CN113277564B - Comprehensive treatment method for oil shale waste - Google Patents
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- CN113277564B CN113277564B CN202110611955.0A CN202110611955A CN113277564B CN 113277564 B CN113277564 B CN 113277564B CN 202110611955 A CN202110611955 A CN 202110611955A CN 113277564 B CN113277564 B CN 113277564B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
Abstract
The invention discloses a comprehensive treatment method of oil shale waste. The method comprises the step of treating the oil shale waste sequentially by hydrochloric acid, fluosilicic acid and concentrated sulfuric acid. The method can obtain various solid and liquid products, has low process cost, no waste gas and waste residue, high efficiency and environmental protection, and can realize large-scale and industrial treatment of the oil shale waste.
Description
Technical Field
The invention relates to the technical field of oil shale slag treatment methods.
Background
The oil shale slag is the material left after the oil shale is dry distilled or burned, the main component of the oil shale slag is similar to coal-fired furnace slag, the oil shale slag has certain granularity and porosity, and the content of SiO accounts for about 60 percent 2 Mainly, the other component comprises Al 2 O 3 About 20% of Fe 2 O 3 About 10 percent of the total weight of the additive, and other CaO, mgO and K 2 O、Na 2 O, etc. about 10%.
At present, most of the oil shale ash is directly discarded and stacked, and after being leached or diffused by rainwater, the oil shale ash seriously pollutes surrounding water sources, land and organisms and harms the health of residents, and the pollution range of the oil shale ash is often more than several times of the occupied land area. Meanwhile, the oil shale ash is piled as solid waste, which not only occupies a large amount of land resources, but also causes serious environmental pollution through the enrichment of heavy metal elements in the oil shale ash.
In order to overcome the problems, part of the prior art develops a comprehensive utilization method of the oil shale waste, and at present, the comprehensive utilization method of the oil shale waste in China mainly comprises the following methods: the method is characterized in that firstly, oil shale waste is directly utilized as a raw material, such as a process for preparing ultra-light ceramsite, cement products, light bricks and the like; secondly, extracting non-metallic raw materials in the oil shale waste to prepare zeolite, molecular sieve and the like; thirdly, preparing fine chemical raw materials, such as extracting hydrated silica to be used as a filler of plastics and rubber; and fourthly, the fertilizer can be used as an agricultural fertilizer to improve the soil property. However, the methods all face the problems of saturated market, high expenditure, large energy consumption and the like, so that a large amount of oil shale waste is still not effectively utilized.
Disclosure of Invention
The invention aims to provide a method for carrying out efficient comprehensive treatment on oil shale slag by a chemical treatment method, which can extract useful elements from the oil shale slag and produce valuable chemical products such as sodium metasilicate, hydrated silicon dioxide, ferric hydroxide, aluminum hydroxide and the like, thereby solving the problem of environmental pollution of the oil shale slag, utilizing oil shale slag resources and simultaneously obtaining the chemical products with high added values.
The technical scheme of the invention is as follows:
the comprehensive treatment method of the oil shale waste comprises the following steps: the oil shale waste is treated by hydrochloric acid, fluosilicic acid and concentrated sulfuric acid in turn.
Wherein, the concentrated sulfuric acid is sulfuric acid with mass fraction of 98% or more.
Preferably, the oil shale waste is oil shale waste dried and crushed to 80-200 meshes, and more preferably, the oil shale waste is oil shale waste dried and crushed to 100 meshes.
According to some preferred embodiments of the invention, the processing comprises: performing first solid-liquid separation on a mixture obtained after the oil shale waste is treated by the hydrochloric acid to obtain a first solid mixture and a first liquid mixture; treating the first solid mixture with fluorosilicic acid to obtain a mixture, and performing second solid-liquid separation to obtain a second solid mixture and a second liquid mixture; carrying out gas-solid separation on a mixture obtained after the second solid mixture is treated by the concentrated sulfuric acid to obtain a first mixed gas and a third solid mixture; separating the first mixed gas into a first liquid product and a first solid product through an absorption process; boiling the third solid mixture in water, and then carrying out third solid-liquid separation to obtain a third liquid mixture and a fourth solid mixture; carrying out first alkali treatment on the third liquid mixture, and then carrying out fourth solid-liquid separation to obtain a fourth liquid mixture and a second solid product; carrying out fifth solid-liquid separation on the fourth solid mixture after carrying out second alkali treatment to obtain a second liquid product and a solid residue; and carrying out third alkali treatment on the fourth liquid mixture, and carrying out sixth solid-liquid separation to obtain a third solid product and a third liquid product.
