Glass packaging containers have a long history. Later, with the ever-changing industrial technology, plastic packaging containers, composite packaging containers and so on appeared, and the glass packaging containers were in severe competition with the above-mentioned new material containers. However, due to its crystal clear and translucent texture, clean and beautiful appearance, good sealing, and excellent chemical stability, the glass packaging container is particularly inexpensive due to the fact that the glass's main raw material is extremely rich quartz sand and various minerals on the earth's crust. So far, glass containers have not been excluded, eliminated, but because of a variety of surface coating technology and the trend of lightweight containers, resulting in a certain degree of development. Common glass packaging containers are bottles (fine bottles, big bottles, spiral sealed bottles, etc.), cans (for canned foods), cups, and medical ampoules.
Glass packaging waste refers to the function of losing or completing the protection of the original value and use value of the contents, becoming a glass packaging container and material for discarding solid waste; comprehensive treatment of glass packaging waste refers to the disposal of glass packaging waste (ie, Reducing the volume and other uses of glass packaging waste, etc.) and utilization (ie, recycling, processing, etc., from glass packaging waste, or converting it into useable resources and other raw materials activities).
I. Content of glass packaging waste in municipal solid waste Glass packaging container When it loses or completes the function of maintaining the original value and use value of the contents, it becomes the same as other packaging waste, and becomes solid waste and is added to the garbage. Ranks. According to statistics, the United States produces 150 million tons of domestic garbage each year; in recent years, the amount of municipal solid waste in China has reached 150 million tons. Take Shanghai and Guangzhou as an example, Shanghai has already produced about 10,000 tons of municipal solid waste, and Guangzhou has produced more than 5,000 tons of municipal solid waste. About one-third to one-half of these municipal solid wastes are packaging wastes, of which glass packaging waste is about 5-10%. For example, packaging waste in the United States accounts for about 33% of municipal solid waste, Japan accounts for about 40%, EU countries account for about 30% to 50%, and China accounts for about 30% to 40%.
Second, the significance of glass packaging waste recycling The world's glass recycling situation is that the United States recycled glass is about 30%; France is about 48%; Germany is about 76%; the Netherlands about 77%.
China is a country with a large population, which consumes a lot of glass containers, and where resources and energy are very scarce. China produced about 9 million tons of glass containers in 1999, and its recovery rate was less than 20%, far behind industrially advanced countries. Recycling of glass packaging waste (recycling of some glass containers in the United States about 8 times) or development of new products not only saves mineral resources, reduces energy consumption, but also reduces pollution to the environment (especially water and air). From the aspect of saving mineral resources, for each ton of broken glass, 700 kg of quartz sand, 150 kg of limestone, and about 160 kg of soda ash can be saved. In total, 1,200 kg of raw materials can be saved; from the perspective of energy saving, melting from glass In the process, if raw materials are used, the chemical reaction is complicated and the heat consumption is high. The system of 1 kg (1500°C) glass consumes about 624 calories. If the glass material is mainly a physical change, the consumption of 1 kg of glass liquid requires only 437 calories; from the time saving point of view, the time required to complete the glass melting with completely powder is about 200 minutes, and 1% of broken glass is used. After the glass can be shortened to 95 minutes; from the reduction of atmospheric pollution, the glass batch material in the high-temperature melting reaction, will produce toxic fumes, such as arsenic compounds, fluorine compounds, lead compounds, cadmium Compounds, etc. In addition, raw materials will generate dust during processing, formulation and feeding. These will bring pollution to the atmosphere. The melting of broken glass is only a simple physical change process, which can greatly reduce the pollution of the atmosphere. Because of the above-mentioned economic and social benefits of glass packaging waste, the amount of cullet used at home and abroad is gradually increasing. “100%†of factories that use cullet have appeared in China. For example, the use of broken glass in glass factories in Beijing and Guangzhou has increased to 50 to 70%.
Third, glass packaging waste sorting technology Glass packaging waste is often mixed with other packaging waste and other household waste. In addition to traditional manual sorting, modern technology can also be used for sorting.
1. Sorting by gravity Firstly, by using different densities of substances, through air separation equipment, coarse-grained materials and dense-density material materials are coarsely separated, and then dense materials dropped on the bottom of the container are further sorted. For example, high-density glass and metal are re-sorted using common vibrating screens. In addition, inertial methods can also be used for sorting. Common equipment includes ballistic sorters, anti-ballistic sorting machines and sloping transport sorting machines; centrifugal sorting methods can also be used to remove large amounts of material with low density. In the middle, the denser glass and metal are selected. The equipment can use a ring screen or a rolling ring, relying on a rotating centrifugal force to move the glass and metal to the outside, and the less dense material moves inside. After the dense glass and metal are separated from the garbage, the glass and metal are separated again by magnetic separation.
