Method for comprehensive treatment of extracting dispersed metals and degrading dioxin from slag and waste incineration fly ash in coordination

Abstract

This invention relates to a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash. The comprehensive treatment method includes: mixing germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash to obtain a mixture; adding a first reagent to the mixture to obtain a composite mixture; the first reagent is at least one selected from silicon dioxide, borax, calcium oxide, alumina, and coke powder; reacting the composite mixture at a first temperature and a first vacuum degree for a first time to obtain a germanium-rich product, thereby decomposing dioxins in the waste incineration fly ash; reacting at a second temperature and a second vacuum degree for a second time; cooling to obtain an intermediate product with a residue upper layer and a gallium- and niobium-rich iron eutectic lower layer; dissolving the gallium- and niobium-rich iron eutectic in acid, and then using resin adsorption separation to obtain gallium and niobium, thus achieving the recovery of rare and dispersed metals. This invention solves the problems of slag waste and the difficulty and potential secondary pollution caused by dioxin treatment in waste incineration fly ash.

Description

Technical Field

[0001] This invention relates to the field of resource utilization technology of slag and waste incineration fly ash, specifically to a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins by co-processing slag and waste incineration fly ash. Background Technology

[0002] In today's rapidly developing technological field, rare metals such as germanium (Ge) and gallium (Ga) have become indispensable key materials in the manufacture of semiconductors, electronic devices, and optical devices. Their strategic value is increasingly prominent, and they are listed as important strategic reserve resources by many countries. Germanium, in particular, has a wide range of applications in cutting-edge fields such as fiber optic communication, photovoltaic industry, infrared detection technology, and efficient chemical catalysis. However, with the continuous increase in global demand for germanium and gallium, an undeniable reality is that the natural reserves of these two metals are extremely limited. Global reserves of germanium are only about 8,600 tons, while gallium reserves are 280,000 tons. Their scarcity has directly led to a year-on-year increase in market prices, exacerbating the tight supply situation.

[0003] Meanwhile, germanium and gallium do not exist in nature as independent mineral deposits, but rather as associated elements in complex minerals such as sphalerite, making extraction difficult and costly. Furthermore, large quantities of solid waste containing germanium, gallium, and niobium, such as fly ash and iron ore slag, are often directly landfilled using traditional methods. This not only occupies valuable land resources and increases the economic burden of landfill disposal, but also leads to a significant waste of valuable resources and may cause environmental pollution problems. In particular, the germanium, gallium, and niobium resources in germanium-containing slag and gallium- and niobium-containing iron ore slag, if not effectively recycled and utilized, undoubtedly represent a blatant disregard for natural resources.

[0004] On the other hand, fly ash generated during waste incineration is classified as hazardous waste due to its high content of chloride salts, volatile heavy metals, and highly toxic dioxins, making its treatment extremely difficult. Current technologies for removing dioxins from fly ash primarily employ high-temperature pyrolysis incineration or melt-solidification techniques, aiming to decompose dioxins under extreme high-temperature conditions and convert them into harmless or low-toxicity substances. However, this process faces significant technical bottlenecks: while dioxins can decompose at high temperatures, they readily recombine with chloride ions during the cooling phase to form dioxin precursors, which in turn regenerate dioxins, seriously threatening environmental safety and human health.

[0005] In summary, from the dual perspectives of environmental protection and efficient resource utilization, existing methods for treating germanium-containing fly ash and waste incineration fly ash all have significant shortcomings. Therefore, developing an innovative technology that can effectively recover valuable resources from germanium-containing fly ash while inhibiting the regeneration of dioxins in waste incineration fly ash is of great significance for alleviating resource shortages, reducing environmental pollution, and promoting the development of a circular economy. Summary of the Invention

