Resourceful treatment method for industrial solid waste

Abstract

The invention discloses a resourceful treatment method of industrial solid waste, which belongs to the technical field of solid waste treatment, and comprises the following steps: firstly, carrying out grading pretreatment on steel slag, fly ash, red mud and copper tailings, then mixing according to a ratio, carrying out acid leaching and alkaline leaching, carrying out coupling purification on the leachate, and treating the purified product to obtain a high-value product. The four typical industrial solid wastes of the steel slag, the fly ash, the red mud and the copper tailings are subjected to cooperative treatment, the problems that single solid wastes are high in treatment difficulty and low in utilization rate are effectively solved, land occupation and environmental pollution caused by solid waste accumulation are greatly reduced, and the method has remarkable environmental protection benefits.

Description

Technical Field

[0001] The present invention relates to the field of solid waste treatment, and in particular to a method for resource treatment of industrial solid waste. Background Art

[0002] Current industrial solid waste treatment faces challenges with complex individual solid waste compositions, 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. Individual treatments of these wastes present several drawbacks: Acid leaching of steel slag requires significant acid to neutralize alkaline components, while alkaline leaching of red mud requires high temperatures and pressures, resulting in high energy consumption. Individual solid wastes are low in valuable elements, making extraction economically unsuitable. For example, the copper content in copper tailings is often less than 0.5%. Furthermore, the treatment process consumes significant amounts of reagents.

[0003] In the current existing technology, the coordinated treatment of multiple solid wastes is mostly limited to the mixing of two solid wastes (such as steel slag and fly ash building materials), and deep extraction of multiple elements has not been achieved.

[0004] Based on the above problems, a resource treatment method for solid waste synergy is proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for resource recovery of industrial solid waste to solve the problems in the background technology.

[0006] To achieve the above object, the present invention provides a method for resource processing of industrial solid waste, wherein the solid waste includes steel slag, fly ash, red mud and copper tailings, and the method is characterized in that it comprises the following steps:

[0007] S1. Pre-treating steel slag, fly ash, red mud, and copper tailings respectively by classification, and mixing the pre-treated solid wastes to obtain a mixed material;

[0008] S2. Mixing the mixture with 5-8% dilute sulfuric acid in a stirring tank, stirring and reacting, and then filtering to obtain leachate A and filter residue A;

[0009] S3, mixing the filter residue A with 15-20% sodium hydroxide solution, reacting in a high-pressure reactor, and then filtering to obtain a leachate B and filter residue B;

[0010] S4, sequentially subjecting leachate A to sulfide precipitation, extraction, ion exchange, and aluminum precipitation processes to obtain an iron solution, a copper solution, a rare earth enriched solution, and aluminum hydroxide, respectively;

[0011] S5, subjecting the leachate B to carbonization precipitation, evaporation concentration, cooling and crystallization to obtain calcium carbonate and sodium silicate crystals;

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

[0013] Preferably, in S1, the steps of classification and processing are:

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

[0015] 2) Fly ash is classified by air flow classifier, and the 50-150 mesh fraction is taken for microwave desulfurization with microwave power of 800-1200W and microwave time of 10-15min;

[0016] 3) The red mud is dehydrated by plate and frame filter pressing, crushed to 80-150 mesh, and then subjected to reverse flotation for desiliconization. The collector used in reverse flotation is hexadecyltrimethylammonium bromide at a dosage of 50-80 g / t;

[0017] 4) The 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 to 0.9 T.

[0018] Preferably, in the mixed material 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 S2, the solid-liquid ratio of the mixed material to the 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 S3, the solid-liquid ratio of filter residue A to sodium hydroxide solution is 1:4-1:7, the reaction temperature is 120-150° C., the reaction pressure is 0.3-0.5 MPa, and the reaction time is 2-3 h.

