A glass bottle formulation and method of making the same

Abstract

This invention discloses a glass bottle formulation comprising the following raw materials: 100-120 parts silica sand, 30-45 parts soda ash, 8-12 parts dolomite, 8-12 parts calcite, 7-9 parts fluorite, 1-1.5 parts mirabilite, 2.5-3.5 parts environmentally friendly glass kiln ash, 3.5-7 parts SiC whisker / mullite whisker / nano TiO₂ composite, 0.8-1.2 parts sodium nitrate, 1-3 parts chromite powder, and 500-600 parts green waste glass slag. The beneficial effects of this invention are: a high proportion of green waste glass slag significantly reduces the consumption of raw materials such as silica sand and soda ash; it achieves the resource utilization of industrial solid waste, reducing solid waste disposal costs and carbon emissions; the sodium sulfate and calcium silicate particles in the environmentally friendly ash synergistically aid melting, reducing melting energy consumption; and the whisker composite, through the synergistic effects of SiC whisker stress dispersion, mullite whisker framework filling, and nano TiO₂ bubble adsorption, improves the impact resistance of beer glass bottles.

Description

Technical Field

[0001] This invention relates to the field of glass bottle manufacturing technology, specifically to a glass bottle formulation and its preparation method. Background Technology

[0002] Glass bottles, as traditional packaging containers, remain the mainstream packaging choice for industries such as beer due to their advantages such as being non-toxic, odorless, having good barrier properties, and being recyclable. However, current glass bottle production faces the following prominent challenges:

[0003] Traditional formulas mainly use virgin raw materials such as silica sand and soda ash, with the amount of green waste glass slag added usually not exceeding 30%, relying heavily on natural mineral resources, resulting in high raw material procurement costs.

[0004] The flue gas generated by the combustion of glass kilns needs to be treated separately, and the environmental ash produced is mostly disposed of as solid waste, which not only increases environmental protection costs but also wastes resources. At the same time, the mining and processing of raw materials are energy-intensive and have large carbon emissions, which is not in line with the trend of green manufacturing.

[0005] Existing high-waste glass formulations are prone to defects such as microbubbles and stones due to uneven raw material composition and insufficient melting, resulting in limited impact strength and crack resistance of the glass. Summary of the Invention

[0006] The purpose of this invention is to overcome the technical shortcomings of existing glass bottle production, such as high raw material costs, heavy environmental pressure, and high product defect rates, and to provide an environmentally friendly glass bottle with high green waste utilization rate and its preparation method.

[0007] To achieve the objectives of this invention, it is implemented through the following methods:

[0008] A glass bottle formulation comprising the following components in parts by weight:

[0009] 100-120 parts of silica sand

[0010] 30-45 parts of soda ash

[0011] 8-12 parts of dolomite

[0012] 8-12 parts of calcite

[0013] 7-9 parts fluorite

[0014] 1-1.5 parts of Glauber's salt

[0015] 2.5-3.5 parts of environmentally friendly ash for glass kilns

[0016] SiC whiskers / mullite whiskers / nano TiO2 composite material 3.5-7 parts

[0017] Sodium nitrate 0.8-1.2 parts

[0018] 1-3 parts chromite powder

[0019] 500-600 portions of green waste glass shards.

[0020] Preferably, the raw materials comprise the following components in parts by weight:

[0021] 111 parts of silica sand

[0022] 39 parts of soda ash

[0023] 10.9 portions of dolomite

[0024] 10.7 parts of calcite

[0025] 8 portions of fluorite

[0026] 1.2 parts of Glauber's salt

[0027] 3.1 parts of environmentally friendly ash from glass kilns

[0028] 5 parts of SiC whiskers / mullite whiskers / nano TiO2 composite

[0029] 1 part sodium nitrate

[0030] 2 parts chromite powder

[0031] 554.7 portions of green waste glass shards.

[0032] Preferably, the preparation method of the SiC whisker / mullite whisker / nano-TiO2 composite is as follows:

[0033] Add SiC whiskers, mullite whiskers, nano TiO2, and dispersant PEG-6000 to a high-speed mixer and dry mix for 15 minutes at a speed of 1000 r / min.

[0034] Take silane coupling agent KH-570, add anhydrous ethanol, and stir for 5 minutes for rapid hydrolysis;

[0035] The hydrolyzed coupling agent solution was evenly sprayed into the mixed powder in the high-speed mixer, and the speed was kept at 800 r / min. The mixture was stirred for 30 min.

[0036] The modified mixed powder was transferred into a vacuum drying oven at 120℃ and a vacuum of -0.08MPa for 2 hours.

