A method for disposing of fireworks production waste residues

Abstract

This invention relates to the field of solid waste treatment technology, and provides a method for disposing of waste residue from fireworks and firecracker production, comprising the following steps: S1, wet collection of the waste residue from fireworks and firecracker production using water to obtain a waste residue slurry; S2, solid-liquid separation of the waste residue slurry to obtain wet residue and washing water; S3, adding the wet residue to a sulfur-dissolving reactor, adding a non-polar organic solvent, stirring, and performing solid-liquid separation to obtain a sulfur-rich organic liquid and residue; S4, distilling the sulfur-rich organic liquid to obtain a non-polar organic solvent and distillate; forcibly cooling the distillate and performing solid-liquid separation to obtain sulfur and residual liquid; S5, washing the residue obtained in step S3 with water and performing solid-liquid separation to obtain washing liquid and aluminum-rich material; S6, sequentially subjecting the washing liquid to acidification, iron-carbon micro-electrolysis, and activated carbon adsorption to obtain purified water. The method provided by this invention cleverly utilizes the addition of an organic solvent to recover elemental sulfur, while simultaneously synergistically reducing perchlorate to achieve full resource recovery.

Description

Technical Field

[0001] This invention relates to a waste disposal method, specifically a method for disposing of waste residue from fireworks and firecracker production, belonging to the field of solid waste treatment and resource utilization technology. Background Technology

[0002] Fireworks and firecrackers production waste mainly originates from discarded or fallen fireworks and firecracker products during production. It often contains aluminum powder, aluminum-magnesium alloy powder, titanium powder, sulfur, and quartz sand. Currently, there are three main methods for disposing of this type of waste: water dissolution, deep burial, and incineration. Water dissolution is the most common method, which involves soaking the hazardous waste in an aqueous solution for a period of time to dissolve water-soluble substances in the explosives, thereby disrupting the composition of the explosives and rendering them ineffective in combustion and explosion. The waste is then buried. However, this method suffers from low waste utilization and generates large amounts of perchlorate-containing wastewater.

[0003] Regarding the disposal of fireworks and firecracker waste, Chinese patent CN115254916A discloses a method for treating hazardous waste from fireworks and firecrackers. The method primarily involves first preparing the waste residue into a slurry, then subjecting it to washing, flotation, and filtration to separate sulfur powder from charcoal powder and metal powder, as well as pulp residue, mud, and sand. Finally, the charcoal powder is separated from the metal powder, achieving resource recovery. However, this method suffers from the problem that sulfur powder and metal powder tightly bind with other components of the slurry, resulting in a low recovery rate. Furthermore, Chinese patent CN108787703A discloses a method for treating fireworks waste, including slurry preparation, cooking, antistatic treatment, ultrasonic treatment, and solid-liquid separation steps. This method primarily utilizes the addition of sodium hydroxide during the cooking process to cause alkaline leaching of the metal components in the waste residue, followed by resource recovery. However, this method faces the challenge of disposing of the leachate. For example, Chinese patent CN120133297A discloses a device and process for recovering and utilizing perchlorate from fireworks and firecracker waste. The process includes primary water washing, primary solid-liquid separation, concentration, secondary water washing, secondary solid-liquid separation, and crystallization steps. It can separate, recover, and utilize perchlorate, aluminum powder, and other substances from solid waste, while simultaneously treating the waste residue to reduce environmental pollution. The main method utilizes multi-stage washing and membrane concentration to achieve the enrichment and crystallization of perchlorate, thereby realizing resource recovery. However, this method only recovers perchlorate.

[0004] Treatment of wastewater from fireworks production primarily focuses on the disposal of perchlorate. For example, Chinese patent CN118515366A discloses a biological co-reduction system for nitrate and perchlorate in fireworks wastewater. This system addresses the limitations of existing physicochemical treatment technologies, such as expensive equipment, high operating costs, low treatment efficiency, and the potential for secondary pollution. The system includes an anaerobic tank for removing pollutants and improving water quality; a co-reduction tank that receives wastewater from the anaerobic tank and reduces and converts perchlorate and nitrate; an aeration tank that receives wastewater from the co-reduction tank, deodorizes the wastewater, and removes residual organic matter and ammonia nitrogen; and a membrane separation tank that receives wastewater from the aeration tank, further purifies it, and discharges it. It mainly utilizes biological reduction of perchlorate to achieve harmlessness. However, its limitation lies in the need to improve the cultivation and treatment efficiency of microorganisms in the wastewater. Summary of the Invention

[0005] To address the technical problems in existing technologies, such as the ineffective utilization of recyclable resources like sulfur and aluminum powder in fireworks and firecracker production waste, and the generation of large amounts of wastewater containing perchlorate, which is difficult to treat and prone to secondary pollution, this application aims to provide a method for disposing of fireworks and firecracker production waste. The method involves wet collection of the waste waste using water to obtain a waste slurry; solid-liquid separation of the waste slurry to obtain wet slag and washing water; adding the wet slag to a sulfur-dissolving reactor, adding a non-polar organic solvent, stirring, and performing solid-liquid separation to obtain a sulfur-rich organic liquid and residue; distilling the sulfur-rich organic liquid to obtain a non-polar organic solvent and distillate; forcibly cooling the distillate and performing solid-liquid separation to obtain sulfur and residual liquid; washing the residue obtained in step S3 with water and performing solid-liquid separation to obtain washing liquid and aluminum-rich material; and sequentially subjecting the washing liquid to acidification, iron-carbon micro-electrolysis, and activated carbon adsorption, performing solid-liquid separation to obtain purified water. The method provided by this invention can efficiently recover resources such as sulfur and aluminum powder from waste residue, while effectively treating wastewater, reducing environmental pollution, and realizing the comprehensive utilization of waste residue.

[0006] According to the first embodiment of the present invention, a method for disposing of waste residue from fireworks and firecracker production is provided.

[0007] A method for disposing of waste residue from fireworks and firecracker production, the method comprising the following steps:

[0008] S1. Use water to wet collect the waste residue from fireworks and firecrackers production to obtain waste residue slurry;

[0009] S2. Solid-liquid separation is performed on the waste residue slurry to obtain wet residue and washing water;

[0010] S3. Add the wet slag to the sulfur dissolving reactor, add a non-polar organic solvent, stir, and separate the solid and liquid to obtain sulfur-rich organic liquid and residue.

[0011] S4. The sulfur-rich organic liquid is distilled to obtain a non-polar organic solvent and a distillate; the distillate is then subjected to forced cooling and solid-liquid separation to obtain sulfur and a residual liquid.

[0012] S5. Wash the residue obtained in step S3 with water to separate the solid and liquid, and obtain washing liquid and aluminum-rich material.

[0013] S6. The washing liquid is sequentially subjected to acidification, iron-carbon micro-electrolysis and activated carbon adsorption, and solid-liquid separation is performed to obtain purified water.

[0014] Preferably, the treatment method further includes the following steps:

[0015] S7. Mix the waste generated from the aluminum-rich liquid obtained in step S5 and the iron-carbon micro-electrolysis and activated carbon adsorption in step S6 to obtain a dephosphorizing agent.

