Method for multi-source carbon-containing solid waste collaborative detoxification and full-component resource utilization

Abstract

The present application belongs to the technical field of solid waste resource utilization, and particularly relates to a method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. The method first controls the particle size and dries the multi-source carbon-containing solid waste to obtain high-fluorine material and solidified material. Then, the high-fluorine material and the solidified material are activated and mixed in proportion to obtain mixed material. The mixed material is co-processed in a high-temperature processing equipment under an air environment to obtain tailings and fluorine-containing flue gas. The fluorine-containing flue gas is then introduced into a collection liquid to obtain cryolite and filtrate. The tailings and aluminosilicate solid waste are mixed to obtain cementing material. The present application realizes synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. The entire synergistic disposal process is a closed-loop process without secondary pollution risk. The carbon component, the fluoride component and other inorganic salt components can be respectively applied to fuel, high-value cryolite products and high-performance cementing material, and have significant economic and environmental benefits.

Description

Technical Field

[0001] This invention belongs to the field of comprehensive utilization technology of solid waste resources, specifically involving a method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. Background Technology

[0002] Currently, the wet recycling of retired lithium-ion batteries, the production of primary aluminum, the pyrolysis of sludge, and coal mining all generate large amounts of solid waste rich in carbonaceous materials and environmentally unfriendly substances, posing both environmental pollution risks and the potential for resource utilization. Therefore, achieving the synergistic detoxification and full-component resource utilization of these multi-source carbonaceous solid wastes is of great significance to the national strategy of ecological civilization construction and resource security. Domestic and international methods for treating these carbonaceous solid wastes mainly fall into the following categories:

[0003] The first method is landfill disposal, which mainly involves refining the carbonaceous solid waste into fine particles, compressing it, and then landfilling it in a seepage-proof site. Simultaneously, drainage pipes are laid at the bottom of the site to divert leachate for detoxification, thus achieving safe disposal of the carbonaceous solid waste. Its disadvantages include large land occupation, a high risk of leakage and environmental pollution, and the failure to effectively utilize a large amount of high-quality carbonaceous materials and high-value fluorides.

[0004] The second method is flotation, which mainly utilizes the difference in wettability between carbon and non-carbon components in carbon-containing solid waste. Through the interaction between surfactants and carbon components, carbon particles in the slurry come into contact with and collide with a large number of bubbles generated by the surfactants, eventually adhering to the surface of the bubbles and floating out, thus achieving effective recovery of carbon components from carbon-containing solid waste. Its disadvantages are that the recovered carbonaceous materials have a relatively low fixed carbon content, lack large-scale resource utilization pathways, and some water-soluble toxic substances enter the flotation solution, posing a serious risk of secondary pollution.

[0005] The third method is direct resource recovery, which mainly utilizes the high energy density of carbon components in carbon-containing solid waste. The carbon-containing solid waste, crushed to a certain particle size, is directly added to the blast furnace ironmaking or cement production process. The carbon components burn, generating a large amount of heat, while the non-carbon components enter the slag or cement matrix, thus achieving detoxification and resource utilization of the carbon-containing solid waste. Its disadvantages include the high sulfur content producing large amounts of polluting gases, and the conversion of high-value fluorides into solid residues, posing a significant risk of secondary pollution.

[0006] The fourth method is the recovery of valuable components. This primarily relies on the phase change characteristics of non-carbon components in carbonaceous solid waste. It involves selecting high-temperature treatment, wet leaching, or molten salt roasting to construct a single- or multi-stage recovery system. This allows for the recovery of the refined carbonaceous solid waste, achieving a tiered recovery of carbon components and various non-carbon valuable components. Its disadvantages include high-temperature treatment resulting in significant energy consumption and carbon emissions, wet leaching involving highly corrosive agents such as acids and alkalis, and molten salt roasting being a complex and costly process. Summary of the Invention

[0007] To address the problems existing in the prior art, the main objective of this invention is to propose a method for the synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. This method enables the synergistic and safe disposal of toxic substances in multi-source carbon-containing solid waste, the dilution of sulfur content, and the optimization of the combustion process. The waste gas and waste residue are used to synthesize high-value fluorides and prepare cementitious materials, respectively. This method is characterized by high efficiency, simple process, and significant economic and environmental benefits.

