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CN-121972498-A - Efficient recycling treatment method for waste residues of fireworks and firecrackers

CN121972498ACN 121972498 ACN121972498 ACN 121972498ACN-121972498-A

Abstract

The invention discloses a high-efficiency recycling treatment method of firework firecracker waste residues, which comprises the following steps of S1, sulfur dissolving and separating, S2, slurrying and leaching, namely, adding the sulfur dissolving residues into concentrated sulfuric acid for slurrying reaction to dissolve magnesium and aluminum components and simultaneously carbonizing and decomposing lead fibers, S3, solid-liquid separating and floating, namely, diluting and cooling materials after slurrying reaction and carrying out solid-liquid separation to obtain leaching solution containing magnesium and aluminum ions and leached residues, S4, preparing magnesia-alumina spinel, namely, adjusting the pH of the leaching solution to precipitate magnesium and aluminum in a precipitation form, filtering, drying filter residues and calcining to obtain the magnesia-alumina spinel. The method can safely and efficiently separate and recycle the resources such as sulfur, magnesium, aluminum and the like in the waste residue, simultaneously harmlessly remove the final residue, greatly reduce the volume and is suitable for industrial-scale continuous production.

Inventors

  • LIU SHAOBO
  • ZHANG GUANGCHUN
  • HONG JIAMING

Assignees

  • 长沙焰盾再生科技有限公司

Dates

Publication Date
20260505
Application Date
20260312

Claims (10)

  1. 1. The efficient recycling treatment method for the waste residues of the fireworks is characterized by comprising the following steps of: S1, sulfur dissolving and separating, namely placing the firework waste residue and/or firecracker waste residue into a sulfur dissolving agent, stirring and dissolving sulfur in the waste residue at 50-90 ℃, and carrying out hot filtration and separation to obtain sulfur-containing clear liquid and desulfurization residues; S2, pulping and leaching, namely adding the desulfurization residues into concentrated sulfuric acid with the mass fraction of 90% -98%, and carrying out pulping reaction according to the solid-to-liquid ratio of 1:0.5-1.5 to dissolve magnesium and aluminum components and simultaneously carbonize and decompose lead fibers in the desulfurization residues; S3, solid-liquid separation and flotation, namely diluting, cooling and solid-liquid separating the pulpified material to obtain leaching liquid containing magnesium aluminum ions and leached slag; And S4, preparing magnesia-alumina spinel, namely regulating the pH value of the leaching solution to 9-10, separating out magnesium and aluminum in a precipitation form, filtering to obtain filtrate and filter residues, drying the filter residues, and calcining to obtain the magnesia-alumina spinel.
  2. 2. The method of claim 1, wherein in the step S1, the sulfur-dissolving agent is composed of tetrahydronaphthalene and a cosolvent, the volume ratio of the tetrahydronaphthalene to the cosolvent is 4-20:1, and the cosolvent is one or more of toluene, ethylbenzene, mixed xylene and styrene.
  3. 3. The method according to claim 1, wherein in step S1, the solid-liquid separation is a pressure filtration separation.
  4. 4. The method according to claim 1, wherein in step S1, the purity of the sulfur is not less than 99.5%.
  5. 5. The method according to claim 1, wherein in step S2, the temperature of the concentrated sulfuric acid pulping leaching reaction is controlled to be 80-120 ℃.
  6. 6. The method according to claim 1, wherein in the step S1, the firework waste residue is waste residue generated in the firework production or combustion process or bottom mud formed by water precipitation of the waste residue, and the firecracker waste residue is waste residue generated in the firecracker production or combustion process or bottom mud formed by water precipitation of the waste residue.
  7. 7. The method according to claim 6, wherein when the firework waste residue is waste residue generated in the firework production process, digestion is carried out before separation of dissolved sulfur, and the digestion agent for digestion is sodium hypochlorite, sodium hydroxide, potassium hydroxide, calcium hypochlorite or one or more of the following.
  8. 8. The method according to claim 1, wherein in the step S3, the leached slag is subjected to flotation separation to obtain carbon powder and silicon dioxide, and the flotation separation further comprises aeration stirring or foaming agent addition.
  9. 9. The method according to claim 1, wherein in step S4, the filtrate is concentrated and supplemented with acid, and is returned to step S3 for recycling.
  10. 10. The method of claim 1, wherein the calcination temperature is 1200-1600 ℃.