[0016] In this invention, the wet collection in step S1 specifically involves using water to wash and slurry the waste residue from fireworks and firecracker production, or spraying and slurrying it, and then stirring it.

[0017] In this invention, the solid-liquid separation in step S2 is filtration, vacuum filtration or pressure filtration.

[0018] Preferably, the washing water obtained in step S2 is returned to step S1 for wet collection of fireworks production waste and / or used for washing in step S5.

[0019] In this invention, in step S3, the nonpolar organic solvent is one or more of tetrahydronaphthalene, styrene, carbon disulfide, and toluene.

[0020] Preferably, the volume ratio of the nonpolar organic solvent to the mass of the wet residue is 2~5:1 L / kg.

[0021] In this invention, the solid-liquid separation is performed by centrifugation, filtration, vacuum filtration, or pressure filtration.

[0022] Preferably, the temperature in the sulfur dissolving reactor is controlled at 20~60℃ and the reaction time is 1~3h.

[0023] Preferably, in step S4, the obtained nonpolar organic solvent is recycled to step S3.

[0024] Preferably, the residual liquid obtained in step S4 is recycled to the sulfur dissolving reactor in step S3.

[0025] Preferably, in step S4, the forced cooling method is flash cooling; preferably, cooling to room temperature. The solid-liquid separation is centrifugation, filtration, vacuum filtration, or pressure filtration.

[0026] Preferably, in step S5, the washing water obtained in step S2 is used. The solid-liquid separation is performed by centrifugation, filtration, vacuum filtration, or pressure filtration.

[0027] Preferably, in step S6, the acidification treatment specifically involves adding an acid solution to the washing liquid and stirring until homogeneous.

[0028] Preferably, the acid solution is at least one of sulfuric acid and hydrochloric acid. The concentration of the acid solution is 5-20%. The amount of acid solution added is used to control the pH of the washing solution to be less than 3.

[0029] In this invention, step S6 specifically involves mixing the acidified solution with iron and carbon, with the amount of iron and carbon added being 0.1-0.5 kg / L of the solution volume. The reaction process requires aeration, with an air flow rate of 2-20 L / min and a reaction time of 10-30 min.

[0030] Preferably, the iron-carbon alloy filler is used, wherein the iron mass fraction is 70-80% and the carbon mass fraction is 20-30%.

[0031] In this invention, the activated carbon adsorption specifically involves mixing the solution after the iron-carbon reaction with activated carbon powder. The activated carbon particle size is 1-50 μm, preferably 1-20 μm. The reaction time is 5-20 min, the activated carbon dosage is 0.1-2%, and the reaction is stirred.

[0032] Preferably, in step S7, the specific preparation method of the dephosphorizing agent is as follows: the aluminum-rich liquid obtained in step S5, the solid waste generated by iron-carbon micro-electrolysis and activated carbon adsorption in step S6, and iron powder and calcium oxide are optionally added and mixed, stirred evenly, pelletized, and then dried or calcined to obtain the dephosphorizing agent.

[0033] Preferably, the dephosphorizing agent contains Al: 3~15%, Si: 5~10%, Fe: 5~15%, C: 5~10%, Ca: 10~15%, with the balance being O.

[0034] Preferably, the dephosphorizing agent is used as a dephosphorizing agent for steel slag.

[0035] This invention provides a specific implementation scheme:

[0036] A method for the resource-based treatment of waste residue and wastewater from fireworks and firecracker production, the specific process flow is as follows: 1) The waste residue from fireworks and firecracker production is collected wet-processed with clean water to form a slurry; 2) Then, solid-liquid separation is performed by pressure filtration to obtain waste residue with a water content of about 20% and washing water, wherein the washing water is returned to step 1) for recycling; 3) The water-containing waste residue obtained in step 2) is added to a sulfur-dissolving reactor, a non-polar organic solvent is added, and after stirring evenly, it is kept at a certain temperature for a period of time, and then solid-liquid separation is performed by pressure filtration to obtain sulfur-rich organic liquid and residue; 4) The sulfur-rich organic liquid obtained in step 3) is... The sulfur-containing organic liquid is distilled in a distillation column to recover the regenerated organic solvent. The high-temperature distillate is then forcibly cooled and centrifuged to obtain solid sulfur and residual liquid. The regenerated organic solvent and residual liquid are returned to step 3) for recycling. 5) The residue obtained in step 3) is washed with part of the washing water obtained in step 2) and separated into solid and liquid to obtain washing liquid and aluminum-rich material. 6) The washing liquid obtained in step 5) is first acidified to make its pH less than 3, and then treated by iron-carbon micro-electrolysis and activated carbon adsorption before being discharged. The waste generated in the iron-carbon micro-electrolysis and activated carbon adsorption processes is used for subsequent pelletizing and disposal. 7) The aluminum-rich material obtained in step 5) and the waste carbon powder generated in step 6) are compounded with added iron powder and calcium oxide in a certain proportion and pelletized. After drying, it can be used as a dephosphorizing agent for steel slag.

[0037] The principle of the technical solution of this invention is as follows:

[0038] 1. Separation and Enrichment of Sulfur from Waste Residue: Analysis of the waste residue showed that its elemental sulfur content was approximately 5-15%. This invention first employs wet collection, allowing sulfur powder to burn under dry conditions. Then, polar organic solvents are used to dissolve the sulfur based on the principle of "like dissolves like," such as tetrahydronaphthalene, styrene, carbon disulfide, and toluene. The sulfur-containing organic solvent is then subjected to distillation to recover 1 / 2-2 / 3 of the solvent. The nearly saturated sulfur-containing organic solvent is then cooled, causing the sulfur to precipitate due to reduced solubility. Centrifugation is then used to separate and enrich the sulfur.

[0039] 2. Synergistic Deep Purification of Perchlorate in Solutions Containing Organic Solvents and Waste Residue: The residue after dissolving sulfur, as well as the final sulfur residue, contains organic solvents. Washing with water yields a solution containing these organic solvents. Perchlorate in the waste residue enters the wash water during wet treatment. This invention mixes the two solutions before disposal, fully leveraging the complementary effects of the high COD of the organic solvents and the strong oxidizing properties of the perchlorate wastewater. By mixing and acidifying the two solutions, this invention promotes the hydrolysis of the organic solvents under acidic conditions, thereby reducing COD. Simultaneously, it allows the perchlorate to undergo a redox reaction with the organic solvents under acidic conditions, achieving both perchlorate elimination and COD reduction. The acidified and hydrolyzed solution is then added to an iron-carbon microelectrolysis system. The remaining organic solvents undergo localized redox reactions under the action of the iron-carbon microelectrolysis system, breaking down into smaller molecules, while the remaining perchlorate undergoes reductive degradation under the same system. After the above two steps of treatment, the COD and perchlorate in the wastewater can be thoroughly purified through the adsorption of activated carbon, so that the effluent meets the discharge standards.

