A method for resourceful treatment of industrial solid waste

Abstract

The application discloses a resource treatment method of industrial solid wastes, and belongs to the technical field of solid waste treatment. First, steel slag, fly ash, red mud and copper tailings are subjected to grading pretreatment, then are mixed in proportion, are subjected to acid leaching and then alkali leaching, the leaching solution is subjected to coupling purification, and the product after purification is treated to obtain a high-value product. The application performs collaborative treatment on four typical industrial solid wastes, i.e. steel slag, fly ash, red mud and copper tailings, effectively solves the problems of great difficulty in single solid waste treatment and low utilization rate, greatly reduces the land occupation and environmental pollution caused by solid waste accumulation, and has remarkable environmental protection benefits.

Description

Technical Field

[0001] This invention relates to the field of solid waste treatment, and in particular to a method for the resource-based treatment of industrial solid waste. Background Technology

[0002] Current industrial solid waste treatment faces challenges such as complex composition of individual solid wastes, low resource utilization, and high treatment costs. Steel slag (containing CaO, Fe2O3, and SiO2), fly ash (containing Al2O3, SiO2, and Fe2O3), red mud (containing Al2O3, Fe2O3, TiO2, and rare earth elements), and copper tailings (containing Cu, Fe, SiO2, and rare metals) are typical industrial solid wastes. Treating them individually presents the following drawbacks: acid leaching of steel slag requires a large amount of acid to neutralize alkaline components, and alkaline leaching of red mud requires high temperature and pressure, resulting in high energy consumption for individual treatments; the content of valuable elements in individual solid wastes is low, leading to poor economic efficiency in extraction, such as copper content in copper tailings often being <0.5%; and reagent consumption is high during the treatment process.

[0003] In current technologies, the co-processing of multiple solid wastes is mostly limited to the mixing of two types of solid waste (such as steel slag-fly ash to make building materials), and the deep extraction of multiple elements has not been achieved.

[0004] Based on the above problems, a resource recovery method for co-processing solid waste is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a method for the resource-based treatment of industrial solid waste to solve the problems in the background art.

[0006] To achieve the above objectives, this invention provides a method for the resource-based treatment of industrial solid waste, including steel slag, fly ash, red mud, and copper tailings, characterized by comprising the following steps:

[0007] S1. Steel slag, fly ash, red mud and copper tailings are pre-treated by classification, and the pre-treated solid wastes are mixed to obtain a mixture.

[0008] S2. The mixture is placed in a stirred tank with 5-8% dilute sulfuric acid and stirred to react. After stirring, the mixture is filtered to obtain leachate A and filter residue A.

[0009] S3. Mix filter residue A with 15-20% sodium hydroxide solution, react in a high-pressure reactor, and then filter to obtain leachate B and filter residue B.

[0010] S4. The leachate A is subjected to sulfidation precipitation, extraction, ion exchange and aluminum precipitation processes in sequence to obtain iron solution, copper solution, rare earth enrichment solution and aluminum hydroxide, respectively.

[0011] S5. Carbonize, precipitate, evaporate, concentrate, cool and crystallize the leachate B to obtain calcium carbonate and sodium silicate crystals.

[0012] S6. Process the multi-component products obtained from S4 and S5 to prepare high-value products.

[0013] Preferably, in step S1, the grading and processing steps are as follows:

[0014] 1) Steel slag is crushed by jaw crusher to a particle size ≤5mm, and iron concentrate is recovered by magnetic separation with a magnetic field strength of 0.8~1.2T. The steel slag tailings are then ball-milled to 100~200 mesh using an intermittent ball milling process.

[0015] 2) Fly ash is classified using an air classifier, and 50-150 mesh components are taken for microwave desulfurization. The microwave power is 800-1200W and the microwave time is 10-15min.

[0016] 3) The red mud is dewatered by plate and frame filter press, crushed to 80-150 mesh, and then desiliconized by reverse flotation. The collector for reverse flotation is hexadecyltrimethylammonium bromide, and the dosage is 50-80 g / t.