[0037] After drying, the powder is cooled to room temperature and sieved through an 80-mesh standard sieve to remove agglomerated particles, thus obtaining the SiC whisker / mullite whisker / nano TiO2 composite.

[0038] Preferably, the SiC whiskers have a purity of ≥99%, a length of 50-100μm, and a diameter of 1-3μm; the mullite whiskers have a purity of ≥98%, a length of 10-50μm, and a diameter of 0.5-2μm; and the nano-TiO2 is anatase type, with a particle size of 20-50nm and a purity of ≥99.5%.

[0039] Preferably, the mass ratio of SiC whiskers, mullite whiskers, and nano-TiO2 is 2:1:0.5, and the amount of dispersant added is 1.0% of the total mass of SiC whiskers, mullite whiskers, and nano-TiO2.

[0040] Preferably, the amount of silane coupling agent KH-570 added is 1.5% of the total mass of SiC whiskers, mullite whiskers, and nano TiO2.

[0041] Preferably, the volume ratio of silane coupling agent KH-570 to ethanol is 1:5.

[0042] Preferably, the environmentally friendly ash from the glass kiln is a solid waste generated during flue gas treatment, originating from the sodium bicarbonate dry desulfurization and dust removal process. The main components of the environmentally friendly ash from the glass kiln are sodium sulfate (60%-75%, the core product of the desulfurization reaction, generated by the reaction of sodium bicarbonate with sulfur dioxide in the flue gas), desulfurization ash (10%-20%, due to the need for excessive spraying of desulfurizing agent to ensure the desulfurization effect, so there is a certain residue), and calcium silicate particles (5%-10%, formed by the original particulate matter in the flue gas being captured and mixed into the desulfurization ash).

[0043] A method for preparing a glass bottle formulation includes the following steps:

[0044] S1. Raw material pretreatment:

[0045] Green waste glass shavings: crush to a particle size ≤5mm, put into a drying oven at 120℃ for 2 hours to remove surface moisture and oil stains;

[0046] Environmentally friendly ash from glass kilns: Passed through an 80-mesh sieve to remove agglomerated particles;

[0047] S2, graded mixing:

[0048] Add silica sand, dolomite, calcite, green waste glass slag, and chromite powder to a twin-screw mixer at 300 rpm and dry mix for 15-20 minutes. Add soda ash, fluorite, mirabilite, and sodium nitrate, and continue mixing at the same speed for 10-15 minutes to ensure the flux evenly covers the surface of the raw materials. Add environmentally friendly glass furnace ash and SiC whiskers / mullite whiskers / nano TiO2 composite, reduce the speed to 200 rpm, and mix for 8-10 minutes.

[0049] S3, Melting and Clarification:

[0050] The mixed materials are continuously fed into the glass furnace, heated to 1480-1520℃, and held for 2.5-3 hours.

[0051] S4: On-demand molding:

[0052] Choose between blow molding or compression molding based on the bottle shape:

[0053] The material temperature is controlled at 1150-1250℃, and the mold is preheated to 200-250℃.

[0054] Blowing pressure: 0.4-0.6 MPa; pressing pressure: 1.0-1.5 MPa; molding time: 3-10 seconds.

[0055] S5: Annealing

[0056] After molding, the glass bottles are immediately sent into an annealing furnace, heated to 380-420℃, held for 20-25 minutes, and then allowed to cool naturally to room temperature.

[0057] S6: Post-processing and Inspection

[0058] Clean the dust off the glass bottle surface, and perform edge grinding and cutting as needed before quality inspection.

[0059] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0060] The high proportion of green waste glass slag significantly reduces the consumption of virgin raw materials such as silica sand and soda ash. The reuse of sodium bicarbonate dry desulfurization ash enables the resource utilization of industrial solid waste, reducing solid waste disposal costs and carbon emissions. Simultaneously, the sodium sulfate and calcium silicate particles in the ash synergistically aid melting, reducing melting energy consumption. The whisker composite enhances the impact resistance of beer glass bottles through the synergistic effects of SiC whisker stress dispersion, mullite whisker framework filling, and nano-TiO2 bubble adsorption.

[0061] This compound system addresses the root causes of defects such as microbubbles and stress concentration caused by high proportions of green waste glass slag through multi-scale defect targeted suppression and synergistic optimization of melt properties, ultimately improving the yield. Its mechanism of action can be divided into two parts: "single-component targeted function" and "three-component synergistic effect," which are explained in detail below in conjunction with the glass manufacturing process:

[0062] I. Single-component targeted action mechanism

[0063] 1. SiC whiskers

[0064] One of the core problems with high proportions of green waste glass slag is the inability to promptly expel residual moisture and gases generated from the combustion of organic matter, leading to the formation of microbubbles (diameter ≤0.1mm). The thermal conductivity of SiC whiskers (120-150W / (m・K)) is more than 150 times that of glass (0.8-1.0W / (m・K)). Adding SiC whiskers can quickly and uniformly distribute the temperature field of the glass melt (avoiding localized overheating leading to gas stagnation and localized undercooling leading to bubble freezing), providing a temperature-driven process for gas diffusion.