[0021] Preferably, in the S4, H2S gas is introduced during the sulfide precipitation process to control the pH to 2-3; the extraction process is extraction and stripping, the extractant is P2O4, the extraction temperature is 40-50°C, and the stripping agent is 1.5-2 mol / L sulfuric acid solution; the flow rate during the ion exchange process is 15-20 BV / h, and the analytical agent is 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:

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

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

[0025] After stopping ventilation, continue stirring for 10 min, and collect the filtrate A1 after centrifugation;

[0026] 2) Extraction: Add the filtrate A1 and the diluted P2O4 solution to the extraction tower in a ratio of 3:1 to 5:1, control the pH to 2 to 3, stir for 15 to 20 minutes, stand for stratification, separate the loaded organic phase and the extract residue, and back-extract the loaded organic phase with 1.5 to 2 mol / L sulfuric acid solution to obtain a copper solution and an iron solution;

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

[0028] 4) Aluminum precipitation: Collect the tail liquid of ion exchange and transfer it into the reaction tank. Slowly add 10-20% ammonia water by mass under stirring conditions, adjust the pH to 5-6, keep stirring for 30 minutes, and the stirring rate is 150-200r / min. After stopping stirring, let it stand for 1-2 hours, separate the precipitate by vacuum filtration, wash the precipitate with deionized water 3-4 times, until no Cl- is detected in the filtrate, and dry to obtain aluminum hydroxide precipitate.

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

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

[0031] 1) The iron solution is oxidized, magnetically separated and impurities removed, and calcined at 600-700°C to obtain red iron oxide; the copper solution is electrolyzed to obtain electrolytic copper;

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

[0033] 3) The rare earth enriched solution is precipitated and calcined to obtain mixed rare earth oxides;

[0034] 4) Calcium carbonate is precipitated and dried to obtain light calcium carbonate;

[0035] 5) Residue iron is recovered from the filter residue B through magnetic separation, and the remaining residue is mixed with quartz sand and soda ash, melted at 1400-1500° C., and then subjected to gradient cooling annealing to obtain glass-ceramics.

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

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

[0038] Therefore, the resource treatment method of 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 ore 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 step leaching process can extract different components separately. Leachate A adopts the combined process of "sulfurization-extraction-ion exchange-precipitation" to selectively remove heavy metals (Cu 2+ , Pb 2+ P204 extracts and separates iron and copper, while D401 resin efficiently adsorbs rare earth elements, ultimately precipitating aluminum. Leachate B, through a combination of carbonization precipitation and crystallization, recovers calcium and silicon. This coupled process solves the separation challenges of multi-element systems, reduces impurity interference, and improves product purity.

[0041] (3) By processing the recovered multi-products, high-value products such as red iron oxide, 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 the resource utilization of industrial solid waste.

[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 implement 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 is further described in detail below through examples. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further illustrated by the following examples.

[0045] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the contents in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0046] Example 1

[0047] This embodiment performs collaborative treatment on four typical industrial solid wastes: steel slag, fly ash, red mud, and copper tailings. The specific steps are as follows:

[0048] S1. Grading pretreatment and mixing:

[0049] 1) Grading pretreatment:

[0050] The steel slag is jaw crushed to a particle size of ≤5mm, and magnetic separation is performed using a 0.8T magnetic field to recover iron ore concentrate (TFe=65%). The steel slag tailings are 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 the tailings particle size distribution is controlled to ≤20μm.

[0051] The fly ash is classified using an airflow classifier, and the 50-mesh component is taken for microwave desulfurization at 800W microwave power for 10 minutes, reducing the sulfur content to below 0.5%. A real-time temperature monitoring device is added during the desulfurization process, and the power is automatically adjusted when the material temperature exceeds 200°C.

[0052] The red mud was dehydrated by plate and frame filter pressing (water content 28%), crushed to 120 mesh, and then subjected to reverse flotation for desiliconization. The amount of collector hexadecyltrimethylammonium bromide was 50g / t. The process used an aeration volume of 0.8-1.2m 3 / (m 2 ·min) flotation machine, adding 20g / t sodium silicate as inhibitor).

[0053] The copper tailings are ball-milled to -200 mesh, accounting for 88%, and then magnetically separated at a magnetic field strength of 0.6T to remove strong magnetic impurities.

[0054] 2) Mixing:

[0055] The pretreated steel slag tailings, fly ash, red mud and copper tailings are mixed in a mass ratio of 2.5:1.5:2.5:1.5 to obtain a mixed material.