[0017] 4) Copper tailings are ball-milled to a -200 mesh ratio of ≥85% and then subjected to magnetic separation with a magnetic field strength of 0.6~0.9T.

[0018] Preferably, in the mixture of materials S1, the mass ratio of steel slag tailings, fly ash, red mud, and copper tailings is (2.5-3):(1.5-2):(2.5-3):(1.5-2).

[0019] Preferably, in step S2, the solid-liquid ratio of the mixture to dilute sulfuric acid is 1:6 to 1:10, the stirring temperature is 60 to 80°C, the stirring speed is 150 to 200 r / min, and the reaction time is 1.5 to 2.5 h.

[0020] Preferably, in step S3, the solid-liquid ratio of filter residue A to sodium hydroxide solution is 1:4 to 1:7, the reaction temperature is 120 to 150°C, the reaction pressure is 0.3 to 0.5 MPa, and the reaction time is 2 to 3 hours.

[0021] Preferably, in step S4, H2S gas is introduced during the sulfidation precipitation process, and the pH is controlled at 2-3; the extraction process involves extraction and back-extraction, with P2O4 as the extractant, an extraction temperature of 40-50℃, and a 1.5-2 mol / L sulfuric acid solution as the back-extraction agent; the flow rate during the ion exchange process is 15-20 BV / h, and the eluent is a 3-4 mol / L hydrochloric acid solution; and the aluminum precipitation process uses ammonia water with a mass fraction of 10-20%.

[0022] Preferably, the specific steps of S4 are as follows:

[0023] 1) Sulfide precipitation: Transfer leachate A into a reaction vessel, and add dilute sulfuric acid or dilute hydrochloric acid dropwise under stirring to adjust the pH of the solution to be stable at 2-3. The stirring rate is 200-300 r / min. Then, under sealed conditions, H2S gas is introduced into the solution at a flow rate of 0.5-1 L / min while stirring is maintained. The reaction time is 30-60 min.

[0024] Then, take a small amount of the solution, filter it, and add Na2S solution. If no new precipitate is formed, it means that the heavy metal ions have been completely precipitated. If a precipitate is formed, continue the aeration reaction until no new precipitate is formed.

[0025] After stopping the aeration, continue stirring for 10 minutes, centrifuge and collect the filtrate A1;

[0026] 2) Extraction: Add the diluted filtrate A1 and P2O4 at a ratio of 3:1 to 5:1 into the extraction tower, control the pH at 2 to 3, stir for 15 to 20 minutes, let stand for layering, and separate the loaded organic phase and the extraction residue. The loaded organic phase is back-extracted with 1.5 to 2 mol / L sulfuric acid solution to obtain copper solution and iron solution.

[0027] 3) Ion exchange: Soak D401 chelating resin in 5% hydrochloric acid for 2 hours, wash with deionized water until neutral; then soak in 5% sodium hydroxide solution for 2 hours, wash with deionized water until neutral, pack into an ion exchange column with a column diameter-to-height ratio of 1:8 to 1:10, pump in the extraction residue, control the flow rate at 15 to 20 BV / h, periodically sample and detect the rare earth ion concentration in the effluent, stop adsorption when the concentration reaches 5% of the initial concentration, pass the eluent into the saturated resin column at a flow rate of 0.5 to 1 BV / h, collect the eluent until the rare earth ion concentration in the effluent is below 0.1 g / L, to obtain the rare earth enriched solution;

[0028] 4) Precipitation of aluminum: The tail liquid from ion exchange is collected and transferred into a reaction tank. Under stirring conditions, 10-20% ammonia water is slowly added dropwise to adjust the pH to between 5 and 6. Stirring is maintained for 30 minutes at a stirring rate of 150-200 r / min. After stirring is stopped, the mixture is allowed to stand for 1-2 hours. The precipitate is separated by vacuum filtration and washed with deionized water 3-4 times until Cl- is not detectable in the filtrate. The precipitate is then dried to obtain aluminum hydroxide precipitate.

