阅读说明：本技术 一种生活垃圾焚烧飞灰电熔玻璃化制品 (Electric melting vitrified product of household garbage incineration fly ash ) 是由 李胜春 朱春江 于 2021-10-25 设计创作，主要内容包括：本发明涉及一种生活垃圾焚烧飞灰电熔玻璃化制品,其原料组份质量百分比为：飞灰为40～50％,石英砂为10～15％,医用玻璃粉为15～18％,纯碱为5～9％,废盐为4～6％,铝灰为3～5％,废陶瓷粉为7～11％,硼砂为1.5～2％,硝酸钠为1～1.5％,三氧化二砷为0.2～0.3％,二氧化铈为0.1～0.4％,电熔玻璃化窑炉选用全电熔冷顶工艺熔制。本申请的优点是具有无害化程度彻底、产品稳定性高、处理运行费用适中、体积减量显著的特点,且有优异的耐酸、耐水、耐碱性能,适用于装饰玻璃、水淬玻璃、玻璃棒、玻璃球等制品,实现飞灰的高值化利用。(The invention relates to a household garbage incineration fly ash electrofusion vitrified product which comprises the following raw materials in percentage by mass: 40-50% of fly ash, 10-15% of quartz sand, 15-18% of medical glass powder, 5-9% of soda ash, 4-6% of waste salt, 3-5% of aluminum ash, 7-11% of waste ceramic powder, 1.5-2% of borax, 1-1.5% of sodium nitrate, 0.2-0.3% of arsenic trioxide and 0.1-0.4% of cerium dioxide, and the electric melting vitrification kiln is melted by an all-electric melting cold top process. The method has the advantages of thorough harmless degree, high product stability, moderate treatment and operation cost and remarkable volume reduction, has excellent acid resistance, water resistance and alkali resistance, is suitable for decorating products such as glass, water-quenched glass, glass rods, glass balls and the like, and realizes high-value utilization of fly ash.)

1. A household garbage incineration fly ash electrofusion vitrified product is characterized by comprising the following raw materials in percentage by mass: 40-50% of fly ash, 10-15% of quartz sand, 15-18% of medical glass powder, 5-9% of soda ash, 4-6% of waste salt, 3-5% of aluminum ash, 7-11% of waste ceramic powder, 1.5-2% of borax, 1-1.5% of sodium nitrate, 0.2-0.3% of arsenic trioxide and 0.1-0.4% of cerium dioxide.

2. The fused vitrified product of fly ash from incineration of household garbage according to claim 1, wherein the raw materials of the fused vitrified product of fly ash comprise 44% of fly ash, 12% of quartz sand, 17% of medical glass powder, 6.5% of soda ash, 5% of waste salt, 4% of aluminum ash, 8% of waste ceramic powder, 1.7% of borax, 1.3% of sodium nitrate, 0.2% of arsenic trioxide and 0.3% of cerium dioxide.

3. The domestic waste incineration fly ash electrofused vitrified product according to claim 1, wherein the fly ash particle size in the raw material of the fly ash electrofused vitrified product is not less than 40 meshes; quartz sand SiO₂The content is more than or equal to 98.5 wt%, and the granularity is more than or equal to 90% in a 40-120 mesh mode; the soda ash is heavy soda ash and is of industrial grade; na in waste salt₂SO₄More than or equal to 85 wt%; borax is of industrial grade; sodium nitrate is of industrial grade; the granularity of the arsenic trioxide is more than or equal to 200 meshes; the granularity of the cerium dioxide is more than or equal to 200 meshes.

4. The household garbage incineration fly ash electrofused vitrified product according to claim 1, wherein the particle size of the medical glass powder in the raw materials of the fly ash electrofused vitrified product is not less than 4 meshes, the varieties are sodium-calcium-silicon series, and Fe₂O₃<0.05 wt%; SiO in aluminum ash₂+Al₂O₃Not less than 65 wt% of Al phase<6.5 wt% and the granularity is more than or equal to 80 meshes; waste ceramic tile powder SiO₂More than or equal to 61 wt%, Al₂O₃Content is less than or equal to 17 wt%, K₂O+Na₂O is more than or equal to 5.5wt percent, and the granularity is more than or equal to 80 meshes.