Description

Efficient recycling treatment method for waste residues of fireworks and firecrackers Technical Field The invention belongs to the technical field of solid waste recycling, and particularly discloses a high-efficiency recycling treatment method for waste residues of fireworks and firecrackers. Background During the production or setting off process of the fireworks, a large amount of waste medicament residues, scattered falling powder and lead fragments can be generated. The waste residues belong to dangerous wastes, and commonly comprise unburned or abandoned white gunpowder, black gunpowder, firing lines and the like, and the quantity is huge. According to investigation and statistics, about 1.2 ten thousand tons of the firework firecracker production waste residue is produced every year in Hunan province, and the waste residue contains about 15% -20% of sulfur (about 2000 tons). In the conventional treatment, in order to eliminate the explosion risk, the sulfur-containing waste residues are often directly poured into a pit with water for soaking. However, this approach not only causes waste of resources (such as sulfur, etc.), but also has serious environmental impact, and the long-term accumulated bottom mud may release toxic gases (such as hydrogen sulfide) to cause personnel injury. In addition, the waste residue also contains metal components such as magnesium powder, aluminum powder and the like, lead fibers difficult to degrade and the like, and if the lead fibers are directly discarded without treatment, the environmental and safety hazards are brought. In the prior art, CN115520837B reports a technology for recovering sulfur from the dangerous waste residues of fireworks and firecrackers, and a method for recovering sulfur from the waste residues by using carbon disulfide (CS 2) as an extractant. The method can extract more than 95% of sulfur in the waste residue by CS 2 extraction and negative pressure evaporation recovery. However, carbon disulfide is a highly toxic flammable solvent, is extremely volatile and can initiate explosion when exposed to open fire, and has safety risks even when operated under the whole process water seal and vacuum conditions. In addition, the components such as magnesium aluminum in the raffinate solid are not utilized, and further treatment is still needed in the follow-up process. Therefore, a high-efficiency recycling treatment process which is safer and more environment-friendly and can comprehensively recycle useful components in the waste residues of fireworks and firecrackers is needed. Disclosure of Invention Aiming at the technical problems that waste residues generated in the production or combustion process of fireworks and bottom mud formed by water precipitation of the waste residues are difficult to recycle, the invention aims to provide an efficient recycling treatment method for the waste residues of the fireworks, which can safely and efficiently separate and recycle resources such as sulfur, magnesium, aluminum and the like in the waste residues, simultaneously harmlessly reduce the final residues, greatly reduce the volume and is suitable for industrial-scale continuous production. In order to achieve the above purpose, the invention provides a high-efficiency recycling treatment method of firework firecracker waste residues, which comprises the following steps: S1, sulfur dissolving and separating, namely placing the firework waste residue and the firecracker waste residue into a sulfur dissolving agent, stirring and dissolving sulfur in the waste residue at 50-90 ℃, and carrying out hot filtration and separation to obtain sulfur-containing clear liquid and desulfurization residues; s2, pulping and leaching, namely adding the desulfurization residues into concentrated sulfuric acid with the mass fraction of 90% -98%, and performing pulping reaction according to the solid-to-liquid ratio of 1:0.5-1.5 to dissolve magnesium and aluminum components and simultaneously carbonize and decompose lead fibers in the desulfurization residues; The concentrated sulfuric acid has strong oxidative dehydration, can rapidly dissolve magnesium aluminum components such as magnesium oxide, aluminum oxide and the like in residues to generate soluble sulfate, and simultaneously carbonizes and decomposes carbonaceous fiber substances such as residual organic firing lines and the like, thereby avoiding the blockage of subsequent pipelines and equipment. S3, solid-liquid separation and flotation, namely diluting, cooling and solid-liquid separating the pulpified material to obtain leaching liquid containing magnesium aluminum ions and leached slag; After the slurrying leaching reaction is finished, adding water into the slurry for dilution and cooling, and then obtaining leaching liquid containing magnesium aluminum ions and insoluble solid slag through solid-liquid separation. The main component of the undissolved residue is silicon dioxide and carbonaceous particles. W