[0040] 3. Preparation of Steel Slag Dephosphorizing Agent: Analysis of the waste slag shows that, in addition to sulfur powder, it contains 5-20% aluminum powder, 10-15% quartz, and calcite, among other substances. This invention, through organic dissolution of sulfur, achieves an aluminum powder content of 8-25%. Furthermore, waste iron-carbon materials and waste activated carbon generated from water treatment have not been effectively utilized. This invention addresses the need for a steel slag dephosphorizing agent by compounding aluminum-rich waste slag, waste iron-carbon materials, waste activated carbon, and added iron and calcium oxide, ultimately obtaining an exothermic dephosphorizing flux with the following proportions: Al: 3-15%, Si: 5-10%, Fe: 5-15%, C: 5-10%, Ca: 10-15%. This co-solvent, when used for dephosphorization of steel slag, primarily utilizes the exothermic oxidation of aluminum powder in the waste slag, the ability of silicon in the waste slag to react with calcium and silicon in the steel slag for secondary slag formation, the ability of carbon in waste iron-carbon materials and waste activated carbon to reduce high-valence phosphorus compounds in the steel slag, and the ability of iron in waste iron-carbon materials to capture reduced phosphorus in the steel slag. Through the formulation of this invention, the valuable components in the waste slag from fireworks and firecracker production can be maximized, and waste generated from wastewater can be synergistically disposed of.

[0041] In the traditional disposal process of fireworks and firecracker production waste, the complex composition of the waste, including aluminum powder, aluminum-magnesium alloy powder, titanium powder, sulfur, and quartz sand, leads to a significant reduction in waste utilization and generates large amounts of perchlorate-containing wastewater due to existing water-soluble methods. Physical separation methods are difficult to effectively separate due to the tight encapsulation of sulfur powder and metal powder in the slurry, resulting in recovery rates that cannot reach the expected levels. Chemical treatment methods face disposal difficulties due to the complex composition of the leachate. Among these, resource recovery efficiency and wastewater treatment effectiveness, as key performance indicators, are directly affected by the above problems, resulting in the inability to fully extract recyclable components from the waste, while pollutants such as perchlorate continue to accumulate during the disposal process, further restricting the overall environmental friendliness and resource recovery potential of the process. For example, at a fireworks manufacturing plant's waste treatment site, after the waste is collected by wet scrubbing to form a slurry, solid-liquid separation is performed. Sulfur powder and other metal powders, such as aluminum powder, adhere tightly to the wet slurry due to physicochemical reactions, making effective separation impossible using conventional mechanical methods. Simultaneously, the resulting wash water contains a high concentration of perchlorate, requiring transfer to a dedicated treatment unit for deep purification. In this scenario, the sulfur powder recovery process is hindered by the encapsulation effect, and the remaining metal powder is difficult to extract from the residue, disrupting the resource recovery path. Furthermore, the wash water treatment unit operates unstablely due to excessive perchlorate load, easily leading to incomplete treatment and increasing subsequent environmental risks.

[0042] For ease of understanding, the following explains some key terms in this embodiment:

[0043] Fireworks and firecrackers production waste refers to the waste generated during the production process of fireworks and firecrackers. It typically contains unburned gunpowder components, metal powders (such as aluminum powder, aluminum-magnesium alloy powder, and titanium powder), sulfur, quartz sand, and other substances. Proper disposal of this type of waste aims to reduce environmental pollution and achieve resource recycling.

[0044] Wet collection refers to the collection of waste residue from fireworks and firecracker production through contact with water. This method utilizes the wetting and dispersing effects of water to transform solid waste residue into a slurry form, facilitating subsequent processing and reducing the risk of dust dispersion.

[0045] Waste residue slurry refers to a suspension or slurry-like mixture formed by mixing waste residue from fireworks and firecracker production with water. This slurry is an intermediate product for subsequent solid-liquid separation and material extraction.

[0046] Solid-liquid separation refers to the process of separating the solid components from the liquid components of a mixture. This process is applied in multiple steps to achieve the effective separation and recovery of different substances.

[0047] Wet slag refers to the water-containing solid material separated from waste slurry after solid-liquid separation. This wet slag still contains components such as sulfur and metals that need to be recovered.

[0048] Wash water refers to water used in wet collection or washing processes, as well as liquids obtained from solid-liquid separation processes. This water may contain dissolved or suspended substances that require further treatment or recycling.

[0049] A sulfur dissolving reactor is a device used for mixing and reacting wet slag with a non-polar organic solvent. In this reactor, sulfur is dissolved by the non-polar organic solvent, thereby achieving the separation of sulfur from other solid components.

[0050] Nonpolar organic solvents are a class of organic compounds whose molecular structure has a uniform charge distribution and does not exhibit significant polarity. These solvents can effectively dissolve sulfur but are immiscible with water, facilitating subsequent separation.

[0051] Sulfur-rich organic liquid refers to an organic solvent solution containing dissolved sulfur after wet residue has reacted with a non-polar organic solvent. This liquid is a key intermediate product in sulfur extraction.

[0052] The residue refers to the solid material remaining after sulfur is dissolved in the sulfur-dissolving reactor. This residue mainly contains metal powder, quartz sand, and other components, and can be further recycled.

[0053] Distillation is a unit operation that separates components based on their differences in volatility. In this method, the nonpolar organic solvent in a sulfur-rich organic liquid is evaporated and condensed for recovery, thereby separating the sulfur from the solvent.

[0054] Distillate liquid refers to the liquid component separated from sulfur-rich organic liquid during the distillation process. This liquid mainly contains sulfur, which is then cooled and crystallized in subsequent steps.

[0055] Forced cooling refers to the process of accelerating the temperature drop of a substance through external means. This method is used to rapidly crystallize sulfur from distillation solutions, thereby improving sulfur recovery efficiency.

[0056] Sulfur refers to solid sulfur that crystallizes from distilled liquid. This sulfur can be purified and recycled as an industrial raw material.

[0057] Residual liquid refers to the liquid separated from the distillate after forced cooling and solid-liquid separation. This liquid may contain small amounts of uncrystallized sulfur and non-polar organic solvents, and can be recycled.

[0058] Aluminum-rich material refers to the solid substance mainly containing aluminum and its compounds, separated from the residue after washing. This substance has recycling value and can be used as a raw material for other industrial processes.

[0059] Acidification treatment refers to the process of adding acidic substances to a liquid to adjust its pH value to the acidic range. This treatment facilitates subsequent iron-carbon microelectrolysis and activated carbon adsorption, improving pollutant removal efficiency.

[0060] Iron-carbon microelectrolysis refers to a method of treating wastewater using micro-cells formed by iron and carbon under acidic conditions. This method removes heavy metal ions and organic pollutants from wastewater through electrochemical reactions.

[0061] Activated carbon adsorption refers to the method of removing dissolved organic matter, color, odor and other pollutants from wastewater by utilizing the porous structure and surface adsorption capacity of activated carbon.

[0062] Purified water refers to treated water that has undergone a series of treatments to meet discharge standards or reuse standards.