[0029] Preferably, in step S5, CO2 is introduced during the carbonization precipitation process to adjust the pH to 9-10.

[0030] Preferably, the specific steps of S6 are as follows:

[0031] 1) Iron solution is subjected to oxidation, magnetic separation to remove impurities, and calcination at 600-700℃ to obtain iron oxide red; copper solution is electrolyzed to obtain electrolytic copper;

[0032] 2) After washing with water, aluminum hydroxide is calcined at 900–1000℃ for 3–4 hours to obtain aluminum oxide;

[0033] 3) The rare earth enrichment solution is subjected to precipitation and calcination to obtain mixed rare earth oxides;

[0034] 4) After drying the calcium carbonate precipitate, light calcium carbonate is obtained;

[0035] 5) The filter residue B is magnetically separated to recover residual iron. The remaining residue is mixed with quartz sand and soda ash, melted at 1400-1500℃, and then annealed by gradient cooling to obtain microcrystalline glass.

[0036] Preferably, in steps S2 and S3, the leaching tail gas is absorbed by a two-stage absorption tower, specifically: the first-stage absorption is the absorption of dilute ammonia water to produce ammonium salt, and the second-stage absorption is the deep purification of sodium hydroxide solution.

[0037] Preferably, the empty gas velocity of the two-stage absorption tower is 0.8–1.2 m / s, and the liquid-to-gas ratio is 15–20 L / m³. 3 .

[0038] Therefore, the resource-based treatment method for industrial solid waste of the present invention has the following beneficial effects:

[0039] (1) The graded pretreatment step adopts appropriate treatment methods according to the characteristics of different solid wastes, such as magnetic separation of steel slag to recover iron concentrate and microwave desulfurization of fly ash, which lays a good foundation for subsequent leaching and separation processes and improves the overall treatment efficiency.

[0040] (2) The acid-base stepwise leaching process can extract different components separately. Leachate A adopts a combination process of "sulfidation-extraction-ion exchange-precipitation", and selectively removes heavy metals (Cu) through sulfidation precipitation. 2+ Pb 2+ (etc.) P204 extraction separates iron and copper, D401 resin efficiently adsorbs rare earth elements, and finally aluminum is precipitated; leaching solution B recovers calcium and silicon through a combination of carbonization precipitation and crystallization. This coupled process solves the separation problem of multi-element coexisting systems, reduces impurity interference, and improves product purity.

[0041] (3) By processing the recovered multi-products, high-value products such as iron oxide red, electrolytic copper, mixed rare earth oxides, aluminum hydroxide, light calcium carbonate, sodium silicate crystals and microcrystalline glass can be prepared, which significantly improves the economic benefits of industrial solid waste resource utilization.

[0042] (4) The process parameters of each step, such as temperature, pressure, reaction time, and flow rate, are all within a reasonable range, making it easy to achieve industrial production. The operation process is stable and reliable, and easy to control and manage. At the same time, the leaching tail gas is treated by two-stage absorption, avoiding secondary pollution and meeting environmental protection requirements.

[0043] The technical solution of the present invention will be further described in detail below through embodiments. Detailed Implementation

[0044] The technical solution of the present invention will be further described below through embodiments.

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the content of the embodiments of the present invention. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0046] Example 1

[0047] This embodiment describes the co-treatment of four typical industrial solid wastes: steel slag, fly ash, red mud, and copper tailings. The specific steps are as follows:

[0048] S1. Staged pretreatment and mixing:

[0049] 1) Staged pretreatment:

[0050] Steel slag is crushed by jaw crusher to a particle size of ≤5mm, and iron concentrate (TFe=65%) is recovered by magnetic separation using a magnetic field strength of 0.8T. The steel slag tailings are then ball-milled to 100 mesh using an intermittent ball milling process with a ball-to-material ratio of 8:1, and the standard deviation of tailings particle size distribution is controlled to be ≤20μm.