[0006] In view of this, the purpose of this invention is to provide a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash, so as to solve the problem that existing germanium-containing slag and gallium-niobium-containing iron slag cannot be effectively recycled and utilized, resulting in resource waste, and to solve the problem that the treatment of dioxins in existing waste incineration fly ash is difficult and easily causes secondary pollution.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash includes the following steps: S1. Germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash are mixed to obtain a mixture. A first reagent is added to the mixture to obtain a composite mixture. The first reagent is at least one of silicon dioxide, borax, calcium oxide, aluminum oxide, and coke powder; S2. The composite mixture is reacted for a first time under a first temperature and a first vacuum to obtain a volatile germanium-rich product and decompose dioxins in the fly ash of waste incineration. Then, it is reacted for a second time under a second temperature and a second vacuum, and cooled to obtain a layered intermediate product. The upper layer of the intermediate product is a residue, and the lower layer is a gallium-rich niobium-iron eutectic. The second temperature is greater than the first temperature; S3. The gallium-rich niobium-iron eutectic is dissolved in acid, and then the gallium and niobium are separated by resin adsorption, thus realizing the recovery of rare dispersed metals.

[0008] Based on the aforementioned technical methods, firstly, through a specific reagent combination (silicon dioxide, borax, calcium oxide, alumina, and coke powder) and specific reaction conditions (different temperatures and vacuum levels), the volatilization and enrichment of germanium in slag, as well as the enrichment of gallium and niobium, are effectively promoted. Further, through acid dissolution and resin adsorption separation, high-purity recovery of gallium and niobium is achieved, thereby improving resource utilization, reducing resource waste, and realizing efficient recovery of rare and dispersed metals. Secondly, during the separation and enrichment process of rare and dispersed metals, dioxins in waste incineration fly ash are also effectively decomposed, reducing dioxin emissions and contributing to environmental protection and ecological security. This solves the problem of ineffective recovery and utilization of existing germanium-containing slag and gallium-niobium-containing iron slag, resulting in resource waste, and also addresses the difficulties in treating dioxins in existing waste incineration fly ash and the potential for secondary pollution.

[0009] This invention's comprehensive processing method achieves a germanium recovery rate exceeding 98%, with gallium and niobium enriched more than 20 times. Compared to traditional methods of enriching germanium through fuming furnace incineration, it overcomes the low germanium recovery rate and pollution problems associated with traditional pyrometallurgical methods, including the generation of large amounts of fine particulate matter. Compared to simple wet germanium recovery, the vacuum reduction process significantly reduces acid usage, resulting in substantial reductions in wastewater and waste acid emissions. This method is not only economically and efficiently advantageous but also environmentally friendly.

[0010] Preferably, the comprehensive processing method further includes: The residue is mixed with the second reagent and reacted at a third temperature for a third time to obtain a microcrystalline glass melt. The molten glass crystal is cooled and shaped, then quenched in water and cooled again to obtain fluorescent glass crystal. The second reagent is at least one of yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide.

[0011] Preferably, the third temperature is 1200℃~3000℃.

[0012] Preferably, the third time is 1 min to 15 min.

[0013] Preferably, the yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide account for 5%~20%, 3%~7%, 5%~20%, 5%~20%, and 5%~10% of the mass percentage of the residue, respectively.

[0014] Preferably, the mass ratio of the residue to the second reagent is 1:1 to 1:3.

[0015] Preferably, the fluorescent microcrystalline glass is used as a material for LED fluorescent lamps.

[0016] Preferably, the method for treating the residue includes: crushing the residue and then adding a second reagent to obtain mixed glass; The mixed glass is placed in a muffle furnace and held at a temperature of 1200℃~3000℃ for 1min~15min to obtain microcrystalline glass melt. While still hot, pour the molten glass into a mold, cool it to solidify, remove it for heat treatment, and then cool it to room temperature to obtain fluorescent glass crystal.

[0017] Preferably, the mass ratio of the germanium-containing slag, the gallium- and niobium-containing iron slag, and the waste incineration fly ash is 5:5:1 to 20:20:1.