[0063] This invention provides a method for disposing of waste residue from fireworks and firecracker production. The method aims to recover valuable components such as sulfur and metals from the waste residue and purify the generated wastewater. In step S1, the waste residue from fireworks and firecracker production is wet-collected with water to obtain a waste residue slurry. This wet collection can be achieved in various ways. For example, the waste residue can be directly poured into a container filled with water to fully mix with the water and form a slurry. Alternatively, the waste residue and water can be manually mixed in a stirring tank to ensure that the waste residue is fully wetted and dispersed by the water. This wet collection process transforms the solid waste residue into a flowable slurry, laying the foundation for subsequent treatment. In step S2, the waste residue slurry undergoes solid-liquid separation to obtain wet residue and washing water. This solid-liquid separation can be carried out using various conventional methods. For example, the waste residue slurry can be allowed to stand, allowing the solid particles to settle due to gravity, and then the supernatant (washing water) can be poured off for separation. Alternatively, the slurry can be filtered or pressure-filtered using a simple sieve or filter cloth to retain the solid wet residue while allowing the liquid wash water to pass through. This step aims to initially separate most of the water, providing a relatively dry solid material for subsequent sulfur extraction. In step S3, the wet residue is added to the sulfur dissolving reactor, a non-polar organic solvent is added, the mixture is stirred, and then solid-liquid separation is performed to obtain a sulfur-rich organic liquid and residue. This step is crucial for sulfur extraction. A variety of non-polar organic solvents can be chosen. After mixing the wet residue with the selected non-polar organic solvent in the sulfur dissolving reactor, thorough mixing can be achieved using a mechanical stirrer to promote sulfur dissolution. After stirring, the organic liquid containing dissolved sulfur can be separated from the insoluble solid residue by simple decantation or filtration using filter paper. In step S4, the sulfur-rich organic liquid is distilled to obtain a non-polar organic solvent and a distillate; subsequently, the distillate is forcibly cooled and solid-liquid separation is performed to obtain sulfur and residue. The distillation process can be achieved by setting up a simple distillation apparatus. For example, the sulfur-rich organic liquid can be heated to the boiling point of the non-polar organic solvent to evaporate it, and then condensed and recovered using a condenser. After distillation, the resulting distillate mainly contains sulfur. Forced cooling of this distillate can be achieved by placing it in a low-temperature environment, such as an ice bath, to rapidly lower its temperature. As the temperature decreases, sulfur crystallizes and precipitates. At this point, a simple filtration operation, such as using a Buchner funnel, can be used to separate the solid sulfur from the residue. In step S5, the residue obtained in step S3 is washed with water, and solid-liquid separation is performed to obtain a washing liquid and aluminum-rich material. This washing process aims to remove any non-polar organic solvent and small amounts of sulfur that may remain on the surface of the residue. Washing can be done simply by adding an appropriate amount of water to the residue, stirring, and then allowing it to settle, or by using a simple filtration device for solid-liquid separation. The separated solid material is the aluminum-rich material, and the liquid is the washing liquid.In step S6, the washing liquid is sequentially subjected to acidification, iron-carbon micro-electrolysis, and activated carbon adsorption, followed by solid-liquid separation to obtain purified water. Acidification can be achieved by directly adding a small amount of acidic substance, such as acetic acid or citric acid, to the washing liquid and stirring to adjust the pH value. Iron-carbon micro-electrolysis can be simply performed by adding a mixture of iron filings and carbon powder to the acidified solution to induce a reaction. Activated carbon adsorption can be achieved by adding commercially available activated carbon powder to the treated solution and stirring to adsorb contaminants. Finally, a simple filtration process separates the solid substances (such as the iron-carbon reaction products and activated carbon) from the purified water.

[0064] Compared to the commonly used water-soluble method in existing technologies, this method, through wet collection (step S1) and subsequent solid-liquid separation (step S2), not only effectively controls dust pollution but, more importantly, provides suitable materials for the subsequent extraction of valuable components. Existing water-soluble methods often result in low waste residue utilization and generate large amounts of perchlorate-containing wastewater, while this method avoids these problems through refined separation. Regarding sulfur recovery, existing technologies such as Chinese patent CN115254916A have attempted to recover sulfur, but their recovery rates are low because sulfur powder is tightly bound to other components of the slurry. This embodiment achieves efficient separation of sulfur from other solid components by adding a non-polar organic solvent to the sulfur dissolving reactor (step S3), utilizing the solubility characteristics of sulfur in non-polar solvents. Subsequently, through distillation and forced cooling (step S4), high-purity sulfur can be obtained, effectively improving the recovery efficiency and quality of sulfur. This recovery path based on dissolution-crystallization effectively overcomes the problem of sulfur being bound, leading to recovery difficulties in traditional physical separation methods. For the treatment of residue, this method further purifies it through water washing (step S5) and obtains aluminum-rich material. This aluminum-rich material can be utilized as a valuable secondary resource instead of being simply landfilled, which contrasts with the low utilization rate of waste residue in existing technologies. The wastewater treatment scheme of this invention (step S6) adopts a combined process of acidification treatment, iron-carbon micro-electrolysis, and activated carbon adsorption. Acidification treatment creates favorable conditions for subsequent reactions; iron-carbon micro-electrolysis utilizes the principle of micro-batteries to efficiently remove heavy metals and some organic matter from wastewater, avoiding the problems of expensive and high operating costs of traditional physicochemical treatment equipment; activated carbon adsorption serves as a deep purification method to further remove residual pollutants, ensuring that the effluent quality meets discharge standards. This combined process works synergistically to effectively solve the challenges of difficult wastewater treatment, insufficient treatment efficiency, and easy generation of secondary pollution in existing technologies, demonstrating significant progress and practical value.

[0065] This application further proposes a step of mixing the aluminum-rich material obtained in step S5 with the waste generated from iron-carbon microelectrolysis and activated carbon adsorption in step S6 to obtain a dephosphorizing agent. The aluminum-rich material obtained in step S5 refers to the solid substance obtained after washing the residue obtained in step S3 with water and performing solid-liquid separation; its main component is an aluminum compound. This aluminum-rich material serves as an aluminum source in the preparation of the dephosphorizing agent, providing the active components required for dephosphorization. It can be used directly in its original form for mixing, or it can be pretreated by drying, grinding, etc., before mixing to optimize its physical properties and reactivity. The waste generated from iron-carbon microelectrolysis and activated carbon adsorption in step S6 refers to the solid residue obtained after acidification treatment, iron-carbon microelectrolysis, and activated carbon adsorption of the washing liquid, followed by solid-liquid separation. These wastes are typically rich in iron, carbon, and adsorbed heavy metals or organic pollutants. In the preparation of the dephosphorizing agent, these wastes can serve as iron and carbon sources; iron helps in phosphorus fixation, while carbon provides a reducing environment or serves as the framework structure of the dephosphorizing agent. These waste materials can be pre-treated by dehydration and drying before being mixed to facilitate subsequent mixing and utilization. The above-mentioned aluminum-rich material is mixed with waste materials generated from iron-carbon micro-electrolysis and activated carbon adsorption to ensure a uniform distribution of different components. Various mechanical mixing equipment can be used in the mixing process, such as mixers, drum mixers, or airflow mixing equipment, to ensure sufficient contact between the components and the formation of a homogeneous mixture. The resulting dephosphorizing agent is a functional material whose main function is to remove phosphorus from the target substance. By utilizing byproducts from waste residue treatment to prepare the dephosphorizing agent, the resource utilization of waste is achieved, and a new material source is provided for subsequent industrial applications (such as dephosphorization in steel smelting).