[0051] Fly ash is classified using an air classifier. A 50-mesh sample is taken and microwave desulfurized for 10 minutes at 800W microwave power, reducing the sulfur content to below 0.5%. A real-time temperature monitoring device is added during the desulfurization process, which automatically adjusts the power when the material temperature exceeds 200℃.

[0052] The red mud was dewatered by plate and frame filter press (moisture content 28%), crushed to 120 mesh, and then subjected to reverse flotation for desilication. The collector, cetyltrimethylammonium bromide, was used at a dosage of 50 g / t. The aeration rate for this process was 0.8–1.2 m³ / t. 3 / (m 2 (For a flotation machine with a capacity of ·min, add 20g / t of sodium silicate as an inhibitor).

[0053] The copper tailings were ball-milled to -200 mesh (88%), and then magnetically separated under a 0.6T magnetic field to remove strongly magnetic impurities.

[0054] 2) Mixing:

[0055] Pretreated steel slag tailings, fly ash, red mud, and copper tailings were mixed in a mass ratio of 2.5:1.5:2.5:1.5 to obtain a mixture.

[0056] S2, dilute sulfuric acid leaching:

[0057] The mixture was placed in a stirred tank with 5% dilute sulfuric acid at a solid-liquid ratio of 1:6. A stepped heating method was used: the temperature was initially raised to 40℃ within the first 30 minutes, held for 30 minutes, and then raised to 60℃. The mixture was stirred at 150 rpm for 1.5 hours, and the solution was filtered to obtain leachate A (containing Fe). 2+ Cu 2+ Al3+, rare earth elements) and filter residue A.

[0058] S3, sodium hydroxide leaching:

[0059] Filter residue A was washed twice and then mixed with 15% sodium hydroxide solution at a solid-liquid ratio of 1:4. The mixture was then reacted in a high-pressure reactor at 120°C and 0.3 MPa for 2 hours. The high-pressure reactor was equipped with an automatic pressure relief device (which automatically opens when the pressure exceeds 0.5 MPa) and a stirring device (speed 60-80 r / min). The filtration yielded leachate B (containing Na2SiO3 and Na2CO3) and filter residue B.

[0060] S4. Treatment of leachate A:

[0061] Sulfide precipitation: Transfer leachate A into a reactor, and adjust the pH to 2 by adding dilute sulfuric acid dropwise while stirring. The stirring rate is 200 r / min, and H2S gas is introduced at a flow rate of 0.5 L / min under sealed conditions. The reaction is carried out for 30 min. A small amount of solution is filtered, and Na2S solution is added dropwise. No new precipitate is formed. The gas flow is stopped, and stirring is continued for 10 min. After centrifugation, filtrate A1 is collected.

[0062] Extraction: The diluted solution of filtrate A1 and P204 was added to the extraction tower at a ratio of 3:1. After stirring for 15 min and allowing to stand for layering, the loaded organic phase and the extraction residue were separated. The loaded organic phase was back-extracted with 1.5 mol / L sulfuric acid solution to obtain copper solution and iron solution. The pH was 2 during this process, so the extraction was not targeted at rare earth ions.

[0063] Ion exchange: D401 chelating resin was soaked in 5% hydrochloric acid for 2 hours and washed with deionized water until neutral; then soaked in 5% sodium hydroxide solution for 2 hours and washed with deionized water until neutral. It was then packed into an ion exchange column with a diameter-to-height ratio of 1:8. The extraction residue was pumped in and the flow rate was controlled at 15 BV / h. When the rare earth ion concentration in the effluent reached 5% of the initial concentration, adsorption was stopped. 3 mol / L hydrochloric acid elution agent was introduced into the saturated resin column at a flow rate of 0.5 BV / h. The eluent was collected until the rare earth ion concentration was below 0.1 g / L to obtain a rare earth enriched solution.