[0018] Preferably, the mass percentages of silica, borax, sodium carbonate, alumina, and coke powder in the total mass of the slag and waste incineration fly ash are 10%~20%, 5%~15%, 5%~15%, 5%~20%, and 2%~15%, respectively.

[0019] Preferably, the first temperature is 500℃~800℃.

[0020] Preferably, the first vacuum degree is 0.1 Pa to 103 Pa.

[0021] Preferably, the first time is 0.01s to 120s.

[0022] Preferably, the second temperature is 1000℃~3000℃.

[0023] Preferably, the second vacuum degree is 0.1 Pa to 103 Pa.

[0024] Preferably, the second time is 0.01s to 120s.

[0025] Preferably, in step S2, the reaction specifically includes: reacting the composite mixture at a temperature of 500℃~800℃ and a vacuum of 0.1Pa~103 Pa for 0.01s~120s to obtain a volatile germanium-rich product. The volatile germanium chloride can promote the decomposition of dioxins in waste incineration fly ash. After the reaction is complete, the temperature is raised to 1000℃~3000℃ and the reaction is carried out at a vacuum of 0.1Pa~103 Pa for 0.01s~120s. The mixture is then cooled to room temperature to obtain a layered intermediate product. The upper layer of the intermediate product is residue, and the lower layer is gallium-rich niobium-iron eutectic.

[0026] Preferably, the acid is a mixture of hydrochloric acid and sulfuric acid.

[0027] Preferably, the resin is a composite resin of aminophosphate and amylopectin.

[0028] Preferably, S3 specifically includes: dissolving the gallium-rich niobium-iron eutectic in a mixed acid of hydrochloric acid and sulfuric acid, and then separating gallium and niobium through an adsorption separation reaction device to achieve the recovery of rare dispersed metals, wherein the adsorption separation reaction device is filled with a composite resin of aminophosphate and a methylamine oxime.

[0029] Preferably, the concentration ratio of hydrochloric acid to sulfuric acid in the mixed acid is 0.05:1 to 1:1.

[0030] Preferably, the mass ratio of aminophosphate to amine oxime in the composite resin is 1:1 to 10:1.

[0031] The beneficial effects of this invention are: This invention relates to a comprehensive method for the co-processing of slag and waste incineration fly ash to extract rare and dispersed metals and degrade dioxins. First, through a specific combination of reagents (including silica, borax, calcium oxide, alumina, and coke powder) and reaction conditions (different temperatures and vacuum levels), the volatilization and enrichment of germanium, as well as gallium and niobium, in the slag are effectively promoted. Subsequently, through acid dissolution and resin adsorption separation steps, high-purity recovery of gallium and niobium is achieved, thereby improving resource utilization, reducing resource waste, and realizing efficient recovery of rare and dispersed metals. Second, during the separation and enrichment of rare and dispersed metals, dioxins in the waste incineration fly ash are also effectively decomposed, reducing dioxin emissions and contributing to environmental protection and ecological security. Furthermore, this comprehensive treatment method transforms slag and waste incineration fly ash, which might otherwise be considered waste, into valuable metal resources and harmless products (such as glass). This not only reduces the amount of solid waste generated but also achieves resource utilization of waste, aligning with the concept of a circular economy. This method integrates multiple steps, including the extraction of rare and dispersed metals from slag, the degradation of dioxins in waste incineration fly ash, and the separation and recovery of products, achieving process integration. By precisely controlling reaction conditions, the operation steps are simplified, and the processing efficiency and stability are improved. It has significant application value in the field of resource utilization technology for slag and waste incineration fly ash. Attached Figure Description

[0032] Figure 1 A flowchart of a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash. Detailed Implementation

[0033] The following description, with reference to preferred embodiments, illustrates the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be understood that the preferred embodiments are merely illustrative of the present invention and not intended to limit the scope of protection of the present invention.

