WO2024040686A1

WO2024040686A1 - Mother glass, and cyclic utilization method and system for alkali metal element in mother glass

Info

Publication number: WO2024040686A1
Application number: PCT/CN2022/122721
Authority: WO
Inventors: 胡伟; 孟鸿
Original assignee: 北京大学深圳研究生院; 深圳市东丽华科技有限公司
Priority date: 2022-08-25
Filing date: 2022-09-29
Publication date: 2024-02-29
Also published as: CN117623642A

Abstract

A mother glass, and a cyclic utilization method and system for an alkali metal element in the mother glass. The cyclic utilization method comprises the following steps: placing an alkali metal ion fixing agent and a first mother glass containing an alkali metal element into an ion exchange salt bath, and reacting same for a certain period of time to obtain a solid resultant containing the alkali metal element; taking out the solid resultant, and pretreating same to obtain a main solid ingredient; mixing an auxiliary solid ingredient with the main solid ingredient to obtain a mixture of mother glass ingredients; and melting the mixture of the mother glass ingredients to prepare a second mother glass containing the alkali metal element. In the cyclic utilization method, the alkali metal ion fixing agent absorbs the alkali metal element Li released from the first mother glass in the ion exchange salt bath and finally forms into the solid resultant containing the alkali metal element Li; and the solid resultant is used as a raw material for preparing the mother glass to obtain the corresponding second mother glass containing the alkali metal element Li, thereby reducing the waste of lithium resources in the field of glass.

Description

Method and system for recycling plain glass and alkali metal elements in plain glass

Technical field

The invention relates to the field of glass manufacturing and processing, and specifically relates to a method and system for recycling alkali metal elements in plain glass and plain glass.

Background technique

In the glass processing industry, chemical strengthening technology is often used to improve the strength of ordinary glass. The principle is to place the glass or glass products that need to be strengthened in a high-temperature molten ion exchange salt bath (nitric acid containing sodium or lithium or both). Soak it in a potassium melt or a mixed melt of potassium nitrate and sodium nitrate for a certain period of time, and replace the sodium and lithium ions with small ionic radii in the glass with the potassium ions and sodium ions with larger ionic radii in the ion exchange salt bath, respectively. This creates a compressive stress layer on the glass surface, thereby improving the strength of the glass.

The industry usually uses surface compressive stress (Compressive Stress: CS) as one of the important indicators to evaluate the chemical strengthening effect of glass. Tests have shown that the higher the K+ concentration in the ion exchange salt bath, the higher the CS value of the strengthened glass. The chemical strengthening of glass The better. On the contrary, when the purity of nitrate in the ion exchange salt bath decreases, the CS value of the strengthened glass decreases, and the effect of chemical strengthening of the glass becomes worse.

Practice has shown that during the process of placing glass or glass products that need to be strengthened in an ion exchange salt bath for chemical strengthening treatment, as the use time of the salt bath increases and the amount of glass processed by the salt bath increases, the garbage ions in the salt bath increase. The content of Na ⁺ and Li ⁺ will also increase accordingly. Although it is only PPM level, it is enough to seriously hinder the normal chemical strengthening, causing the CS value of subsequent strengthened glass to drop and the strength to drop significantly, making the quality of the final product difficult. Control. The above-mentioned problems in the field of reinforcement are called "salt bath poisoning". Research and analysis show that the main reason for the decrease in CS value is that the ion exchange salt bath is diluted and contaminated by sodium ions and lithium ions released from the glass due to ion exchange. As the total area of the glass treated by the ion exchange salt bath increases, The concentration of sodium ions and lithium ions in the ion exchange salt bath gradually increases, the K ⁺ concentration in the ion exchange salt bath gradually decreases, and the Li ⁺ concentration gradually increases, resulting in a decrease in the surface CS value of the strengthened chemically strengthened glass and a smaller dimensional expansion rate.

In order to strengthen chemically strengthened glass to obtain qualified and stable CS value and dimensional expansion rate, the traditional method is to replace the ion exchange salt bath in the strengthening furnace every time one or several batches of glass are produced. However, the ion exchange salt bath should be replaced with a new one. The process is time-consuming, laborious and delays production, resulting in increased costs and reduced efficiency. In addition, the main components of ion exchange salt baths are potassium nitrate and sodium nitrate, both of which are key substances controlled by public safety. The replaced and discarded "poisoned" ion exchange salt baths will cause great damage to the environment.

To solve the above problems, major manufacturers in the industry have proposed salt bath regeneration methods or solutions to extend the life of the salt bath. For example:

Corning Co., Ltd. provides a regeneration method for a poisoned salt bath in its invention patent application number CN201680068029.0, which includes providing a salt bath containing at least one of KNO ₃ and NaNO ₃ ; providing an ion-exchangeable lithium cation Substrate; contacting at least a portion of the ion-exchangeable substrate with the salt bath, whereby lithium cations in the salt bath diffuse from the ion-exchangeable substrate and dissolve in the salt bath; utilizing phosphate to selectively precipitate the dissolved lithium cations from the salt bath . The method also includes preventing or reducing the formation of crystals on the surface of the ion-exchangeable substrate when removing the ion-exchangeable substrate from the salt bath, thereby preventing or reducing the formation of surface defects in the ion-exchangeable substrate.

In the invention patent application number CN201380048664.9, Asahi Glass Co., Ltd. provides a molten salt containing potassium nitrate used in chemical strengthening of glass that fully extends the service life. The glass-strengthening molten salt is used to form a compressive stress layer on the glass surface through ion exchange, wherein the glass-strengthening molten salt contains potassium nitrate and at least one of carbonate anions and phosphate anions.

Asahi Glass Co., Ltd., in its invention patent application number CN201380048567. method. The regeneration method of the molten salt is to regenerate the molten salt for glass strengthening used to form a compressive stress layer on the glass surface through ion exchange, the molten salt contains potassium nitrate, and the regeneration method includes the molten salt after the ion exchange treatment. The process of adding potassium orthophosphate.

The common point of the above patents is that they use phosphate to treat the poisoned ion exchange salt bath. The phosphate is dissolved in the salt bath, and the phosphate radicals and lithium ions form lithium phosphate and precipitate, thereby reducing the content of garbage ions Li. However, the applicant should point out that the reaction of lithium phosphate after it is introduced into the salt bath requires a chemical reaction time of more than 10 hours. The formation of precipitates will make the salt bath turbid and requires a long period of clarification before use; therefore, online salt treatment cannot be achieved. The real-time management of bath and glass quality can only be managed in batches at best; when powdered sodium phosphate is added to the salt bath, a large amount of sodium ions are brought in, changing the effective ratio of the salt bath itself; sodium phosphate is highly alkaline and water-absorbing When the salt bath is introduced, a large amount of OH radical ions are also introduced, which causes strong corrosion to the glass and destroys the glass network. If used for more than 30 hours, it will not only fail to increase the strength of the glass, but will also significantly reduce the strength of the glass; the precipitated lithium phosphate will When there is too much "sludge" formed at the bottom of the salt bath, the effective working area of the salt bath will be reduced, the output will be reduced, and cleaning will be difficult; excessive precipitation of lithium phosphate after being used for a long time will cause it to adhere to the surface of the strengthened glass, causing defects in the glass; salt The residual strong alkali phosphate salt in the bath adheres to the surface of the glass. When the glass is taken out of the salt bath, it comes into contact with water in the air, causing a second strong corrosion on the glass. The most important thing is that lithium phosphate is not recycled but treated as waste, resulting in a large amount of waste of lithium element.

In addition, in glass processing plants, salt bath furnaces are generally 10 tons or more, and the number of glass sheets processed in one strengthening process can reach tens of thousands. In such a large-scale ion exchange environment, if environmental control of the salt bath is not carried out, it is extremely easy to This leads to surface defects in the strengthened glass, a significant decrease in glass strength between batches, and successive failure of the salt bath.

Furthermore, the main materials of glass-strengthened salt bath are potassium nitrate and sodium nitrate. Potassium nitrate is a strong oxidant, flammable, explosive, and the main component of explosives; sodium phosphate is a strong alkali and weak acid salt, which is highly water-absorbent and corrosive. ; Both of these are key substances under public safety control. During the glass processing process, these materials cannot be recycled and need to be used in huge amounts, which not only causes great damage to the environment, but also leads to high production costs.

Based on the above reasons, the applicant proposed a salt bath purification additive material and its use method in the invention patent with application number CN201910758511.2. The salt bath purification additive material can be quickly absorbed and used to produce chemically strengthened glass. The lithium ions and sodium ions in the ion exchange salt bath ensure that the concentration of lithium ions and sodium ions in the ion exchange salt bath is at a low level, ensuring the dimensional stability and surface stress stability of mass production of chemically strengthened glass. Moreover, the salt bath purification additive material can be quickly and conveniently taken out, reducing the impact on production efficiency.

However, the applicant found that although the salt bath purification additive material proposed in the above-mentioned patent proposed by the applicant can be reused many times after being processed to release the absorbed impurity ions (lithium ions, sodium ions), the released lithium ions The final disposal method is to directly discard it together with the purified additive materials, which results in a large amount of lithium being wasted.