[0065] The surface of SiC whiskers has a porous structure (specific surface area ≥30m² / g), which can act as a bubble adsorption carrier. It adsorbs the micro bubble nuclei dispersed in the melt, promotes their aggregation to form large-sized bubbles, and rapidly rises along the whisker surface to the melt surface for discharge, thereby improving the micro bubble removal rate.

[0066] (2) Relieve stress concentration: The rigid frame disperses stress.

[0067] The uneven composition of waste glass makes it prone to microscopic compositional segregation zones during cooling due to inconsistent thermal expansion and contraction, which become stress concentration points. SiC whiskers, with an elastic modulus much higher than that of glass, form a uniformly distributed rigid framework within the glass, dispersing locally concentrated stress over a wider area and preventing microcracks caused by stress accumulation in segregation zones.

[0068] 2. Mullite whiskers

[0069] (1) Improve melt compatibility and reduce interface defects

[0070] The chemical composition of mullite whiskers is highly compatible with the glass matrix, and its addition will not produce new interfacial reactions, thus solving the problem of slightly poor compatibility between single SiC whiskers and the glass interface.

[0071] (2) Filling micropores to inhibit defect expansion

[0072] When a high proportion of waste glass is melted, "micropores" (diameter ≤0.05mm) are easily formed due to insufficient melt fluidity (impurities in the waste glass cause viscosity to increase). Mullite whiskers have a fibrous structure (length 10-50μm, diameter 0.5-2μm), which can physically fill these micropores. At the same time, its surface hydroxyl groups (-OH) can form hydrogen bonds with the Si-O bonds in the glass melt, enhancing the bonding force between the whiskers and the glass and preventing the pores from becoming the "starting point" of subsequent cracking.

[0073] (3) Stabilize component distribution and reduce stress sources

[0074] Mullite whiskers have a melting point (1850℃) higher than the glass melting temperature (1450-1550℃). They maintain a stable fibrous morphology in the melt and can "anchor" impurities that are prone to agglomeration in waste glass, preventing them from accumulating and forming compositional segregation zones, thus reducing stress concentration at the source.

[0075] 3. Nano TiO2: Assists in bubble nucleus adsorption, microcrystal suppression, and impurity passivation.

[0076] (1) Enhanced microbubble removal: targeted adsorption of bubble nuclei

[0077] The specific surface area of ​​nano TiO2 (≥100m² / g) is more than 10 times that of conventional clarifying agents (such as sodium sulfate). The oxygen vacancies on its surface can specifically adsorb bubble nuclei in the melt, promoting the rapid growth of bubble nuclei (nano TiO2 acts as a "bubble growth center"). This synergizes with the "bubble conduit" effect of SiC whiskers, further improving the microbubble removal rate.

[0078] (2) Suppress microcrystal precipitation and avoid stress concentration

[0079] High proportions of waste glass contain numerous impurities, which easily precipitate microcrystals (such as calcite and dolomite microcrystals) upon cooling. These microcrystals have a large difference in thermal expansion coefficients with the glass matrix, leading to interfacial stress concentration. Nano-TiO2 can act as a microcrystal growth inhibitor, adsorbing onto the microcrystal surface to prevent its growth. Simultaneously, it forms a stable solid solution with the microcrystals, reducing the difference in thermal expansion coefficients and alleviating interfacial stress.

[0080] (3) Passivate harmful impurities and reduce the causes of defects.

[0081] Trace amounts of heavy metal impurities may remain in green waste glass slag. These impurities can cause difficulties in clarifying the glass melt, uneven color, and even the formation of micro-defects. Nano-TiO2 can undergo coordination reactions with these impurities to form stable chelates, reducing the activity of the impurities and preventing them from catalyzing the generation of bubbles or the precipitation of microcrystals.

[0082] Synergistic effect mechanism of two and three components

[0083] 1. Multi-scale defect coverage:

[0084] Nano TiO2 (particle size 20-50nm): Targeted solution for nanoscale bubble nuclei and minute impurities;

[0085] Mullite whiskers (0.5-2 μm in diameter, 10-50 μm in length): fill micron-sized pores and suppress mesoscale component segregation;

[0086] SiC whiskers (diameter 1-3μm, length 50-100μm): disperse micron-level stress and guide the expulsion of large-scale bubbles;

[0087] The three components form a multi-scale defect suppression system of "nano-submicron-micron", avoiding the problem that a single-scale component cannot cover all defects.