[0034] The present invention aims to disclose a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash, in order to solve the problem that existing germanium-containing slag and gallium-niobium-containing iron slag cannot be effectively recycled and utilized, resulting in resource waste, and to solve the problem that the treatment of dioxins in existing waste incineration fly ash is difficult and easily causes secondary pollution.

[0035] like Figure 1 As shown, the integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash includes the following steps: S1. Germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash are mixed to obtain a mixture. A first reagent is added to the mixture to obtain a composite mixture. The first reagent is a mixture of silicon dioxide, borax, calcium oxide, aluminum oxide and coke powder; S2. The composite mixture is reacted for a first time under a first temperature and a first vacuum to obtain a volatile germanium-rich product and decompose dioxins in the fly ash of waste incineration. Then, it is reacted for a second time under a second temperature and a second vacuum, and cooled to obtain a layered intermediate product. The upper layer of the intermediate product is residue, and the lower layer is gallium-rich niobium-iron eutectic. The second temperature is greater than the first temperature; S3. The gallium-rich niobium-iron eutectic is dissolved in acid, and then the gallium and niobium are separated by resin adsorption, thus realizing the recovery of rare dispersed metals.

[0036] The aforementioned method, through a specific reagent combination (silicon dioxide, borax, calcium oxide, alumina, and coke powder) and specific reaction conditions (different temperatures and vacuum levels), effectively promotes the volatilization and enrichment of germanium in slag, as well as the enrichment of gallium and niobium. Further, through acid dissolution and resin adsorption separation, high-purity recovery of gallium and niobium is achieved, thereby improving resource utilization, reducing resource waste, and realizing efficient recovery of rare and dispersed metals. Secondly, during the rare and dispersed metal separation and enrichment process, dioxins in the fly ash from waste incineration are also effectively decomposed, reducing dioxin emissions and contributing to environmental protection and ecological security. The germanium recovery rate exceeds 98%, and gallium and niobium are enriched more than 20 times. Compared with traditional methods of enriching germanium through incineration in fuming furnaces, this method overcomes the low germanium recovery rate and the pollution problems of large amounts of fine particulate pollutants generated during traditional pyrometallurgical methods. Compared with simple wet germanium recovery, the vacuum reduction process significantly reduces acid usage and the discharge of wastewater and waste acid. This method is not only economically and efficiently advantageous but also environmentally friendly.

[0037] In some embodiments, the comprehensive processing method further includes: The residue was mixed with the second reagent and reacted at a third temperature for a third time to obtain a microcrystalline glass melt. The molten glass crystal is cooled and shaped, then heat-treated and cooled to obtain fluorescent glass crystal. The second reagent is a mixture of yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide.

[0038] In some embodiments, the third temperature is 1200°C to 3000°C.

[0039] In some embodiments, the third time is 1 min to 15 min.

[0040] In some embodiments, yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide account for 5%~20%, 3%~7%, 5%~20%, 5%~20%, and 5%~10% of the mass percentage of the residue, respectively.

[0041] In some embodiments, the mass ratio of the residue to the second reagent is 1:1 to 1:3.

[0042] In some embodiments, fluorescent microcrystalline glass is used as a material for LED fluorescent lamps, etc.

[0043] For example, the method for treating the residue includes: crushing the residue and then adding a second reagent to obtain mixed glass; The mixed glass is placed in a muffle furnace and held at a temperature of 1200℃~3000℃ for 1min~15min to obtain microcrystalline glass melt. While still hot, pour the molten glass into a mold, cool it to solidify, remove it for heat treatment, and then cool it to room temperature to obtain fluorescent glass crystal.

[0044] In some embodiments, the mass ratio of germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash is 5:5:1 to 20:20:1.

[0045] In some embodiments, silica, borax, sodium carbonate, alumina, and coke powder account for 10%~20%, 5%~15%, 5%~15%, 5%~20%, and 2%~15% of the total mass of the slag and waste incineration fly ash, respectively.