[0008] To address the aforementioned technical problems, according to one aspect of the present invention, the present invention provides the following technical solution:

[0009] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0010] S1. The multi-source carbon-containing solid waste is subjected to particle size control and drying treatment in sequence, and is divided into high-fluorine materials and solidified materials.

[0011] S2. Add the high-fluorine material and the cured material in a certain proportion and then perform activation and mechanical mixing to obtain a mixture.

[0012] S3. The mixture is subjected to high-temperature co-treatment in an air environment to obtain tailings and fluorine-containing flue gas;

[0013] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Induction agent is added, pH is adjusted, and solid-liquid separation is performed in sequence to obtain cryolite and filtrate.

[0014] S5. Mix the tailings and aluminosilicate solid waste, add an alkaline activator, and sequentially process through wet mixing, alkaline activation, gas generation, curing, and autoclaving to obtain a cementitious material.

[0015] The multi-source carbon-containing solid waste in this invention refers to solid waste with carbon as its main component from different industries, primarily coal gangue from the coal industry, waste cathode carbon blocks from the aluminum electrolysis industry, pyrolysis residue of oily sludge from the petroleum industry, and wet leaching carbon slag from retired lithium-ion batteries generated from the waste battery recycling industry. Among these, waste cathode carbon blocks and wet leaching carbon slag from retired lithium-ion batteries have high soluble fluorine content and are classified as high-fluorine materials. Coal gangue and oily sludge pyrolysis residue have abundant aluminum, silicon, and calcium content, exhibiting good solidification effects for soluble fluorine, and are classified as solidified materials.

[0016] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste described in this invention, the high-fluorine material includes at least one of wet leaching carbon slag from retired lithium-ion batteries and waste cathode from aluminum electrolysis, and the solidified material includes at least one of pyrolysis carbon slag from oily sludge and coal gangue.

[0017] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste described in this invention, in step S1, the high-fluorine material and the solidified material have the same particle size range, which is one of 3-5mm, 1-3mm, 0.15-1mm, 0.074-0.15mm, and <0.074mm.

[0018] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste described in this invention, in step S2, the mass ratio of high-fluorine material to solidified material is 0.5:1 to 10:1, and the activation mixing time is 10 to 120 minutes. Mechanical activation is used to mix the high-fluorine material and the solidified material to simultaneously enhance their reactivity.

[0019] In a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste described in this invention, in step S3, the co-treatment temperature is 400–1000°C, and the co-treatment time is 0.5–5 hours. During the co-treatment process, the appropriate reaction temperature allows the soluble fluorine in the high-fluorine material and the aluminum, silicon, and calcium in the solidified material to undergo a solidification reaction. Simultaneously, the combustion of carbon can promote this process and generate calorific value as fuel, thus achieving resource utilization.

[0020] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to the present invention, in step S4, the inducing agent is one or more of aluminum hydroxide, sodium hydrogen fluoride, sodium aluminate, aluminum fluoride, and aluminum oxide, the amount of the inducing agent added is 1wt%-10wt%, and the pH adjustment range is 4-8.

[0021] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to the present invention, in step S4, the filtrate is refluxed into the aqueous solution of step S4.

[0022] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to the present invention, in step S4, the molecular ratio of cryolite is 2.8 to 3.0.

[0023] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste described in this invention, in step S5, the tailings and aluminosilicate solid waste are mixed at a mass ratio of 1:99-20:80, and the amount of alkali activator added is 5% to 20% of the total mass of the tailings and aluminosilicate solid waste, wherein the alkali activator is one of quicklime and hydrated lime.

[0024] As a preferred embodiment of the method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste described in this invention, in step S5, the aluminosilicate solid waste is one or more of lead-zinc slag, electrolytic manganese slag, slag, fly ash, silicon slag, and gold slag.