[0088] 2. Synergistic optimization of melt properties:

[0089] Flowability optimization: Mullite whiskers can reduce melt viscosity, and the high thermal conductivity of SiC whiskers prevents local solidification of the melt. The two work together to improve melt flowability, making it easier for gases and impurities to be discharged.

[0090] Improved clarification efficiency: Nano-TiO2 adsorbs bubble nuclei, SiC whiskers guide the bubbles to rise, and mullite whiskers reduce melt resistance, thus shortening the clarification time and avoiding secondary defects caused by prolonged high temperatures.

[0091] 3. Synergistic compatibility with original formula components:

[0092] Synergistic effect with fluxes (fluorite, sodium sulfate): The whisker system does not affect the fluxing effect of fluorite (the melting temperature remains at 1450-1500℃), and the thermal conductivity of SiC whiskers can enhance the clarifying effect of sodium sulfate.

[0093] Synergistic effect with coloring systems (chromium ore powder, green waste glass slag): Nano-TiO2 can slightly improve the light transmission uniformity of green glass (avoiding color difference caused by impurities), and the whisker system does not react with Cr. 3 The reaction occurs but does not affect the coloring effect;

[0094] Synergistic effect with desulfurized solid waste: The CaO component of desulfurized solid waste can form a stable Ca-Al-Si-O system with mullite whiskers, enhancing the bonding force between the whiskers and the glass matrix. At the same time, the whiskers can adsorb tiny impurities in the desulfurized solid waste, reducing the generation of new defects. Detailed Implementation

[0095] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0096] In subsequent embodiments, the preparation method of the SiC whisker / mullite whisker / nano-TiO2 composite is as follows:

[0097] Add SiC whiskers, mullite whiskers, nano TiO2, and dispersant PEG-6000 to a high-speed mixer and dry mix for 15 minutes at a speed of 1000 r / min.

[0098] Take silane coupling agent KH-570, add anhydrous ethanol, and stir for 5 minutes for rapid hydrolysis;

[0099] The hydrolyzed coupling agent solution was evenly sprayed into the mixed powder in the high-speed mixer, and the speed was kept at 800 r / min. The mixture was stirred for 30 min.

[0100] The modified mixed powder was transferred into a vacuum drying oven at 120℃ and a vacuum of -0.08MPa for 2 hours.

[0101] After drying, the powder is cooled to room temperature and sieved through an 80-mesh standard sieve to remove agglomerated particles, thus obtaining the SiC whisker / mullite whisker / nano TiO2 composite.

[0102] The SiC whiskers have a purity ≥99%, a length of 50-100 μm, and a diameter of 1-3 μm; the mullite whiskers have a purity ≥98%, a length of 10-50 μm, and a diameter of 0.5-2 μm; the nano-TiO2 is anatase type, with a particle size of 20-50 nm and a purity ≥99.5%. The mass ratio of SiC whiskers, mullite whiskers, and nano-TiO2 is 2:1:0.5, and the amount of dispersant added is 1.0% of the total mass of SiC whiskers, mullite whiskers, and nano-TiO2. The amount of silane coupling agent KH-570 added is 1.5% of the total mass of SiC whiskers, mullite whiskers, and nano-TiO2. The volume ratio of silane coupling agent KH-570 to ethanol is 1:5.

[0103] <Example 1>

[0104] A glass bottle formulation comprising the following components in parts by weight:

[0105] 100 parts of silica sand

[0106] 30 parts of soda ash

[0107] 8 portions of dolomite

[0108] 8 parts of calcite

[0109] 7 parts of fluorite

[0110] 1 part of Glauber's salt

[0111] 2.5 parts of environmentally friendly ash for glass kilns

[0112] 3.5 parts of SiC whisker / mullite whisker / nano TiO2 composite

[0113] Sodium nitrate 0.8 parts

[0114] 1 part chromite powder

[0115] 500 portions of green waste glass shards.

[0116] The environmentally friendly ash from glass kilns is a solid waste generated during flue gas treatment, originating from the sodium bicarbonate dry desulfurization and dust removal process. The main components of this ash are sodium sulfate (60%-75%, a core product of the desulfurization reaction, generated by the reaction of sodium bicarbonate with sulfur dioxide in the flue gas), desulfurization ash (10%-20%, due to the need for excessive spraying of desulfurizing agent to ensure desulfurization effect, hence some residue), and calcium silicate particles (5%-10%, formed by the capture of original particulate matter in the flue gas followed by mixing with the desulfurization ash).

