CN112939046A - Comprehensive recycling method of coal-based solid waste - Google Patents
Comprehensive recycling method of coal-based solid waste Download PDFInfo
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- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
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- C01F5/38—Magnesium nitrates
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/308—Thermal decomposition of nitrates
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- C05C5/04—Fertilisers containing other nitrates containing calcium nitrate
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- C22B21/00—Obtaining aluminium
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- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a comprehensive recycling method of coal-based solid waste, belonging to the cross field of metallurgy and chemical industry. The method comprises the steps of firstly, crushing and finely grinding coal-based solid wastes to obtain mineral powder, and magnetically separating and floating the mineral powder to obtain a decarbonized material; and (3) carrying out nitric acid pressurization two-stage reverse leaching reaction on the decarbonized material, and then sequentially recovering elements such as silicon, gallium, aluminum, magnesium and the like. The method has high dissolution rate of the extracted alumina, and can effectively separate aluminum and iron in the pickle liquor; the aluminum nitrate and magnesium nitrate solution obtained in the process is evaporated and concentrated to obtain crystals for subsequent decomposition and regeneration to obtain acid and alkali, so that acid-alkali double-medium regeneration circulation is realized; meanwhile, the elements of aluminum, iron, calcium, magnesium, gallium and other metals in the coal-based solid waste are better comprehensively utilized. The method has the advantages of low acid consumption, low impurity content of the leaching solution, low impurity removal cost, low equipment requirement, simple process and the like, and all elements can be comprehensively recycled.
Description
Technical Field
The invention belongs to the cross field of metallurgy and chemical industry, and particularly relates to a comprehensive recycling method for leaching fly ash or coal gangue through nitric acid pressurization.
Background
The coal-based solid waste comes from the mining, processing and utilization processes of coal. Among them, coal gangue and fly ash are industrial solid wastes with the largest production amount of thermal power plants, and the large amount of stockpiling thereof brings serious environmental pollution.
At present, the utilization modes of coal gangue and fly ash mainly comprise construction and building materials, and are single and low in utilization level. The method for extracting the alumina from the coal gangue or the fly ash as the bauxite resource is a mode with higher utilization rate, and has important significance for improving the utilization level of the coal-series solid wastes.
The method for extracting the alumina from the coal gangue or the fly ash mainly comprises an acid leaching method and an alkali leaching method. The alkaline leaching method has mature recovery process, but has long process flow and high recovery cost; the acid leaching method comprises a hydrochloric acid leaching method and a sulfuric acid leaching method at present, the content of iron in the fly ash is high, the fly ash is directly leached by acid in the existing acid method recovery process, and almost all iron in the fly ash enters a leaching solution, so that the acid consumption is high, the leaching cost is high, the content of iron impurities in the leaching solution is high, and the impurity removal cost is high.
At present, there are many methods for removing iron in the process of producing alumina by acid leaching, for example, goethite method is used industrially to remove iron. Patent document CN103805779A proposes an iron removal method in the process of extracting aluminum by acid method, the temperature of a reaction tank is controlled to be 60-100 ℃, the aging time is 30-120min, Na is used2CO3Adjusting the pH value<3.0, the method can effectively solve the problem of separation of gallium from iron. However, this method requires the preparation of goethite seeds so that the concentration of the goethite seeds becomes 0.9 to 3.0g/L, and Na is added during the reaction2CO3The pH value of the solution is controlled, and the process is complex.
Qiwan et al (keemun, king resolute, exploration of iron-removing process of vanadium-containing leachate [ J ]. nonferrous mining metallurgy. 2015,31(3):37-39) report a precipitation method for removing iron, a lime neutralization precipitation method is adopted to control the pH of solution to be 2, part of iron in pickle liquor is removed in advance, and then the aim of separating vanadium and iron is achieved by extraction of reducing solvent. The method can also effectively remove iron, but the loss of vanadium is reduced by a multi-stage washing mode in the neutralization process, so that the process is longer, the process is complex, and the separation of iron and aluminum in alumina is not suitable.
In addition, the iron removal process also comprises a magnetizing roasting method, an extraction method, a recrystallization method and the like, and although the iron removal effect is good, the process flow is relatively complex, the production cost is relatively high, and industrialization is difficult to realize.