[0056] S2, dilute sulfuric acid leaching:

[0057] The mixture was mixed with 5% dilute sulfuric acid at a solid-liquid ratio of 1:6 in a stirred tank. The temperature was raised to 40°C within the first 30 minutes using a step-by-step heating method. After keeping the temperature for 30 minutes, the temperature was raised to 60°C and stirred at 150 r / min for 1.5 hours. The leachate A (containing Fe 2+ 、Cu 2+ , Al3+, rare earth) and filter residue A.

[0058] S3, sodium hydroxide leaching:

[0059] The 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 reacted for 2 hours at 120°C and 0.3 MPa in a high-pressure reactor. The high-pressure reactor was equipped with an automatic pressure relief device (automatically opened when the pressure exceeded 0.5 MPa) and a stirring device (speed 60-80 r / min). The leachate B (containing Na2SiO3 and Na2CO3) and the filter residue B were obtained by filtration.

[0060] S4. Treatment of leachate A:

[0061] Sulfide precipitation: Transfer leachate A to a reactor and adjust the pH to 2 by adding dilute sulfuric acid dropwise while stirring at 200 r / min. In a sealed container, introduce H₂S gas at a flow rate of 0.5 L / min and allow to react for 30 min. A small amount of the solution is filtered and Na₂S solution is added dropwise. If no new precipitate forms, stop aeration and continue stirring for 10 min. Centrifuge and collect filtrate A1.

[0062] Extraction: Add filtrate A1 and diluted P204 solution into the extraction tower at a ratio of 3:1, stir for 15 minutes, let stand and separate the loaded organic phase and the extract residue, and use 1.5 mol / L sulfuric acid solution to back-extract the loaded organic phase to obtain copper solution and iron solution. The pH in this process is 2, so the extraction does not target rare earth ions.

[0063] Ion exchange: Soak D401 chelating resin in 5% hydrochloric acid for 2 hours and wash with deionized water until neutral; then soak it in 5% sodium hydroxide solution for 2 hours and wash with deionized water until neutral, load it into an ion exchange column with a column diameter-to-height ratio of 1:8, pump in the residual extract, and control the flow rate at 15BV / h. When the rare earth ion concentration in the effluent reaches 5% of the initial concentration, stop adsorption, and pass 3mol / L hydrochloric acid analytical agent into the saturated resin column at a flow rate of 0.5BV / h. Collect the eluate until the rare earth ion concentration is lower than 0.1g / L to obtain a rare earth enriched solution.

[0064] Aluminum precipitation: Collect the tail liquid of ion exchange and move it into the reaction tank. Slowly add 10% ammonia water under stirring conditions, adjust the pH to 5, keep stirring for 30 minutes, and the stirring rate is 150r / min. After stopping stirring, let it stand and age for 1 hour. Vacuum filtration to separate the precipitate, wash the precipitate with deionized water 3 times until there is no Cl- in the filtrate, and dry to obtain aluminum hydroxide precipitate.

[0065] S5. Treatment of leachate B:

[0066] The leachate B is introduced with CO2 of purity ≥99% to adjust the pH to 9 and the pressure to 0.3 MPa, and a spray-type reaction device is used to carry out the reaction to obtain calcium carbide precipitation;

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

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

[0069] The iron solution was oxidized (adding 30% H2O2, reacting at 80℃ for 2h), magnetically separated to remove impurities (magnetic field intensity 0.4T), and calcined at 600℃ to obtain red iron oxide; the copper solution was electrolyzed (using an insoluble anode, i.e., a titanium-based coated electrode, with a current density of 250A / m 2 , electrolyte temperature 60℃, electrolyte purified every 24h) to obtain electrolytic copper.

[0070] After aluminum hydroxide was washed with deionized water three times, it was calcined at 900°C for 3 hours to obtain aluminum oxide with a whiteness of ≥92%.

[0071] The rare earth enriched solution is precipitated and calcined to obtain mixed rare earth oxides.

[0072] Light calcium carbonate is obtained after calcium carbonate precipitation and drying.

[0073] The residual iron was recovered from the filter residue B by magnetic separation (magnetic field strength 0.6T), and the remaining residue was mixed with quartz sand and soda ash in the ratio of 8:1:1. After melting at 1400°C (nitrogen protection, flow rate 1.0L / min), the mixture was subjected to gradient cooling annealing at 600°C (50°C per hour to 300°C, and then naturally cooled) to obtain microcrystalline glass.