[0025] The beneficial effects of this invention are as follows:

[0026] This invention starts from the resource and environmental interaction attributes of multi-source carbon-containing solid waste, and realizes the synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. The entire synergistic treatment process is a closed-loop treatment with no risk of secondary pollution. At the same time, it does not require the use of additional chemical agents and has low treatment costs. The carbon components, fluoride components and other inorganic salt components in multi-source carbon-containing solid waste can be used for fuels, high-value cryolite products and high-performance cementitious materials, respectively, and have significant economic and environmental benefits. Detailed Implementation

[0027] The technical solutions described below in conjunction with the embodiments will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] According to one aspect of the present invention, the present invention provides the following technical solution:

[0029] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0030] S1. The multi-source carbon-containing solid waste is subjected to particle size control and drying treatment in sequence, and is divided into high-fluorine materials and solidified materials.

[0031] S2. Add the high-fluorine material and the cured material in a certain proportion and then perform activation and mechanical mixing to obtain a mixture.

[0032] S3. The mixture is subjected to high-temperature co-treatment in an air environment to obtain tailings and fluorine-containing flue gas;

[0033] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Induction agent is added, pH is adjusted, and solid-liquid separation is performed in sequence to obtain cryolite and filtrate.

[0034] S5. Mix the tailings and aluminosilicate solid waste, add an alkaline activator, and sequentially process through wet mixing, alkaline activation, gas generation, curing, and autoclaving to obtain a cementitious material.

[0035] On the one hand, this invention fully utilizes the environmental interaction properties of multi-source carbon-containing solid waste to achieve synergistic detoxification of various toxic substances (soluble fluorides, highly toxic cyanides, organic matter, and heavy metals). First, by utilizing the abundant calcium, aluminum, silicon, iron, and sulfur components in the solidified materials (including pyrolysis carbon slag from oily sludge and coal gangue), and relying on the high-heat environment created by the combustion of carbonaceous materials, highly efficient solidification of soluble fluorides with high leaching concentrations in high-fluoride materials (wet leaching carbon slag from retired lithium-ion batteries and waste cathodes from aluminum electrolysis) is achieved, with a solidification rate of ≥99.4%. Second, by designing a high-temperature oxidation environment and utilizing the high-heat environment generated by the combustion of carbonaceous materials, the oxidative decomposition of cyanides and organic matter in high-fluoride materials can be achieved, with a decomposition rate of ≥95.0%. Furthermore, heavy metals (Ni, Zn, Pb) in carbonaceous solid waste are simultaneously solidified by the aluminosilicate system in the solidified material during the soluble fluoride solidification process, with leaching concentrations ≤0.01 mg / L, 0.02 mg / L, and 0.001 mg / L, respectively. Finally, a cementitious material was innovatively prepared by blending tailings, where residual soluble fluorides achieved deep solidification under the synergistic effect of quicklime calcification and the cementitious system, with a leaching concentration ≤5 mg / L.

[0036] On the other hand, this invention fully utilizes the resource interaction attributes of multi-source carbon-containing solid waste to achieve the resource utilization of all components (carbon components, fluoride components, and other inorganic salt components) of carbon-containing solid waste. First, by co-treating low-sulfur carbon-containing solid waste (wet leaching carbon slag from decommissioned lithium-ion batteries and waste cathodes from aluminum electrolysis) with high-sulfur carbon-containing solid waste (including pyrolysis carbon slag from oily sludge and coal gangue), the sulfur content is diluted (≤2%) while ensuring calorific value, effectively enhancing the application potential and product value of multi-source carbon-containing hazardous waste in the power and cement industries. Second, by co-treating high-ignition-point carbon-containing solid waste (wet leaching carbon slag from decommissioned lithium-ion batteries and waste cathodes from aluminum electrolysis) with low-ignition-point carbon-containing solid waste (including pyrolysis carbon slag from oily sludge and coal gangue), the combustion process can be effectively slowed down, improving the combustion performance of multi-source carbon-containing hazardous waste. Furthermore, through an innovative design utilizing the synergistic effect of inducing agents and pH, high-value cryolite with a high molecular weight ratio (2.8-3.0) and qualified elemental composition (F≥52%, Al≥52%, Na≤33%) was synthesized from fluorinated flue gas, successfully achieving high-value utilization of fluoride components. Finally, based on the high reactivity of silicon and aluminum components in tailings after high-temperature treatment, a cementitious material with excellent mechanical properties (compressive strength ≥4.0MPa) was prepared by low-dosage blending, realizing the resource utilization of multiple valuable components (aluminum, silicon, calcium, iron) in multi-source carbonaceous solid waste.