Therefore, the iron removal process in the process of producing the alumina by the existing acid leaching method can reasonably utilize major elements such as aluminum, gallium and silicon in the coal-based solid waste, but small elements such as iron, calcium, magnesium and the like are not effectively recovered.
In conclusion, the existing iron removal method is difficult to effectively remove impurity iron in pickle liquor in the acid method aluminum extraction process; meanwhile, a large amount of elements in the solid waste can cause certain environmental pollution problems in the recycling process.
Disclosure of Invention
Aiming at the problems of long process flow and high recovery cost of the alkaline leaching method in the existing method for extracting the alumina from the coal-based solid waste; the invention provides a comprehensive recycling method of coal-based solid wastes, which has high leaching rate of extracting alumina and can effectively separate aluminum and iron in pickle liquor; meanwhile, the aluminum nitrate and magnesium nitrate solution obtained in the process is evaporated and concentrated to obtain crystals for subsequent decomposition and regeneration to obtain acid (nitric acid) and alkali (aluminum oxide and magnesium oxide), so that acid-alkali double-medium regeneration circulation is realized; meanwhile, the elements of aluminum, iron, calcium, magnesium, gallium and other metals in the coal-based solid waste are better comprehensively utilized. The process has the advantages of low acid consumption, low impurity content of the leaching solution, low impurity removal cost, low equipment requirement, simple process and the like, and all elements can be comprehensively recycled.
In order to achieve the purpose, the invention provides the following technical scheme:
a comprehensive recycling method of coal-based solid waste comprises the following steps:
(1) crushing and finely grinding coal-based solid waste to obtain mineral powder, magnetically separating the mineral powder into magnetic ore and non-magnetic ore, and carrying out flotation separation and decarbonization on the non-magnetic ore to obtain a decarbonized material;
(2) carrying out nitric acid pressurization two-stage reverse leaching reaction on the carbon-removed material, filtering the first-stage leached material to obtain a first filtrate and a first filter residue, carrying out second-stage leaching on the first filter residue to obtain a second filtrate and a second filter residue, wherein the second filtrate is used for reverse first-stage leaching, and the second filter residue is processed into a silicon-containing product;
(3) co-precipitating iron from the first filtrate by using metastannic acid, and filtering to obtain a third filtrate and a third filter residue;
(4) allowing the third filtrate to pass through resin to adsorb gallium, and obtaining a post-resin solution, namely a fourth solution;
(5) resolving the resin saturated with adsorbed gallium with dilute nitric acid solution to obtain nitric acid solution containing aluminum and gallium, namely fifth solution;
(6) adding sulfuric acid or aluminum sulfate into the fourth solution to precipitate calcium, and filtering to obtain a sixth filtrate and a fourth filter residue;
(7) adding sodium hydroxide into the fifth solution for dissolving to obtain the GaO-containing solution2-/AlO2-Electrolyzing the alkaline solution to obtain a gallium metal product;
(8) evaporating and concentrating the sixth filtrate to obtain aluminum nitrate crystals and aluminum nitrate mother liquor, returning the low-magnesium aluminum nitrate mother liquor to the third filtrate obtained in the step (3) according to the content of magnesium in the aluminum nitrate mother liquor, and continuously circulating the low-magnesium aluminum nitrate mother liquor and then concentrating and crystallizing the low-magnesium aluminum nitrate mother liquor to obtain an industrial-grade aluminum nitrate product; adjusting the pH value of the high-magnesium aluminum nitrate mother liquor, completely precipitating aluminum, separating the aluminum from a magnesium nitrate solution, and filtering to obtain a seventh filtrate and a fifth filter residue;
(9) calcining and decomposing the aluminum nitrate crystal obtained in the step (8) to obtain aluminum oxide, and using the generated mixed gas for producing nitric acid;
(10) adding alkali to the fifth filter residue for dissolving, converting aluminum hydroxide in the filter residue into aluminate ions, dissolving the aluminate ions in alkali liquor, and adding carbon dioxide or aluminum hydroxide seed crystal into the filtered solution for precipitation to obtain aluminum hydroxide;
(11) and evaporating and concentrating the seventh filtrate to obtain magnesium nitrate crystals for preparing magnesium oxide or calcium magnesium nitrate fertilizer.