Contents of the invention

The technical problem to be solved by the present invention is to provide a recycling method for alkali metal elements in plain glass. At the same time, the invention also provides a kind of plain glass and a recycling system for alkali metal elements in the plain glass. This will achieve the purpose of reducing the waste of lithium resources and carbon dioxide emissions in the glass field.

The method for recycling alkali metal elements in plain glass provided by the invention includes the following steps:

Place the first element glass containing alkali metal elements and an alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain a solid product containing alkali metal elements;

The solid product is taken out from the ion exchange salt bath and pretreated to obtain the main solid ingredient;

Mix the auxiliary solid ingredients with the main solid ingredients to obtain a plain glass ingredient mixture;

The raw glass batch mixture is melted and prepared to obtain a second raw glass containing an alkali metal element.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the components of the second plain glass and the first plain glass and the percentage content of each component are the same.

In the recycling method of alkali metal elements in plain glass provided by the present invention, in the plain glass ingredient mixture, the mass percentage of the main solid ingredient is less than or equal to 50wt%.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the pretreatment includes at least one of cleaning, drying, and crushing.

In the method for recycling alkali metal elements in plain glass provided by the present invention, the plain glass contains all the metal compounds contained in the solid product.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the plain glass contains all the metal compounds contained in the main solid ingredients.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the alkali metal elements at least include Li.

In the recycling method of alkali metal elements in plain glass provided by the invention, the alkali metal elements further include Na or K.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the alkali metal elements exist in the form of covalent compounds or ionic compounds in the plain glass;

The ion exchange salt bath contains the alkali metal element in an ionic form;

The alkali metal element exists in the form of a covalent compound or an ionic compound in the solid product and the main solid ingredient.

In the method for recycling alkali metal elements in plain glass provided by the present invention, the ion exchange salt bath contains a nitrate with a mass fraction of greater than or equal to 50 wt%.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the "first plain glass containing alkali metal elements and an alkali metal ion fixative are placed in an ion exchange salt bath to react for a certain period of time to obtain alkali metal-containing In the step of "solid product of an element", the alkali metal ion fixative absorbs the alkali metal element in the ionic form released from the first plain glass through a chemical reaction.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the alkali metal ion fixing agent is a compound that can absorb the alkali metal element existing in ionic form; the alkali metal ion fixing agent and the alkali metal ion fixing agent contain alkali. The solid products of metal elements are solid in the atmosphere at normal temperature and pressure and in the ion exchange salt bath.

In the recycling method of alkali metal elements in plain glass provided by the present invention, the alkali metal ion fixative includes one or more of silicate, phosphate, borate and antimonate.

In the recycling method of alkali metal elements in plain glass provided by the present invention, in terms of mole percentage, the plain glass contains:

SiO ₂ , 39-75mol%;

Li ₂ O, 0.5-30mol%;

Al ₂ O ₃ , 0-28 mol%.

In the recycling method of alkali metal elements in plain glass provided by the invention, the auxiliary solid ingredients include ZrO, MgO, MgCO ₃ , CaO, CaCO ₃ , Na ₂ O, NaNO ₃ , NaCO ₃ , K ₂ O, KNO ₃ , K ₂ CO ₃ , B ₂ O ₃ , P ₂ O ₅ , Y ₂ O ₃ , at least one of ZnO, SnO ₂ , Sb ₂ O ₃ and NaCl.

The present invention provides a kind of plain glass prepared by the recycling method as described above, and the plain glass contains all kinds of elements contained in the main solid ingredient.

In the plain glass provided by the present invention, the plain glass contains a shaped or amorphous structure. The stereotyped structure includes at least one of lithium disilicate, lithium silicate, feldspar, and beta quartz.

The invention provides a recycling system for alkali metal elements in plain glass. The recycling system includes:

Raw material supply module, used to manufacture first element glass and alkali metal ion fixative;

The processing and recycling module is used to place the first plain glass and the alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain strengthened chemically strengthened glass and a solid product containing alkali metal elements; The solid product is taken out from the ion exchange salt bath and pretreated to obtain the main solid ingredient;

The reprocessing module is used to mix the auxiliary solid ingredients with the main solid ingredients to obtain a plain glass ingredient mixture; and is used to melt and prepare the plain glass ingredient mixture to obtain a second plain glass containing alkali metal elements.

In the recycling system provided by the invention, the reprocessing module includes a detection unit and a calculation unit;

The detection unit is used to detect the components of the main solid ingredients and the content of each component;

The calculation unit is used to analyze and obtain the composition of the auxiliary solid batching based on the required composition and content of each component of the second plain glass and the detected composition and content of each component of the main solid batching. The content of each component and the added amount of the auxiliary solid ingredients are divided into: the added amount is the mass ratio of the auxiliary solid ingredients to the main solid ingredients.

Implementing the present invention can at least achieve the following beneficial effects:

1. Realize the recycling of Li element. In the Li recycling method, the alkali metal ion fixative absorbs the alkali metal element Li released from the first plain glass in the ion exchange salt bath and finally forms the solid containing the alkali metal element Li. The product is then recycled in subsequent processes as a raw material for preparing plain glass to obtain a corresponding second plain glass containing alkali metal element Li, so that the The alkali metal element Li released from the first glass enters the second glass, realizing the recycling of the Li element, thereby reducing the waste of lithium resources in the glass field.

2. Can significantly reduce carbon emissions. It should be noted that in the preparation process of existing plain glass, the raw materials used are usually carbonates or sulfates, so the preparation process of existing plain glass will inevitably produce a large amount of CO ₂ and SO ₂ . In the recycling method of the present application, the main solid ingredients in the raw glass batch mixture used to prepare the second raw glass are silicate, phosphate, borate or antimonate, that is to say, in the During the melting and preparation process of the raw glass batch mixture, the main solid batch will not release CO ₂ and SO ₂ . Therefore, it can be understood that compared with the existing raw glass preparation method, the same amount of raw glass can be prepared. In this case, the emission of CO ₂ and SO ₂ can be significantly reduced by adopting the recycling method of this application.

3. Can significantly reduce energy consumption. Following the above, the main solid ingredients in the raw glass batch mixture used to prepare the second raw glass do not undergo endothermic decomposition to produce CO ₂ and SO ₂ but are directly melted. That is to say, the raw glass provided by the application is used. In the process of melting the ingredient mixture to prepare the second plain glass, due to the presence of the main solid ingredients, the heat energy consumption in the process of endothermic decomposition to produce CO ₂ and SO ₂ can be reduced. In this way, a significant reduction in energy consumption is achieved.

Description of drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only It is an embodiment of the utility model. For those of ordinary skill in the art, other drawings can also be obtained based on the provided drawings without exerting creative efforts:

Figure 1 is a block diagram of the recycling system provided by this application;

Figure 2 is the XRD pattern of the first prime glass RG’-22;

Figure 3 is the XRD pattern of the first prime glass RG’-23;

Figure 4 is the XRD pattern of the first prime glass RG’-24;

Figure 5 is the XRD pattern of the first prime glass RG’-26.

Detailed ways

With the development brought about by digital technology, human society has entered the third industrial revolution. Digital technology has developed greatly, affecting all aspects of people's livelihood. The first two industrial revolutions brought about great liberation and progress in the productivity of human society, but climate and environmental issues have become major issues threatening mankind. The signing of the "Kyoto Protocol" is to protect mankind from the threat of climate warming. China in 1998 The Protocol was signed in May 2002 and approved in August 2002. The EU and its member states formally ratified the Kyoto Protocol on May 31, 2002. On November 5, 2004, Russian President Putin Signed on, it officially became a legal text of Russia. As of August 13, 2005, 142 countries and regions around the world had signed the protocol, including 30 industrialized countries. The population of the ratifying countries accounted for 10% of the world's total population. 80%. On September 22, 2020, the Chinese President stated at the general debate of the 75th United Nations General Assembly that China will increase its nationally determined contributions, adopt more powerful policies and measures, and strive to achieve carbon dioxide emissions by 2030. peak, and strive to achieve "carbon neutrality" by 2060. With the development of the Internet of Things and increasingly faster network technologies and instant communication technologies, such as 5G communications, new energy vehicles combine cutting-edge energy technologies to achieve goals such as "green" and "carbon reduction" and are sought after by people and governments around the world. The penetration rate is also getting higher and higher, and its impact on human life is increasing. Traditional car manufacturers have released timetables for the suspension of production of traditional gasoline vehicles, and major economies such as the European Union, the United States, Japan, and China have released timetables for banning the sale of traditional fuel vehicles.

Among new energy vehicles, electric vehicles are currently relatively mature and widely used. The vast majority of electric vehicles use batteries as energy source to drive the vehicle. Currently, the most efficient batteries include lithium iron phosphate batteries, ternary polymer lithium batteries, etc. Lithium iron phosphate battery is a lithium-ion battery using lithium iron phosphate (LiFePO ₄ ) as the positive electrode material and carbon as the negative electrode material; ternary polymer lithium battery refers to the positive electrode material using lithium nickel cobalt manganate (Li(NiCoMn) O ₂ ) or lithium battery with ternary cathode material of lithium nickel cobalt aluminate, both mainstream batteries use a large amount of lithium. As global electric vehicles replace traditional oil vehicles, lithium, which has limited reserves on the planet, is unable to cope with such rapid demand. Lithium is very sparsely distributed on the earth. Most of it is found in the "salt lakes" on the plateau, and some is found in associated ores. Both forms of reserves are poor ores, and the costs of mining and utilizing them are very high. , causing the price of lithium carbonate to rise, directly or indirectly causing the price of batteries and electric vehicles to skyrocket.