[0064] Aluminum precipitation: The tail liquid from ion exchange is collected and transferred into a reaction tank. 10% ammonia water is slowly added dropwise under stirring to adjust the pH to 5. Stirring is maintained for 30 minutes at a stirring rate of 150 r / min. After stirring is stopped, the mixture is allowed to stand for 1 hour. The precipitate is separated by vacuum filtration. The precipitate is washed three times with deionized water until no Cl- is present in the filtrate. The precipitate is then dried to obtain aluminum hydroxide precipitate.

[0065] S5. Treatment of leachate B:

[0066] The pH of the leachate B was adjusted to 9 by introducing CO2 with a purity of ≥99% and the pressure was 0.3 MPa. The reaction was carried out using a spray-type reaction device to obtain calcium carbide precipitate.

[0067] The remaining liquid was then evaporated, concentrated, cooled, and crystallized to obtain sodium silicate crystals.

[0068] S6. Preparation of high-value products:

[0069] Iron solution was subjected to oxidation (adding 30% H2O2, reacting at 80℃ for 2 hours), magnetic separation for impurity removal (magnetic field strength 0.4T), and calcination at 600℃ to obtain iron oxide red; copper solution was electrolyzed (using an insoluble anode, i.e., a titanium-based coated electrode, with a current density of 250 A / m). 2 Electrolytic copper is obtained by purifying the electrolyte at a temperature of 60℃ every 24 hours.

[0070] Aluminum hydroxide was washed three times with deionized water and then calcined at 900℃ for 3 hours to obtain aluminum oxide with a whiteness ≥92%.

[0071] The rare earth enrichment solution was subjected to precipitation and calcination to obtain mixed rare earth oxides.

[0072] After drying, calcium carbonate precipitate yields light calcium carbonate.

[0073] Filter residue B is subjected to magnetic separation (magnetic field strength 0.6T) to recover residual iron. The remaining residue is mixed with quartz sand and soda ash in a ratio of 8:1:1 and melted at 1400℃ (with nitrogen protection and a flow rate of 1.0L / min). Then, it is annealed at 600℃ using a gradient cooling method (reducing the temperature by 50℃ per hour until it reaches 300℃, and then naturally cooled) to obtain microcrystalline glass.

[0074] Exhaust gas treatment:

[0075] In steps S2 and S3, the leaching tail gas (containing SO2, H2S, etc.) is absorbed by a two-stage packed tower (the packing is Pall rings, 50 mm in diameter), with an empty tower gas velocity of 1.2 m / s and a liquid-to-gas ratio of 20 L / m³. 3 The process involves two stages of absorption. The first stage uses dilute ammonia to absorb and produce ammonium salt (the pH is monitored during this process and adjusted by adding ammonia if it is too low). The second stage uses sodium hydroxide solution for deep purification.

[0076] Wastewater treatment: Wastewater from each stage is collected in an equalization tank, flocculated with 100 mg / L polyferric sulfate, subjected to reverse osmosis (1.8 MPa, recovery rate 75%), reused as greywater, and used to make roadbed materials from salt residue. All the above steps are carried out using conventional methods in this field.

[0077] Example 2

[0078] This embodiment is prepared in the same way as in Example 1, except that the mass ratio of steel slag tailings, fly ash, red mud and copper tailings is changed to 2.8:1.8:2.8:1.8.

[0079] Example 3

[0080] The preparation steps in this embodiment are the same as in Example 1, except that the mass ratio of steel slag tailings, fly ash, red mud, and copper tailings is changed to 3:2:3:2.

[0081] The process of Example 3 was tested, and the iron recovery rate was 96%, the copper recovery rate was 92%, the purity of the rare earth enrichment solution was 96.5%, the purity of sodium silicate crystals was 96%, the purity of alumina was 95%, and the silicon leaching rate was 92%.

[0082] Comparative Example 1

[0083] The comparative example is prepared using the same method as Example 3, except that the graded pretreatment in step S1 is removed, and the untreated steel slag tailings, fly ash, red mud, and copper tailings are directly mixed to obtain a mixture.