Further, in the step (1), the coal-based solid waste comprises one or a mixture of fly ash and coal gangue.
Further, the mass fraction of the chemical element composition of the decarbonized material in the step (1) comprises: fe is 0.2-4.0%; 15.6 to 28.9 percent of Al; 15-39% of Si; ca is 0.15-2.46%; mg is 0.01-0.1%; ga is 100-240 g/t.
Further, the first stage leaching conditions in step (2) include: the solid-liquid ratio of the material to the second filtrate is 1:1-1:8g/mL, the acid concentration of the second filtrate is 50-350g/L, the leaching temperature is 160-220 ℃, the stirring speed is 150-850rpm, and the leaching time is 0.5-3 h.
The second stage leaching conditions include: the solid-liquid ratio of the first filter residue to the nitric acid is 1:2-1:6g/mL, the concentration of the nitric acid is 200-.
Further, in the step (3), the pH of the first filtrate is 1-2.5, and the coprecipitation reaction conditions include: the solid-to-liquid ratio of the metastannic acid to the first filtrate is 2-8:100g/mL, and the temperature is kept for 0.5-2h under continuous stirring at the temperature of 40-90 ℃.
Further, the third filter residue in the step (3) is washed by a small amount of dilute nitric acid, the washed metastannic acid can be reused, and the washed ferric nitrate solution can be used for preparing the calcium magnesium nitrate fertilizer in the step (11).
Further, in the step (6), according to the content of calcium in the solution (1-10g/L), the adding amount of sulfuric acid or aluminum sulfate is 1.5-4 times of the theoretical amount of calcium sulfate, the temperature can be 20-80 ℃, the stirring reaction is carried out for 30min, the solution is filtered after standing for 4-24h, the precipitate is calcium sulfate, and the solution is the solution after calcium removal.
Further, the temperature of the evaporation concentration in the step (8) is 60-100 ℃.
Further, the magnesium content in the low-magnesium aluminum nitrate mother liquor in the step (8) is lower than 10 g/L; the magnesium content in the high-magnesium aluminum nitrate mother liquor is more than or equal to 10 g/L.
Further, in the step (8), magnesium oxide or magnesium carbonate is added into the high-magnesium aluminum nitrate mother liquor to adjust the pH value to 4.0-7.0, the reaction temperature of the precipitation reaction is 40-100 ℃, and the reaction time is 0.5-3.5 h.
Further, in the step (9), the aluminum nitrate crystal is aluminum nitrate nonahydrate, and the preparation method of the aluminum oxide comprises the following steps: and continuously evaporating and concentrating the aluminum nitrate crystal to aluminum nitrate dihydrate solution, then spraying the aluminum nitrate solution into a decomposing furnace for decomposition, directly heating the decomposing furnace by adopting natural gas or coal gas or indirectly heating the decomposing furnace by adopting a decomposition circulating gas mode, calcining and decomposing the aluminum nitrate crystal at the temperature of 400-800 ℃ for 0.3-5min, preparing nitric acid by adopting the decomposing gas, and collecting dust from the solid powder at high temperature and cooling the solid powder to obtain an aluminum oxide product.
Further, in the step (10), the reaction temperature for dissolving the fifth filter residue by adding alkali is 140-; the base used includes any one of sodium hydroxide and potassium hydroxide and combinations thereof.
Further, the preparation process of the magnesium oxide in the step (11) comprises the following steps: heating and concentrating the magnesium nitrate crystal (magnesium nitrate hexahydrate) to magnesium nitrate dihydrate, spraying the magnesium nitrate dihydrate into a decomposition furnace, quickly calcining and decomposing at the temperature of 500-1000 ℃ for 0.3-5min, using the decomposition mode and equipment as aluminum nitrate, removing the decomposition gas to prepare nitric acid, and collecting dust from solid powder at high temperature and cooling to obtain magnesium oxide.