2, the use of heavy media for sorting First fine magnetite or ferrosilicon alloy into a water suspension, and then crush the garbage or packaging waste placed in the heavy medium, the density of small floating floating, high density The glass precipitate is separated. This heavy medium can be used repeatedly to reduce the cost of sorting.
3. Sorting using optical technology In order to separate colored and colorless glass, electronic color pickers can be used for sorting. The method is: the glass is crushed into fragments of 6-16 mm, placed on a belt conveyor to form a line, and sent to a photocell and a special background stage. The optical method is used to detect the drop on the way. Colored glass or other debris is blown open by means of an air cap.
IV. Recycling of glass packaging waste 1. The glass bottle cans are cleaned and sterilized. The surface of the glass bottle cans is smooth and neutral. No additional coating is required. Easy to clean and easy to re-seal. If used properly, a bottle can be used about ten times. Recovered empty bottles can be reused only if they are carefully cleaned and sterilized. The key to the reuse of glass jars is bottle washing and disinfection. The inside and outside of glass jars must be cleaned, and a certain cleaning speed must be guaranteed. In order to guarantee the quality and speed of the glass bottles, mechanical equipment must be used. As for the disinfection of glass bottles, according to the requirements of the contents of the selection of disinfection and sterilization process, and then determine the disinfection of sterilizing liquid and mechanical equipment.
2. Reflow treatment of glass packaging waste If the glass packaging container can no longer be used, it has been damaged or it has become fragmented, and it can be returned to the furnace. Remelting processing not only saves raw materials and soda ash for glass production, saves energy and time, but also acts as a fluxing agent.
Recycling broken glass is the result of more than 20 years of scientific and technological progress. Prior to this, the glass factory had controlled the amount of broken glass to be contained within 10%. The reason was that the recovered shredded glass was dirty and contained various impurities such as iron, aluminum, paper, plastic, and cork. , stones, broken tiles, etc., and the broken glass itself is complex and its particle size is not uniform. The smashed glass remanufacturing must strictly control the three major barriers: it is an early-stage treatment. The collected cullet must be carefully sorted, washed, shredded, and blended in order to ensure that the glass is subjected to rigorous compositional testing and analysis, and that the rest is the basis for a practical process recipe; According to the specific circumstances of the production process, and in strict accordance with the actual operation of the process.
3. Development of new products for glass packaging waste (1) Development of glass-wrapped waste glass-ceramics Glass-ceramics are polycrystalline solids containing a large amount of microcrystals obtained by controlled crystallization of glass in the molten state. Compared with ordinary glass, it has higher mechanical properties, good thermal shock resistance, stable chemical properties and certain cutting performance. The main raw materials for the production of glass-ceramics are power plant fly ash, waste non-ferrous metal ore, blast furnace slag, aluminum sludge and waste glass, together with a small amount of nucleating agents such as sulfides, fluorides, and chromium oxides. Stir and then put it into the furnace. Melting at 1400 ~ 1500 °C, stable 1 ~ 2 hours and then released, the glass quickly quenched into water, remove the broken glass, drying, ball milling, sieving; then between 800 ~ 950 °C nucleation, sintering 0.5 ~ 1 Hours, heating up to 1000 ~ 1150 °C between the crystallization, flattening, removed after 0.5 to 1 hour; finally natural cooling, annealing, denucleation, grinding, polishing made of glass-ceramic products. The glass-ceramics produced by the sintering method can give a sparkling and beautiful pattern. This is because when the glass water is quenched into particles for heat treatment, the particle surface has a high degree of crystallization, the degree of internal crystallization is low, the high degree of crystallinity and low degree of crystallinity Some colors and reflections of light are different, so that the crystallized glass will show a pattern after grinding. In order to obtain a clear pattern, the glass particles should be sifted and graded, and the layers should be layered in the mold according to a certain level of granularity. Note that the surface particles cannot be too fine, otherwise the surface pattern will not be obvious. The color of glass-ceramic is extremely important. To increase the whiteness of the product, an appropriate amount of zinc oxide can be introduced into the base glass. Due to its good color, no brittleness, and high strength properties, the crystallized glass has no impact on the human body, so it has been widely popularized and popularized.