[0074] Exhaust gas treatment:

[0075] In steps S2 and S3, the leached tail gas (containing SO2, H2S, etc.) is absorbed by a two-stage packed tower (filler is ball ring, diameter 50mm), the superficial gas velocity is 1.2m / s, and the liquid-gas ratio is 20L / m 3 , carry out two-stage absorption, the first stage is dilute ammonia water absorption to produce ammonium salt (the pH value of this process is detected at 6.5-7.5, if it is too low, add ammonia water to adjust), and the second stage is sodium hydroxide solution for deep purification.

[0076] Wastewater treatment: The wastewater from each stage is collected in a regulating tank, flocculated with 100 mg / L polyferric sulfate, and reverse osmosis (1.8 MPa, 75% recovery rate) is performed. The reclaimed water is reused, and the salt residue is used to make roadbed materials. The above steps are all carried out using conventional means in the field.

[0077] Example 2

[0078] The preparation steps of this embodiment are the same as those of embodiment 1, except that the mass ratio of steel slag tailings, fly ash, red mud, and copper tailings is modified to 2.8:1.8:2.8:1.8.

[0079] Example 3

[0080] The preparation steps of this embodiment are the same as those of embodiment 1, except that the mass ratio of steel slag tailings, fly ash, red mud, and copper tailings is modified 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 enriched solution was 96.5%, the purity of the sodium silicate crystals was 96%, and the purity of the aluminum oxide was 95%; the silicon leaching rate was 92%.

[0082] Comparative Example 1

[0083] The preparation method of this comparative example is the same as that of Example 3, except that the classification 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 mixed material.

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

[0085] The test data from Comparative Example 1 and Example 3 demonstrate that the graded pretreatment in Example 3 significantly improves the recovery rate of valuable elements. In the graded pretreatment of Example 3, steel slag is crushed and magnetically separated to recover iron ore concentrate (taking advantage of its high iron content), and the tailings are ball-milled to increase the specific surface area. Fly ash is microwave-desulfurized (reducing SO2 emissions from subsequent acid leaching). Red mud is reverse-flotated for desiliconization (increasing aluminum and titanium enrichment). The copper tailings are ultra-finely crushed and then magnetically separated for impurity removal (facilitating the exposure of rare metals). After pretreatment, the copper tailings are mixed in a 3:2:3:2 ratio. The CaO in the steel slag neutralizes excess acid from the fly ash acid leaching, and the aluminum in the red mud forms a synergistic extraction system with the rare metals in the copper tailings.

[0086] Comparative Example 2

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

[0088] Comparative Example 2 was tested and found to have a sodium silicate crystal purity of 72% and an alumina purity of 80%. This was because the acid-base interference resulted in incomplete separation of calcium and iron.

[0089] The above results show that the order of acid-base step-by-step leaching is crucial to product purity. The primary acid leaching targets acid-soluble elements (iron, copper, rare earth, and aluminum), and utilizes the alkaline buffering effect of the steel slag in the mixture to reduce sulfuric acid consumption. The secondary alkaline leaching targets alkaline-soluble silicon and calcium. High-pressure conditions promote the decomposition of aluminosilicates in filter residue A. Step-by-step leaching realizes the separation of elements according to their solubility characteristics, which can improve the subsequent purification efficiency.

[0090] Comparative Example 3

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

[0092] Comparing the process of Comparative Example 3 with that of Example 3, the excessive amount of dilute sulfuric acid in Comparative Example 3 resulted in a 30% increase in ammonia consumption in the subsequent aluminum precipitation process, insufficient sodium hydroxide dosage resulted in a silicon leaching rate reduced to 58%, and the overall process energy consumption increased by 25%, indicating that the solid-liquid ratio can take into account both efficiency and cost within the preferred range.