[0066] This application proposes a solution that effectively integrates two main solid byproducts generated during the disposal of waste residue from fireworks and firecracker production—namely, the aluminum-rich material obtained in step S5 and the waste generated from iron-carbon micro-electrolysis and activated carbon adsorption in step S6—to prepare a dephosphorizing agent with specific functions. The aluminum-rich material provides the aluminum component required for dephosphorization; aluminum can form stable aluminum phosphate compounds with phosphorus, thereby achieving phosphorus fixation. Simultaneously, the waste generated from iron-carbon micro-electrolysis and activated carbon adsorption provides iron and carbon components. Iron can form iron phosphate with phosphorus, further enhancing the dephosphorization effect, while carbon can serve as a framework material for the dephosphorizing agent or provide a reducing environment under high-temperature conditions, promoting phosphorus removal. By precisely proportioning and thoroughly mixing these wastes with different chemical properties and functions, the active components such as aluminum, iron, and carbon can work synergistically to form a multi-component, highly efficient dephosphorization system. This integrated treatment method not only avoids the complexity and cost of disposing of individual waste materials separately, but more importantly, it transforms waste that might otherwise cause an environmental burden into functional products with market value, realizing the high-value utilization of waste and thus constructing a closed-loop resource recycling model in the entire waste disposal process.

[0067] Through the above technical solution, the disposal method of this application achieves effective resource utilization of aluminum-rich materials and iron-carbon micro-electrolysis and activated carbon adsorption waste generated during the treatment of fireworks and firecracker production waste. This solution transforms waste that originally required further disposal into a high-value-added dephosphorizing agent, significantly reducing the cost and environmental risks of waste disposal and avoiding secondary pollution. Simultaneously, by synergistically integrating the effective components (such as aluminum, iron, and carbon) in different wastes, the prepared dephosphorizing agent exhibits excellent dephosphorizing performance, providing a new source of functional materials for related industrial fields, thereby improving the economic and environmental benefits of the entire waste disposal process.

[0068] In this invention, wet collection is the first step in waste disposal, aiming to transform solid waste into a easily treatable slurry. Using rinsing or spraying methods, the impact of water flow or the coverage of spray can more effectively separate and mix the waste from the production equipment or collection area with water. Both methods ensure sufficient contact between the waste and water, forming a uniform waste slurry. Furthermore, stirring further promotes the dispersion and suspension of the waste, preventing sedimentation or clumping during collection, thereby improving the uniformity of the waste slurry and the efficiency of subsequent treatment.

[0069] In this invention, the washing water obtained in step S2 is mainly water, and may contain small amounts of soluble substances or fine suspended solids. Returning it to step S1 for wet collection of fireworks production waste enables water resource recycling and significantly reduces the consumption of fresh water. Simultaneously, this washing water can also be used for washing residues in step S5, further improving water resource utilization efficiency. This recycling not only saves water resources but also reduces the total amount of wastewater requiring treatment, lowering overall disposal costs and environmental impact.

[0070] This application further proposes that in step S3, the nonpolar organic solvent can be one or more of tetrahydronaphthalene, styrene, carbon disulfide, and toluene. Nonpolar organic solvents refer to organic compounds with a uniform charge distribution in their molecules and a dipole moment of zero or near zero. They typically possess good hydrophobicity and can effectively dissolve nonpolar substances such as sulfur. In the sulfur dissolution reaction, such solvents serve as a medium to dissolve and separate sulfur from the wet slag, forming a sulfur-rich organic liquid. The volume ratio of the nonpolar organic solvent to the mass of the wet slag is preferably 2-5:1 L / kg. This ratio aims to optimize the sulfur dissolution efficiency and the economic efficiency of solvent use. An appropriate amount of solvent ensures sufficient sulfur dissolution, while too little solvent may lead to incomplete dissolution, and too much solvent will increase the energy consumption and cost of subsequent distillation recovery. The determination of this ratio is usually based on experimental optimization of factors such as the sulfur content in the wet slag, the solubility of the selected solvent for sulfur, and the reaction temperature.

[0071] This application further proposes recycling the nonpolar organic solvent obtained in step S4 to step S3; and recycling the residual liquid obtained in step S4 to the sulfur dissolution reactor in step S3.

[0072] The recycling of the non-polar organic solvent obtained in step S3 means that the non-polar organic solvent separated by distillation in step S4 is not treated as waste, but is reintroduced into the sulfur dissolving reactor in step S3 for subsequent batches of wet slag sulfur dissolving processes. This recycling can be achieved through pipeline transportation, pumping, etc., aiming to reduce the consumption of fresh non-polar organic solvent. The recycling of the residual liquid obtained in step S4 into the sulfur dissolving reactor in step S3 means that after the distillate in step S4 is forcibly cooled and subjected to solid-liquid separation, the remaining liquid portion, i.e., the residual liquid, besides recovering sulfur, is also returned to the sulfur dissolving reactor in step S3. This residual liquid may still contain a small amount of incompletely extracted sulfur or non-polar organic solvent. Recycling it to the sulfur dissolving reactor can further improve the sulfur recovery rate and reduce waste liquid discharge. This can also be achieved through pipeline transportation, pumping, etc.

[0073] This application further proposes that in step S4, the forced cooling method is flash cooling, preferably cooling to room temperature; simultaneously, the solid-liquid separation can be centrifugation, filtration, vacuum filtration, or pressure filtration. Flash cooling is a technique that rapidly cools the system by abruptly reducing the ambient pressure of the liquid, causing some of the solvent to evaporate quickly, thereby removing heat from the system. This rapid cooling mechanism can effectively promote a rapid increase in the supersaturation of the target substance (such as sulfur), inducing its rapid crystallization and forming crystals with relatively uniform particle size that are easy to separate. In addition to flash cooling, forced cooling can also be achieved through direct contact cooling (e.g., by spraying cold water or cold air) or indirect contact cooling (e.g., by a heat exchanger). Cooling the distillate to room temperature typically means cooling to ambient temperature, such as 20°C to 30°C. This temperature range is conducive to the full crystallization and precipitation of sulfur, while avoiding problems such as increased energy consumption or equipment icing that may occur due to excessively low temperatures. In some cases, the temperature can also be cooled to a specific temperature slightly higher or slightly lower than room temperature, based on the solubility curve of sulfur and actual production needs, to optimize the crystallization effect.

[0074] This application further proposes that in step S6, the acidification treatment specifically involves adding an acid solution to the washing liquid and stirring until homogeneous. Preferably, the acid solution can be at least one of sulfuric acid and hydrochloric acid. The concentration of the acid solution is preferably 5% to 20%. The amount of acid solution added is intended to control the pH value of the washing liquid to be less than 3.

[0075] Acidification is a crucial step in adjusting the pH of the washing solution. Its purpose is to provide an optimal reaction environment for subsequent iron-carbon microelectrolysis and activated carbon adsorption, thereby improving pollutant removal efficiency. This process is achieved by adding acidic substances to the washing solution. To ensure the acidic substances are fully dispersed and achieve a uniform pH, stirring is usually required. Stirring can be performed in various ways, such as mechanical stirring, gas stirring, or circulating mixing via a circulating pump. The acid solution is a chemical reagent used to adjust the pH of the washing solution. Sulfuric acid and hydrochloric acid are common strong inorganic acids with good acidity adjustment capabilities and cost-effectiveness, and are widely used in industrial wastewater treatment. Controlling the pH of the washing solution to an acidic range of less than 3 provides a favorable reaction environment for subsequent iron-carbon microelectrolysis and activated carbon adsorption, for example, promoting iron corrosion and the generation of active substances in iron-carbon microelectrolysis, or enhancing the adsorption capacity of activated carbon for certain organic pollutants.