(2) Development of glass-wrapped waste Foam-glass foam glass is characterized by low water absorption, low thermal conductivity, low thermal expansion rate, high strength, good resistance to freezing and durability, and the ability to be sawed and bonded. Lightweight, heat-insulating, moisturizing and fireproof building materials are now widely used for the insulation and thermal insulation of ceilings, enclosure walls, internal partitions, heating pipes, ventilation pipes, cold storage, oil and gas pipelines. It can also play a role in sound insulation. Some noise-producing areas, such as compressors and fan rooms, use it as a wall to protect the walls from noise and sound absorption. With the development of science and technology, foam glass will be widely used in petrochemical, cold-mao, underground engineering, construction, power and shipbuilding. The manufacturing method is usually a certain amount of foaming agent is added to the glass raw material powder, uniformly mixed and then put into a forming mold, in the heat recovery so that it is heated foam molding, and then slowly annealing and cooling can be obtained in the porosity More than 90% glass foam consisting of independent pores. The raw material of the product is the soda-lime-silica glass with low softening point in the packaging waste of glass products. There are two production methods: one is the powder melting method and the other is the float method. Currently, the former method is used in China. The process flow of the powder melting method is as follows: The auxiliary materials such as washing, drying, and foaming agent of the waste glass are mixed according to an accurate ratio and sent to a ball mill for grinding. When the material reaches the specified particle size, it is removed from the ball mill, poured into the mold frame, and sent to the tunnel kiln. It is first preheated at 350-400°C for 0.5 hour and then heated to 850°C to melt, expand, foam, and fire. , Annealed into the annealing furnace, cooled and cut into products according to the required specifications. The common formula for foam glass is: waste glass 75-80%, water quenching 10-15%, foaming agent (graphite) 1.0-1.5, fusible modifier (Na2B4O7) 2-4%, foam booster (Sb2O3) ) 1 to 3%.
(3) The use of glass packaging waste to develop glass microspheres Glass beads have different types according to different classifications. According to their use, they can be divided into industrial beads, optical beads and special beads; according to hollow and solid points, they can be divided into hollow beads and solid beads; according to their size, can be divided into fine beads (diameter 0.8 ~ 5 mm) and microbeads (diameter less than 0.8 mm). The glass beads have stable chemical properties, large mechanical strength, good smoothness, and good light reflectivity (especially directional regressivity). It has a unique and wide range of uses, with the largest amount of low-refractive type. For example, mixed in paint as a road sign; for interior decoration and crafts. It can have a magical lighting effect at night. The production methods are often produced by the fire-fighting floater method, the spacer agent method, and the jet-blowing method. The first two methods are secondary molding methods, which are usually based on recycled waste glass. The basic principle of the fire floatation method is to break the recycled waste glass into particles of a certain size and send the glass particles in a certain way. Into the flames. Under the influence of fire, glass
Glass packaging waste refers to the function of losing or completing the protection of the original value and use value of the contents, becoming a glass packaging container and material for discarding solid waste; comprehensive treatment of glass packaging waste refers to the disposal of glass packaging waste (ie, Reducing the volume and other uses of glass packaging waste, etc.) and utilization (ie, recycling, processing, etc., from glass packaging waste, or converting it into useable resources and other raw materials activities).
I. Content of glass packaging waste in municipal solid waste Glass packaging container When it loses or completes the function of maintaining the original value and use value of the contents, it becomes the same as other packaging waste, and becomes solid waste and is added to the garbage. Ranks. According to statistics, the United States produces 150 million tons of domestic garbage each year; in recent years, the amount of municipal solid waste in China has reached 150 million tons. Take Shanghai and Guangzhou as an example, Shanghai has already produced about 10,000 tons of municipal solid waste, and Guangzhou has produced more than 5,000 tons of municipal solid waste. About one-third to one-half of these municipal solid wastes are packaging wastes, of which glass packaging waste is about 5-10%. For example, packaging waste in the United States accounts for about 33% of municipal solid waste, Japan accounts for about 40%, EU countries account for about 30% to 50%, and China accounts for about 30% to 40%.
Second, the significance of glass packaging waste recycling The world's glass recycling situation is that the United States recycled glass is about 30%; France is about 48%; Germany is about 76%; the Netherlands about 77%.