[0037] Preferably, the high-fluorine material includes at least one of wet leaching carbon slag from decommissioned lithium-ion batteries and waste cathode from aluminum electrolysis, and the solidified material includes at least one of pyrolysis carbon slag containing oily sludge and coal gangue.

[0038] Preferably, in step S1, the high-fluorine material and the cured material have the same particle size range, which is one of 3-5 mm, 1-3 mm, 0.15-1 mm, 0.074-0.15 mm, and <0.074 mm.

[0039] Preferably, in step S2, the mass ratio of the high-fluorine material to the cured material is 0.5:1 to 10:1, and the activation mixing time is 10 to 120 min.

[0040] Preferably, in step S3, the total processing temperature is 400-1000℃ and the total processing time is 0.5-5h.

[0041] Preferably, in step S4, the inducing agent is one or more of aluminum hydroxide, sodium hydrogen fluoride, sodium aluminate, aluminum fluoride, and aluminum oxide, and the amount of the inducing agent added is 1wt%-10wt%, with the pH range being 4-8.

[0042] Preferably, in step S4, the filtrate is refluxed into the aqueous solution of step S4. Before reflux, the concentrations of Na, Al, and F in the filtrate are measured. Based on this, the addition of the inducing agent is appropriately reduced to ensure that the ion concentration of the solution in step S4 remains near the theoretical concentration.

[0043] Preferably, in step S4, the molecular ratio of cryolite is 2.8 to 3.0.

[0044] Preferably, in step S5, the tailings and aluminosilicate solid waste are mixed at a mass ratio of 1:99-20:80, and the amount of alkali activator added is 5% to 20% of the total amount of tailings and aluminosilicate solid waste.

[0045] Preferably, in step S5, the aluminosilicate solid waste is one or more of lead-zinc slag, electrolytic manganese slag, slag, fly ash, silicon slag, and gold slag.

[0046] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0047] In the following embodiments, the specific component mass percentages of the multi-source carbonaceous solid waste used are as follows:

[0048] Waste cathode from aluminum electrolysis: 58.41% C, 19.63% F, 12.07% Na, 3.02% Al, 1.48% Ca, 0.83% Si, balance impurities.

[0049] Pyrolysis carbon residue of oily sludge: 34.86% C, 23.35% Fe, 1.05% Na, 3.82% Al, 5.15% Ca, 4.29% Si, balance impurities.

[0050] Retired lithium-ion battery wet leaching carbon residue: 85.00% C, 3.92% Al, 0.80% Si, 0.39% P, balance impurities.

[0051] Coal gangue: 25.66% C, 5.06% Fe, 1.15% Ca, 11% Al, 16.73% Si, 0.77% Na, balance impurities.

[0052] Example 1

[0053] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0054] S1. The waste cathode from aluminum electrolysis and the pyrolysis carbon residue of oily sludge are subjected to particle size control and drying treatment in sequence to obtain high-fluorine material and solidified material with a particle size range of 0.15-0.074mm.

[0055] S2. Mix the high-fluorine material and the cured material in a planetary ball mill at a mass ratio of 3:7 for 30 minutes and a mixing speed of 250 r / min to obtain a mixture.

[0056] S3. The mixture was placed in a corundum boat and loaded into a muffle furnace, then co-treated in air at a temperature of 800℃ for 1.5 hours to obtain tailings and fluorine-containing flue gas. The solidification rate of soluble fluoride was 99.46%, and the decomposition rate of cyanide was 99.34% (the soluble fluoride and soluble cyanide content of the waste cathode were measured before treatment; after high-temperature treatment with pyrolysis carbon slag containing oily sludge, the soluble fluoride and soluble cyanide content of the residue were measured, and the results were calculated based on the changes before and after treatment).