[0046] In some embodiments, the first temperature is 500°C to 800°C.

[0047] In some embodiments, the first vacuum degree is 0.1 Pa to 103 Pa.

[0048] In some embodiments, the first time is 0.01s to 120s.

[0049] In some embodiments, the second temperature is 1000°C to 3000°C.

[0050] In some embodiments, the second vacuum degree is 0.1 Pa to 103 Pa.

[0051] In some embodiments, the second time is 0.01s to 120s.

[0052] For example, S2 specifically includes: reacting the composite mixture at a temperature of 500℃~800℃ and a vacuum of 0.1Pa~103 Pa for 0.01s~120s to obtain a volatile germanium-rich product, which can promote the decomposition of dioxins in waste incineration fly ash. After the reaction is complete, the temperature is raised to 1000℃~3000℃ and the reaction is carried out at a vacuum of 0.1Pa~103 Pa for 0.01s~120s, and then cooled to room temperature to obtain a layered intermediate product. The upper layer of the intermediate product is residue, and the lower layer is gallium-rich niobium-iron eutectic.

[0053] In some embodiments, the acid is a mixture of hydrochloric acid and sulfuric acid.

[0054] In some embodiments, the resin is a composite resin of aminophosphate and amylopectin.

[0055] For example, S3 specifically includes: dissolving the gallium-rich niobium-iron eutectic in a mixed acid of hydrochloric acid and sulfuric acid, and then separating gallium and niobium through an adsorption separation reaction device to achieve the recovery of rare dispersed metals, wherein the adsorption separation reaction device is filled with a composite resin of aminophosphate and a methylamine oxime.

[0056] In some embodiments, the concentration ratio of hydrochloric acid to sulfuric acid in the mixed acid is 0.05:1 to 1:1.

[0057] In some embodiments, the mass ratio of aminophosphate to amine oxime in the composite resin is 1:1 to 10:1.

[0058] To make the technical problems, technical solutions, and beneficial effects solved by this application clearer, the integrated treatment method for extracting rare and dispersed metals and degrading dioxins from synergistic slag and waste incineration fly ash of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. Obviously, the specific embodiments described are only a part of the embodiments of this application, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this application or its application. Based on the specific embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0059] Where specific techniques or conditions are not specified in the detailed embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0060] like Figure 1 As shown, a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash includes the following steps: S1. Mix 10g of germanium-containing slag, 10g of gallium- and niobium-containing iron slag and 2g of waste incineration fly ash to obtain a mixture. Add 4.8g of the first reagent to the mixture to obtain a composite mixed powder. The first reagent is a mixture of silica, borax, calcium oxide and coke powder, which account for 15%, 8%, 5% and 5% of the total mass of the slag and the fly ash from the waste incineration, respectively. S2. The composite powder obtained in S1 is placed in a flash Joule furnace and reacted for 60s at a temperature of 650℃ and a vacuum of 100Pa to volatilize germanium chloride, zinc chloride and lead chloride, and to obtain the volatilized germanium-rich product germanium chloride, i.e., vacuum chlorinated volatiles. At the same time, the synergistic effect of vacuum conditions, chlorine source removal and germanium reaction and germanium chloride promotes the decomposition of dioxins in waste incineration fly ash. After the reaction is complete, the temperature is raised to 2000℃, the vacuum is kept constant, and the reaction is carried out for 120s. The mixture is then quenched and cooled to room temperature to obtain a layered intermediate product. The upper layer of the intermediate product is a residue (i.e. gallium-rich, niobium-rich roasting residue), and the lower layer is a gallium-rich, niobium-iron eutectic. S3. The lower layer of gallium-rich niobium-iron eutectic obtained in S2 is dissolved in a mixed acid of hydrochloric acid and sulfuric acid with a concentration of 1:1, and then placed in an adsorption separation reaction device containing a composite resin of aminophosphoric acid and niobium oxime with a mass ratio of 5:1 to perform adsorption separation to obtain gallium and niobium, thereby realizing the recovery of rare dispersed metals. S4. After crushing the upper layer residue obtained in S2, add 15g of the second reagent to obtain mixed glass; The mixed glass was placed in a muffle furnace and held at 2100℃ for 10 minutes to obtain microcrystalline glass melt. While still hot, pour the molten microcrystalline glass into a mold. After cooling and shaping, remove it and quench it in water. Then cool it to room temperature to obtain fluorescent microcrystalline glass, which can be used as a material for LED fluorescent lamps, etc. The second reagent consists of yttrium oxide, calcium oxide, and silicon dioxide, which account for 10%, 5%, and 5% of the mass of the residue, respectively.