The main purpose of the Kyoto Protocol is to solve the problem of global warming. As a signatory, China has also issued a target time for "carbon peak and carbon neutrality". To solve the dual carbon problem, the traditional smelting, cement, and glass industries are the focus. It is undoubtedly more difficult for the glass industry. On the one hand, it must find alternative energy sources and reduce the use of petrochemical energy. On the other hand, from the perspective of glass formation, it is difficult to eliminate the emission of carbon dioxide, because the formation of glass is a process of silicate formation. This process mainly requires the use of a variety of carbonate materials mixed and melted with silica sand to achieve, during which the conversion of carbonate into silicate will release a large amount of carbon dioxide. From the perspective of silicate formation, reducing carbon dioxide emissions is determined by natural properties, which is very difficult and difficult to overcome.

Based on the above issues, what the applicant wants to say is that in the field of glass, people have an increasing demand for high strength, lightweight and high safety of glass. Ordinary glass can no longer meet human needs, and lithium-containing glass Glass is increasingly being invented and used in various fields. For example: aviation aircraft windshields and high-speed rail window glass with high safety and high strength requirements, high-strength and lightweight new energy automobile glass, lightweight, high-strength and high-transmittance electronic terminal cover glass, etc. The new glass used in these fields not only uses scarce lithium resources, but also releases large amounts of carbon dioxide during production.

In order to reduce the waste of lithium resources and the emission of carbon dioxide in the glass field, this application proposes a recycling method for alkali metal elements in plain glass. The recycling method includes the following steps S1 to S4.

Step S1: Place the first glass containing alkali metal elements and an alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain a solid product containing alkali metal elements.

It should be noted that the step S1 can be understood as a chemical strengthening process for plain glass containing alkali metal elements; ordinary plain glass contains at least SiO ₂ , Al ₂ O ₃ , and alkali metal element Li. The alkali metal element Elements exist in the form of covalent compounds or ionic compounds in the plain glass. Specifically, the plain glass contains: 39-75 mol% SiO ₂ , 0.5-30 mol% Li ₂ O, and 0-28 mol% Al. ₂ O ₃ , preferably, the plain glass contains: 39-75 mol% SiO ₂ , 0.5-29.8 mol% Li ₂ O, and 4.13-28 mol% Al ₂ O ₃ .

The ion exchange salt bath can be understood as the ion exchange salt bath mentioned above. The ion exchange salt bath contains the alkali metal elements in the form of ionic states. Specifically, the ion exchange salt bath contains The mass fraction of nitrate is greater than or equal to 50wt%;

The alkali metal ion fixative can be understood as the salt bath purification additive material mentioned above, which can quickly absorb lithium ions in the ion exchange salt bath. Specifically, the alkali metal ion fixative can be combined with the ionic state The compound in which the alkali metal element exists in the form of a precipitation reaction is preferably one or more combinations of silicate, phosphate, borate, and antimonate. More specifically, the alkali metal ion The fixative contains 20-65mol% SiO ₂ , 25-55mol% Na ₂ O, 0-16mol% Al ₂ O ₃ , 0-35mol% B ₂ O ₃ , 0-35mol% P ₂ O ₅ ; In the step S1, the alkali metal ion fixative absorbs the alkali metal element Li released from the first plain glass in the ion exchange salt bath and finally forms the solid product containing the alkali metal element Li. . It should be understood that in step S1, the plain glass will eventually form strengthened chemically strengthened glass with higher strength.

Of course, the alkali metal element Na may also be contained in the plain glass. Specifically, the plain glass also contains 0-17 mol% Na ₂ O. In the step S1, the alkali metal ion fixing agent absorbs Na from the alkali metal ion fixing agent. The alkali metal elements Li and Na released by the first plain glass in the ion exchange salt bath finally form the solid product containing the alkali metal elements Li and Na.

Step S2: Take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient.

In the above step S2, the pretreatment includes at least one of washing, drying, and crushing. It should be understood that the chemical composition of the solid product will not change only after the pretreatment, that is, , the chemical composition of the main solid ingredient obtained in the step S2 and the solid product obtained in the step S1 are the same, and the difference between the two lies in the physical properties and existence in different media. It should be understood that the alkali metal element exists in the form of a covalent compound or an ionic compound in both the solid product and the main solid ingredient. The most critical thing in this application is that the plain glass contains all the metal oxides contained in the solid product. In other words, the metal oxides contained in the main solid ingredients can be found in the plain glass. For example, if the main solid ingredient (for example, silicate, borate, phosphate or antimonate, etc.) contains lithium oxide, sodium oxide, silicon oxide, boron oxide, antimony oxide, etc., then the element Glass also corresponds to lithium oxide, sodium oxide, silicon oxide, boron oxide, antimony oxide, etc.

Step S3: Mix the auxiliary solid ingredients and the main solid ingredients to obtain a plain glass ingredient mixture.

In the above step S3, the auxiliary solid ingredients include ZrO, MgO, MgCO ₃ , CaO, CaCO ₃ , Na ₂ O, NaNO ₃ , NaCO ₃ , K ₂ O, KNO ₃ , K ₂ CO ₃ , B ₂ O ₃ , P ₂ O ₅ , Y ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , and at least one of NaCl; given that the main solid ingredients are silicate or borate, phosphate, and antimonate, these salts Oxygen cannot be provided when forming the virgin glass. If the addition ratio is too high, the virgin glass will form chemical bond structural defects such as silicon-oxygen bonds and bridge-oxygen bonds due to lack of oxygen, thus causing the glass to become brittle. Preferably, in the prime glass In the glass ingredient mixture, the mass percentage of the main solid ingredients is less than or equal to 50wt%, and the oxygen required for the chemical bond of the plain glass will be decomposed and formed by the oxides in the auxiliary solid ingredients, or by carbonates, nitrates, sulfates, etc. Supplied in the silicate process. The auxiliary solid ingredients and the main solid ingredients are mixed according to a certain proportion to obtain a raw glass ingredient mixture for preparing the raw glass. Preferably, the mass percentage of the main solid ingredients is less than or equal to 48.70wt%.

Step S4: The raw glass batch mixture is melted and prepared to obtain a second raw glass containing an alkali metal element.

In the above step S4, the plain glass batch mixture can be prepared into the corresponding plain glass using a conventional glass melting preparation method. Since the main solid batch in the plain glass batch mixture contains the alkali metal element Li, the corresponding plain glass The plain glass produced also contains the alkali metal element Li. On the other hand, the applicant would like to point out that in the preparation process of existing plain glass, the raw materials used are usually carbonates or sulfates. Therefore, the preparation process of existing plain glass will inevitably produce a large amount of CO ₂ and SO ₂ . In the recycling method of the present application, the main solid ingredients in the raw glass batch mixture used to prepare the second raw glass are silicate, phosphate, borate or antimonate, that is to say, in the During the melting and preparation process of the raw glass batch mixture, the main solid batch will not release CO ₂ and SO ₂ . Therefore, it can be understood that compared with the existing raw glass preparation method, the same amount of raw glass can be prepared. In this case, the emission of CO ₂ and SO ₂ can be significantly reduced by adopting the recycling method of this application.

In summary, it can be seen that in step S1, the alkali metal ion fixative absorbs the alkali metal element Li released from the first plain glass in the ion exchange salt bath and finally forms the alkali metal element Li-containing The solid product, and then the solid product containing the alkali metal element Li is recycled through the subsequent steps S2 to S4 as a raw material for preparing plain glass to obtain the corresponding second plain glass containing the alkali metal element Li . Thereby reducing the waste of lithium resources in the glass field. In addition, since CO ₂ and SO ₂ gas will not be generated in step S4, at the same time, the purpose of reducing carbon emissions and saving energy is achieved.

The present application also provides a kind of plain glass, which is prepared by the above-mentioned recycling method. The plain glass contains a shaped or amorphous structure, and the shaped structure includes at least one of lithium disilicate, lithium silicate, lucite, beta quartz, and spinel.

This application also provides a recycling system for alkali metal elements in plain glass. See Figure 1. The recycling system includes a raw material supply module, a processing and recovery module, and a reprocessing module.

Raw material supply module, used to manufacture the first prime glass and alkali metal ion fixative. Specifically, the raw material supply module may be a raw glass manufacturer, which is responsible for producing the first raw glass and alkali metal ion fixative whose composition meets the design value; it should be noted that the first raw glass manufacturer produces Plain glass and alkali metal ion fixatives will be sold to the processing and recycling module.