The preparation process of the calcium nitrate magnesium fertilizer comprises the following steps: adding calcium oxide and trace elements such as iron, zinc, boron and the like into the magnesium nitrate concentrated solution, adjusting the mixture ratio of the magnesium nitrate solution to calcium 15-16%, magnesium 5.5-7%, 12.5-14% nitrogen, trace elements such as iron, zinc, boron and the like and the concentration of mixed salt, and then preparing the calcium magnesium nitrate fertilizer by adopting spray granulation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention realizes the recovery of various valuable metals of aluminum, iron, gallium, calcium and magnesium in the coal-series solid waste, and can obtain aluminum nitrate, aluminum oxide, aluminum hydroxide, magnesium nitrate, magnesium oxide and calcium nitrate magnesium fertilizer series products;
(2) the invention adopts the nitric acid pressurizing two-stage reverse leaching method, so that the whole process has higher recovery rate of alumina, which can reach more than 90%;
(3) the acid and alkali used in the process can be recycled, so that the purchase of auxiliary materials is reduced, and the direct processing cost is reduced.
Drawings
Fig. 1 is a schematic view of a process flow of comprehensively recycling fly ash by a nitric acid pressure leaching method in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
Example 1
Referring to the schematic process flow diagram of FIG. 1:
(1) crushing and finely grinding the fly ash to obtain mineral powder, magnetically separating the mineral powder into magnetic ores and nonmagnetic ores, and carrying out flotation separation and decarbonization on the nonmagnetic ores to obtain a decarbonized material; the mass fraction of the chemical element composition of the decarbonized material comprises: fe is 3.8%; 20.3 percent of Al; the Si content is 27%; ca is 2.12%; mg is 0.08%; ga is 185 g/t.
(2) Carrying out nitric acid pressurization two-stage reverse leaching reaction on the carbon-removed material, filtering the first-stage leached material to obtain a first filtrate and a first filter residue, carrying out second-stage leaching on the first filter residue to obtain a second filtrate and a second filter residue, wherein the second filtrate is used for reverse first-stage leaching, and the second filter residue is processed into a silicon-containing product; the first stage leaching conditions include: the solid-liquid ratio of the material to the second filtrate is 1:1g/mL, the acid concentration of the second filtrate is 50g/L, the leaching temperature is 160 ℃, the stirring speed is 150rpm, and the leaching time is 0.5 h; the second stage leaching conditions include: the solid-liquid ratio of the first filter residue to nitric acid is 1:2g/mL, the concentration of the nitric acid is 200g/L, the leaching temperature is 160 ℃, the stirring speed is 150rpm, and the leaching time is 0.5 h.
(3) Co-precipitating iron from the first filtrate by using metastannic acid, and filtering to obtain a third filtrate and a third filter residue; the pH value of the first filtrate is 1, and the coprecipitation reaction conditions comprise: and the solid-to-liquid ratio of the metastannic acid to the first filtrate is 2:100g/mL, and the first filtrate is continuously stirred and kept at the temperature of 40 ℃ for 0.5 h.
(4) Allowing the third filtrate to pass through resin to adsorb gallium, and obtaining a post-resin solution, namely a fourth solution;
(5) resolving the resin saturated with adsorbed gallium with dilute nitric acid solution to obtain nitric acid solution containing aluminum and gallium, namely fifth solution;
(6) adding sulfuric acid into the fourth solution to precipitate calcium, and filtering to obtain a sixth filtrate and a fourth filter residue; further, in the step (6), according to the calcium content (1g/L) in the solution, the adding amount of sulfuric acid is 1.5 times of the theoretical amount of the generated calcium sulfate, the reaction temperature is 20 ℃, the stirring reaction is carried out for 30min, the solution is filtered after standing for 4h, the precipitate is calcium sulfate, and the solution is the solution after calcium removal.
(7) Adding sodium hydroxide into the fifth solution for dissolving to obtain the GaO-containing solution2-/AlO2-Electrolyzing the alkaline solution to obtain a gallium metal product;
(8) evaporating and concentrating the sixth filtrate to obtain aluminum nitrate crystals and aluminum nitrate mother liquor, returning the low-magnesium aluminum nitrate mother liquor to the third filtrate obtained in the step (3) according to the magnesium content (7.63g/L) in the aluminum nitrate mother liquor, and continuously circulating the low-magnesium aluminum nitrate mother liquor, and then concentrating and crystallizing the low-magnesium aluminum nitrate mother liquor to obtain an industrial-grade magnesium nitrate product;
(9) and (4) continuously evaporating and concentrating the aluminum nitrate nonahydrate crystal obtained in the step (8) to obtain an aluminum nitrate dihydrate solution, spraying the aluminum nitrate dihydrate solution into a decomposing furnace for decomposition, directly heating the decomposing furnace by using natural gas, calcining and decomposing at the temperature of 400 ℃ for 5min, removing the decomposed gas to prepare nitric acid, and collecting dust from the solid powder at high temperature and cooling to obtain an aluminum oxide product.