[0061] like Figure 1 As shown, a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash includes the following steps: S1. Mix 20g of germanium-containing slag, 20g of gallium- and niobium-containing iron slag and 2g of waste incineration fly ash to obtain a mixture. Add 13g of the first reagent to the mixture to obtain a composite mixed powder. The first reagent is a mixture of silica, borax, calcium oxide and coke powder, which account for 10%, 10%, 10% and 5% of the total mass of the slag and the fly ash from the waste incineration, respectively. S2. The composite powder obtained in S1 is placed in a flash Joule furnace and reacted for 60s at a temperature of 600℃ and a vacuum of 10Pa to volatilize germanium chloride, zinc chloride and lead chloride, and to obtain the volatilized germanium-rich product germanium chloride, i.e. vacuum chlorinated volatiles. At the same time, germanium chloride can promote the decomposition of dioxins in the fly ash of waste incineration. After the reaction is complete, the temperature is raised to 2000℃ and the vacuum is kept constant. The reaction is carried out for 120s, and then quenched and cooled to room temperature to obtain the layered intermediate product. The upper layer of the intermediate product is residue, and the lower layer is gallium-rich niobium-iron eutectic. S3. The lower layer of gallium-rich niobium-iron eutectic obtained in S2 is dissolved in a mixed acid of hydrochloric acid and sulfuric acid with a concentration of 1:1, and then placed in an adsorption separation reaction device containing a composite resin of aminophosphoric acid and niobium oxime with a mass ratio of 7:1 to perform adsorption separation to obtain gallium and niobium, thereby realizing the recovery of rare dispersed metals. S4. After crushing the upper layer residue obtained in S2, add 10g of the second reagent to obtain mixed glass; The mixed glass was placed in a muffle furnace and held at 2100℃ for 10 minutes to obtain microcrystalline glass melt. While still hot, pour the molten microcrystalline glass into a mold. After cooling and shaping, remove it and quench it in water. Then cool it to room temperature to obtain fluorescent microcrystalline glass, which can be used as a material for LED fluorescent lamps, etc. The second reagent consists of yttrium oxide, calcium oxide, and silicon dioxide, which account for 8%, 5%, and 10% of the mass of the residue, respectively.