[0057] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducer consists of aluminum fluoride and aluminum hydroxide, added at 4 wt%, and the pH adjustment range is 6.

[0058] S5. Mix the tailings and lead-zinc slag at a mass ratio of 5:95, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0059] In this embodiment, the molecular ratio of the synthesized cryolite is 2.86, and the mass percentages of F, Al, and Na are 54.16%, 12.88%, and 31.37%, respectively; the compressive strength of the cementitious material is 5.5 MPa, and the concentration of soluble fluoride is 2.47 mg / L.

[0060] Example 2

[0061] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0062] S1. The carbon slag and coal gangue from the wet leaching of retired lithium-ion batteries are subjected to particle size control and drying treatment in sequence to obtain high-fluorine material and solidified material with a particle size range of <0.074mm.

[0063] S2. Mix the high-fluorine material and the cured material in a vibratory ball mill at a mass ratio of 4:6 for 60 minutes and a mixing speed of 200 r / min to obtain a mixture.

[0064] S3. The mixture is placed in a corundum boat and loaded into a muffle furnace, then co-treated in air at a temperature of 800℃ for 2 hours to obtain tailings and fluorinated flue gas. The solidification rate of soluble fluorides is 99.76%, and the decomposition rate of organic matter is 95.81%.

[0065] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducers are sodium aluminate and aluminum hydroxide, added at 3%, with a pH adjustment range of 6.

[0066] S5. Mix the tailings and lead-zinc slag at a mass ratio of 7:93, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0067] In this embodiment, the molecular ratio of the synthesized cryolite is 2.84, and the mass percentages of F, Al, and Na are 54.56%, 12.85%, and 31.08%, respectively; the compressive strength of the cementitious material is 4.2 MPa, and the concentration of soluble fluoride is 1.08 mg / L.

[0068] Example 3

[0069] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0070] S1. The carbon residue from wet leaching of retired lithium-ion batteries, the carbon residue from pyrolysis of oily sludge, and coal gangue are sequentially subjected to particle size control and drying treatment to obtain high-fluorine material and solidified material with a particle size range of <0.074mm.

[0071] S2. The high-fluorine material and the solidified material are mixed in a planetary ball mill at a mass ratio of 2:8 for 15 minutes at a speed of 300 r / min to obtain a mixture. The mass ratio of oily sludge pyrolysis carbon residue to coal gangue in the solidified material is 1:1.

[0072] S3. The mixture is placed in a corundum boat and loaded into a muffle furnace, then co-treated in air at a temperature of 700℃ for 1 hour to obtain tailings and fluorinated flue gas. The solidification rate of soluble fluorides is 99.54%, and the decomposition rate of organic matter is 99.04%.

[0073] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducers are aluminum hydroxide and aluminum fluoride, added at 5 wt%, and the pH adjustment range is 5.5.

[0074] S5. Mix the tailings and lead-zinc slag at a mass ratio of 3:97, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0075] In this embodiment, the molecular ratio of the synthesized cryolite is 2.87, and the mass percentages of F, Al, and Na are 54.38%, 12.78%, and 31.28%, respectively; the compressive strength of the cementitious material is 5.1 MPa, and the concentration of soluble fluoride is 1.14 mg / L.

[0076] Example 4

[0077] A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste includes the following steps:

[0078] S1. The aluminum electrolysis waste cathode, oily sludge pyrolysis carbon slag and coal gangue are sequentially subjected to particle size control and drying treatment to obtain high-fluorine material and solidified material with a particle size range of 0.15-0.074mm.

[0079] S2. The high-fluorine material and the solidified material are mixed in a planetary ball mill at a mass ratio of 3:7 for 15 minutes at a speed of 300 r / min to obtain a mixture. The mass ratio of oily sludge pyrolysis carbon residue to coal gangue in the solidified material is 2.5:1.

[0080] S3. The mixture is placed in a corundum boat and loaded into a muffle furnace, then co-treated in air at a temperature of 900℃ for 3 hours to obtain tailings and fluorine-containing flue gas. The solidification rate of soluble fluorides is 99.98%, and the decomposition rate of cyanides is 98.16%.