Example 2
(1) Crushing and finely grinding a mixture of fly ash and coal gangue to obtain mineral powder, magnetically separating the mineral powder into magnetic ore and nonmagnetic ore, and carrying out flotation separation and decarbonization on the nonmagnetic ore to obtain a decarbonized material; the mass fraction of the chemical element composition of the decarbonized material comprises: fe is 4.0%; 18.7 percent of Al; the Si content is 35%; ca is 2.18%; mg accounts for 0.03%; ga is 135 g/t.
(2) Carrying out nitric acid pressurization two-stage reverse leaching reaction on the carbon-removed material, filtering the first-stage leached material to obtain a first filtrate and a first filter residue, carrying out second-stage leaching on the first filter residue to obtain a second filtrate and a second filter residue, wherein the second filtrate is used for reverse first-stage leaching, and the second filter residue is processed into a silicon-containing product; wherein the first stage leaching conditions comprise: the solid-liquid ratio of the material to the second filtrate is 1:8g/mL, the acid concentration of the second filtrate is 350g/L, the leaching temperature is 220 ℃, the stirring speed is 850rpm, and the leaching time is 3 h. The second stage leaching conditions include: the solid-liquid ratio of the first filter residue to nitric acid is 1:6g/mL, the concentration of the nitric acid is 800g/L, the leaching temperature is 220 ℃, the stirring speed is 850rpm, and the leaching time is 5 h.
(3) Co-precipitating iron from the first filtrate by using metastannic acid, and filtering to obtain a third filtrate and a third filter residue; wherein the pH value of the first filtrate is 2.5, and the coprecipitation reaction conditions comprise: and the solid-to-liquid ratio of the metastannic acid to the first filtrate is 8:100g/mL, and the first filtrate is continuously stirred and kept at the temperature of 90 ℃ for 2 hours. And (4) washing the third filter residue by using a small amount of dilute nitric acid, wherein the washed metastannic acid can be reused, and the washed ferric nitrate solution can be used for preparing the calcium magnesium nitrate fertilizer in the step (11).
(4) Allowing the third filtrate to pass through resin to adsorb gallium, and obtaining a post-resin solution, namely a fourth solution;
(5) resolving the resin saturated with adsorbed gallium with dilute nitric acid solution to obtain nitric acid solution containing aluminum and gallium, namely fifth solution;
(6) adding aluminum sulfate into the fourth solution to precipitate calcium, and filtering to obtain a sixth filtrate and a fourth filter residue; further, in the step (6), according to the content of calcium in the solution (2.2g/L), adding sulfuric acid or sulfuric acid in an amount which is 1.8 times of the theoretical amount of the sulfuric acid for generating calcium sulfate, stirring and reacting at the reaction temperature of 80 ℃ for 30min, standing for 24h, filtering, precipitating to obtain calcium sulfate, and obtaining the solution after calcium removal.
(7) Adding sodium hydroxide into the fifth solution for dissolving to obtain the GaO-containing solution2-/AlO2-Electrolyzing the alkaline solution to obtain a gallium metal product;
(8) and (3) evaporating and concentrating the sixth filtrate to obtain aluminum nitrate crystals and aluminum nitrate mother liquor, adding magnesium oxide into the high-magnesium aluminum nitrate mother liquor to adjust the pH value of the high-magnesium aluminum nitrate mother liquor to 6.5 according to the magnesium content (10.2g/L) in the aluminum nitrate mother liquor, carrying out precipitation reaction at the reaction temperature of 40 ℃ for 0.5h, and filtering to obtain fifth filter residue and seventh filtrate.