[0062] like Figure 1 As shown, a comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash includes the following steps: S1. Mix 8g of germanium-containing slag, 8g of gallium- and niobium-containing iron slag and 2g of waste incineration fly ash to obtain a mixture. Add 4.8g of the first reagent to the mixture to obtain a composite mixed powder. The first reagent is a mixture of silica, borax, calcium oxide and coke powder, which account for 10%, 5%, 8% and 5% of the total mass of the slag and the fly ash from the waste incineration, respectively. S2. The composite powder obtained in S1 is placed in a flash Joule furnace and reacted for 60s at a temperature of 650℃ and a vacuum of 10Pa to volatilize germanium chloride, zinc chloride and lead chloride, and to obtain the volatilized germanium-rich product germanium chloride. At the same time, the vacuum conditions, the removal of chlorine source and the reaction of germanium and germanium chloride work together to promote the decomposition of dioxins in the fly ash of waste incineration. After the reaction is complete, the temperature is raised to 2000℃, the vacuum is kept constant, and the reaction is carried out for 120s. The mixture is then quenched and cooled to room temperature to obtain the layered intermediate product. The upper layer of the intermediate product is residue, and the lower layer is gallium-rich niobium-iron eutectic. S3. The lower layer of gallium-rich niobium-iron eutectic obtained in S2 is dissolved in a mixed acid of hydrochloric acid and sulfuric acid with a concentration of 1:1, and then placed in an adsorption separation reaction device containing a composite resin of aminophosphoric acid and niobium oxime with a mass ratio of 5:1 to perform adsorption separation to obtain gallium and niobium, thereby realizing the recovery of rare dispersed metals. S4. After crushing the upper layer residue obtained in S2, add 15g of the second reagent to obtain mixed glass; The mixed glass was placed in a muffle furnace and held at 2100℃ for 10 minutes to obtain microcrystalline glass melt. While still hot, pour the molten microcrystalline glass into a mold. After cooling and shaping, remove it and quench it in water. Then cool it to room temperature to obtain fluorescent microcrystalline glass, which can be used as a material for LED fluorescent lamps, etc. The second reagent consists of yttrium oxide, calcium oxide, and silicon dioxide, which account for 5%, 10%, and 5% of the mass of the residue, respectively.

[0063] Detection and analysis: 1) The germanium-containing slag, gallium- and niobium-containing iron slag and waste incineration fly ash used in S1 of Examples 1 to 3 were analyzed by XRF, and the results are shown in Table 1.

[0064] Table 1. Elemental analysis results of germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash. As can be seen from the analysis in Table 1, the germanium content in the germanium-containing slag is 0.56%.

[0065] 2) The samples obtained in Example 1, including germanium-containing slag, gallium- and niobium-containing iron slag, vacuum chlorination volatiles, and gallium- and niobium-rich roasting residues, were subjected to a temperature of 150°C. o The nitric acid digestion of C was performed, and the contents of Ge, Ga, and Nb were determined. The results are shown in Table 2.

[0066] Table 2 shows the results of Ge, Ga, and Nb content in each sample. As can be seen from the analysis of Table 2, the recovery rate of germanium exceeds 98%, and the enrichment of gallium and niobium is more than 5 times.

[0067] 3) Analysis of dioxin content in the waste incineration fly ash used in S1 of Example 1 and the residue in S2 Table 3 Results of dioxin content in fly ash and residue from waste incineration In summary, the integrated treatment method of the present invention for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash effectively promotes the volatilization or enrichment of rare metal elements such as germanium, gallium, and niobium in slag through specific reagent combinations (silicon dioxide, borax, calcium oxide, alumina, and coke powder) and specific reaction conditions (different temperatures and vacuum levels), making it easier to separate these rare and dispersed metals from the mixture. In particular, the acid dissolution and resin adsorption separation steps achieve high-purity recovery of gallium and niobium, improving resource utilization, reducing resource waste, and realizing efficient recovery of rare and dispersed metals. Secondly, by controlling the reaction conditions (such as temperature and vacuum level), not only can rare and dispersed metals be extracted, but also harmful substances such as dioxins in waste incineration fly ash can be effectively decomposed simultaneously. Dioxins are highly toxic substances produced during waste incineration, posing long-term hazards to human health and the environment. This method reduces dioxin emissions through an integrated treatment approach, which is beneficial to environmental protection and ecological security. Thirdly, it transforms slag and incineration fly ash, which might otherwise be considered waste, into valuable metal resources and harmless byproducts (such as glass). This not only reduces the amount of solid waste generated but also achieves resource utilization of waste, aligning with the concept of a circular economy. Fourthly, this treatment method integrates multiple steps, including the extraction of rare and dispersed metals from slag, the degradation of dioxins in incineration fly ash, and the separation and recovery of products, achieving a high degree of process integration. Simultaneously, precise control of reaction conditions simplifies the operation steps and improves treatment efficiency and stability. Finally, compared with traditional methods of separately treating slag and incineration fly ash, this integrated treatment method has significant advantages in reducing environmental pollution and improving resource recovery rates. Furthermore, due to the recovery of rare and dispersed metals and the resource utilization of waste, this method also has significant economic and social benefits, demonstrating both environmental friendliness and significant economic benefits. The integrated treatment method of extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash of the present invention has shown outstanding beneficial effects in terms of resource recovery, environmental protection and economic benefits. It has promotion and application value in the field of resource utilization technology of slag and waste incineration fly ash.