[0084] Comparative Example 1 showed that the iron recovery rate dropped to 68%, the copper recovery rate dropped to 55%, and the purity of the rare earth enrichment solution was only 65%.

[0085] The test data from Comparative Example 1 and Example 3 demonstrate that the staged pretreatment in Example 3 can significantly improve the recovery rate of valuable elements. In the staged pretreatment of Example 3, steel slag is crushed and magnetically separated to recover iron concentrate (utilizing its high iron content), and tailings are ball-milled to increase the specific surface area; fly ash is desulfurized by microwave (reducing SO2 emissions from subsequent acid leaching); red mud is desiliconized by reverse flotation (increasing the enrichment of aluminum and titanium); and copper tailings are ultra-finely crushed and then magnetically separated to remove impurities (facilitating the exposure of rare metals). After pretreatment, the mixture is prepared in a 3:2:3:2 ratio. The CaO in the steel slag can neutralize the excess acid from the acid leaching of fly ash, and the aluminum in the red mud and the rare metals in the copper tailings form a synergistic extraction system.

[0086] Comparative Example 2

[0087] The preparation method of this comparative example is the same as that in Example 3, except that the order of steps S2 and S3 is reversed, with sodium hydroxide leaching performed first and then dilute sulfuric acid leaching performed.

[0088] Comparative Example 2 was tested and found that the purity of sodium silicate crystals was 72% and the purity of alumina was 80%. This was because the acid-base interference caused incomplete separation of calcium and iron.

[0089] The above results indicate that the order of acid-base leaching is crucial to product purity. The primary acid leaching targets acid-soluble elements (iron, copper, rare earth, and aluminum), utilizing the alkaline buffering effect of steel slag in the mixture to reduce sulfuric acid consumption. The secondary alkaline leaching targets alkaline-soluble silicon and calcium, with high pressure promoting the decomposition of aluminosilicates in filter residue A. Stepwise leaching achieves element separation based on solubility characteristics, which can improve subsequent purification efficiency.

[0090] Comparative Example 3

[0091] This comparative example uses the same preparation method as in Example 3, except that in step S2, the solid-liquid ratio of the mixture to 5% dilute sulfuric acid is 1:12, and in step S3, the solid-liquid ratio of filter residue A to 15% sodium hydroxide solution is modified to 1:3.

[0092] Comparing the processes of Comparative Example 3 and Example 3, the excess dilute sulfuric acid in Comparative Example 3 led to a 30% increase in ammonia consumption in the subsequent aluminum precipitation process, while the insufficient amount of sodium hydroxide resulted in a decrease in silicon leaching rate to 58%, and an overall increase in process energy consumption of 25%. This indicates that the solid-liquid ratio within the preferred range can balance efficiency and cost.

[0093] Therefore, the present invention provides a resource-based treatment method for industrial solid waste, which co-processes four typical industrial solid wastes: steel slag, fly ash, red mud, and copper tailings. This method effectively solves the problems of high difficulty in treating single solid wastes and low utilization rates, significantly reduces the land occupation and environmental pollution caused by solid waste accumulation, and has significant environmental protection benefits.