(9) And (4) continuously evaporating and concentrating the aluminum nitrate nonahydrate crystal obtained in the step (8) to obtain an aluminum nitrate dihydrate solution, spraying the aluminum nitrate dihydrate solution into a decomposing furnace for decomposition, directly heating the decomposing furnace by adopting coal gas, calcining and decomposing at 800 ℃ for 0.3min, removing the decomposed gas to prepare nitric acid, and collecting dust from the solid powder at high temperature and cooling to obtain an aluminum oxide product.
(10) Adding alkali to the fifth filter residue for dissolving, converting aluminum hydroxide in the filter residue into aluminate ions, dissolving the aluminate ions in alkali liquor, and adding carbon dioxide or aluminum hydroxide seed crystal into the filtered solution for precipitation to obtain aluminum hydroxide; dissolving the fifth filter residue by adding alkali at 200 deg.C for 3h, wherein the pH value is 14.0; the base used was potassium hydroxide.
(11) And evaporating and concentrating the seventh filtrate to obtain magnesium nitrate hexahydrate crystals, continuously heating and concentrating the crystals to obtain magnesium nitrate dihydrate, spraying the magnesium nitrate dihydrate crystals into a decomposing furnace, quickly calcining and decomposing the magnesium nitrate dihydrate crystals at 1000 ℃ for 0.3min in a decomposing mode and equipment, preparing nitric acid from decomposed gas, collecting dust from solid powder at high temperature, and cooling to obtain magnesium oxide.
Example 3
(1) Crushing and finely grinding the coal gangue to obtain mineral powder, magnetically separating the mineral powder into magnetic ore and non-magnetic ore, and carrying out flotation separation and carbon removal on the non-magnetic ore to obtain a carbon-removed material; the mass fraction of the chemical element composition of the decarbonized material comprises: fe is 2.7%; al is 22.9%; the content of Si is 39%; ca is 2.46%; mg is 0.09%; ga is 235 g/t.
(2) Carrying out nitric acid pressurization two-stage reverse leaching reaction on the carbon-removed material, filtering the first-stage leached material to obtain a first filtrate and a first filter residue, carrying out second-stage leaching on the first filter residue to obtain a second filtrate and a second filter residue, wherein the second filtrate is used for reverse first-stage leaching, and the second filter residue is processed into a silicon-containing product; wherein the first stage leaching conditions comprise: the solid-liquid ratio of the material to the second filtrate is 1:6g/mL, the acid concentration of the second filtrate is 280g/L, the leaching temperature is 180 ℃, the stirring speed is 400rpm, and the leaching time is 2.5 h. The second stage leaching conditions include: the solid-liquid ratio of the first filter residue to nitric acid is 1:5g/mL, the concentration of the nitric acid is 650g/L, the leaching temperature is 180 ℃, the stirring speed is 640rpm, and the leaching time is 3.5 h.
(3) Co-precipitating iron from the first filtrate by using metastannic acid, and filtering to obtain a third filtrate and a third filter residue; wherein the pH value of the first filtrate is 2, and the coprecipitation reaction conditions comprise: and the solid-to-liquid ratio of the metastannic acid to the first filtrate is 6:100g/mL, and the temperature is kept for 1.5h under continuous stirring at the temperature of 65 ℃. And (4) washing the third filter residue by using a small amount of dilute nitric acid, wherein the washed metastannic acid can be reused, and the washed ferric nitrate solution can be used for preparing the calcium magnesium nitrate fertilizer in the step (11).
(4) Allowing the third filtrate to pass through resin to adsorb gallium, and obtaining a post-resin solution, namely a fourth solution;
(5) resolving the resin saturated with adsorbed gallium with dilute nitric acid solution to obtain nitric acid solution containing aluminum and gallium, namely fifth solution;
(6) adding sulfuric acid into the fourth solution to precipitate calcium, and filtering to obtain a sixth filtrate and a fourth filter residue; further, in the step (6), according to the content of calcium in the solution (9.5g/L), the adding amount of sulfuric acid is 3.5 times of the theoretical amount of the generated calcium sulfate, the reaction temperature is 60 ℃, the stirring reaction is carried out for 30min, the solution is filtered after standing for 16h, the precipitate is calcium sulfate, and the solution is the solution after calcium removal.