The processing and recycling module is used to place the first plain glass and the alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain strengthened chemically strengthened glass and a solid product containing alkali metal elements; The solid product is taken out from the ion exchange salt bath and pretreated to obtain the main solid ingredient. Specifically, the processing and recycling module includes a tempered glass manufacturer. Here, the tempered glass manufacturer is responsible for chemically strengthening the first prime glass using the first prime glass as raw material in accordance with the specifications and requirements of the prime glass manufacturer. To increase the strength of glass, chemically strengthened glass is obtained. That is, the first glass and an alkali metal ion fixative are placed together in an ion exchange salt bath to achieve chemical strengthening of the first glass. This process strengthens the first glass to Chemically strengthened glass, at the same time, the alkali metal ion fixative adsorbs the alkali metal ions released from the first glass to form the solid product; the strengthened glass manufacturer is also responsible for taking out the solid product from the ion exchange salt bath and After preprocessing, the main solid ingredients are obtained, which are then packaged and recorded in the warehouse for sale.

The reprocessing module is used to mix the auxiliary solid ingredients with the main solid ingredients to obtain a plain glass ingredient mixture; and is used to melt and prepare the plain glass ingredient mixture to obtain a second plain glass containing alkali metal elements. Specifically, the reprocessing module may be a raw glass manufacturer. It should be noted that the reprocessing module and the raw material supply module may be the same raw glass manufacturer. Here, the reprocessing module includes a detection unit and a calculation unit. Among them, the detection unit determines the composition of the main solid ingredients produced by the processing and recycling module; the calculation unit determines the components of the second plain glass and the content of each component and the detected components of the main solid ingredients. and the content of each component. The analysis results in the components of the auxiliary solid ingredients and the content of each component and the amount of the auxiliary solid ingredients added. The amount added is the mass of the auxiliary solid ingredients and the main solid ingredients. Compare. The reprocessing module also includes a manufacturing unit, which prepares the required auxiliary solid ingredients according to the components of the auxiliary solid ingredients and the content of each component obtained through analysis, and then prepares the required auxiliary solid ingredients according to the analysis of the auxiliary solid ingredients. The added amount of ingredients and the main solid ingredients are weighed, stirred, and kept warm according to a predetermined ratio to form a plain glass ingredient mixture. Finally, the plain glass ingredient mixture is put into the feeding section of the plain glass manufacturing process, so that it can be prepared Obtain the required second plain glass.

It should be noted that the calculation unit can be understood as a computer program. When the computer program is run, it realizes "according to the required components of the second plain glass and the content of each component and the detected main solid The components and contents of each component of the ingredients, and the analysis results in the components and contents of each component of the auxiliary solid ingredients and the amount of the auxiliary solid ingredients added."

Of course, it should be understood that the computer program can be stored in a computer storage medium, including read-only memory (Read-Only Memory, ROM), random access memory (Random Access Memory, RAM), programmable read-only memory (Programmable Read-only Memory (PROM), erasable programmable read-only memory (ErasableProgrammable Read Only Memory, EPROM), one-time programmable read-only memory (One-timeProgrammable Read-Only Memory, OTPROM), electronically erasable rewritable memory Electrically-Erasable Programmable Read-Only Memory (EEPROM), CompactDisc Read-Only Memory (CD-ROM) or other optical disk storage, magnetic disk storage, tape storage, or computers that can be used to carry or store data any other medium for reading.

In some other embodiments, the computing unit may be an intelligent device running or installing the above computer program. The intelligent device includes a processor and a memory; the memory stores the above computer program; the processor is used to run the computer program to achieve "according to the required components of the second plain glass and the content of each component. The detected components and contents of each component of the main solid ingredients are analyzed to obtain the components and contents of each component of the auxiliary solid ingredients and the added amount of the auxiliary solid ingredients. Specifically, the smart device may be a computer, a laptop, or other device with computing and storage functions.

In order to have a clearer understanding of the technical features, purposes and effects of the present invention, specific implementation modes of the present invention will now be described in detail. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In order to better explain each specific embodiment, here are listed:

There are 26 specific primary glasses with different component contents. The symbols of these 26 different primary glasses are RG-1 to RG-26 respectively. The first primary glasses RG-1 to RG-26 are listed below in Table 1. The components and content of each component (mol%) of the first porcelain glass RG-8 are listed in Table 2. The components and content of each component of the first porcelain glass RG-9 to the first porcelain glass RG-18 are listed in Table 2 ( mol%), the components of the first crystal glass RG-18 to the first crystal glass RG-26 and the content of each component (mol%) are listed in Table 3.

There are 11 kinds of alkali metal ion fixatives with different component contents. The symbols of these 11 different alkali metal ion fixatives are pre-S-1 to pre-S-11 respectively. The alkali metal ion fixatives are listed below in Table 4. The components of the agent pre-S-1 to the alkali metal ion fixative pre-S-11 and the content of each component (mol%); among them, the alkali metal ion fixatives pre-S-1 to pre-S-8 are silicon The alkali metal ion fixative pre-S-9 is a phosphate, the alkali metal ion fixative pre-S-10 is a borate, and the alkali metal ion fixative pre-S-11 is an antimonate; the above 11 types The raw material formulas of alkali metal ion fixatives pre-S-1 to pre-S-11 are shown in Table 5;

There are 8 kinds of auxiliary solid ingredients with different component contents. The marks of these 8 different auxiliary solid ingredients are AS-1 to AS-8 respectively. The auxiliary solid ingredients AS-1 to auxiliary solid ingredients AS- are listed below in Table 6. 8 components and content (parts) of each component.

Table 1

成份名称Ingredient name	RG-1RG-1	RG-2RG-2	RG-3RG-3	RG-4RG-4	RG-5RG-5	RG-6RG-6	RG-7RG-7	RG-8RG-8
SiO ₂ SiO ₂	65.75％65.75%	68.25％68.25%	59.75％59.75%	70.75％70.75%	64.75％64.75%	62.75％62.75%	69.25％69.25%	54.75％54.75%
Al ₂O ₃ Al ₂ O ₃	8.00％8.00%	9.50％9.50%	10.00％10.00%	7.00％7.00%	15.00％15.00%	10.00％10.00%	8.00％8.00%	18.00％18.00%
P ₂O ₅ P ₂ O ₅	0.50％0.50%					1.00％1.00%		6.80％6.80%
B ₂O ₃ B ₂ O ₃					0.50％0.50%	0.50％0.50%	3.50％3.50%	0.20％0.20%
Li ₂O Li ₂ O	1.00％1.00%	14.00％14.00%	3.50％3.50%	7.50％7.50%	11.00％11.00%	8.50％8.50%	0.50％0.50%	1.00％1.00%
MgOMgO	10.00％10.00%	7.20％7.20%	3.40％3.40%	7.00％7.00%	2.00％2.00%	6.00％6.00%	7.30％7.30%	3.00％3.00%
CaOCaO		0.10％0.10%	0.80％0.80%
SrOsO
BaOBO
ZnOZnO
ZrO ₂ ZrO ₂	0.40％0.40%		0.50％0.50%	1.00％1.00%		1.30％1.30%
TiO ₂ TiO ₂				0.50％0.50%			0.50％0.50%
Na ₂O Na ₂ O	12.60％12.60%		16.70％16.70%	5.00％5.00%	5.00％5.00%	7.00％7.00%	9.50％9.50%	16.00％16.00%
K ₂O K ₂ O	1.50％1.50%	0.70％0.70%	5.10％5.10%	1.00％1.00%	1.50％1.50%	1.70％1.70%	1.20％1.20%

Sb ₂O ₃ Sb ₂ O ₃	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%
Y ₂O ₃ Y ₂ O ₃						1.00％1.00%

Table 2

table 3

成份名称Ingredient name	RG-18RG-18	RG-19RG-19	RG-20RG-20	RG-21RG-21	RG-22RG-22	RG-23RG-23	RG-24RG-24	RG-25RG-25	RG-26RG-26
SiO ₂ SiO ₂	39.00％39.00%	71.75％71.75%	60.25％60.25%	64.95％64.95%	53.95％53.95%	68.75％68.75%	68.51％68.51%	67.45％67.45%	43.75％43.75%
Al ₂O ₃ Al ₂ O ₃	25.75％25.75%	7.50％7.50%	11.00％11.00%	7.50％7.50%	6.00％6.00%	4.20％4.20%	4.13％4.13%	14.30％14.30%	28.00％28.00%
P ₂O ₅ P ₂ O ₅				1.00％1.00%	1.95％1.95%	0.80％0.80%	0.81％0.81%	0.45％0.45%
B ₂O ₃ B ₂ O ₃	5.00％5.00%			2.50％2.50%	0.15％0.15%	1.50％1.50%	1.49％1.49%		0.50％0.50%
Li ₂O Li ₂ O	15.00％15.00%	8.00％8.00%	1.00％1.00%	15.00％15.00%	29.80％29.80%	21.30％21.30%	20.71％20.71%	11.45％11.45%	4.50％4.50%
MgOMgO	5.00％5.00%	5.00％5.00%	10.50％10.50%	1.60％1.60%	0.70％0.70%		0.98％0.98%	1.60％1.60%	5.50％5.50%
CaOCaO		0.20％0.20%	0.80％0.80%	0.50％0.50%
SrOsO
BaOBO
ZnOZnO				2.20％2.20%			0.98％0.98%	1.60％1.60%	10.30％10.30%
ZrO ₂ ZrO ₂	2.00％2.00%	1.00％1.00%		3.20％3.20%	3.00％3.00%	1.70％1.70%	1.69％1.69%	0.90％0.90%	3.60％3.60%
TiO ₂ TiO ₂			4.20％4.20%					1.30％1.30%
Na ₂O Na ₂ O		5.30％5.30%	11.00％11.00%	0.80％0.80%	2.40％2.40%	1.50％1.50%	0.45％0.45%	0.50％0.50%	3.60％3.60%
K ₂O K ₂ O		1.00％1.00%	1.00％1.00%	0.50％0.50%	1.10％1.10%			0.20％0.20%
Sb ₂O ₃ Sb ₂ O ₃	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%	0.25％0.25%
Y ₂O ₃ Y ₂ O ₃	8.00％8.00%				0.70％0.70%