5. The fused vitrified product of fly ash from incineration of household garbage according to claim 1, wherein the fly ash is fly ash from incineration of household garbage.

6. The domestic waste incineration fly ash electrofusion vitrified product of claim 1, wherein the fly ash electrofusion vitrification kiln is melted by an all-electric cold top process, and the production control temperature system is as follows: the production method comprises the following steps of discharging at 1350 ℃ for molding by molding equipment, and producing decorative glass, water-quenched glass, glass rods and glass balls, wherein the temperature rise time is 50min, 500-800 ℃, 25min, 800-1000 ℃, 25min, 1000-1300 ℃, 100min, 1300-1550 ℃, 50min, 150min at 1550 ℃, 1550 ℃ and 1350 ℃ and 80min at room temperature-500 ℃, the temperature rise time is 50min, 500-800 ℃, the temperature rise time is 25min, and the temperature rise time is 100 min.

7. The electric melting vitrified product of the incineration fly ash of the household garbage according to claim 1, wherein the content of the vitreous body of the electric melting vitrified product of the fly ash is more than or equal to 99 wt%, the water leaching and the acid leaching meet the limit value of the content of the harmful substances when the vitrified product of table 2 in the technical requirement of vitrified product of solid waste (survey, 2020.3) is used as the building material and the sand blasting raw material, and the total content of the harmful elements and the leaching amount of the harmful elements meet the maximum limit amount of the total content of the harmful elements in the ornament of table 1 and the maximum amount of the leaching amount of the harmful elements in the ornament of table 2 in the regulation of the limit amount of the harmful elements of the ornament of GB 28480-.

Technical Field

The invention relates to the technical field of high-value utilization of fly ash, in particular to an electric melting vitrified product of household garbage incineration fly ash.

Background

The domestic garbage has complicated composition, and combustible components such as paper, kitchen garbage, plastics, rubber and the like are easy to generate NOx, HCl and SO in the incineration process₂And harmful pollutants such as furan, heavy metals, dioxin, smoke dust and the like. Particularly, fly ash is used as a main carrier for enriching harmful substances such as heavy metals, dioxin, furan, soluble salts and the like after waste incineration, the yield of fly ash is about 3-15 wt% of the total amount of waste incineration, and the composition of fly ash is greatly different from the type of waste entering a furnace, the type of the furnace, the incineration process and the purification configuration of flue gas. The total amount of garbage incineration reaches 59.14 ten thousand tons per day, and the generation amount of fly ash exceeds 1000 ten thousand tons per year. The harm of the fly ash to the environment is mainly reflected in two main aspects of dioxin and heavy metal pollution, seriously harms the health of people and is caused by carcinogenesis, teratogenesis and carcinogenesisThe highly toxic pollutants with mutation function are easily dissolved in fat, and accumulated in organisms, thereby causing long-term harm to the human bodies and the organisms. Fly ash, therefore, is a hazardous waste and requires special disposal.

In view of the serious hazard of the fly ash, the fly ash is listed in a dangerous waste directory in China and needs to be strictly and specially treated according to relevant management regulations. At present, fly ash disposal methods mainly comprise: safe landfill method, solidification stabilization method, wet extraction method, heat treatment method, etc. Compared with other treatment methods, the electric melting vitrification method is the safest and most reliable treatment method, can realize the maximum reduction of the fly ash, has the highest harmless degree and the minimum secondary pollution, almost has no potential risk, but consumes relatively more electric energy, and becomes a main obstacle restricting the large-scale popularization of the fly ash. Therefore, how to improve the quality of the glass after the fly ash vitrification and make the glass be used as a product and be utilized in a high-value way, thereby reducing the operation cost is an important development trend of fly ash disposal work in economically developed areas.

The Chinese invention patent (application number: 202110684330.7) discloses a formula for preparing light partition bricks and boards by using fly ash, which comprises the following raw materials in parts by weight: 25-40 parts of cement, 25-35 parts of fly ash or sand, 10-20 parts of lime, 15-40 parts of waste incineration fly ash, 5-15 parts of gypsum, 5-10 parts of kaolin, 0.1-0.5 part of foaming agent and 0.015-0.75 part of chelating agent; the foaming agent is one or more of aluminum powder, zinc powder or hydrogen peroxide; the chelating agent is: one or more of soda ash, borax, water glass, magnesia and the like. Also provides a method for preparing light partition wall bricks and plates by using the fly ash, wherein the plasma melting technology is used in the process to remove all dioxin and chlorine salt in the fly ash; on one hand, the method can realize the thorough harmless treatment of the fly ash, on the other hand, the method can realize the complete reclamation of the fly ash, and produce the partition brick and the partition board products with high added value and wide application prospect.

