0.04%, etc.) of the total mass of the supernatant of the frosting liquid.

[0065] Specifically, the present invention limits the added chelating agent to 0.01-0.05% of the total mass of the supernatant of the frosting liquid, which not only ensures the effective removal of metal ions, but also avoids affecting the pH value, acidity or other key parameters of the pickling process liquid, thereby significantly improving the efficiency of the entire treatment process and the stability of product quality. However, it is worth noting that if the amount of chelating agent added is too much, although it may theoretically further increase the removal efficiency of metal ions, it may also cause unnecessary changes in the chemical properties of the pickling liquid, such as a decrease in pH value, an increase in acidity, etc., which in turn affects the pickling effect and product quality. On the contrary, if the amount added is too little, the metal ions in the supernatant may not be fully removed, resulting in residual metal ions, which will also have an adverse effect on the pickling process and product quality. Therefore, the addition amount range of 0.01-0.05% defined by the present invention not only ensures the effective removal of metal ions, but also avoids the negative impact on the pickling process due to improper addition, and is the best choice for both efficiency and stability.

[0066] The present invention will be further described in detail below with reference to specific embodiments and comparative examples.

[0067] Example 1

[0068] like Figure 1 As shown, the following steps are included:

[0069] (1) Place the glass of group A (200 pieces) in pickling solution A for 1-2 minutes, then rinse with water for 0.5-1 minute, and take out for use;

[0070] The pickling solution A is a mixed acid solution of 10% hydrofluoric acid, 10% hydrochloric acid and 8% sulfuric acid.

[0071] (2) 30 parts of ammonium bifluoride, 5 parts of ammonium chloride, 5 parts of sodium fluorosilicate particles, 50 parts of hydrochloric acid, and 10 parts of water are placed in a container, stirred until uniformly mixed, and then the container is sealed and heated in a 60° C. water bath for 70 h; during the heating process, the container is opened and stirred once every 5 h, and the container is sealed after the stirring is completed; after the water bath heating is completed, a reusable glass frosting liquid is obtained.

[0072] (3) The glass of group A to be frosted is placed in a reusable glass frosting liquid cooled to 20° C. for frosting.

[0073] (4) After the glass is frosted, the frosting liquid is precipitated until the insoluble matter in the solution is completely precipitated and the solid-liquid stratification is obvious.

[0074] (5) After the supernatant of the frosting liquid is taken out, sodium metasilicate accounting for 0.02% of the total mass of the supernatant is added, and the mixture is allowed to stand for 8 hours. The precipitate is filtered, and the filtrate and water are mixed and diluted in a ratio of 1:1. After stirring evenly, a regenerated pickling liquid A is obtained.

[0075] (6) The precipitate of the frosting liquid is taken out, and 5 parts of ethylenediaminetetraacetate are added to 10 parts of the precipitate of the frosting liquid and mixed for 2 hours, and then 20 parts of ammonium bifluoride, 5 parts of ammonium chloride, 5 parts of sodium fluorosilicate, 40 parts of hydrochloric acid, and 15 parts of water are added and stirred. The container is sealed and heated in a 60°C water bath for 70 hours; during the heating process, the container is opened and stirred once every 5 hours, and the container is closed after the stirring is completed; after the water bath heating is completed, the regenerated glass frosting liquid A is obtained.

[0076] Example 2

[0077] This embodiment uses the regenerated glass frosting liquid A prepared in Example 1 to perform glass frosting. Figure 2 As shown, the following steps are included:

[0078] The glasses of group B (200 pieces) were placed in the regenerated acid cleaning solution A for pickling for 1-2 minutes, then washed with water for 0.5-1 minute, and then taken out for use;

[0079] The glass of group B is placed in the regenerated glass frosting solution A prepared in Example 1 for frosting. After frosting is completed, steps (4) to (6) in Example 1 are repeated to obtain regenerated glass frosting solution B and regenerated acid washing solution B.

[0080] Example 3

[0081] This embodiment uses the regenerated glass frosting liquid B prepared in Example 2 to perform glass frosting. Figure 3 As shown, the following steps are included:

[0082] The glasses of group C (200 pieces) were placed in the regenerated acid cleaning solution B for pickling for 1-2 minutes, then washed with water for 0.5-1 minute, and then taken out for use;

[0083] The glass of group C is placed in the regenerated glass frosting solution B prepared in Example 2 for frosting. After frosting is completed, steps (4) to (6) in Example 1 are repeated to obtain regenerated glass frosting solution C and regenerated pickling solution C.