[0117] The chromite powder is 40-41% chromite powder, and the particle size can be 100 mesh, 200 mesh, 325 mesh, or 400 mesh, as in subsequent examples.

[0118] A method for preparing a glass bottle formulation includes the following steps:

[0119] S1. Raw material pretreatment:

[0120] Green waste glass shavings: crush to a particle size ≤5mm, put into a drying oven at 120℃ for 2 hours to remove surface moisture and oil stains;

[0121] Environmentally friendly ash from glass kilns: Passed through an 80-mesh sieve to remove agglomerated particles;

[0122] S2, graded mixing:

[0123] Add silica sand, dolomite, calcite, green waste glass slag, and chromite powder to a twin-screw mixer and dry mix for 15 minutes at a speed of 300 rpm. Add soda ash, fluorite, mirabilite, and sodium nitrate, and continue mixing for 10 minutes while maintaining the speed to ensure the flux evenly covers the surface of the raw materials. Add environmentally friendly glass furnace ash and SiC whiskers / mullite whiskers / nano TiO2 composite, reduce the speed to 200 rpm, and mix for 8 minutes.

[0124] S3, Melting and Clarification:

[0125] The mixed materials are continuously fed into the glass furnace, heated to 1480-1520℃, and held at that temperature for 2.5 hours.

[0126] S4: On-demand molding:

[0127] Choose between blow molding or compression molding based on the bottle shape:

[0128] The material temperature is controlled at 1150℃, and the mold is preheated to 200℃;

[0129] Blowing pressure: 0.4 MPa; pressing pressure: 1.0 MPa; molding time: 10 s.

[0130] S5: Annealing

[0131] After molding, the glass bottles are immediately sent into an annealing furnace, heated to 380-420℃, held for 20 minutes, and then cooled naturally to room temperature.

[0132] S6: Post-processing and Inspection

[0133] Clean the dust off the glass bottle surface, and perform edge grinding and cutting as needed before quality inspection.

[0134] <Example 2>

[0135] A glass bottle formulation comprising the following components in parts by weight:

[0136] 120 parts of silica sand

[0137] 45 parts of soda ash

[0138] 12 portions of dolomite

[0139] 12 portions of calcite

[0140] 9 portions of fluorite

[0141] 1.5 parts Glauber's salt

[0142] 3.5 parts of environmentally friendly ash from glass kilns

[0143] 7 parts of SiC whisker / mullite whisker / nano TiO2 composite

[0144] Sodium nitrate 1.2 parts

[0145] 3 parts chromite powder

[0146] 600 portions of green waste glass shards.

[0147] The environmentally friendly ash from glass kilns is a solid waste generated during flue gas treatment, originating from the sodium bicarbonate dry desulfurization and dust removal process. The main components of this ash are sodium sulfate (60%-75%, a core product of the desulfurization reaction, generated by the reaction of sodium bicarbonate with sulfur dioxide in the flue gas), desulfurization ash (10%-20%, due to the need for excessive spraying of desulfurizing agent to ensure desulfurization effect, hence some residue), and calcium silicate particles (5%-10%, formed by the capture of original particulate matter in the flue gas followed by mixing with the desulfurization ash).

[0148] A method for preparing a glass bottle formulation includes the following steps:

[0149] S1. Raw material pretreatment:

[0150] Green waste glass shavings: crush to a particle size ≤5mm, put into a drying oven at 120℃ for 2 hours to remove surface moisture and oil stains;

[0151] Environmentally friendly ash from glass kilns: Passed through an 80-mesh sieve to remove agglomerated particles;

[0152] S2, graded mixing:

[0153] Add silica sand, dolomite, calcite, green waste glass slag, and chromite powder to a twin-screw mixer and dry mix for 20 minutes at a speed of 300 r / min. Add soda ash, fluorite, mirabilite, and sodium nitrate, and continue mixing for 15 minutes while maintaining the speed to ensure the flux evenly covers the surface of the raw materials. Add environmentally friendly glass furnace ash and SiC whiskers / mullite whiskers / nano TiO2 composite, reduce the speed to 200 r / min, and mix for 10 minutes.

[0154] S3, Melting and Clarification:

[0155] The mixed materials are continuously fed into the glass furnace, heated to 1480-1520℃, and held for 3 hours.

[0156] S4: On-demand molding:

[0157] Choose between blow molding or compression molding based on the bottle shape:

[0158] The material temperature is controlled at 1250℃, and the mold is preheated to 250℃.

[0159] Blowing pressure: 0.6 MPa; pressing pressure: 1.5 MPa; molding time: 3 seconds.

[0160] S5: Annealing

[0161] After molding, the glass bottles are immediately sent into an annealing furnace, heated to 380-420℃, held for 25 minutes, and then cooled naturally to room temperature.