(7) Adding sodium hydroxide into the fifth solution for dissolving to obtain the GaO-containing solution2-/AlO2-Electrolyzing the alkaline solution to obtain a gallium metal product;
(8) and (3) evaporating and concentrating the sixth filtrate to obtain aluminum nitrate crystals and aluminum nitrate mother liquor, adding magnesium oxide or magnesium carbonate into high-magnesium aluminum nitrate mother liquor to adjust the pH value to 5.5 according to the magnesium content (15.6g/L) in the aluminum nitrate mother liquor, wherein the reaction temperature of the precipitation reaction is 100 ℃, and the reaction time is 3.5 hours.
(9) And (4) continuously evaporating and concentrating the aluminum nitrate nonahydrate crystal obtained in the step (8) to obtain an aluminum nitrate dihydrate solution, spraying the aluminum nitrate dihydrate solution into a decomposing furnace for decomposition, calcining and decomposing for 2min at the temperature of 650 ℃ by adopting a decomposition circulating gas indirect heating mode, preparing nitric acid from the decomposition gas, and collecting dust from solid powder at high temperature and cooling to obtain an aluminum oxide product.
(10) Adding alkali to the fifth filter residue for dissolving, converting aluminum hydroxide in the filter residue into aluminate ions, dissolving the aluminate ions in alkali liquor, and adding carbon dioxide or aluminum hydroxide seed crystal into the filtered solution for precipitation to obtain aluminum hydroxide; in the step (10), the reaction temperature for dissolving the fifth filter residue by adding alkali is 185 ℃, the reaction time is 2.5 hours, and the pH value of the reaction is 13; the base used was sodium hydroxide.
(11) And adding calcium oxide and trace elements such as iron, zinc, boron and the like into the seventh filtrate, adjusting the proportion of the magnesium nitrate solution and the concentration of the mixed salt, and preparing the calcium magnesium nitrate fertilizer by adopting spray granulation.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A comprehensive recycling method of coal-based solid waste is characterized by comprising the following steps:
(1) crushing and finely grinding coal-based solid waste to obtain mineral powder, magnetically separating the mineral powder into magnetic ore and non-magnetic ore, and carrying out flotation separation and decarbonization on the non-magnetic ore to obtain a decarbonized material;
(2) carrying out nitric acid pressurization two-stage reverse leaching reaction on the carbon-removed material, filtering the first-stage leached material to obtain a first filtrate and a first filter residue, carrying out second-stage leaching on the first filter residue to obtain a second filtrate and a second filter residue, wherein the second filtrate is used for reverse first-stage leaching, and the second filter residue is processed into a silicon-containing product;
(3) co-precipitating iron from the first filtrate by using metastannic acid, and filtering to obtain a third filtrate and a third filter residue;
(4) allowing the third filtrate to pass through resin to adsorb gallium, and obtaining a post-resin solution, namely a fourth solution;
(5) resolving the resin saturated with adsorbed gallium with dilute nitric acid solution to obtain nitric acid solution containing aluminum and gallium, namely fifth solution;
(6) adding sulfuric acid or aluminum sulfate into the fourth solution to precipitate calcium, and filtering to obtain a sixth filtrate and a fourth filter residue;
(7) adding sodium hydroxide into the fifth solution for dissolving to obtain the GaO-containing solution2-/AlO2-Electrolyzing the alkaline solution to obtain a gallium metal product;
(8) evaporating and concentrating the sixth filtrate to obtain aluminum nitrate crystals and aluminum nitrate mother liquor, returning the low-magnesium aluminum nitrate mother liquor to the third filtrate obtained in the step (3) according to the content of magnesium in the aluminum nitrate mother liquor, and continuously circulating the low-magnesium aluminum nitrate mother liquor and then concentrating and crystallizing the low-magnesium aluminum nitrate mother liquor to obtain aluminum nitrate; adjusting the pH value of the high-magnesium aluminum nitrate mother liquor, completely precipitating aluminum, separating the aluminum from a magnesium nitrate solution, and filtering to obtain a seventh filtrate and a fifth filter residue;
(9) calcining and decomposing the aluminum nitrate crystal obtained in the step (8) to obtain aluminum oxide, and using the generated mixed gas for producing nitric acid;
(10) adding alkali to the fifth filter residue for dissolving, converting aluminum hydroxide in the filter residue into aluminate ions, dissolving the aluminate ions in alkali liquor, and adding carbon dioxide or aluminum hydroxide seed crystal into the filtered solution for precipitation to obtain aluminum hydroxide;
(11) and evaporating and concentrating the seventh filtrate to obtain magnesium nitrate crystals for preparing magnesium oxide or calcium magnesium nitrate fertilizer.