[0093] Therefore, the resource-based treatment method of industrial solid waste provided by the present invention synergistically treats four typical industrial solid wastes, namely steel slag, fly ash, red mud and copper tailings, effectively solving the problems of difficulty in treating a single solid waste and low utilization rate, greatly reducing the land occupation and environmental pollution caused by solid waste accumulation, and having 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 rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements 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-based treatment of industrial solid waste, wherein the solid waste includes steel slag, fly ash, red mud and copper tailings, characterized in that: The following steps are involved: S1. Pre-treating steel slag, fly ash, red mud, and copper tailings respectively by classification, and mixing the pre-treated solid wastes to obtain a mixed material; S2. Mixing the mixture with 5-8% dilute sulfuric acid in a stirring tank, stirring and reacting, and then filtering to obtain leachate A and filter residue A; S3, mixing the filter residue A with 15-20% sodium hydroxide solution, reacting in a high-pressure reactor, and then filtering to obtain a leachate B and filter residue B; S4, sequentially subjecting leachate A to sulfide precipitation, extraction, ion exchange, and aluminum precipitation processes to obtain an iron solution, a copper solution, a rare earth enriched solution, and aluminum hydroxide, respectively; S5, subjecting the leachate B to carbonization precipitation, evaporation concentration, cooling and crystallization to obtain calcium carbonate and sodium silicate crystals; S6. Process the multi-products obtained in S4 and S5 to prepare high-value products.

2. The method for recycling industrial solid waste according to claim 1, characterized in that: In S1, the steps of classification and processing are: 1) The steel slag is jaw crushed to a particle size of ≤5mm, and the iron ore concentrate is recovered by magnetic separation with a magnetic field strength of 0.8 to 1.2T. The steel slag tailings are ball milled to 100 to 200 mesh using an intermittent ball milling process; 2) Fly ash is classified by air flow classifier, and the 50-150 mesh fraction is taken for microwave desulfurization with microwave power of 800-1200W and microwave time of 10-15min; 3) The red mud is dehydrated by plate and frame filter pressing, crushed to 80-150 mesh, and then subjected to reverse flotation for desiliconization. The collector used in reverse flotation is hexadecyltrimethylammonium bromide at a dosage of 50-80 g / t; 4) The 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 to 0.9 T.

3. The method for recycling industrial solid waste according to claim 1, wherein: In the mixed material 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).

4. The method for recycling industrial solid waste according to claim 1, wherein: In the S2, the solid-liquid ratio of the mixed material to the 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.

5. The method for recycling industrial solid waste according to claim 1, wherein: In the S3, the solid-liquid ratio of the filter residue A to the sodium hydroxide solution is 1:4-1:7, the reaction temperature is 120-150° C., the reaction pressure is 0.3-0.5 MPa, and the reaction time is 2-3 h.

6. The method for recycling industrial solid waste according to claim 1, characterized in that: In the S4, H2S gas is introduced during the sulfide precipitation process to control the pH to 2-3; the extraction process is extraction and stripping, the extractant is P2O4, the extraction temperature is 40-50°C, and the stripping agent is 1.5-2 mol / L sulfuric acid solution; the flow rate during the ion exchange process is 15-20 BV / h, and the analytical agent is 3-4 mol / L hydrochloric acid solution; and the aluminum precipitation process uses ammonia water with a mass fraction of 10-20%.

7. The method for recycling industrial solid waste according to claim 1, wherein: In S5, CO2 is introduced during the carbonization precipitation process to adjust the pH to 9-10.

8. The method for recycling industrial solid waste according to claim 1, characterized in that: The specific steps of S6 are: 1) The iron solution is oxidized, magnetically separated and impurities removed, and calcined at 600-700°C to obtain red iron oxide; the copper solution is electrolyzed to obtain electrolytic copper; 2) After washing with water, aluminum hydroxide is calcined at 900-1000°C for 3-4 hours to obtain aluminum oxide; 3) The rare earth enriched solution is precipitated and calcined to obtain mixed rare earth oxides; 4) Calcium carbonate is precipitated and dried to obtain light calcium carbonate; 5) Residue iron is recovered from the filter residue B through magnetic separation, and the remaining residue is mixed with quartz sand and soda ash, melted at 1400-1500° C., and then subjected to gradient cooling annealing to obtain glass-ceramics.

9. The method for recycling industrial solid waste according to claim 1, wherein: In the steps S2 and S3, the leached tail gas is absorbed by a two-stage absorption tower, specifically: the first-stage absorption is absorption with dilute ammonia water to produce ammonium salt, and the second-stage absorption is deep purification with sodium hydroxide solution.

10. The method for recycling industrial solid waste according to claim 9, characterized in that: The superficial gas velocity of the two-stage absorption tower is 0.8-1.2 m / s, and the liquid-gas ratio is 15-20 L / m 3 .