[0162] S6: Post-processing and Inspection

[0163] Clean the dust off the glass bottle surface, and perform edge grinding and cutting as needed before quality inspection.

[0164] <Example 3>

[0165] A glass bottle formulation comprising the following components in parts by weight:

[0166] 111 parts of silica sand

[0167] 39 parts of soda ash

[0168] 10.9 portions of dolomite

[0169] 10.7 parts of calcite

[0170] 8 portions of fluorite

[0171] 1.2 parts of Glauber's salt

[0172] 3.1 parts of environmentally friendly ash from glass kilns

[0173] 5 parts of SiC whiskers / mullite whiskers / nano TiO2 composite

[0174] 1 part sodium nitrate

[0175] 2 parts chromite powder

[0176] 554.7 portions of green waste glass shards.

[0177] The environmentally friendly ash from glass kilns is a solid waste generated during flue gas treatment, originating from the sodium bicarbonate dry desulfurization and dust removal process. The main components of this ash are sodium sulfate (60%-75%, a core product of the desulfurization reaction, generated by the reaction of sodium bicarbonate with sulfur dioxide in the flue gas), desulfurization ash (10%-20%, due to the need for excessive spraying of desulfurizing agent to ensure desulfurization effect, hence some residue), and calcium silicate particles (5%-10%, formed by the capture of original particulate matter in the flue gas followed by mixing with the desulfurization ash).

[0178] A method for preparing a glass bottle formulation includes the following steps:

[0179] S1. Raw material pretreatment:

[0180] Green waste glass shavings: crush to a particle size ≤5mm, put into a drying oven at 120℃ for 2 hours to remove surface moisture and oil stains;

[0181] Environmentally friendly ash from glass kilns: Passed through an 80-mesh sieve to remove agglomerated particles;

[0182] S2, graded mixing:

[0183] Add silica sand, dolomite, calcite, green waste glass slag, and chromite powder to a twin-screw mixer and dry mix for 18 minutes at a speed of 300 rpm. Add soda ash, fluorite, mirabilite, and sodium nitrate, and continue mixing for 12 minutes while maintaining the speed to ensure the flux evenly covers the surface of the raw materials. Add environmentally friendly glass furnace ash and SiC whiskers / mullite whiskers / nano TiO2 composite, reduce the speed to 200 rpm, and mix for 9 minutes.

[0184] S3, Melting and Clarification:

[0185] The mixed materials are continuously fed into a glass furnace, heated to 1480-1520℃, and held at that temperature for 2.8 hours.

[0186] S4: On-demand molding:

[0187] Choose between blow molding or compression molding based on the bottle shape:

[0188] The material temperature is controlled at 1200℃, and the mold is preheated to 220℃;

[0189] Blowing pressure: 0.5 MPa; pressing pressure: 1.3 MPa; molding time: 6 seconds.

[0190] S5: Annealing

[0191] After molding, the glass bottles are immediately sent into an annealing furnace, heated to 380-420℃, held for 22 minutes, and then cooled naturally to room temperature.

[0192] S6: Post-processing and Inspection

[0193] Clean the dust off the glass bottle surface, and perform edge grinding and cutting as needed before quality inspection.

[0194] <Comparative Example 1>

[0195] Traditional formula (no high levels of green waste, no environmentally friendly ash, no whiskering compounds)

[0196] Formula (parts by weight): 280 parts silica sand, 85 parts soda ash, 25 parts dolomite, 25 parts calcite, 15 parts fluorite, 3 parts mirabilite, 2 parts sodium nitrate, 4 parts chromite powder, and 150 parts green waste glass slag (30%).

[0197] Preparation method: Conventional process was adopted, without graded mixing step, melting temperature 1550℃, holding temperature for 3.5 hours, annealing temperature 400℃, holding temperature for 20 minutes.

[0198] <Comparative Example 2>

[0199] High-green waste formulation (no environmentally friendly ash, no whiskering compounds)

[0200] Formula (parts by weight): 111 parts silica sand, 39 parts soda ash, 10.9 parts dolomite, 10.7 parts calcite, 8 parts fluorite, 1.2 parts mirabilite, 1 part sodium nitrate, 2 parts chromite powder, and 554.7 parts green waste glass slag (consistent with Example 3);

[0201] Preparation method: Same as in Example 3, but without the addition of glass furnace environmentally friendly ash and whisker compound.