In the scheme, the obtained solid residue can be further returned to the first step to be mixed with the oil shale residue and then the treatment is continued.
According to some preferred embodiments of the invention, the processing further comprises: and carrying out fourth alkali treatment on the first liquid mixture, carrying out seventh solid-liquid separation to obtain a fifth liquid mixture and a fourth solid product, carrying out fifth alkali treatment on the fifth liquid mixture, and carrying out eighth solid-liquid separation to obtain a fifth solid product and a fourth liquid product.
According to some preferred embodiments of the invention, the processing further comprises: crystallizing the second liquid product by condensation to obtain a sixth solid product.
According to some preferred embodiments of the invention, the processing further comprises: and concentrating and crystallizing the third liquid product to obtain a seventh solid product.
According to some preferred embodiments of the invention, the processing further comprises: and concentrating and crystallizing the fourth liquid product to obtain an eighth solid product.
According to some preferred embodiments of the present invention, the first solid product is hydrated silica, the second solid product is ferric hydroxide, the third solid product is aluminum hydroxide, the fourth solid product is ferric hydroxide, the fifth solid product is aluminum hydroxide, the sixth solid product is sodium metasilicate nonahydrate, the seventh solid product is ammonium sulfate solid, the eighth solid product is a mixture of calcium chloride and magnesium chloride; the first liquid product is fluosilicic acid, the second liquid product is a sodium silicate solution, the third liquid product is an ammonium sulfate solution, and the fourth liquid product is a mixed solution of calcium chloride and magnesium chloride.
According to some preferred embodiments of the present invention, the pH of the system in which the first alkali treatment is performed is adjusted to 3 to 5, the pH of the system in which the third alkali treatment is performed is adjusted to 6 to 8, the pH of the system in which the fourth alkali treatment is performed is adjusted to 2 to 6, and the pH of the system in which the fifth alkali treatment is performed is adjusted to 6 to 8.
According to some preferred embodiments of the present invention, an alkaline agent ammonia is used in the first alkaline treatment and the third alkaline treatment.
According to some preferred embodiments of the invention, an alkaline agent sodium hydroxide solution is used in the second alkaline treatment.
According to some preferred embodiments of the invention, the concentration of the sodium hydroxide solution is 30 to 53wt%.
According to some preferred embodiments of the present invention, an alkali agent lime emulsion is used in the fourth alkali treatment and the fifth alkali treatment.
According to some preferred embodiments of the invention, the lime emulsion has a concentration of 10 to 20wt%.
According to some preferred embodiments of the present invention, in any one of the above treatment methods, the concentration of the hydrochloric acid is 4 to 30wt%, and the concentration of the fluorosilicic acid is 20 to 45wt%.
According to some preferred embodiments of the present invention, in any of the above methods, the treatment with hydrochloric acid comprises: and heating and boiling the oil shale waste and the hydrochloric acid for 0.5-4 hours under normal pressure.
According to some preferred embodiments of the present invention, in any one of the above methods, the treating of the fluorosilicic acid comprises: and carrying out solid-liquid separation on the oil shale slag treated by the hydrochloric acid, and carrying out heating reaction on the obtained solid and the fluosilicic acid at 130-150 ℃.
According to some preferred embodiments of the present invention, in any of the above treatment methods, the treatment of the concentrated sulfuric acid comprises: and carrying out solid-liquid separation on the oil shale waste after the fluorosilicic acid treatment, and reacting the obtained solid with the concentrated sulfuric acid at the temperature of 100-338 ℃.
According to some preferred embodiments of the present invention, in any one of the above treatment methods, the mass ratio of the oil shale waste to the hydrochloric acid is 1.5 to 1:8.
According to some preferred embodiments of the present invention, in any one of the above treatment methods, a solid-to-liquid ratio of a solid obtained by solid-liquid separation of the hydrochloric acid-treated oil shale waste to the fluorosilicic acid is 1: 10-1.