Table 4

Element

pre-S-

名称name	11	22	33	44	55	66	77	88	99	1010	1111
SiO ₂ SiO ₂	60.3％60.3%	52％52%	48％48%	48％48%	40％40%	40％40%	40％40%	28％28%	20％20%	25％25%	20％20%
Al ₂O ₃ Al ₂ O ₃	7.7％7.7%	16％16%	10％10%	10％10%	10％10%	10％10%			5％5%	5％5%	5％5%
Na ₂O Na ₂ O	28.8％28.8%	32％32%	30％30%	30％30%	36％36%	36％36%	45％45%	54％54%	35％35%	35％35%	35％35%
B ₂O ₃ B ₂ O ₃	3.1％3.1%			12％12%		14％14%				35％35%
Sb ₂O ₃ Sb ₂ O ₃											35％35%
P ₂O ₅ P ₂ O ₅			12％12%		14％14%		15％15%	18％18%	40％40%		5％5%

table 5

Table 6

Example 1

In this embodiment, the above-mentioned first glass RG-7, alkali metal ion fixative pre-S-1, and auxiliary solid ingredient AS-1 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-7 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-1 in the first ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and the corresponding 1500 pieces of first strengthened glass; among them, the amount of alkali metal ion fixative pre-S-1 added is 0.5 of the mass of the first ion exchange salt bath %; the first ion exchange salt bath is a pure NaNO ₃ salt bath; the ion exchange conditions are a temperature of 420°C and a time of 45 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the first ion exchange salt bath after the reaction The Li+ concentration in the glass is 10ppm; an Orihara SLP2000 scattered light laser stress meter was used to sample 1,500 pieces of the first tempered glass, and it was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) of the first chemically strengthened glass is 80Mpa , DOL_0 (compressive stress depth) is 128um, CT_CV (internal tensile stress maximum value) is 35Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-1; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-1. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement, and the measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-1 was measured as: SiO ₂ 56.8wt%, Al ₂ O ₃ 12.3wt%, Na ₂ O 27.1wt%, Li ₂ O 0.4wt%, B ₂ O ₃ 3.4wt%. It is not difficult to find that the first plain glass RG-7 contains all kinds of elements contained in the main solid ingredient post-S-1.

Step S3, mix the auxiliary solid ingredient AS-1 with the main solid ingredient post-S-1 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-1 in the plain glass ingredient mixture is 30.24%.

Step S4: The raw glass batch mixture is melted and prepared to obtain the second raw glass RG'-7 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicate formation, glass formation, clarification, The stages of glass liquid homogenization and glass liquid cooling; in order to prove that the second plain glass RG'-7 contains Li element, and the content of Li element is greater than the Li element in the added auxiliary solid ingredient AS-1. Content, we also measured the composition of the second prime glass RG'-7. The measurement results show that the components of the second prime glass RG'-7 and the mass percentage of each component are approximately: SiO ₂ 65.59wt%, Al ₂ O ₃ 12.86wt%, B ₂ O ₃ 3.84wt%, Li ₂ O 0.24wt%, MgO 4.64wt%, TiO ₂ 0.63wt%, Na ₂ O 9.28wt%, K ₂ O 1.78wt%, Sb ₂ O ₃ 1.15wt%. Obviously, the second plain glass RG'-7 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-1. That is to say, the main solid ingredient post-S The Li element in -1 eventually entered the second prime glass RG'-7. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-7 and the mole percentage of each component are: SiO ₂ 69.25%, Al ₂ O ₃ 8.00%, B ₂ O ₃ 3.50 %, Li ₂ O 0.50%, MgO 7.30%, TiO ₂ 0.50%, Na ₂ O 9.50%, K ₂ O 1.20%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and contents of each component of the second plain glass RG'-7 are completely consistent with those of the first plain glass RG-7.

Example 2

In this embodiment, the above-mentioned first glass RG-10, alkali metal ion fixative pre-S-6, and auxiliary solid ingredient AS-2 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-10 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-6 in the second ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and corresponding 1500 pieces of second strengthened glass; among them, the amount of alkali metal ion fixative pre-S-6 added is 1.0 of the mass of the second ion exchange salt bath %; the second ion exchange salt bath is a NaNO ₃ salt bath containing 150 ppmLi+; the ion exchange conditions are a temperature of 410°C and a time of 90 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the second ion exchange after the reaction The Li+ concentration in the salt bath is 70ppm; an Orihara SLP2000 scattered light laser stress meter was used to sample 1500 pieces of second-strengthened glass, and it was found that the CS_50 of the second chemically strengthened glass (corresponding surface compressive stress when the ion exchange depth is 50um) The value is 190Mpa, the DOL_0 (compressive stress depth) value is 135um, and the CT_CV (internal tensile stress maximum value) is 65Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-6; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-6. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-6 was measured as: SiO ₂ 39.1wt%, Al ₂ O ₃ 16.6wt%, Na ₂ O 21.0wt%, Li ₂ O 7.4wt%, B ₂ O ₃ 15.9wt%. It is not difficult to find that the first plain glass RG-10 contains all kinds of elements contained in the main solid ingredient post-S-6.

Step S3, mix the auxiliary solid ingredient AS-2 with the main solid ingredient post-S-6 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-6 in the plain glass ingredient mixture is 9.62%.

Step S4: The raw glass batch mixture is melted and prepared to obtain the second raw glass RG'-10 containing alkali metal elements; it should be understood that the process of melting and preparing roughly includes silicate formation, glass formation, clarification, The stages of glass liquid homogenization and glass liquid cooling; in order to prove that the second plain glass RG'-10 contains Li element, and the content of Li element is greater than the Li element in the added auxiliary solid ingredient AS-2 Content, we also measured the composition of the second prime glass RG'-10. The measurement results show that the composition of the second prime glass RG'-10 and the mass percentage of each component are approximately: SiO ₂ 71.08wt%, Al ₂ O ₃ 17.29wt%, B ₂ O ₃ 3.29wt%, Li ₂ O 3.30wt%, MgO 0.15wt%, ZnO 1.03wt%, Na ₂ O 2.35wt%, Sb ₂ O ₃ 1.15wt%. Obviously, the second plain glass RG'-10 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-2. That is to say, the main solid ingredient post-S The Li element in -6 eventually entered the second prime glass RG'-10. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-10 and the mole percentage of each component are: SiO ₂ 75.00%, Al ₂ O ₃ 10.75%, B ₂ O ₃ 3.00 %, Li ₂ O 7.00%, MgO 0.80%, ZnO 0.80%, Na ₂ O 2.40%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and content of each component of the second plain glass RG'-10 are completely consistent with those of the first plain glass RG-10.

Example 3

In this embodiment, the above-mentioned first prime glass RG-12, alkali metal ion fixative pre-S-2, and auxiliary solid ingredient AS-3 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-12 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-2 in the third ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and corresponding 1500 pieces of third strengthened glass; among them, the amount of alkali metal ion fixative pre-S-2 added is 0.5 of the mass of the third ion exchange salt bath %; the third ion exchange salt bath is a pure NaNO ₃ salt bath; the ion exchange conditions are a temperature of 390°C and a time of 60 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the third ion exchange salt bath after the reaction The Li+ concentration in the glass is 50ppm; an Orihara SLP2000 scattered light laser stress meter was used to sample 1,500 pieces of third-strengthened glass, and it was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) value of the third chemically strengthened glass is: 180Mpa, DOL_0 (compressive stress depth) value is 121um, CT_CV (internal tensile stress maximum value) is 65Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-2; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-2. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-2 was determined to be: SiO ₂ 48.7wt%, Al ₂ O ₃ 25.4wt%, Na ₂ O 21.2wt%, Li ₂ O 4.7wt%. It is not difficult to find that the first plain glass RG-12 contains all kinds of elements contained in the main solid ingredient post-S-6.

Step S3, mix the auxiliary solid ingredient AS-3 with the main solid ingredient post-S-2 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-2 in the plain glass ingredient mixture is 48.70%.