[0202] <Comparative Example 3>

[0203] High-quality green waste and environmentally friendly ash formula (no whisker-free compound)

[0204] Formula (parts by weight): 111 parts silica sand, 39 parts soda ash, 10.9 parts dolomite, 10.7 parts calcite, 8 parts fluorite, 1.2 parts mirabilite, 1 part sodium nitrate, 2 parts chromite powder, 554.7 parts green waste glass slag, and 3.1 parts environmentally friendly ash from glass kilns (consistent with Example 3);

[0205] Preparation method: Same as in Example 3, but without adding SiC whiskers / mullite whiskers / nano TiO2 composite.

[0206] <Test Experiment>

[0207] 1. Test Sample

[0208] Take 500mL standard glass bottles prepared in Examples 1-3 and Comparative Examples 1-3, randomly select 10 samples from each group, and conduct the following index tests, taking the average value.

[0209] 2. Test Items and Methods

[0210] Test items:

[0211] Impact strength (J), GB / T4544-2020 "Beer Bottles", CJY-03 glass bottle impact tester, average value taken;

[0212] Vertical load strength (N), GB / T4544-2020 "Beer Bottle", KYJ-50S glass bottle vertical load tester, average value taken;

[0213] Finished product yield (%) is calculated as the average of the number of qualified products / total number of products produced and 100%.

[0214] The number of air bubbles (number / cm³) is determined by visual inspection. One cross-section is randomly selected from each glass bottle, and the total number of air bubbles in 10 samples is then averaged.

[0215] Heavy metal leaching (mg / L), GB4806.5-2016 "Glass products for food contact", inductively coupled plasma mass spectrometry (ICP-MS), average value;

[0216] The test results are shown in Table 1 below:

[0217] Table 1

[0218] Test Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength (J) 0.85 0.96 0.94 0.65 0.60 0.68 Vertical load intensity (N) 14086 15262 15858 12694 11356 13593 Finished product yield (%) 92.1 93.8 94.3 82.6 83.5 86.8 Number of bubbles (bubbles / cm³) 4.2 4.3 3.8 7.5 6.5 6.1 Heavy metal leaching (Pb) 0.03 0.02 0.02 0.04 0.03 0.03 <![CDATA[Heavy metal dissolution amount (Cr 6 ⁺)]]> 0.02 0.01 0.02 0.03 0.02 0.02

[0219] 3. Results Analysis

[0220] Performance comparison:

[0221] The impact strength of Examples 1-3 (0.85-0.94 J) was significantly improved compared to that of Comparative Examples 1-3 (0.65-0.68 J), and the vertical load strength was also significantly improved, demonstrating that the synergistic reinforcing effect of the SiC whisker / mullite whisker / nano TiO2 composite was significant.

[0222] The yield of Example 3 was 94.3%, which was significantly higher than that of Comparative Example 1 (82.6%). The number of bubbles was also greatly reduced, indicating that the synergistic effect of high-quality waste glass slag, environmentally friendly ash, and SiC whiskers / mullite whiskers / nano-TiO2 composite effectively solved the defect problems of high-quality waste glass formulation.

[0223] The heavy metal leaching levels in all embodiments met the GB4806.5-2016 standard (≤0.05mg / L) and were lower than those in Comparative Example 1, indicating that the addition of environmentally friendly ash and whisker compound did not introduce any safety risks.

[0224] Finished Product Inspection

[0225] Eighty 500 mL green glass beer bottles prepared in Example 3 were submitted for testing. The testing items were as follows:

[0226] Maximum permissible deviation of full capacity, maximum deviation of bottle height, inner diameter of bottle mouth, outer diameter of bottle mouth, outer diameter tolerance of bottle body, outer diameter of bottle neck within 35mm below the self-sealing surface, roundness of bottle body, vertical axis deviation, impact resistance, internal pressure resistance, thermal shock resistance, internal stress, water resistance of inner surface, thickness of bottle body, thickness of bottle bottom, thickness ratio of the same bottle body, thickness ratio of the same bottle bottom, vertical load strength, maximum permissible deviation of nominal capacity, sliding angle, thickness of hot-end spray coating of bottle mouth, thickness of hot-end spray coating of bottle body, cracks, internal wall defects, stones, bubbles, seam line (mold seam line) and surface defects (smoothness), bottle mouth defects, knurling of bottle bottom.

[0227] Test method:

[0228] GB / T GB / T 22934-2008.

[0229] Sample condition and description: The sample is intact.

[0230] The various test indicators of the finished product samples are shown in Tables 2 and 3 below:

[0231] Table 2

[0232]

[0233] Table 3

[0234]

[0235] The above embodiments are only for illustrating the technical solutions and features of the present invention, and are intended to enable those skilled in the art to implement them better. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention are within the scope of protection of the present invention. The parts not described in detail are prior art.