The Chinese invention patent (application number: 201910275077.2) discloses an additive for vitrification treatment of incineration fly ash, which comprises the following components in parts by weight: 5-60 parts of SiO₂1 to 10 parts of H₃BO₃、1～10 parts of carbonate and 1-5 parts of nitrate. SiO 2₂And H₃BO₃The fly ash and the incineration fly ash form a network structure to stabilize heavy metal ions, carbonate and nitrate are used as a clarifying agent and a fluxing agent to be beneficial to forming a compact melting system, and all components synergistically act to improve the immobilization degree of the incineration fly ash and reduce the vitrification treatment temperature. The invention also provides a method for vitrifying incineration fly ash, which sequentially comprises the following steps: (1) providing an incineration fly ash sample and the additive for vitrification treatment of incineration fly ash; (2) preparing a mixture of an incineration fly ash sample and an additive for vitrification treatment of incineration fly ash, drying, mixing and granulating; (3) putting the mixture into a plasma melting furnace for melting treatment; (4) and after the molten slag is completely melted, cooling to obtain the glassy state slag. The method improves the solidification rate of heavy metal, greatly reduces the volume of incineration fly ash, and protects the environment.

The Chinese invention patent (application number: 202011176741.7) discloses foam glass prepared by using fly ash and a preparation method and application thereof, belonging to the technical field of foam glass preparation. The foam glass is prepared by adopting fly ash and glass powder as raw materials, mixing the fly ash and glass powder with a foaming agent, adding PVB (polyvinyl butyral) alcohol solution for granulation, and performing high-temperature foaming after twice heating after molding. Through twice temperature rise and heat preservation, partial dioxin can be effectively decomposed, and meanwhile, the formation amount of a high-temperature melt phase is promoted so as to effectively coat residual dioxin, high chlorine, high calcium and heavy metal components. The invention effectively realizes the coating of high-temperature melt relative to high chlorine, high calcium, heavy metal components and residual dioxin, and has little leakage of heavy metal elements, high calcium and high chlorine components after standing in water for a long time, thereby avoiding the harm of the components to the environment. The method has simple process and is suitable for large-scale production, and the fly ash is used as the raw material, so that the problem of environmental pollution is solved while the low-cost raw material is obtained.

The Chinese invention patent (application number: 201810665222.3) discloses an incineration fly ash molten glass slag decorative building block and a preparation method thereof, wherein the decorative building block comprises the following raw materials: the household garbage incineration fly ash fusion glass slag with the particle diameter smaller than 8 mm, facing sand with the particle diameter of 0-5 mm, cement and water. The decorative building block and the preparation method thereof provided by the application use a large amount of the fused glass slag of the fly ash from the incineration of the household garbage, provide a feasible way for the fly ash from the incineration of the household garbage, and have the advantages of simple manufacturing process, less investment, better benefit and no secondary pollution. The aggregate required by production uses a large amount of the domestic garbage incineration fly ash molten glass slag, so that the recycling of the domestic garbage incineration fly ash can be realized to the maximum extent, and the waste is changed into valuable. The average value of the compressive strength of the decorative building blocks made of the household garbage incineration fly ash molten glass slag is 5-15.5 MPa, and the decorative building blocks can be widely applied to various building decoration projects.