[0076] This application further specifies that in step S6, the iron-carbon micro-electrolysis specifically involves: mixing the acidified solution with iron and carbon, wherein the amount of iron and carbon added is 0.1-0.5 kg / L of the solution volume; aeration is required during the reaction process, with an air flow rate of 2-20 L / min; and the reaction time is 10-30 min. Preferably, the iron and carbon are iron-carbon alloy fillers, wherein the iron mass fraction is 70-80% and the carbon mass fraction is 20-30%. The activated carbon adsorption specifically involves: mixing the iron-carbon reaction solution with activated carbon powder, wherein the activated carbon particle size is 1-50 μm, preferably 1-20 μm; the reaction time is 5-20 min; the activated carbon dosage is 0.1-2%; and stirring is performed during the reaction process.

[0077] Iron-carbon microelectrolysis is a technology that utilizes the formation of micro-batteries between iron and carbon under acidic conditions to remove pollutants from wastewater through electrochemical reactions. Its function lies in effectively degrading organic pollutants, removing heavy metal ions, and breaking down complexes through multiple mechanisms such as oxidation-reduction, flocculation, and adsorption, thereby achieving preliminary wastewater purification. This technology can be implemented using packed bed reactors or fluidized bed reactors, with iron-carbon particles serving as the reaction medium. The initial step of the iron-carbon microelectrolysis reaction is the mixing of the acidified solution with iron and carbon. Acidification aims to provide a suitable acidic environment for iron-carbon microelectrolysis, promoting the formation of micro-couples between iron and carbon and accelerating the electrochemical reaction. Mixing methods can include mechanical stirring, pneumatic stirring, or static mixing to ensure sufficient contact between the solution and iron and carbon, improving reaction efficiency. Aeration plays multiple roles in the iron-carbon microelectrolysis reaction. On one hand, aeration provides oxygen, promoting the oxidation of iron and generating ferric hydroxide precipitate with adsorption and flocculation effects; on the other hand, aeration can stir the solution, preventing the iron-carbon particles from caking and promoting contact between pollutants and the iron-carbon surface, improving mass transfer efficiency. Aeration can be achieved by introducing air or oxygen to the bottom of the reactor using a blower, or it can be done using a mechanical aeration device.

[0078] Activated carbon adsorption is a deep treatment technology that utilizes the porous structure of activated carbon to physically adsorb dissolved organic matter, color, odor, and other pollutants from wastewater. Its function is to further remove persistent organic pollutants that remain after micro-electrolysis treatment, improving effluent quality to meet discharge or reuse standards. Activated carbon adsorption can be implemented using various adsorption tower types, such as fixed-bed, moving-bed, or pulsed-bed adsorption. The solution after the iron-carbon reaction is mixed with activated carbon powder. Activated carbon adsorption typically occurs after iron-carbon micro-electrolysis treatment to remove pollutants that were not completely removed by micro-electrolysis. Mixing the solution with activated carbon powder increases the contact area and time between the activated carbon and pollutants, improving adsorption efficiency. Mixing methods can include mechanical stirring, pneumatic stirring, or static mixers.

[0079] This application further proposes a specific preparation method for the dephosphorizing agent, which includes: mixing the aluminum-rich liquid obtained in step S5, the solid waste generated by iron-carbon micro-electrolysis and activated carbon adsorption in step S6, and optionally adding or not adding iron powder and calcium oxide, stirring evenly, pelletizing, and then drying or calcining to finally obtain the dephosphorizing agent.

[0080] Specifically, mixing the aluminum-rich liquid obtained in step S5 with the solid waste generated from iron-carbon micro-electrolysis and activated carbon adsorption in step S6 utilizes two byproducts with different properties produced during waste residue treatment. The aluminum-rich liquid mainly provides aluminum, while the solid waste is rich in iron and carbon. Optional addition of iron powder and calcium oxide further optimizes the composition of the dephosphorizing agent. Iron powder increases the iron content in the dephosphorizing agent, enhancing its reactivity with phosphorus; calcium oxide, as an alkaline component, effectively captures phosphorus oxides, forming stable calcium phosphate, thereby improving dephosphorization efficiency. The mixing process requires stirring to achieve homogenization, ensuring sufficient contact and dispersion of all components, laying the foundation for subsequent pelletizing and heat treatment. Pelletizing involves shaping the homogenized material into particles of specific size and shape, which helps improve the physical properties of the dephosphorizing agent, such as flowability, bulk density, and reaction contact area, while reducing dust pollution and facilitating storage and transportation. Pelletizing can be achieved using equipment such as disc granulators, drum granulators, or extrusion granulators. After pelletizing, the material needs to be dried or roasted. Drying aims to remove moisture from the material, improving the mechanical strength and storage stability of the particles. Roasting, on the other hand, involves heat treatment at higher temperatures, which can promote internal chemical reactions in the material, forming a more stable crystal structure or active phase, further enhancing the reactivity and high-temperature stability of the dephosphorizing agent. Roasting can be carried out in a rotary kiln, vertical kiln, or tunnel kiln. The final dephosphorizing agent has a specific elemental composition range (aluminum, silicon, iron, carbon, calcium, and oxygen) that is optimized to ensure its best performance in the dephosphorization process of steel slag.

[0081] This invention addresses the separation of sulfur from metal elements in fireworks and firecracker production waste. First, waste is collected using a wet method. Then, sulfur is leached from the waste using an organic solvent. The leachate is then subjected to distillation, strong cooling, and centrifugal filtration to obtain high-purity elemental sulfur. Residual metal elements enter the solid phase, which is washed and filtered to obtain a filter cake containing aluminum, iron, calcium, and other metals. The filtrate is then purified by iron-carbon micro-electrolysis and activated carbon adsorption to remove organic impurities. The filter cake containing metal components is mixed with the solid phase obtained from the iron-carbon micro-electrolysis and activated carbon adsorption treatment. Iron powder and calcium oxide are added and stirred until homogeneous. After pelleting, drying, and calcination, a composite dephosphorizing agent with both high dephosphorization rate and good thermal stability is finally obtained. The technical solution provided by this invention for treating fireworks and firecracker waste not only achieves efficient recovery of sulfur resources and targeted enrichment of metal components, but also transforms residues traditionally considered hazardous waste into high-value functional materials. In the pilot application of this dephosphorizing agent in converter steel slag treatment, the dephosphorization rate reached a stable 91.3%, which is 12.6 percentage points higher than that of commercially available dephosphorizing agents, and the strength retention rate after thermal shock exceeded 85%, demonstrating excellent industrial adaptability.

[0082] Compared with the prior art, the technical solution provided by the present invention has the following beneficial technical effects:

[0083] 1. This invention provides a systematic resource utilization solution for the treatment of waste residue and wastewater from fireworks and firecracker production, which can significantly reduce costs compared to treating waste residue and wastewater separately.