[0084] Example 4

[0085] This embodiment uses the regenerated glass frosting liquid C prepared in Example 3 to perform glass frosting. Figure 4 As shown, the following steps are included:

[0086] The glass of group D (200 pieces) was placed in the regenerated acid cleaning solution C for pickling for 1-2 minutes, then washed with water for 0.5-1 minute, and then taken out for use;

[0087] The glass of group D is placed in the regenerated glass frosting solution C prepared in Example 3 for frosting. After frosting is completed, steps (4) to (6) in Example 1 are repeated to obtain the regenerated glass frosting solution D and the regenerated pickling solution D.

[0088] Example 5

[0089] This embodiment uses the regenerated glass frosting liquid D prepared in Example 4 to perform glass frosting. Figure 5 As shown, the following steps are included:

[0090] The glass of group E (200 pieces) was placed in the regenerated acid washing solution D for pickling for 1-2 minutes, then washed with water for 0.5-1 minute, and then taken out for use;

[0091] The glass of group E is placed in the regenerated glass frosting liquid D prepared in Example 4 for frosting. After frosting is completed, steps (4) to (6) in Example 1 are repeated to obtain the regenerated glass frosting liquid E and the regenerated pickling liquid E.

[0092] Performance Testing

[0093] The frosted AE group glasses in Examples 1-5 are cleaned respectively to remove the residual frosting liquid, and then dried and taken out for use;

[0094] The AE group of glasses were placed under an electron microscope for observation. By measuring the etching depth of the glass under the microscope, the average etching depth of each group of glasses is shown in Table 1:

[0095] Table 1

[0096]

[0097] Among them, the qualified rate of glass is an important indicator to measure the treatment effect of frosting liquid. When the qualified rate of glass is lower than 90%, it means that the performance of the frosting liquid has been significantly reduced and can no longer meet the production needs of high-quality products. In this case, continuing to use the frosting liquid for recycling will not only fail to achieve the expected treatment effect, but may also cause adverse effects on the glass surface, such as producing uneven frosting effects, increasing surface defects, etc. Therefore, the present invention clearly stipulates that once the qualified rate of glass drops below 90%, the regenerated frosting liquid prepared in this batch will be deemed unqualified and must be stopped from use, and normal centralized treatment must be carried out in accordance with environmental protection regulations, and then safely discharged to avoid pollution to the environment.

[0098] The glass of group E was frosted with the regenerated frosting liquid D prepared in Example 4. Since the glass of group E was unqualified, only the total usable time of the reusable frosting liquid, the regenerated frosting liquid A, the regenerated frosting liquid B and the regenerated frosting liquid C prepared in Examples 1-3 was counted, as shown in Table 2:

[0099] Table 2

[0100]

[0101] According to Table 1 and Table 2, the reusable glass frosting liquid provided by the present invention shows significant superiority in performance. It can still maintain a good treatment effect after repeated use. The data shows that it can be reused up to 3 times, which means that after each batch of frosting liquid is prepared, it can be used continuously for 3 production batches without significantly reducing the glass qualification rate, which greatly improves the resource utilization efficiency, reduces production costs, and also reduces the generation of waste, which meets the requirements of green production and circular economy.

[0102] Comparative Example 1

[0103] Compared with Example 1, the main difference between this comparative example and Example 1 is that 7 parts of complexing agent are added to the regenerated glass frosting liquid, specifically:

[0104] Steps (1) to (5) are the same as in Example 1;

[0105] (6) The obtained frosting liquid precipitate is taken out, and 7 parts of ethylenediaminetetraacetate are first added to 10 parts of the frosting liquid precipitate and mixed for 2 hours, and then 20 parts of ammonium bifluoride, 5 parts of ammonium chloride, 5 parts of sodium fluorosilicate, 40 parts of hydrochloric acid, and 13 parts of water are added and stirred, and the container is sealed and heated in a 60° C. water bath for 70 hours; during the heating process, the container is opened and stirred once every 5 hours, and the container is closed after the stirring is completed; after the water bath heating is completed, the regenerated glass frosting liquid A is obtained ， .