The Chinese invention patent (application number: 201811321368.2) discloses a microcrystalline glass for architectural decoration prepared by melting municipal solid waste incineration fly ash by microwave and application thereof. The microcrystalline glass for architectural decoration comprises the following components in percentage by mass: 50-70% of municipal solid waste incineration fly ash; SiO 2₂ 17～35％；Al₂O₃13-15%; the microcrystalline glass is prepared by the following method: burning fly ash and SiO in municipal solid waste₂And Al₂O₃Ball milling and mixing uniformly, sieving and then carrying out microwave melting treatment to obtain the microcrystalline glass for architectural decoration. The invention can realize harmless, resource and high added value treatment of the garbage incineration fly ash by utilizing the microwave one-step melting method, each heavy metal index of the obtained microcrystalline glass is lower than the limit value specified by the national hazardous waste identification standard, and tests such as Mohs hardness, bending strength, acid and alkali resistance and the like all accord with the national standard of the microcrystalline glass for architectural decoration, and the microcrystalline glass can be applied to the fields of high-grade architectural decoration materials, watches, quartz jewelry and the like.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, provides a domestic garbage incineration fly ash electric melting vitrification product which has the characteristics of thorough harmless degree, high product stability, moderate treatment and operation cost and obvious volume reduction, has excellent acid resistance, water resistance and alkali resistance, is suitable for products such as decorative glass, water quenching glass, glass rods, glass balls and the like, and realizes high-value utilization of fly ash.

The purpose of the invention is realized by the following technical scheme:

a household garbage incineration fly ash electrofusion vitrified product comprises the following raw material components in percentage by mass: 40-50% of fly ash, 10-15% of quartz sand, 15-18% of medical glass powder, 5-9% of soda ash, 4-6% of waste salt, 3-5% of aluminum ash, 7-11% of waste ceramic powder, 1.5-2% of borax, 1-1.5% of sodium nitrate, 0.2-0.3% of arsenic trioxide and 0.1-0.4% of cerium dioxide.

The raw materials of the fly ash electric melting vitrified product comprise 44 percent of fly ash, 12 percent of quartz sand, 17 percent of medical glass powder, 6.5 percent of soda ash, 5 percent of waste salt, 4 percent of aluminum ash, 8 percent of waste ceramic powder, 1.7 percent of borax, 1.3 percent of sodium nitrate, 0.2 percent of arsenic trioxide and 0.3 percent of cerium dioxide.

The particle size of the fly ash in the raw materials of the fly ash electric melting vitrified product is more than or equal to 40 meshes; quartz sand SiO₂The content is more than or equal to 98.5 wt%, and the granularity is more than or equal to 90% in a range of 40-120 meshes; the soda ash is heavy soda ash and is of industrial grade; na in waste salt₂SO₄More than or equal to 85 wt%; borax is of industrial grade; sodium nitrate is of industrial grade; the granularity of the arsenic trioxide is more than or equal to 200 meshes; the granularity of the cerium dioxide is more than or equal to 200 meshes.

The particle size of the medical glass powder in the raw materials of the fly ash electric melting vitrified product is more than or equal to 4 meshes, the variety is sodium-calcium-silicon series, and the variety is Fe₂O₃<0.05 wt%; SiO in aluminum ash₂+Al₂O₃Not less than 65 wt% of Al phase<6.5 wt% and the granularity is more than or equal to 80 meshes; waste ceramic tile powder SiO₂More than or equal to 61 wt%, Al₂O₃Content is less than or equal to 17 wt%, K₂O+Na₂O is more than or equal to 5.5wt percent, and the granularity is more than or equal to 80 meshes.

The fly ash is household garbage incineration fly ash.

The fly ash electric melting vitrification kiln is melted by adopting an all-electric melting cold top process, and the production control temperature system is as follows: the production method comprises the following steps of discharging at 1350 ℃ for molding by molding equipment, and producing decorative glass, water-quenched glass, glass rods and glass balls, wherein the temperature rise time is 50min, 500-800 ℃, 25min, 800-1000 ℃, 25min, 1000-1300 ℃, 100min, 1300-1550 ℃, 50min, 150min at 1550 ℃, 1550 ℃ and 1350 ℃ and 80min at room temperature-500 ℃, the temperature rise time is 50min, 500-800 ℃, the temperature rise time is 25min, and the temperature rise time is 100 min.

The content of the glass body of the fly ash electric melting vitrified product is more than or equal to 99 wt%, the water leaching and the acid leaching meet the limit value of the content of the harmful substances when the vitrified product 2 is used as a building material and a sand blasting raw material in the technical requirement of vitrified product of solid waste (proposal of comments, 2020.3), and the total content and the leaching amount of the harmful elements meet the maximum limit amount of the total content of the harmful elements in the ornament 1 and the maximum limit amount of the leaching amount of the harmful elements in the ornament of children 2 in the regulation of the limit amount of the harmful elements in the ornament GB 28480 and 2012.