[0084] 2. This invention cleverly utilizes the characteristics of adding an organic solvent to recover elemental sulfur, while simultaneously reducing perchlorate.

[0085] 3. This invention can realize the full resource utilization of waste residue from fireworks and firecracker production without generating new waste. Attached Figure Description

[0086] Figure 1 This is a process flow diagram of a method for disposing of waste residue from fireworks and firecrackers production according to the present invention. Detailed Implementation

[0087] The technical solution of the present invention will be illustrated below with examples. The scope of protection sought by the present invention includes, but is not limited to, the following embodiments.

[0088] Example 1

[0089] A method for disposing of waste residue from fireworks and firecracker production, the method comprising the following steps:

[0090] S1. Use water to wet collect the waste residue from fireworks and firecrackers production to obtain waste residue slurry;

[0091] S2. Solid-liquid separation is performed on the waste residue slurry to obtain wet residue and washing water;

[0092] S3. Add the wet slag to the sulfur dissolving reactor, add a non-polar organic solvent, stir, and separate the solid and liquid to obtain sulfur-rich organic liquid and residue.

[0093] S4. The sulfur-rich organic liquid is distilled to obtain a non-polar organic solvent and a distillate; the distillate is then subjected to forced cooling and solid-liquid separation to obtain sulfur and a residual liquid.

[0094] S5. Wash the residue obtained in step S3 with water to separate the solid and liquid, and obtain washing liquid and aluminum-rich material.

[0095] S6. The washing liquid is sequentially subjected to acidification, iron-carbon micro-electrolysis and activated carbon adsorption, and solid-liquid separation is performed to obtain purified water.

[0096] Example 2

[0097] A method for disposing of waste residue from fireworks and firecracker production, the method comprising the following steps:

[0098] S1. Use water to wet collect the waste residue from fireworks and firecrackers production to obtain waste residue slurry;

[0099] S2. Solid-liquid separation is performed on the waste residue slurry to obtain wet residue and washing water;

[0100] S3. Add the wet slag to the sulfur dissolving reactor, add a non-polar organic solvent, stir, and separate the solid and liquid to obtain sulfur-rich organic liquid and residue.

[0101] S4. The sulfur-rich organic liquid is distilled to obtain a non-polar organic solvent and a distillate; the distillate is then subjected to forced cooling and solid-liquid separation to obtain sulfur and a residual liquid.

[0102] S5. Wash the residue obtained in step S3 with water to separate the solid and liquid, and obtain washing liquid and aluminum-rich material.

[0103] S6. The washing liquid is sequentially subjected to acidification, iron-carbon micro-electrolysis and activated carbon adsorption, and solid-liquid separation is performed to obtain purified water.

[0104] S7. Mix the waste generated from the aluminum-rich liquid obtained in step S5 and the iron-carbon micro-electrolysis and activated carbon adsorption in step S6 to obtain a dephosphorizing agent.

[0105] Example 3

[0106] Example 2 is repeated, except that the wet collection in step S1 specifically involves washing and pulping the waste residue from fireworks and firecracker production with water; the solid-liquid separation in step S2 is centrifugal filtration, and the washing water obtained in step S2 is returned to step S1 for wet collection of the waste residue from fireworks and firecracker production.

[0107] Example 4

[0108] Example 3 was repeated, except that in step S3, the non-polar organic solvent was tetrahydronaphthalene, and the volume ratio of the non-polar organic solvent to the wet slag was 2:1 L / kg. The temperature in the sulfur dissolving reactor was controlled at 30°C, and the reaction time was 1 hour.

[0109] Example 5

[0110] Example 3 was repeated, except that in step S3, the non-polar organic solvent was styrene, and the volume ratio of the non-polar organic solvent to the mass of the wet slag was 4:1 L / kg. The temperature in the sulfur dissolving reactor was controlled at 40°C, and the reaction time was 2 hours.

[0111] Example 6

[0112] Example 3 was repeated, except that in step S3, the non-polar organic solvent was toluene, and the volume ratio of the non-polar organic solvent to the wet slag was 3:1 L / kg. The temperature in the sulfur dissolving reactor was controlled at 250°C, and the reaction time was 1.5 h.

[0113] Example 7

[0114] Example 4 is repeated, except that in step S4, the non-polar organic solvent obtained is recycled to step S3; and the residual liquid obtained in step S4 is recycled to the sulfur dissolving reactor in step S3.

[0115] Example 8

[0116] Repeat Example 7, except that the forced cooling method is flash cooling, cooling to room temperature.

[0117] Example 9

[0118] Repeat Example 8, except that in step S5, the washing water obtained in step S2 is used.

[0119] Example 10

[0120] Example 9 is repeated, except that in step S6, the iron-carbon micro-electrolysis specifically involves mixing the acidified solution with iron and carbon at a concentration of 0.3 kg / L of the solution volume. Aeration is required during the reaction process, with an air flow rate of 10 L / min and a reaction time of 20 min. The iron and carbon are iron-carbon alloy fillers, wherein the iron mass fraction is 75% and the carbon mass fraction is 25%.

[0121] The activated carbon adsorption process specifically involves mixing the solution after the iron-carbon reaction with activated carbon powder. The activated carbon used has a particle size of 10 μm, the reaction time is 10 min, the activated carbon dosage is 1%, and the reaction is stirred during the process.

[0122] Example 11

[0123] Example 10 is repeated, except that in step S7, the specific preparation method of the dephosphorizing agent is as follows: the aluminum-rich liquid obtained in step S5, the solid waste generated by iron-carbon micro-electrolysis and activated carbon adsorption in step S6, iron powder and calcium oxide are mixed, stirred evenly, pelletized, and then dried or calcined to obtain the dephosphorizing agent; wherein, in the dephosphorizing agent, the mass content percentage of each element is: Al: 10%, Si: 8%, Fe: 10%, C: 8%, Ca: 12%, O: 52%.

[0124] Application Example 1

[0125] 100 kg of sulfur-containing waste residue from a fireworks manufacturing company was collected using 80 L of water, and the sulfur content was determined to be 18.7%. After preliminary washing and separation, 85 kg of wet residue was obtained. 1 kg of wet residue was added to a sulfur-dissolving reactor along with 2 L of carbon disulfide. The reaction was stirred at 25 °C for 1.5 h. After filtration, a sulfur-rich organic liquid and residue were obtained, with a sulfur dissolution rate of 90.42%. The sulfur-rich organic liquid was then distilled to obtain carbon disulfide and a distillate. The carbon disulfide was returned to the sulfur-dissolving reactor, and the distillate was forcibly cooled using a flash evaporator. After filtration, sulfur was obtained, with a sulfur recovery rate of 87.35%. The residue from the sulfur-dissolving reaction was washed with water to remove residual organic matter, yielding an aluminum-rich material. The COD content of the washing liquid was 866.39 mg / L. The pH of the washing solution was adjusted to 2.5 using 10% sulfuric acid. Then, 0.2 kg / L of iron-carbon was added to the adjusted solution. The iron-carbon mixture contained 77% iron and 23% carbon. Aeration was performed during the reaction at an air flow rate of 10 L / min for 15 min. After the reaction, the water was drained, and 0.5% powdered activated carbon with a particle size of 10 μm was added. The mixture was stirred for 10 min, and the COD of the effluent was measured to be 43.72 mg / L. The resulting waste activated carbon was mixed with iron-carbon and aluminum-rich material, ball-milled, pelletized, and then dried to obtain a steel slag dephosphorizing agent. The composition of the obtained dephosphorizing agent was Al: 8.73%, Si: 6.54%, Fe: 9.82%, C: 8.96%, Ca: 11.42%, with the balance being O. This dephosphorizing agent exhibited excellent stability and activity in converter steelmaking dephosphorization tests, with a stable dephosphorization rate exceeding 87.6%, and a low phosphorus distribution ratio in the slag (L... p The concentration was increased to 48.3, which is nearly 1.8 times higher than that of traditional calcium-based dephosphorizing agents.