China is a country with a large population, which consumes a lot of glass containers, and where resources and energy are very scarce. China produced about 9 million tons of glass containers in 1999, and its recovery rate was less than 20%, far behind industrially advanced countries. Recycling of glass packaging waste (recycling of some glass containers in the United States about 8 times) or development of new products not only saves mineral resources, reduces energy consumption, but also reduces pollution to the environment (especially water and air). From the aspect of saving mineral resources, for each ton of broken glass, 700 kg of quartz sand, 150 kg of limestone, and about 160 kg of soda ash can be saved. In total, 1,200 kg of raw materials can be saved; from the perspective of energy saving, melting from glass In the process, if raw materials are used, the chemical reaction is complicated and the heat consumption is high. The system of 1 kg (1500°C) glass consumes about 624 calories. If the glass material is mainly a physical change, the consumption of 1 kg of glass liquid requires only 437 calories; from the time saving point of view, the time required to complete the glass melting with completely powder is about 200 minutes, and 1% of broken glass is used. After the glass can be shortened to 95 minutes; from the reduction of atmospheric pollution, the glass batch material in the high-temperature melting reaction, will produce toxic fumes, such as arsenic compounds, fluorine compounds, lead compounds, cadmium Compounds, etc. In addition, raw materials will generate dust during processing, formulation and feeding. These will bring pollution to the atmosphere. The melting of broken glass is only a simple physical change process, which can greatly reduce the pollution of the atmosphere. Because of the above-mentioned economic and social benefits of glass packaging waste, the amount of cullet used at home and abroad is gradually increasing. “100%†of factories that use cullet have appeared in China. For example, the use of broken glass in glass factories in Beijing and Guangzhou has increased to 50 to 70%.
Third, glass packaging waste sorting technology Glass packaging waste is often mixed with other packaging waste and other household waste. In addition to traditional manual sorting, modern technology can also be used for sorting.
1. Sorting by gravity Firstly, by using different densities of substances, through air separation equipment, coarse-grained materials and dense-density material materials are coarsely separated, and then dense materials dropped on the bottom of the container are further sorted. For example, high-density glass and metal are re-sorted using common vibrating screens. In addition, inertial methods can also be used for sorting. Common equipment includes ballistic sorters, anti-ballistic sorting machines and sloping transport sorting machines; centrifugal sorting methods can also be used to remove large amounts of material with low density. In the middle, the denser glass and metal are selected. The equipment can use a ring screen or a rolling ring, relying on a rotating centrifugal force to move the glass and metal to the outside, and the less dense material moves inside. After the dense glass and metal are separated from the garbage, the glass and metal are separated again by magnetic separation.
2, the use of heavy media for sorting First fine magnetite or ferrosilicon alloy into a water suspension, and then crush the garbage or packaging waste placed in the heavy medium, the density of small floating floating, high density The glass precipitate is separated. This heavy medium can be used repeatedly to reduce the cost of sorting.
3. Sorting using optical technology In order to separate colored and colorless glass, electronic color pickers can be used for sorting. The method is: the glass is crushed into fragments of 6-16 mm, placed on a belt conveyor to form a line, and sent to a photocell and a special background stage. The optical method is used to detect the drop on the way. Colored glass or other debris is blown open by means of an air cap.
IV. Recycling of glass packaging waste 1. The glass bottle cans are cleaned and sterilized. The surface of the glass bottle cans is smooth and neutral. No additional coating is required. Easy to clean and easy to re-seal. If used properly, a bottle can be used about ten times. Recovered empty bottles can be reused only if they are carefully cleaned and sterilized. The key to the reuse of glass jars is bottle washing and disinfection. The inside and outside of glass jars must be cleaned, and a certain cleaning speed must be guaranteed. In order to guarantee the quality and speed of the glass bottles, mechanical equipment must be used. As for the disinfection of glass bottles, according to the requirements of the contents of the selection of disinfection and sterilization process, and then determine the disinfection of sterilizing liquid and mechanical equipment.
2. Reflow treatment of glass packaging waste If the glass packaging container can no longer be used, it has been damaged or it has become fragmented, and it can be returned to the furnace. Remelting processing not only saves raw materials and soda ash for glass production, saves energy and time, but also acts as a fluxing agent.
Recycling broken glass is the result of more than 20 years of scientific and technological progress. Prior to this, the glass factory had controlled the amount of broken glass to be contained within 10%. The reason was that the recovered shredded glass was dirty and contained various impurities such as iron, aluminum, paper, plastic, and cork. , stones, broken tiles, etc., and the broken glass itself is complex and its particle size is not uniform. The smashed glass remanufacturing must strictly control the three major barriers: it is an early-stage treatment. The collected cullet must be carefully sorted, washed, shredded, and blended in order to ensure that the glass is subjected to rigorous compositional testing and analysis, and that the rest is the basis for a practical process recipe; According to the specific circumstances of the production process, and in strict accordance with the actual operation of the process.