[0094] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for resource recovery of industrial solid waste, the solid waste comprising steel slag, fly ash, red mud and copper tailings, characterized in that, Includes the following steps: S1. Steel slag, fly ash, red mud, and copper tailings are separately pre-treated by classification. The pre-treated solid wastes are then mixed to obtain a mixture. The classification pre-treatment steps are as follows: 1) Steel slag is crushed by jaw crusher to a particle size ≤5mm, and iron concentrate is recovered by magnetic separation with a magnetic field strength of 0.8~1.2T. The steel slag tailings are then ball-milled to 100~200 mesh using an intermittent ball milling process. 2) Fly ash is classified using an air classifier, and 50-150 mesh components are taken for microwave desulfurization. The microwave power is 800-1200W and the microwave time is 10-15min. 3) The red mud is dewatered by plate and frame filter press, crushed to 80-150 mesh, and then desiliconized by reverse flotation. The collector for reverse flotation is hexadecyltrimethylammonium bromide, and the dosage is 50-80 g / t. 4) Copper tailings are ball-milled to a -200 mesh size of ≥85% and then subjected to magnetic separation with a magnetic field strength of 0.6~0.9T; In the mixture, the mass ratio of steel slag tailings, fly ash, red mud, and copper tailings is (2.5~3):(1.5~2):(2.5~3):(1.5~2). S2. Mix the mixture with 5-8% dilute sulfuric acid in a stirred tank, stir and react, then filter to obtain leachate A and filter residue A. S3. Mix filter residue A with 15-20% sodium hydroxide solution, react in a high-pressure reactor, and then filter to obtain leachate B and filter residue B. S4. The leachate A is subjected to sulfidation precipitation, extraction, ion exchange and aluminum precipitation processes in sequence to obtain iron solution, copper solution, rare earth enrichment solution and aluminum hydroxide, respectively. During the sulfidation precipitation process, H2S gas is introduced and the pH is controlled at 2-3; the extraction process involves extraction and back-extraction, with P2O4 as the extractant, an extraction temperature of 40-50℃, and a 1.5-2 mol / L sulfuric acid solution as the back-extraction agent; during the ion exchange process, the flow rate is 15-20 BV / h, and the eluent is a 3-4 mol / L hydrochloric acid solution; the aluminum precipitation process uses a 10-20% (w / w) ammonia solution. S5. Carbonize, precipitate, evaporate, concentrate, cool and crystallize the leachate B to obtain calcium carbonate and sodium silicate crystals. S6. Process the multi-component products obtained from S4 and S5 to prepare high-value products.

2. The method for resource utilization of industrial solid waste according to claim 1, characterized in that: In step S2, the solid-liquid ratio of the mixture to dilute sulfuric acid is 1:6 to 1:10, the stirring temperature is 60 to 80°C, the stirring speed is 150 to 200 r / min, and the reaction time is 1.5 to 2.5 h.

3. The method for resource-based treatment of industrial solid waste according to claim 1, characterized in that: In step S3, the solid-liquid ratio of filter residue A to sodium hydroxide solution is 1:4 to 1:7, the reaction temperature is 120 to 150°C, the reaction pressure is 0.3 to 0.5 MPa, and the reaction time is 2 to 3 hours.

4. The method for resource-based treatment of industrial solid waste according to claim 1, characterized in that: In step S5, CO2 is introduced during the carbonization precipitation process to adjust the pH to 9-10.

5. The method for resource-based treatment of industrial solid waste according to claim 1, characterized in that: The specific steps of S6 are as follows: 1) Iron solution is subjected to oxidation, magnetic separation to remove impurities, and calcination at 600~700℃ to obtain iron oxide red; copper solution is electrolyzed to obtain electrolytic copper; 2) After washing with water, aluminum hydroxide is calcined at 900~1000℃ for 3~4 hours to obtain aluminum oxide; 3) The rare earth enrichment solution is subjected to precipitation and calcination to obtain mixed rare earth oxides; 4) After drying the calcium carbonate precipitate, light calcium carbonate is obtained; 5) The filter residue B is magnetically separated to recover residual iron. The remaining residue is mixed with quartz sand and soda ash, melted at 1400~1500℃, and then subjected to gradient cooling annealing to obtain microcrystalline glass.

6. The method for resource-based treatment of industrial solid waste according to claim 1, characterized in that: In steps S2 and S3, the leaching tail gas is absorbed by two-stage absorption towers: the first stage absorption is the absorption of dilute ammonia water to produce ammonium salt, and the second stage absorption is the deep purification of sodium hydroxide solution.

7. The method for resource-based treatment of industrial solid waste according to claim 6, characterized in that: The empty tower gas speed of the two-stage absorption tower is 0.8-1.2 m / s, and the liquid-gas ratio is 15-20 L / m 3 .