[0126] Application Example 2

[0127] Another batch of 95 kg of fireworks waste (sulfur content 19.2%) was treated using the same process, yielding 82 kg of wet slag. 1 kg of wet slag was added to a sulfur-dissolving reactor along with 3 L of tetrahydronaphthalene. The reaction was stirred at 25°C for 1.5 h. Filtration yielded a sulfur-rich organic liquid and residue, with a total sulfur recovery rate of 91.17% and a COD of 902.15 mg / L for the washing liquid. After iron-carbon-activated carbon synergistic treatment, the COD decreased to 45.63 mg / L. The prepared dephosphorizing agent had the following composition: Al: 8.81%, Si: 6.47%, Fe: 9.90%, C: 8.89%, Ca: 11.50%, with the balance being O. In the converter dephosphorization test, the dephosphorization rate was 89.8%. p It reached 48.7.

[0128] Application Example 3

[0129] 98 kg of the third batch of fireworks waste (sulfur content 19.5%) was treated using the same process, yielding 83.5 kg of wet slag. 1 kg of the wet slag was added to a sulfur-dissolving reactor, along with 2.5 L of carbon disulfide and 0.5 L of tetrahydronaphthalene mixed solvent. The mixture was stirred at 25°C for 1.2 h, and filtered to obtain a sulfur-rich organic liquid and residue. The total sulfur recovery rate reached 98.42%, and the COD of the washing liquid was 873.61 mg / L. After the same iron-carbon-activated carbon synergistic treatment, the COD decreased to 42.85 mg / L. The dephosphorizing agent was composed of Al: 8.79%, Si: 6.51%, Fe: 9.87%, C: 8.92%, Ca: 11.47%, with the balance being O. In the converter dephosphorization test, the dephosphorization rate reached 93.1%. p Increased to 49.2.

[0130] The above description is merely an embodiment of this application and is not intended to limit the scope of protection of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application.

Claims

1. A method for disposing of waste residue from fireworks and firecracker production, the method comprising the following steps: S1. Use water to wet collect the waste residue from fireworks and firecrackers production to obtain waste residue slurry; S2. Solid-liquid separation is performed on the waste residue slurry to obtain wet residue and washing water; S3. Add the wet slag to the sulfur dissolving reactor, add a non-polar organic solvent, stir, and separate the solid and liquid to obtain sulfur-rich organic liquid and residue. S4. The sulfur-rich organic liquid is distilled to obtain a non-polar organic solvent and a distillate; the distillate is then subjected to forced cooling and solid-liquid separation to obtain sulfur and a residual liquid. S5. Wash the residue obtained in step S3 with water to separate the solid and liquid, and obtain washing liquid and aluminum-rich material. S6. The washing liquid is sequentially subjected to acidification, iron-carbon micro-electrolysis and activated carbon adsorption, and solid-liquid separation is performed to obtain purified water.

2. The treatment method of claim 1, characterized in that: The treatment method also includes the following steps: S7. Mix the waste generated from the aluminum-rich liquid obtained in step S5 and the iron-carbon micro-electrolysis and activated carbon adsorption in step S6 to obtain a dephosphorizing agent.

3. The treatment method of claim 1, characterized in that: The wet collection method described in step S1 specifically involves washing or spraying water to slurry the waste residue from fireworks and firecracker production, followed by stirring; and / or The solid-liquid separation in step S2 is filtration, vacuum filtration or pressure filtration; preferably, the washing water obtained in step S2 is returned to step S1 for wet collection of fireworks and firecracker production waste and / or used for washing in step S5.

4. The treatment method of claim 1, characterized in that: In step S3, the non-polar organic solvent is one or more of tetrahydronaphthalene, styrene, carbon disulfide, and toluene; preferably, the volume ratio of the non-polar organic solvent to the mass of the wet residue is 2~5:1 L / kg; and / or The solid-liquid separation is performed by centrifugation, filtration, vacuum filtration, or pressure filtration. Preferably, the temperature in the sulfur dissolving reactor is controlled at 20~60℃ and the reaction time is 1~3h.

5. The treatment method of claim 1, characterized in that: In step S4, the obtained nonpolar organic solvent is recycled to step S3; The residual liquid obtained in step S4 is recycled to the sulfur dissolving reactor in step S3.

6. The treatment method of claim 1, characterized in that: In step S4, the forced cooling method is flash cooling; preferably, cooling to room temperature; and / or The solid-liquid separation is performed by centrifugation, filtration, vacuum filtration, or pressure filtration.

7. The treatment method of claim 1, characterized in that: In step S5, the washing process uses the washing water obtained in step S2; and / or The solid-liquid separation is performed by centrifugation, filtration, vacuum filtration, or pressure filtration.

8. The treatment method according to claim 1, characterized in that: In step S6, the acidification treatment specifically involves adding an acid solution to the washing liquid and stirring until homogeneous; Preferably, the acid solution is at least one of sulfuric acid and hydrochloric acid; the concentration of the acid solution is 5-20%; and the amount of acid solution added is such that the pH of the washing solution is less than 3.

9. The treatment method according to claim 1, characterized in that: In step S6, the iron-carbon micro-electrolysis specifically involves mixing the acidified solution with iron and carbon. The amount of iron and carbon added is 0.1-0.5 kg / L of the solution volume. Aeration is required during the reaction process, with an air flow rate of 2-20 L / min and a reaction time of 10-30 min. Preferably, the iron and carbon are iron-carbon alloy fillers, wherein the iron mass fraction is 70-80% and the carbon mass fraction is 20-30%. The activated carbon adsorption specifically involves mixing the solution after the iron-carbon reaction with activated carbon powder. The activated carbon particle size is 1~50μm, preferably 1~20μm. The reaction time is 5~20 min, and the activated carbon dosage is 0.1~2%. The reaction is stirred during the process.

10. The treatment method according to claim 2, characterized in that: In step S7, the specific preparation method of the dephosphorizing agent is as follows: the aluminum-rich liquid obtained in step S5, the solid waste generated by iron-carbon micro-electrolysis and activated carbon adsorption in step S6, and iron powder and calcium oxide are optionally added or not mixed, stirred evenly, pelletized, and then dried or calcined to obtain the dephosphorizing agent. Preferably, in the dephosphorizing agent, Al: 3~15%, Si: 5~10%, Fe: 5~15%, C: 5~10%, Ca: 10~15%, and the balance is O; Preferably, the dephosphorizing agent is used as a dephosphorizing agent for steel slag.

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