Step S4: The raw glass batch mixture is melted and prepared to obtain the second raw glass RG'-12 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicate formation, glass formation, clarification, The stages of glass liquid homogenization and glass liquid cooling; in order to prove that the second plain glass RG'-12 contains Li element, and the content of Li element is greater than the Li element in the added auxiliary solid ingredient AS-3. Content, we also measured the composition of the second prime glass RG'-12. The measurement results show that the components of the second prime glass RG'-12 and the mass percentage of each component are approximately: SiO ₂ 62.18wt%, Al ₂ O ₃ 17.27wt%, B ₂ O ₃ 0.56wt%, Li ₂ O 3.68wt%, MgO 2.25wt%, ZnO 1.30wt%, Na ₂ O 11.59wt%, Sb ₂ O ₃ 1.16wt%. Obviously, the second plain glass RG'-12 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-3. That is to say, the main solid ingredient post-S The Li element in -2 eventually entered the second prime glass RG'-12. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-12 and the mole percentage of each component are: SiO ₂ 64.75%, Al ₂ O ₃ 10.60%, B ₂ O ₃ 0.50 %, Li ₂ O 7.70%, MgO 3.50%, ZnO 1.00%, Na ₂ O 11.70%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and contents of each component of the second plain glass RG'-12 are completely consistent with those of the first plain glass RG-12.

Example 4

In this embodiment, the above-mentioned first glass RG-16, alkali metal ion fixative pre-S-2, and auxiliary solid ingredient AS-4 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-16 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-2 in the fourth ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and corresponding 1500 pieces of fourth strengthened glass; among them, the amount of alkali metal ion fixative pre-S-2 added is 5.0 of the mass of the fourth ion exchange salt bath %; the fourth ion exchange salt bath is a NaNO ₃ salt bath containing 300 ppmLi+; the ion exchange conditions are a temperature of 390°C and a time of 300 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the fourth ion exchange after the reaction The Li+ concentration in the salt bath is 80 ppm.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-2; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-2. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-2 was measured as: SiO ₂ 50.1wt%, Al ₂ O ₃ 26.2wt%, Na ₂ O 16.2wt%, Li ₂ O 7.6wt%. It is not difficult to find that the first plain glass RG-16 contains all kinds of elements contained in the main solid ingredient post-S-2.

Step S3, mix the auxiliary solid ingredient AS-4 with the main solid ingredient post-S-2 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-2 in the plain glass ingredient mixture is 18.80%.

Step S4: The raw glass batch mixture is melted and prepared to obtain the second raw glass RG'-16 containing alkali metal elements; it should be understood that the process of melting and preparing roughly includes silicate formation, glass formation, clarification, The stages of glass liquid homogenization and glass liquid cooling; in order to prove that the second plain glass RG'-16 contains Li element, and the content of Li element is greater than the Li element in the added auxiliary solid ingredient AS-4 Content, we also measured the composition of the second prime glass RG'-16. The measurement results show that the components of the second prime glass RG'-16 and the mass percentage of each component are approximately: SiO ₂ 29.09wt%, Al ₂ O ₃ 32.6wt%, Li ₂ O 5.57wt%, MgO 2.50wt%, ZrO 3.06%, Na ₂ O 3.85wt%, Sb ₂ O ₃ 0.9wt%, Y ₂ O ₃ 22.43wt%. Obviously, the second plain glass RG'-16 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-4. That is to say, the main solid ingredient post-S The Li element in -2 eventually entered the second prime glass RG'-16. Further, by converting the mass percentage into mole percentage, the components of the second prime glass RG'-16 and the mole percentage of each component are: SiO ₂ 39.00%, Al ₂ O ₃ 25.75%, Li ₂ O 15.00% , MgO 5.00%, ZrO 2.00%, Na ₂ O 5.00%, Sb ₂ O ₃ 0.25%, Y ₂ O ₃ 8.00%. It is not difficult to see from this that the components and contents of each component of the second plain glass RG'-16 are completely consistent with those of the first plain glass RG-16.

Example 5

In this embodiment, the above-mentioned first glass RG-22, alkali metal ion fixative pre-S-3, and auxiliary solid ingredient AS-5 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-22 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-3 in the fifth ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and the corresponding 1500 pieces of fifth strengthened glass; among them, the amount of alkali metal ion fixative pre-S-3 added is 2.0 of the mass of the fifth ion exchange salt bath %; the fifth ion exchange salt bath is a pure NaNO ₃ salt bath; the ion exchange conditions are a temperature of 460°C and a time of 480 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the fifth ion exchange salt bath after the reaction The Li+ concentration in is 50ppm. The Orihara SLP2000 scattered light laser stress meter was used to sample 1,500 pieces of fifth-strengthened glass. It was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) value of the fifth chemically strengthened glass was 80Mpa, and DOL_0 (compressive stress depth) ) value is 131um, CT_CV (maximum internal tensile stress) 48Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-3; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-3. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-3 was determined to be: SiO ₂ 41wt%, Al ₂ O ₃ 14.5wt%, Na ₂ O 14.5wt%, Li ₂ O 5.8wt%, P ₂ O ₅ 24.2wt%. It is not difficult to find that the first plain glass RG-22 contains all kinds of elements contained in the main solid ingredient post-S-3.

Step S3, mix the auxiliary solid ingredient AS-5 with the main solid ingredient post-S-3 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-3 in the plain glass ingredient mixture is 12.38%.

Step S4: The plain glass batch mixture is subjected to melting preparation, nucleation treatment and crystallization treatment to obtain the second plain glass RG'-22 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicic acid Nucleation treatment in the stages of salt formation, glass formation, clarification, glass liquid homogenization and glass liquid cooling is to heat the base glass prepared by melting for a period of time under certain high temperature conditions to form crystal nuclei; crystallization treatment, The base material glass that forms the crystal nucleus is heat treated for a period of time under certain high temperature conditions to precipitate crystals. In this embodiment, the specific nucleation treatment is heat treatment at 525°C for 200 minutes, and the crystallization treatment is heat treatment at 700°C for 200 minutes. In order to prove that the second plain glass RG'-22 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-5, we also tested the second plain glass RG'-22 The composition of the second plain glass RG'-22 was measured. The measurement results show that the components of the second plain glass RG'-22 and the mass percentage of each component are approximately: SiO ₂ 54.83wt%, Al ₂ O ₃ 10.35wt%, P ₂ O ₅ 4.68wt %, B ₂ O ₃ 0.18wt%, Li ₂ O 15.06wt%, MgO 0.48wt%, ZrO ₂ 6.25wt%, Na ₂ O 2.52wt%, K ₂ O 1.75wt%, Sb ₂ O ₃ 1.23wt%, Y ₂ O ₃ 2.67wt%. Obviously, the second plain glass RG'-22 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-5. That is to say, the main solid ingredient post-S The Li element in -3 eventually entered the second prime glass RG'-22. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-22 and the mole percentage of each component are: SiO ₂ 53.95%, Al ₂ O ₃ 6.00%, P ₂ O ₅ 1.95 %, B ₂ O ₃ 0.15%, Li ₂ O 29.80%, MgO 0.70%, ZrO ₂ 3.00%, Na ₂ O 2.40%, K ₂ O 1.10%, Sb ₂ O ₃ 0.25%, Y ₂ O ₃ 0.70%. It is not difficult to see from this that the components and content of each component of the second plain glass RG'-22 are completely consistent with those of the first plain glass RG-22. In order to prove that the second plain glass RG'-22 prepared in this example contains a stereotyped structure, we also conducted XRD detection on the second plain glass RG'-22. The test results are shown in Figure 2. You can see in Figure 2 The second prime glass, RG'-22, contains lithium silicate with a fixed structure. Among them, the parameters of the XRD test instrument are set as:

Target line requirements: Cu target line;

Scanning method: using Cu target line, step width 0.02°;

Tube current setting: current 20-50mA;

Tube voltage setting: voltage 20-50kV;

Angle range: 10°-50° or 10°-80°;

Instrument selection: Shimadzu XRD_6100;

The X-ray diffractometer uses a Cu target, X-ray wavelength λ (Cu kα) = 0.1540476nm, voltage 40mV, current 30mA, test range 10°-50°, scanning speed 6°/min, and step length setting of 0.02°/step.

Example 6

In this embodiment, the above-mentioned first prime glass RG-23, alkali metal ion fixative pre-S-9, and auxiliary solid ingredient AS-6 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-23 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-9 in the sixth ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and corresponding 1500 pieces of sixth strengthened glass; among them, the amount of alkali metal ion fixative pre-S-9 added is 2.0 of the mass of the sixth ion exchange salt bath %; the sixth ion exchange salt bath is a NaNO ₃ salt bath containing 80 ppmLi+; the ion exchange conditions are a temperature of 450°C and a time of 420 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the sixth ion exchange after the reaction The Li+ concentration in the salt bath is 70 ppm. The Orihara SLP2000 scattered light laser stress meter was used to sample 1,500 pieces of sixth tempered glass. It was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) value of the sixth chemically strengthened glass was 120Mpa, and DOL_0 (compressive stress depth) ) value is 118um, CT_CV (maximum internal tensile stress) 45Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-9; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-9. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement, and the measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-9 was determined to be: SiO ₂ 13.2wt%, Al ₂ O ₃ 5.6wt%, Na ₂ O 13.8wt%, Li ₂ O 4.9wt%, P ₂ O ₅ 62.5wt%. It is not difficult to find that the first plain glass RG-23 contains all kinds of elements contained in the main solid ingredient post-S-9.