According to some preferred embodiments of the invention, the processing method comprises:
(1) Drying and crushing the oil shale waste to obtain oil shale waste to be comprehensively treated;
(2) Uniformly mixing the oil shale waste obtained in the step (1) with hydrochloric acid with the concentration of 4-30wt% according to the mass ratio of 1;
(3) Adding a solid-liquid ratio of 1:10-1 g/ml, 20-45wt% fluosilicic acid, reacting at 130-150 ℃, and after the reaction is finished, carrying out solid-liquid separation;
(4) Adding concentrated sulfuric acid into the solid separated in the step (3), reacting at 100-338 ℃, absorbing the gas generated in the reaction by using an absorption tower to obtain liquid and white precipitate, wherein the liquid obtained by absorption is fluosilicic acid, and the white precipitate obtained by absorption is hydrated silicon dioxide; adding water into the residual solid after gas absorption, boiling, and performing centrifugal separation to obtain solid and liquid;
(5) Adding 30-53wt% sodium hydroxide into the solid obtained by separation in the step (4) for alkali dissolution, reacting for 0.5-4 hours under 0.2-0.6MPa, performing solid-liquid separation, and crystallizing and condensing the obtained liquid to obtain sodium metasilicate nonahydrate; and (4) adding ammonia water into the liquid obtained by separation in the step (4) to adjust the pH value to 3-5, then carrying out solid-liquid separation to obtain ferric hydroxide, continuously adding ammonia water to adjust the pH value to 7, then carrying out solid-liquid separation to obtain aluminum hydroxide, and concentrating and crystallizing the residual liquid to obtain ammonium sulfate.
The invention solves the problems that the oil shale waste seriously pollutes surrounding air, water sources, land and organisms, harms the health of residents, occupies a large amount of land resources and the like, and simultaneously, the oil shale waste is utilized to process and produce chemical raw materials, thereby obviously improving the economic benefit.
Drawings
FIG. 1 is an embodiment of the present invention.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
Some specific embodiments according to the technical solution of the present invention are shown in fig. 1, and include the following processes:
(1) Firstly, drying the oil shale waste and crushing to 80-200 meshes;
(2) And (3) hydrochloric acid treatment:
uniformly mixing the oil shale residue obtained in the step (1) with hydrochloric acid with the concentration of 4-30wt% according to the mass ratio of 1:0.5-1:8, heating and boiling under normal pressure to react for 0.5-4 hours, filtering and separating solid and liquid, allowing the solid to remain in the step (3) for treatment, adding one or more of alkaline reagents such as lime emulsion, ammonia water, sodium hydroxide and potassium hydroxide into the filtrate to adjust the pH to 2-6, further performing solid-liquid separation to obtain solid precipitated iron hydroxide, continuously adding one or more of alkaline reagents such as lime emulsion, ammonia water, sodium hydroxide and potassium hydroxide into the residual filtrate to adjust the pH to 6-8, further performing solid-liquid separation to obtain solid precipitated aluminum hydroxide, and performing multi-effect concentration treatment on the residual filtrate to obtain a crystalline mixture of calcium chloride and magnesium chloride which can be further applied, such as being used as a snow melting agent;
(3) And (3) treating fluosilicic acid:
adding fluosilicic acid with the concentration of 20-45wt% into the solid obtained by the first solid-liquid separation in the step (2) to ensure that the solid-liquid ratio of the two is 1:10-1:1 (unit: g/ml), reacting at 130-150 ℃, after the reaction is finished, performing solid-liquid separation by using a filter press, recovering the separated liquid for use as fluosilicic acid, adding concentrated sulfuric acid into the separated solid, heating for reaction at 100-338 ℃, absorbing the gas containing silicon tetrafluoride and hydrofluoric acid generated by the reaction by using an absorption tower to obtain liquid and white precipitate, wherein the liquid obtained by absorption is fluosilicic acid which can be recycled and concentrated according to needs, such as to be concentrated to 30-45%, so as to continuously return to the treatment of the fluosilicic acid in the second step for recycling, and the white precipitate obtained by absorption is hydrated silicon dioxide which can be further washed and dried to obtain a finished product; adding water into the residual solid treated by concentrated sulfuric acid, boiling to dissolve the residual iron, aluminum, calcium and magnesium, performing centrifugal separation to obtain liquid, adding an alkaline reagent such as ammonia water to adjust the pH value to 3-5, performing solid-liquid separation to obtain ferric hydroxide solid, continuously adjusting the pH value to 6-8, performing solid-liquid separation to obtain aluminum hydroxide solid, and performing multi-effect concentration and crystallization on the residual liquid to obtain ammonium sulfate.