[0106] In this comparative example, the recycled glass frosting liquid A ， The average etch depth (2 min) of frosted glass is 18 μm, and the qualified rate is 91%. It can only be reused twice. This is because too much complexing agent is added, and its strong complexing ability interferes with newly added ammonium bifluoride, ammonium chloride and other substances, destroying the balance of these chemical components, resulting in a decrease in the performance of the frosting liquid, affecting the quality and performance of the final product.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A reusable glass frosting liquid, characterized in that: The composition comprises the following components by weight: 20-40 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 40-50 parts of inorganic acid, and 10-30 parts of water; The reusable glass frosting liquid is subjected to a precipitation treatment after a glass frosting process to obtain a frosting liquid precipitate. The frosting liquid precipitate is used as one of the components to prepare a regenerated glass frosting liquid. The regenerated glass frosting liquid comprises the following components by mass: 2-10 parts of frosting liquid precipitate, 20-30 parts of fluoride salt, 5-10 parts of inorganic salt, 5-10 parts of solid particles, 30-40 parts of inorganic acid, 2-5 parts of complexing agent, and 10-20 parts of water.

2. The reusable glass frosting liquid according to claim 1, characterized in that: The complexing agent includes one or more of ethylenediaminetetraacetate, diethylenetriaminepentacarboxylate, sodium nitrilotriacetate, and sodium ethylenediaminetetramethylenephosphate.

3. The reusable glass frosting liquid according to claim 1, characterized in that: The fluoride salt is one or more of ammonium fluoride, ammonium bifluoride, sodium fluoride, magnesium fluoride, and calcium fluoride, preferably ammonium bifluoride.

4. The reusable glass frosting liquid according to claim 1, characterized in that: The inorganic salt is one or more of sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, and ammonium sulfate, preferably ammonium chloride and ammonium sulfate.

5. The reusable glass frosting liquid according to claim 1, characterized in that: The solid particles include one or more of sodium fluorosilicate, potassium fluorosilicate, bentonite, and ammonium fluorosilicate.

6. The reusable glass frosting liquid according to claim 1, characterized in that: The inorganic acid includes hydrochloric acid or sulfuric acid.

7. A method for preparing a reusable glass frosting liquid as claimed in any one of claims 1 to 6, characterized in that: The steps include: Fluoride salt, inorganic salt, solid particles, inorganic acid and water are placed in a container in proportion, stirred, and then the container is sealed and heated in a 55-65°C water bath for 60-72 hours. During the heating process, the container is opened and stirred once every 4-6 hours, and the container is sealed after the stirring is completed. After the water bath heating is completed, a reusable glass frosting liquid is obtained.

8. A use of the reusable glass frosting liquid as claimed in any one of claims 1 to 6 or the reusable glass frosting liquid prepared by the preparation method of the reusable glass frosting liquid as claimed in claim 7, characterized in that: It can be used to prepare regenerated glass frosting solution and regenerated pickling solution.

9. The use according to claim 8, characterized in that: The method for preparing the regenerated glass frosting liquid comprises the following steps: A1: frosting the glass with reusable frosting liquid and then precipitating it to obtain a frosting liquid precipitate; A2: first add a complexing agent to the frosting liquid precipitate and mix for 1-2 hours, then add fluoride salt, inorganic salt, solid particles, inorganic acid and water and stir, then seal the container and heat in a 55-65° C. water bath for 60-72 hours; during the heating process, open the container seal and stir once every 4-6 hours, and seal the container after stirring; after the water bath heating is completed, obtain the regenerated glass frosting liquid.

10. The use according to claim 8, characterized in that: The method for preparing the regenerated pickling solution comprises the following steps: B1: the reusable glass frosting liquid is precipitated after frosting the glass to obtain a frosting liquid supernatant; B2: adding a chelating agent to the supernatant of the frosting liquid to perform precipitation, and filtering to obtain a filtrate; B3: diluting the filtrate to obtain a regenerated acid wash solution; Wherein, the chelating agent includes one or more of sodium metasilicate, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid; The added amount of the chelating agent is 0.01-0.05% of the total mass of the supernatant of the frosting liquid.

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