Step S3, mix the auxiliary solid ingredient AS-6 with the main solid ingredient post-S-9 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-9 in the plain glass ingredient mixture is 2.57%.

Step S4: The plain glass batch mixture is subjected to melting preparation, nucleation treatment and crystallization treatment to obtain the second plain glass RG'-23 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicic acid Nucleation treatment in the stages of salt formation, glass formation, clarification, glass liquid homogenization and glass liquid cooling is to heat the base glass prepared by melting for a period of time under certain high temperature conditions to form crystal nuclei; crystallization treatment, The base material glass that forms the crystal nucleus is heat treated for a period of time under certain high temperature conditions to precipitate crystals. In this embodiment, the specific nucleation treatment is heat treatment at 538°C for 240 minutes, and the crystallization treatment is first heat treatment at 612°C for 240 minutes, and then heat treatment at 637°C for 240 minutes. In order to prove that the second plain glass RG'-23 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-6, we also tested the second plain glass RG'-23 The composition of the second plain glass RG'-23 was measured. The measurement results showed that the components of the second plain glass RG'-23 and the mass percentage of each component were approximately: SiO ₂ 71.36wt%, Al ₂ O ₃ 7.40wt%, P ₂ O ₅ 1.96wt %, B ₂ O ₃ 1.80wt%, Li ₂ O 10.99wt%, ZrO ₂ 3.62wt%, Na ₂ O 1.61wt%, Sb ₂ O ₃ 1.26wt%. Obviously, the second plain glass RG'-23 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-6. That is to say, the main solid ingredient post-S The Li element in -9 eventually entered the second prime glass RG'-23. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-23 and the mole percentage of each component are: SiO ₂ 68.75%, Al ₂ O ₃ 4.20%, P ₂ O ₅ 0.80 %, B ₂ O ₃ 1.50%, Li ₂ O 21.30%, ZrO ₂ 1.70%, Na ₂ O 1.50%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and contents of each component of the second plain glass RG'-23 are completely consistent with those of the first plain glass RG-23. In order to prove that the second plain glass RG'-23 prepared in this example contains a stereotyped structure, we also conducted XRD detection on the second plain glass RG'-23. The test results are shown in Figure 3. You can see in Figure 3 The second prime glass RG'-23 contains lithium disilicate 820 with a fixed structure. Among them, the parameters of the XRD test instrument are set as:

Target line requirements: Cu target line;

Scanning method: using Cu target line, step width 0.02°;

Tube current setting: current 20-50mA;

Tube voltage setting: voltage 20-50kV;

Angle range: 10°-50° or 10°-80°;

Instrument selection: Shimadzu XRD_6100;

The X-ray diffractometer uses a Cu target, X-ray wavelength λ (Cu kα) = 0.1540476nm, voltage 40mV, current 30mA, test range 10°-80°, scanning speed 6°/min, and step length setting of 0.02°/step.

Example 7

In this embodiment, the above-mentioned first glass RG-24, alkali metal ion fixative pre-S-11, and auxiliary solid ingredient AS-7 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-24 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-11 in the seventh ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and the corresponding 1500 pieces of seventh strengthened glass; among them, the amount of alkali metal ion fixative pre-S-11 added is 2.0 of the mass of the seventh ion exchange salt bath %; the seventh ion exchange salt bath is a NaNO ₃ salt bath containing 80 ppmLi+; the ion exchange conditions are a temperature of 450°C and a time of 420 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption instrument to quantitatively measure the seventh ion exchange after the reaction The Li+ concentration in the salt bath is 80 ppm. Orihara SLP2000 scattered light laser stress meter was used to sample 1,500 pieces of the seventh tempered glass. It was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) value of the seventh chemically strengthened glass was 90Mpa, and DOL_0 (compressive stress depth) ) value is 120um, CT_CV (maximum internal tensile stress) 46Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-11; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-11. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-11 was determined to be: SiO ₂ 8.4wt%, Al ₂ O ₃ 3.6wt%, Na ₂ O 8.8wt%, Li ₂ O 3.1wt%, Sb ₂ O ₃ 71.3wt%, P ₂ O ₅ 5.0wt%. It is not difficult to find that the first plain glass RG-24 contains all kinds of elements contained in the main solid ingredient post-S-11.

Step S3, mix the auxiliary solid ingredient AS-7 with the main solid ingredient post-S-11 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-11 in the plain glass ingredient mixture is 0.86%.

Step S4: The plain glass batch mixture is subjected to melting preparation, nucleation treatment and crystallization treatment to obtain the second plain glass RG'-24 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicic acid Nucleation treatment in the stages of salt formation, glass formation, clarification, glass liquid homogenization and glass liquid cooling is to heat the base glass prepared by melting for a period of time under certain high temperature conditions to form crystal nuclei; crystallization treatment, The base material glass that forms the crystal nucleus is heat treated for a period of time under certain high temperature conditions to precipitate crystals. In this embodiment, the specific nucleation treatment is heat treatment at 555°C for 200 minutes, and the crystallization treatment is first heat treatment at 610°C for 200 minutes, and then heat treatment at 650°C for 140 minutes. In order to prove that the second plain glass RG'-24 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-7, we also tested the second plain glass RG'-24 The composition of the second plain glass RG'-24 was measured. The measurement results show that the components of the second plain glass RG'-24 and the mass percentage of each component are approximately: SiO ₂ 70.94wt%, Al ₂ O ₃ 7.26wt%, P ₂ O ₅ 1.97wt %, B ₂ O ₃ 1.79wt%, Li ₂ O 10.67wt%, MgO 0.68wt%, ZnO 1.38wt%, ZrO ₂ 3.59wt%, Na ₂ O 0.48wt%, Sb ₂ O ₃ 1.26wt%. Obviously, the second plain glass RG'-24 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-7. That is to say, the main solid ingredient post-S The Li element in -11 eventually entered the second prime glass RG'-24. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-24 and the mole percentage of each component are: SiO ₂ 68.51%, Al ₂ O ₃ 4.13%, P ₂ O ₅ 0.81 %, B ₂ O ₃ 1.49%, Li ₂ O 20.71%, MgO 0.98%, ZnO 0.98%, ZrO ₂ 1.69%, Na ₂ O 0.45%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and contents of each component of the second plain glass RG'-24 are completely consistent with those of the first plain glass RG-24. In order to prove that the second plain glass RG'-24 prepared in this example contains a stereotyped structure, we also conducted XRD detection on the second plain glass RG'-24. The test results are shown in Figure 4. You can see in Figure 4 To date, the first prime glass RG'-24 contains lithium disilicate 820 with a fixed structure. Among them, the parameters of the XRD test instrument are set as:

Target line requirements: Cu target line;

Scanning method: using Cu target line, step width 0.02°;

Tube current setting: current 20-50mA;

Tube voltage setting: voltage 20-50kV;

Angle range: 10°-50° or 10°-80°;

Instrument selection: Shimadzu XRD_6100;

Example 8

In this embodiment, the above-mentioned first glass RG-26, alkali metal ion fixative pre-S-10, and auxiliary solid ingredient AS-8 are selected as raw materials to implement the recycling method provided by this application. The specific implementation process includes the following steps S1 to S4.

Step S1, place 1500 pieces of the first plain glass RG-26 with dimensions of length × width × thickness = 146mm × 74mm × 0.65mm and the alkali metal ion fixative pre-S-10 in the eighth ion exchange salt with a mass of 1200kg React in the bath for a certain period of time to obtain a solid product containing alkali metal elements and the corresponding 1500 pieces of the eighth strengthened glass; among them, the amount of the alkali metal ion fixative pre-S-10 added is 2.0 of the mass of the eighth ion exchange salt bath %; the eighth ion exchange salt bath is a pure NaNO ₃ salt bath; the ion exchange conditions are a temperature of 480°C and a time of 420 minutes; after the reaction is completed, use a Shimadzu AA-6880 atomic absorption meter to quantitatively measure the eighth ion exchange salt bath after the reaction The Li+ concentration in is 30ppm. Orihara SLP2000 scattered light laser stress meter was used to sample 1500 pieces of the eighth tempered glass. It was found that the CS_50 (corresponding surface compressive stress when the ion exchange depth is 50um) value of the eighth chemically strengthened glass was 70Mpa, and DOL_0 (compressive stress depth) ) value is 150um, CT_CV (maximum internal tensile stress) 51Mpa.