Claims

1. A glass bottle formulation, characterized in that, The raw materials include the following components in parts by weight: 100-120 parts of silica sand 30-45 parts of soda ash 8-12 parts of dolomite 8-12 parts of calcite 7-9 parts fluorite 1-1.5 parts of Glauber's salt 2.5-3.5 parts of environmentally friendly ash for glass kilns SiC whiskers / mullite whiskers / nano TiO2 composite material 3.5-7 parts Sodium nitrate 0.8-1.2 parts 1-3 parts chromite powder 500-600 portions of green waste glass shards; The preparation method of the SiC whisker / mullite whisker / nano TiO2 composite is as follows: Add SiC whiskers, mullite whiskers, nano TiO2, and dispersant PEG-6000 to a high-speed mixer and dry mix for 15 minutes at a speed of 1000 r / min. Take silane coupling agent KH-570, add anhydrous ethanol, and stir for 5 minutes for rapid hydrolysis; The hydrolyzed coupling agent solution was evenly sprayed into the mixed powder in the high-speed mixer, and the speed was kept at 800 r / min. The mixture was stirred for 30 min. The modified mixed powder was transferred into a vacuum drying oven at 120℃ and a vacuum of -0.08MPa for 2 hours. After drying, the powder is cooled to room temperature and sieved through an 80-mesh standard sieve to remove agglomerated particles, thus obtaining the SiC whisker / mullite whisker / nano TiO2 composite.

2. The glass bottle formulation according to claim 1, characterized in that, The raw materials include the following components in parts by weight: 111 parts of silica sand 39 parts of soda ash 10.9 portions of dolomite 10.7 parts of calcite 8 portions of fluorite 1.2 parts of Glauber's salt 3.1 parts of environmentally friendly ash from glass kilns 5 parts of SiC whiskers / mullite whiskers / nano TiO2 composite 1 part sodium nitrate 2 parts chromite powder 554.7 portions of green waste glass shards.

3. The glass bottle formulation according to claim 1, characterized in that, The SiC whiskers have a purity of ≥99%, a length of 50-100μm, and a diameter of 1-3μm; the mullite whiskers have a purity of ≥98%, a length of 10-50μm, and a diameter of 0.5-2μm; and the nano-TiO2 anatase type has a particle size of 20-50nm and a purity of ≥99.5%.

4. The glass bottle formulation according to claim 1, characterized in that, The mass ratio of SiC whiskers, mullite whiskers, and nano TiO2 is 2:1:0.5, and the amount of dispersant added is 1.0% of the total mass of SiC whiskers, mullite whiskers, and nano TiO2.

5. The glass bottle formulation according to claim 1, characterized in that, The amount of silane coupling agent KH-570 added is 1.5% of the total mass of SiC whiskers, mullite whiskers, and nano TiO2.

6. The glass bottle formulation according to claim 1, characterized in that, The volume ratio of silane coupling agent KH-570 to ethanol is 1:

5.

7. The glass bottle formulation according to claim 1, characterized in that, The environmentally friendly ash from the glass kiln is a solid waste generated during flue gas treatment, originating from the sodium bicarbonate dry desulfurization and dust removal process.

8. A method for preparing a glass bottle formulation according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Raw material pretreatment: Green waste glass shavings: crush to a particle size ≤5mm, put into a drying oven at 120℃ for 2 hours to remove surface moisture and oil stains; Environmentally friendly ash from glass kilns: Passed through an 80-mesh sieve to remove agglomerated particles; S2, graded mixing: Add silica sand, dolomite, calcite, green waste glass slag, and chromite powder to a twin-screw mixer at 300 rpm and dry mix for 15-20 minutes. Add soda ash, fluorite, mirabilite, and sodium nitrate, and continue mixing at the same speed for 10-15 minutes to ensure the flux evenly covers the surface of the raw materials. Add environmentally friendly glass furnace ash and SiC whiskers / mullite whiskers / nano TiO2 composite, reduce the speed to 200 rpm, and mix for 8-10 minutes. S3, Melting and Clarification: The mixed materials are continuously fed into the glass furnace, heated to 1480-1520℃, and held for 2.5-3 hours. S4: On-demand molding: Choose between blow molding or compression molding based on the bottle shape: The material temperature is controlled at 1150-1250℃, and the mold is preheated to 200-250℃. Blowing pressure: 0.4-0.6 MPa; pressing pressure: 1.0-1.5 MPa; molding time: 3-10 seconds. S5: Annealing After molding, the glass bottles are immediately sent into an annealing furnace, heated to 380-420℃, held for 20-25 minutes, and then allowed to cool naturally to room temperature. S6: Post-processing and Inspection Clean the dust off the glass bottle surface, and perform edge grinding and cutting as needed before quality inspection.

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