The invention selects fly ash as the main raw material of vitrified products, the fly ash is evenly mixed with quartz sand, aluminum ash and waste ceramic powder, then the mixture is heated to a certain temperature by an electric heating method to be melted, and then the mixture is rapidly cooled down to form vitreous products, and the solidification and stabilization of heavy metals are realized by virtue of the compact silica tetrahedral network structure of the vitreous bodies. The technical principle is as follows: under the condition that the high temperature exceeds 1400 ℃, organic matters such as dioxin, furan and the like in the fly ash are pyrolyzed and gasified to generate substances with small molecular weight, and quartz sand, aluminum ash, waste ceramic powder and inorganic additives are melted and vitrified to form good glass bodies. Test research shows that the fly ash is added with proper amount of SiO₂、Al₂O₃The glass network structure forms a stable Si-O, Al-O network structure after melting treatment to form a glass body, and heavy metal ions in the fly ash participate in the network structure of the glass as the glass network structure or network filler to form a rigid amorphous glass substance and form a form which is not easy to leach out (participate in the network structure of the glass in the form of atomic bonds).

The invention selects the sodium carbonate, the waste salt and the borax to mainly reduce the melting temperature, promote the flow performance of the melt, reduce the volatilization of heavy metals in the fly ash melting process, improve the physical and chemical properties of the melt, promote the clarification and homogenization processes of the glass body, obviously improve the material property of the melt in the forming process, and improve the yield and the easy processing performance.

The invention selects the medical glass powder to enhance the vitrification capability of the fly ash, accelerate the vitrification process, promote the melting of materials, reduce the melting temperature and reduce the melting energy consumption. Meanwhile, the medical glass powder belongs to medical solid wastes, reduces resource consumption, changes waste into valuable, greatly reduces the raw material cost of vitrified products, and has good vitrification capacity and reduced leaching concentration of heavy metals.

The invention selects sodium nitrate and cerium dioxide as decolouring agents mainly, achieves the aim of decolouring mainly by weakening and neutralizing the coloring effect of iron, and simultaneously, the cerium dioxide also plays the role of clarifying agent, promotes the clarification and homogenization process of melt and eliminates the micro-defect in the melt. The invention selects arsenic trioxide to be mainly used as a clarifying agent, can reduce the high-temperature viscosity of the melt, can suck small bubbles in the melt to rise and be discharged to the outside of the glass melt, and eliminates the defects in the glass product melting process.

Compared with the prior art, the invention has the following positive effects:

(1) heavy metals in the fly ash participate in forming a new network structure body in the process of electric smelting treatment to be completely stabilized, and the leaching concentration of the heavy metals is far lower than the standard limit of national hazardous waste identification.

(2) The glass liquid generated after the electric melting treatment can be used for producing high-quality decorative glass, microcrystalline glass, glass fiber and centrifugal glass through forming equipment; the water-quenched glass can be used as a high-quality raw material for producing foam glass, and can be used for producing a high-performance heat-insulating material through processes such as foaming, annealing and the like, so that the requirements of decoration and building material markets are met, and the recycling of fly ash is really realized.

(3) The organic pollutants in the fly ash, including dioxin, are thoroughly decomposed, and the fly ash is really harmless.

(4) The whole treatment process does not generate waste water and waste residues, and the smoke generation amount in the whole process is extremely small due to the adoption of an electric melting process and combination of a cold top design and a deep material layer layout, and the smoke is discharged after being subjected to tail gas purification treatment such as a dust remover and the like.

(5) The melting heat efficiency is high, and the energy is saved and the consumption is reduced. Has good effect on reducing and eliminating bubbles, stripes and stones of the glass.

(6) The method conforms to the national environmental protection requirements, industrial policies and sustainable development strategies, is initiative under the condition of coping with the change of energy sources at home and abroad, is leading in the fierce product market competition, and gains the lead in the aspect of improving the technical management level of enterprises.

Detailed Description

The following provides a specific embodiment of the electric melting vitrified product of the household garbage incineration fly ash.