3. Development of new products for glass packaging waste (1) Development of glass-wrapped waste glass-ceramics Glass-ceramics are polycrystalline solids containing a large amount of microcrystals obtained by controlled crystallization of glass in the molten state. Compared with ordinary glass, it has higher mechanical properties, good thermal shock resistance, stable chemical properties and certain cutting performance. The main raw materials for the production of glass-ceramics are power plant fly ash, waste non-ferrous metal ore, blast furnace slag, aluminum sludge and waste glass, together with a small amount of nucleating agents such as sulfides, fluorides, and chromium oxides. Stir and then put it into the furnace. Melting at 1400 ~ 1500 °C, stable 1 ~ 2 hours and then released, the glass quickly quenched into water, remove the broken glass, drying, ball milling, sieving; then between 800 ~ 950 °C nucleation, sintering 0.5 ~ 1 Hours, heating up to 1000 ~ 1150 °C between the crystallization, flattening, removed after 0.5 to 1 hour; finally natural cooling, annealing, denucleation, grinding, polishing made of glass-ceramic products. The glass-ceramics produced by the sintering method can give a sparkling and beautiful pattern. This is because when the glass water is quenched into particles for heat treatment, the particle surface has a high degree of crystallization, the degree of internal crystallization is low, the high degree of crystallinity and low degree of crystallinity Some colors and reflections of light are different, so that the crystallized glass will show a pattern after grinding. In order to obtain a clear pattern, the glass particles should be sifted and graded, and the layers should be layered in the mold according to a certain level of granularity. Note that the surface particles cannot be too fine, otherwise the surface pattern will not be obvious. The color of glass-ceramic is extremely important. To increase the whiteness of the product, an appropriate amount of zinc oxide can be introduced into the base glass. Due to its good color, no brittleness, and high strength properties, the crystallized glass has no impact on the human body, so it has been widely popularized and popularized.
(2) Development of glass-wrapped waste Foam-glass foam glass is characterized by low water absorption, low thermal conductivity, low thermal expansion rate, high strength, good resistance to freezing and durability, and the ability to be sawed and bonded. Lightweight, heat-insulating, moisturizing and fireproof building materials are now widely used for the insulation and thermal insulation of ceilings, enclosure walls, internal partitions, heating pipes, ventilation pipes, cold storage, oil and gas pipelines. It can also play a role in sound insulation. Some noise-producing areas, such as compressors and fan rooms, use it as a wall to protect the walls from noise and sound absorption. With the development of science and technology, foam glass will be widely used in petrochemical, cold-mao, underground engineering, construction, power and shipbuilding. The manufacturing method is usually a certain amount of foaming agent is added to the glass raw material powder, uniformly mixed and then put into a forming mold, in the heat recovery so that it is heated foam molding, and then slowly annealing and cooling can be obtained in the porosity More than 90% glass foam consisting of independent pores. The raw material of the product is the soda-lime-silica glass with low softening point in the packaging waste of glass products. There are two production methods: one is the powder melting method and the other is the float method. Currently, the former method is used in China. The process flow of the powder melting method is as follows: The auxiliary materials such as washing, drying, and foaming agent of the waste glass are mixed according to an accurate ratio and sent to a ball mill for grinding. When the material reaches the specified particle size, it is removed from the ball mill, poured into the mold frame, and sent to the tunnel kiln. It is first preheated at 350-400°C for 0.5 hour and then heated to 850°C to melt, expand, foam, and fire. , Annealed into the annealing furnace, cooled and cut into products according to the required specifications. The common formula for foam glass is: waste glass 75-80%, water quenching 10-15%, foaming agent (graphite) 1.0-1.5, fusible modifier (Na2B4O7) 2-4%, foam booster (Sb2O3) ) 1 to 3%.
(3) The use of glass packaging waste to develop glass microspheres Glass beads have different types according to different classifications. According to their use, they can be divided into industrial beads, optical beads and special beads; according to hollow and solid points, they can be divided into hollow beads and solid beads; according to their size, can be divided into fine beads (diameter 0.8 ~ 5 mm) and microbeads (diameter less than 0.8 mm). The glass beads have stable chemical properties, large mechanical strength, good smoothness, and good light reflectivity (especially directional regressivity). It has a unique and wide range of uses, with the largest amount of low-refractive type. For example, mixed in paint as a road sign; for interior decoration and crafts. It can have a magical lighting effect at night. The production methods are often produced by the fire-fighting floater method, the spacer agent method, and the jet-blowing method. The first two methods are secondary molding methods, which are usually based on recycled waste glass. The basic principle of the fire floatation method is to break the recycled waste glass into particles of a certain size and send the glass particles in a certain way. Into the flames. Under the influence of fire, glass
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