[0068] The above embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention.

Claims

1. A comprehensive treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash, characterized in that, Includes the following steps: S1. Germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash are mixed to obtain a mixture. A first reagent is added to the mixture to obtain a composite mixture. The first reagent is silica, borax, calcium oxide, aluminum oxide, and coke powder; S2. The composite mixture is reacted for a first time under a first temperature and a first vacuum to obtain a germanium-rich product and decompose dioxins in the fly ash of waste incineration. Then, it is reacted for a second time under a second temperature and a second vacuum, and cooled to obtain a layered intermediate product. The first temperature is 500℃~800℃; The first vacuum degree is 0.1 Pa to 10 Pa. 3 Pa; The first time interval is 0.01s to 120s; The upper layer of the intermediate product is a residue, and the lower layer is a gallium-rich niobium-iron eutectic. The second temperature is greater than the first temperature; S3. The gallium-rich niobium-iron eutectic is dissolved in acid, and then the gallium and niobium are separated by resin adsorption, thus realizing the recovery of rare dispersed metals.

2. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 1, characterized in that, The comprehensive processing method further includes: The residue is mixed with the second reagent and reacted at a third temperature for a third time to obtain a microcrystalline glass melt. The molten glass crystal is cooled and shaped, then heat-treated and cooled to obtain fluorescent glass crystal. The second reagent is at least one of yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide.

3. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 2, characterized in that, The third temperature is 1200℃~3000℃; And / or, the third time is 1 min to 15 min.

4. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 2, characterized in that, The yttrium oxide, europium oxide, calcium oxide, silicon dioxide, and aluminum oxide account for 5%~20%, 3%~7%, 5%~20%, 5%~20%, and 5%~10% of the mass percentage of the residue, respectively. And / or, the mass ratio of the residue to the second reagent is 1:1 to 1:3; And / or, the fluorescent microcrystalline glass is used as a material for LED fluorescent lamps.

5. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 1, characterized in that, The mass ratio of germanium-containing slag, gallium- and niobium-containing iron slag, and waste incineration fly ash is 5:5:1 to 20:20:

1. And / or, the mass ratio of the germanium-containing slag to the gallium- and niobium-containing iron slag is 1:

1.

6. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 1, characterized in that, The silicon dioxide, borax, calcium oxide, aluminum oxide, and coke powder account for 10%~20%, 5%~15%, 5%~15%, 5%~20%, and 2%~15% of the total mass of the slag and waste incineration fly ash, respectively.

7. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 1, characterized in that, The second temperature is 1000℃~3000℃; And / or, the second vacuum degree is 0.1 Pa to 10 Pa. 3 Pa; And / or, the second time is 0.01s to 120s.

8. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 1, characterized in that, The acid is a mixture of hydrochloric acid and sulfuric acid; And / or, the resin is a composite resin of aminophosphate and amylopectin.

9. The integrated treatment method for extracting rare and dispersed metals and degrading dioxins from slag and waste incineration fly ash according to claim 8, characterized in that, The concentration ratio of hydrochloric acid to sulfuric acid in the mixed acid is 0.05:1 to 1:1; And / or, the mass ratio of aminophosphate to amine oxime in the composite resin is 1:1 to 10:1.

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