The components of the raw materials of the electric melting vitrified product of the incineration fly ash of the household garbage in the embodiments 1 to 6 and the comparative examples 1 to 4 are shown in the table 1.

Table 1 compositions of raw materials of examples 1 to 6 and comparative examples 1 to 4 in wt%

Various raw materials of the household garbage incineration fly ash electric melting vitrified product of the embodiment 1-6 and the comparative example 1-4 are mixed, the electric melting vitrification kiln is melted by adopting an all-electric melting cold top process, and the production control temperature system is as follows: the method comprises the following steps of (1) heating at room temperature to 500 ℃, 50min to 500 ℃ and 25min to 1000 ℃, 1000 to 1300 ℃, 100min to 1300 ℃, 50min to 1550 ℃, 150min at 1550 ℃, 80min at 1550 ℃ and 1350 ℃, discharging, molding by molding equipment, producing decorative glass, water-quenched glass, glass rods and glass balls, and then carrying out performance testing.

The content of the vitreous body of the jewelry is measured according to an X-ray diffraction method specified in appendix C of GB/T18046-2017, the leaching amount of the water and the acid leaching amount are tested according to the specification of the limit value of the content of the leachable harmful substances when the vitrified product is used as a building material and a sand blasting raw material in the technical requirement of vitrified product of solid waste (draft of comments, 3 months 2020), the total content of the harmful elements and the leaching amount of the harmful elements are tested according to the specification of the limit value of the harmful elements in the jewelry of GB 28480-2012, and the total content of the harmful elements and the leaching amount of the harmful elements are tested according to the specification of the maximum limit value of the harmful elements in the jewelry of the children in the Table 1 and the table 2, and the test results are listed in the Table 2.

TABLE 2 test results of examples 1 to 6 and comparative examples 1 to 4

From a comparison of the data in tables 1 and 2, it can be seen that: the electric melting vitrified product of the household garbage incineration fly ash has the characteristics of thorough harmless degree, high product stability, moderate operation cost and obvious reduction, has excellent acid resistance, water resistance and alkali resistance, is suitable for products such as decorative glass, water quenching glass, glass rods, glass balls and the like, and realizes high-value utilization of the fly ash.

In comparative example 1, the content of fly ash was 58 wt% and the content of silica sand was 8 wt% and waste tile powder was not added, resulting in SiO in the glass melt₂、Al₂O₃And the number of network structures is too small, so that the chemical stability of the vitrified product is reduced. The test result shows that the zinc content in the acid leaching detection is 1.43mg/L, and the lead content in the harmful element dissolution detection is 156mg/kg, which do not reach the standard.

In comparative example 2, the content of the quartz sand is 58 wt% higher, the content of the soda ash is 2 wt% lower, and no borax is added, so that the flux component in the glass melt is too little, the melting temperature cannot be reduced, the high-temperature viscosity is too high, the forming is difficult, the clarification and homogenization processes of the glass body cannot be effectively completed, and a small amount of components cannot form a good glass body. The test result shows that the content of the vitreous body is 94.6 wt%, and the vitreous body cannot reach the standard.

In the comparative example 3, the content of arsenic trioxide is 2.2 wt% which is higher, so that the total content of arsenic element in the fly ash electrofused product is too high, and further the arsenic element is easily dissolved out to cause the occurrence of the hazard condition. Test results show that the arsenic content in water leaching detection is 0.0138mg/L, the arsenic content in acid leaching detection is 0.124mg/L, the arsenic content in total harmful element content detection is 2641mg/kg, and the arsenic content in harmful element leaching amount detection is 43mg/kg, which do not reach the standard.

Comparative example 4 the content of the glass powder for traditional Chinese medicine is higher than 26.2 wt%, and no aluminum ash or waste tile powder is added, so that SiO in the glass body is caused₂、Al₂O₃Too few isoreticular structure, Na₂O、K₂The excessive content of the O fluxing component reduces the chemical stability of the electric melting vitrified product, and is not beneficial to the solidification of harmful elements in the network structure of the glass. Test results show that the mercury in the water leaching detection is 0.004mg/L, the mercury in the acid leaching detection is 0.023mg/L, the arsenic in the harmful element leaching detection is 64mg/kg, and the lead in the harmful element leaching detection is 144mg/kg, which do not reach the standard.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.