[0081] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducer consists of aluminum hydroxide and aluminum fluoride, added at 6 wt%, and the pH adjustment range is 5.

[0082] S5. Mix the tailings and lead-zinc slag at a mass ratio of 10:90, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0083] In this embodiment, the molecular ratio of the synthesized cryolite is 2.84, and the mass percentages of F, Al, and Na are 54.27%, 12.92%, and 31.24%, respectively; the compressive strength of the cementitious material is 4.2 MPa, and the concentration of soluble fluoride is 0.12 mg / L.

[0084] Comparative Example 1

[0085] S1. The waste cathode from aluminum electrolysis and the pyrolysis carbon residue of oily sludge are subjected to particle size control and drying treatment in sequence to obtain high-fluorine material and solidified material with a particle size range of 0.15-0.074mm.

[0086] S2. Mix the high-fluoride material and the cured material in an agate mortar at a mass ratio of 3:7 to obtain a mixture.

[0087] S3. The mixture is placed in a corundum boat and loaded into a muffle furnace, then co-treated in air at a temperature of 800℃ for 1.5 hours to obtain tailings and fluorine-containing flue gas. The solidification rate of soluble fluorides is 97.68%, and the decomposition rate of cyanides is 98.12%.

[0088] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducers are aluminum fluoride and aluminum hydroxide, added at 4%, and the pH adjustment range is 6.

[0089] S5. Mix the tailings and lead-zinc slag at a mass ratio of 5:95, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0090] In this comparative example, the molecular ratio of the synthetic cryolite was 2.61, and the mass percentages of F, Al, and Na were 57.14%, 12.88%, and 28.66%, respectively; the compressive strength of the cementitious material was 3.2 MPa, and the concentration of soluble fluoride was 76.47 mg / L.

[0091] In Comparative Example 1, the mixing method of the high-fluorine material and the solidified material in step S2 was changed from mechanical mixing to grinding mixing, which reduced the uniformity of mixing and resulted in the failure to effectively improve the reactivity. In step S3, the solidification rate of soluble fluoride and the decomposition rate of cyanide both decreased, leading to an increase in F content, a decrease in cryolite molecular ratio, a decrease in the compressive strength of gel material, and an increase in the leaching concentration of soluble fluoride in subsequent steps. As a result, the components in the multi-source carbon-containing solid waste were not fully utilized.

[0092] Comparative Example 2

[0093] 1. The waste cathode from aluminum electrolysis and the pyrolysis carbon residue of oily sludge are subjected to particle size control and drying treatment in sequence to obtain high-fluorine material and solidified material with a particle size range of 0.15-0.074mm;

[0094] S2. Mix the high-fluorine material and the cured material in a planetary ball mill at a mass ratio of 3:7 for 30 minutes and a mixing speed of 250 r / min to obtain a mixture.

[0095] S3. The mixture was placed in a corundum boat and loaded into a muffle furnace, then co-treated under nitrogen atmosphere at 800℃ for 1.5 hours to obtain tailings and fluorine-containing flue gas. The solidification rate of soluble fluorides was 97.16%, and the decomposition rate of cyanides was 98.04%.

[0096] S4. Fluorine-containing flue gas is passed into an aqueous solution for collection. Inducer addition, pH adjustment, and solid-liquid separation are performed sequentially to obtain cryolite product and filtrate. The filtrate is recycled for flue gas collection. The inducers are aluminum fluoride and aluminum hydroxide, added at 4%, and the pH adjustment range is 6.

[0097] S5. Mix the tailings and lead-zinc slag at a mass ratio of 5:95, then add an additional 15% alkali activator, and proceed with wet mixing, alkali activation, gas generation, curing, and autoclaving to obtain the cementitious material.

[0098] In this comparative example, the molecular ratio of the synthetic cryolite was 2.59, and the mass percentages of F, Al, and Na were 57.01%, 12.92%, and 28.48%, respectively; the compressive strength of the cementitious material was 3.0 MPa, and the concentration of soluble fluoride was 54.78 mg / L.