2. The method for comprehensively recycling coal-based solid wastes according to claim 1, wherein the coal-based solid wastes in the step (1) comprise one or a mixture of fly ash and coal gangue.
3. The comprehensive recycling method of coal-based solid waste as claimed in claim 1, wherein the mass fraction of the chemical element composition of the decarbonized material in step (1) comprises: fe is 0.2-4.0%; 15.6 to 28.9 percent of Al; 15-39% of Si; ca is 0.15-2.46%; mg is 0.01-0.1%; ga is 100-240 g/t.
4. The method for comprehensively recycling coal-based solid waste according to claim 1, wherein the first stage leaching conditions in the step (2) include: the solid-liquid ratio of the material to the second filtrate is 1:1-1:8g/mL, the acid concentration of the second filtrate is 50-350g/L, the leaching temperature is 160-220 ℃, the stirring speed is 150-850rpm, and the leaching time is 0.5-3 h; the second stage leaching conditions include: the solid-liquid ratio of the first filter residue to the nitric acid is 1:2-1:6g/mL, the concentration of the nitric acid is 200-.
5. The method for comprehensively recycling coal-based solid waste according to claim 1, wherein the pH of the first filtrate in step (3) is 1 to 2.5, and the coprecipitation reaction conditions include: the solid-to-liquid ratio of the metastannic acid to the first filtrate is 2-8:100g/mL, and the temperature is kept for 0.5-2h under continuous stirring at the temperature of 40-90 ℃.
6. The method for comprehensively recycling coal-based solid wastes according to claim 1, wherein the amount of the sulfuric acid or the aluminum sulfate added in the step (6) is 1.5 to 4 times of the theoretical amount for producing the calcium sulfate; stirring the mixed solution at 20-80 deg.C for reaction for 30min, standing for 4-24h, and filtering to obtain calcium sulfate precipitate.
7. The method for comprehensively recycling coal-based solid wastes according to claim 1, wherein the temperature of the evaporation concentration in the step (8) is 60-100 ℃; the magnesium content in the low-magnesium aluminum nitrate mother liquor is lower than 10 g/L; the magnesium content in the high-magnesium aluminum nitrate mother liquor is more than or equal to 10 g/L; adding magnesium oxide or magnesium carbonate into the high-magnesium aluminum nitrate mother liquor to adjust the pH value to 4.0-7.0, wherein the reaction temperature of the precipitation reaction is 40-100 ℃, and the reaction time is 0.5-3.5 h.
8. The method for comprehensively recycling coal-based solid waste according to claim 1, wherein the aluminum nitrate crystal in the step (9) is aluminum nitrate nonahydrate, and the method for preparing the aluminum oxide comprises: and continuously evaporating and concentrating the aluminum nitrate crystal to aluminum nitrate dihydrate solution, and then spraying the aluminum nitrate solution into a decomposing furnace for decomposition, wherein the decomposing furnace adopts natural gas or coal gas for direct heating or adopts a decomposition circulating gas indirect heating mode, and the aluminum nitrate crystal is calcined and decomposed for 0.3-5min at the temperature of 400-.
9. The comprehensive recycling method of coal-based solid waste as claimed in claim 1, wherein the reaction temperature of the fifth filter residue in the step (10) with alkali dissolution is 140-; the base used includes any one of sodium hydroxide and potassium hydroxide and combinations thereof.
10. The method for comprehensively recycling coal-based solid waste according to claim 1, wherein in the step (11), the magnesium nitrate crystal is magnesium nitrate hexahydrate; the preparation process of the magnesium oxide comprises the following steps: heating and concentrating the magnesium nitrate crystal to magnesium nitrate dihydrate, and spraying the magnesium nitrate crystal into a decomposition furnace to calcine and decompose at the temperature of 500-1000 ℃ for 0.3-5 min.
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