Step S2, take out the solid product from the ion exchange salt bath and perform pretreatment to obtain the main solid ingredient post-S-10; wherein the pretreatment specifically involves cleaning and removing the salt bath components condensed on the surface of the solid product. The post-drying process; here, we also measured the chemical composition of the main solid ingredient post-S-10. Among them, Na and Li were quantitatively measured using a Shimadzu AA-6880 atomic absorption meter, and other elements were measured using a ThermoFisher 4200 X-ray Fluorescence spectrometer (XRF) was used for quantitative measurement. The measurement results were reviewed and normalized by manual measurement to form a ratio. The final composition of the main solid ingredient post-S-10 was determined to be: SiO ₂ 23.6wt%, Al ₂ O ₃ 8.0wt%, Na ₂ O 26.5wt%, Li ₂ O 3.7wt%, B ₂ O ₃ 38.3wt%. It is not difficult to find that the first plain glass RG-26 contains all kinds of elements contained in the main solid ingredient post-S-10.

Step S3, mix the auxiliary solid ingredient AS-8 with the main solid ingredient post-S-10 to obtain a plain glass ingredient mixture; wherein the mass proportion of the main solid ingredient post-S-10 in the plain glass ingredient mixture is 0.96%.

Step S4: The plain glass batch mixture is subjected to melting preparation, nucleation treatment and crystallization treatment to obtain the second plain glass RG'-26 containing alkali metal elements; it should be understood that the melting preparation process generally includes silicic acid Nucleation treatment in the stages of salt formation, glass formation, clarification, glass liquid homogenization and glass liquid cooling is to heat the base glass prepared by melting for a period of time under certain high temperature conditions to form crystal nuclei; crystallization treatment, The base material glass that forms the crystal nucleus is heat treated for a period of time under certain high temperature conditions to precipitate crystals. In this embodiment, the specific nucleation treatment is heat treatment at 710°C for 240 minutes, and the crystallization treatment is heat treatment at 760°C for 240 minutes. In order to prove that the second plain glass RG'-26 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-8, we also tested the second plain glass RG'-26 The composition of the second plain glass RG'-26 was measured. The measurement results show that the components of the second plain glass RG'-26 and the mass percentage of each component are approximately: SiO ₂ 35.27wt%, Al ₂ O ₃ 38.31wt%, B ₂ O ₃ 0.47wt %, Li ₂ O 1.80wt%, MgO 2.97wt%, ZnO 11.25wt%, ZrO ₂ 5.95wt%, Na ₂ O 2.99wt%, Sb ₂ O ₃ 0.98wt%. Obviously, the second plain glass RG'-26 contains Li element, and the content of Li element is greater than the content of Li element in the added auxiliary solid ingredient AS-8. That is to say, the main solid ingredient post-S The Li element in -10 eventually entered the second prime glass RG'-26. Further, by converting the mass percentage into mole percentage, the components of the second plain glass RG'-26 and the mole percentage of each component are: SiO ₂ 43.75%, Al ₂ O ₃ 28.00%, B ₂ O ₃ 0.50 %, Li ₂ O 4.50%, MgO 5.50%, ZnO 10.30%, ZrO ₂ 3.60%, Na ₂ O 3.60%, Sb ₂ O ₃ 0.25%. It is not difficult to see from this that the components and content of each component of the second plain glass RG'-26 are completely consistent with those of the first plain glass RG-26. In order to prove that the second prime glass RG'-26 prepared in this example contains a stereotyped structure, we also conducted XRD detection on the second prime glass RG'-26. The detection results are shown in Figure 5. You can see in Figure 5 To date, the first prime glass, RG'-26, contains a fixed structure of spinel. Among them, the parameters of the XRD test instrument are set as:

Target line requirements: Cu target line;

Scanning method: using Cu target line, step width 0.02°;

Tube current setting: current 20-50mA;

Tube voltage setting: voltage 20-50kV;

Angle range: 10°-50° or 10°-80°;

Instrument selection: Shimadzu XRD_6100;

Based on the above-mentioned Examples 1-8, it can be learned that plain glass containing alkali metal elements can be prepared through the recycling method provided by the present application. In addition, comparing the content of Li or Na element in the finally obtained plain glass and the corresponding auxiliary solid ingredient, it can be seen that the content of Li or Na element in the finally obtained plain glass is greater than the content of Li or Na element in the auxiliary solid ingredient. Then it can be inferred without any doubt that the corresponding main solid ingredient contains Li or Na elements, and the main solid ingredient is obtained from the physical change of the solid product, and the solid product is made from an alkali that originally does not contain Li or Na elements. The metal ion fixative is formed by absorbing the Li ions or Na ions released from the first glass in the ion exchange salt bath. From this, it can be seen that the Li or Na element contained in the main solid ingredients essentially comes from the first glass, that is That is to say, the Li ions or Na ions released from the first glass finally enter the second glass, thus realizing the recycling of Li ions or Na ions released from the first glass. The embodiments of the invention have been described above in conjunction with the accompanying drawings. However, the invention is not limited to the above-mentioned specific implementations. The above-mentioned specific implementations are only illustrative and not restrictive. Those of ordinary skill in the art will be able to Under the inspiration of the invention, many forms can be made without departing from the purpose of the invention and the scope of protection of the claims, and these all fall within the protection of the invention.

Claims

A method for recycling alkali metal elements in plain glass, characterized in that the recycling method includes the following steps:

Place the first element glass containing alkali metal elements and an alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain a solid product containing alkali metal elements;

The solid product is taken out from the ion exchange salt bath and pretreated to obtain the main solid ingredient;

Mix the auxiliary solid ingredients with the main solid ingredients to obtain a plain glass ingredient mixture;

The raw glass batch mixture is melted and prepared to obtain a second raw glass containing an alkali metal element.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that the components of the second plain glass and the first plain glass and the percentage content of each component are the same.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that, in the plain glass ingredient mixture, the mass percentage of the main solid ingredients is less than or equal to 50wt%.
The method for recycling alkali metal elements in plain glass according to claim 1, wherein the pretreatment includes at least one of cleaning, drying, and crushing.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that the plain glass contains all the metal compounds contained in the main solid ingredients.
The method for recycling alkali metal elements in plain glass according to claim 1, wherein the alkali metal elements at least include Li.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that the alkali metal elements further include Na or K.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that:

The alkali metal element exists in the form of a covalent compound or an ionic compound in the plain glass;

The ion exchange salt bath contains the alkali metal element in an ionic form;

The alkali metal element exists in the form of a covalent compound or an ionic compound in the solid product and the main solid ingredient.
The recycling method of alkali metal elements in plain glass according to claim 8, characterized in that the ion exchange salt bath contains a nitrate with a mass fraction of greater than or equal to 50wt%.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that "the first plain glass containing alkali metal elements and the alkali metal ion fixative are placed in an ion exchange salt bath for a certain reaction In the step of "obtaining a solid product containing an alkali metal element", the alkali metal ion fixative absorbs the alkali metal element in the ionic form released from the first plain glass through a chemical reaction.
The recycling method of alkali metal elements in plain glass according to claim 10, characterized in that the alkali metal ion fixative is a compound that can absorb the alkali metal element existing in ionic form; the alkali metal The ionic fixative and the solid product containing alkali metal elements are solid in the atmosphere at normal temperature and pressure and in the ion exchange salt bath.
The recycling method of alkali metal elements in plain glass according to claim 11, characterized in that the alkali metal ion fixative includes one or more of silicate, phosphate, borate and antimonate. kind.
The recycling method of alkali metal elements in plain glass according to claim 11, characterized in that, in terms of mole percentage, the plain glass contains:

SiO 2 , 39-75mol%;

Li 2 O, 0.5-30mol%;

Al 2 O 3 , 0-28 mol%.
The recycling method of alkali metal elements in plain glass according to claim 1, characterized in that the auxiliary solid ingredients include ZrO, MgO, MgCO 3 , CaO, CaCO 3 , Na 2 O, NaNO 3 , NaCO 3 , At least one of K 2 O, KNO 3 , K 2 CO 3 , B 2 O 3 , P 2 O 5 , Y 2 O 3 , ZnO, SnO 2 , Sb 2 O 3 and NaCl.
A kind of plain glass prepared by the recycling method according to any one of claims 1 to 14, characterized in that the plain glass contains all kinds of elements contained in the main solid ingredients.
The plain glass according to claim 15, characterized in that the plain glass contains a shaped or amorphous structure.
A recycling system for alkali metal elements in plain glass, characterized in that the recycling system includes:

Raw material supply module, used to manufacture first element glass and alkali metal ion fixative;

The processing and recycling module is used to place the first plain glass and the alkali metal ion fixative in an ion exchange salt bath to react for a certain period of time to obtain strengthened chemically strengthened glass and a solid product containing alkali metal elements; The solid product is taken out from the ion exchange salt bath and pretreated to obtain the main solid ingredient;

The reprocessing module is used to mix the auxiliary solid ingredients with the main solid ingredients to obtain a plain glass ingredient mixture; and is used to melt and prepare the plain glass ingredient mixture to obtain a second plain glass containing alkali metal elements.
The recycling system according to claim 17, wherein the reprocessing module includes a detection unit and a calculation unit;

The detection unit is used to detect the components of the main solid ingredients and the content of each component;

The calculation unit is used to analyze and obtain the composition of the auxiliary solid batching based on the required composition and content of each component of the second plain glass and the detected composition and content of each component of the main solid batching. The content of each component and the added amount of the auxiliary solid ingredients are divided into: the added amount is the mass ratio of the auxiliary solid ingredients to the main solid ingredients.