[0099] In Comparative Example 2, the atmosphere in step S3 was changed from air to nitrogen, which prevented the carbon material from burning and provided insufficient heat to promote the curing of fluorides and the decomposition of cyanides. As a result, the curing rate of soluble fluorides and the decomposition rate of cyanides decreased in step S3, leading to an increase in F content, a decrease in cryolite molecular ratio, a decrease in the compressive strength of the gel material, and an increase in the leaching concentration of soluble fluorides in subsequent steps. Consequently, the components in the multi-source carbon-containing solid waste were not fully utilized.

[0100] As can be seen from the above embodiments and comparative examples, the present invention starts from the resource and environmental interaction attributes of multi-source carbon-containing solid waste, and realizes the synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste. The entire synergistic treatment process is a closed-loop treatment with no risk of secondary pollution. At the same time, no additional chemical agents are required, and the treatment cost is low. The carbon components, fluoride components and other inorganic salt components in multi-source carbon-containing solid waste can be used for fuels, high-value cryolite products and high-performance cementitious materials, respectively, which has significant economic and environmental benefits.

[0101] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste, characterized in that, Includes the following steps: S1. The multi-source carbon-containing solid waste is subjected to particle size control and drying treatment in sequence, and divided into high-fluorine materials and solidified materials; the high-fluorine materials include at least one of the wet leaching carbon slag of retired lithium-ion batteries and waste cathodes of aluminum electrolysis, and the solidified materials include at least one of the pyrolysis carbon slag of oily sludge and coal gangue. S2. Add the high-fluorine material and the cured material in a certain proportion and then perform activation and mechanical mixing to obtain a mixture. S3. The mixture is placed in a high-temperature treatment device and co-treated in an air environment to obtain tailings and fluorine-containing flue gas; the co-treatment temperature is 400~1000℃. S4. Fluorine-containing flue gas is passed into an aqueous solution for collection, and induction agent is added, pH is adjusted, and solid-liquid separation is performed sequentially to obtain cryolite and filtrate; the induction agent is one or more of aluminum hydroxide, sodium hydrogen fluoride, sodium aluminate, aluminum fluoride, and aluminum oxide. S5. Mix the tailings and aluminosilicate solid waste, add an alkaline activator, and sequentially process through wet mixing, alkaline activation, gas generation, curing, and autoclaving to obtain a cementitious material.

2. The method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste according to claim 1, characterized in that, In step S1, the high-fluorine material and the cured material have the same particle size range, which is one of 3~5mm, 1~3mm, 0.15~1mm, 0.074~0.15mm, and <0.074mm.

3. The method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste according to claim 1, characterized in that, In step S2, the mass ratio of the high-fluorine material to the cured material is 0.5:1 to 10:1, and the activation mixing time is 10 to 120 minutes.

4. The method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to claim 1, characterized in that, In step S3, the total processing time is 0.5-5 hours.

5. The method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste according to claim 1, characterized in that, In step S4, the amount of the inducer added is 1wt%-10wt%, and the pH range is 4-8.

6. The method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to claim 1, characterized in that, In step S4, the filtrate is returned to the aqueous solution of step S4.

7. The method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste according to claim 1, characterized in that, In step S4, the molecular ratio of cryolite is 2.8 to 3.

0.

8. The method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to claim 1, characterized in that, In step S5, the tailings and aluminosilicate solid waste are mixed at a mass ratio of 1:99-20:80, and the amount of alkali activator added is 5% to 20% of the total mass of the tailings and aluminosilicate solid waste. The alkali activator is one of quicklime and hydrated lime.

9. The method for synergistic detoxification and full-component resource utilization of multi-source carbonaceous solid waste according to claim 8, characterized in that, In step S5, the aluminosilicate solid waste is slag.

10. The method for synergistic detoxification and full-component resource utilization of multi-source carbon-containing solid waste according to claim 8, characterized in that, In step S5, the aluminosilicate solid waste is one or more of lead-zinc slag, electrolytic manganese slag, fly ash, silicon slag, and gold ore slag.