Adding 40-53wt% of sodium hydroxide into the solid after the water boiling separation for alkali dissolution, reacting for 0.5-2 hours under 0.2-0.6MPa, separating to obtain solid residue which is the final residual insoluble residue, returning to the first step for continuous treatment, and pumping the obtained liquid into a settling tank for condensation and crystallization to obtain the sodium metasilicate nonahydrate.
Example 1
10g of oil shale waste which was dry-pulverized to 100 mesh was taken and put into a three-necked flask, 20ml of 20wt% HCl was added thereto, and under continuous stirring, the mixture was heated to boiling, and was subjected to condensation reflux for 2 hours, and solid-liquid separation was carried out. And adding 10wt% lime emulsion into the filtrate to adjust the pH value to 4, and separating and washing to obtain 0.8368g of ferric hydroxide. Continuously adding lime emulsion with the concentration of 10wt% to adjust the pH value to 7, and then separating and washing to obtain 2.2569g of aluminum hydroxide; the filtrate after the reaction is concentrated to obtain 6.1161g of a mixture of calcium chloride and magnesium chloride.
3.4525g of filter residue obtained by the first-step filtration is added with 30ml of fluosilicic acid with the concentration of 40wt%, the mixture is stirred and heated to 145 ℃ for reaction for two hours, the generated gas is absorbed by water through an absorption tower, the absorption tower obtains hydrated silicon dioxide and fluosilicic acid solution, and the hydrated silicon dioxide and the fluosilicic acid solution are recycled after being absorbed to a certain concentration. And (3) carrying out solid-liquid separation on the product obtained after the reaction of the fluosilicic acid and the filter residue obtained by the first-step filtration, returning the liquid fluosilicic acid for reuse, adding 10ml of concentrated sulfuric acid into the filtered solid-phase intermediate, reacting at 100-338 ℃, adding 50ml of water to boil and dissolve solid-phase soluble salts after the fluosilicic acid is volatilized, and filtering and separating the solid silica gel again to obtain 4.5006g of water-containing silica gel filter residue. 15ml of 40wt% sodium hydroxide was added and alkali-dissolved in a 0.4MPa pressure cooker to obtain 16.3921g of sodium metasilicate nonahydrate. Adding ammonia water into the filtrate after water boiling to adjust the pH value to 4, carrying out solid-liquid separation to obtain 0.4601g of ferric hydroxide, continuously adjusting the pH value to 7, and carrying out solid-liquid separation to obtain 1.2324g of aluminum hydroxide. The filtrate is concentrated under multiple effects to obtain 3.9798g of ammonium sulfate.
Example 2
1t of air-dried oil shale waste and 6wt% of 8.0M hydrochloric acid 3 Uniformly mixing according to the proportion of 1:8, heating and boiling under normal pressure, stirring to react for one hour, filtering and separating solid and liquid, and leaving the solid to be used for next step of silicon recovery. Adding calcium oxide into the filtrate to adjust the pH value to 4, carrying out solid-liquid separation to generate ferric hydroxide, continuously adding calcium oxide into the liquid, adjusting the pH value to 7, carrying out solid-liquid separation to generate aluminum hydroxide, and treating the filtrate to obtain a mixture of calcium chloride and magnesium chloride which can be used as a snow-melting agent.
Adding 30M to the solid obtained in the first filtration step 3 Heating and stirring 20wt% of fluosilicic acid for reaction for 2 hours, performing filter pressing separation on a solid-liquid intermediate generated by the reaction, returning the liquid fluosilicic acid for recycling, adding sufficient concentrated sulfuric acid into the solid-phase residue obtained by separation for reaction at 100-338 ℃, recovering the generated gas to obtain hydrated silicon dioxide and fluosilicic acid, and returning the fluosilicic acid for recycling.
And the solid phase residue after no gas generation is boiled and dissolved to obtain soluble salt ferric sulfate, calcium sulfate and insoluble silica gel. And carrying out solid-liquid separation again to obtain a solid, carrying out alkali dissolution, adding a 40wt% sodium hydroxide solution, reacting for one hour under 0.4MPa, and pumping into a crystallization tank to obtain the sodium metasilicate nonahydrate.
Adding ammonia water into the filtrate after water boiling to adjust the pH value of the solution to be faintly acid, namely pH =4, carrying out solid-liquid separation to obtain ferric hydroxide, continuously adjusting the solution to be neutral, carrying out solid-liquid separation to obtain aluminum hydroxide, and carrying out concentration and crystallization on the residual liquid to obtain ammonium sulfate.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (5)
1. A comprehensive treatment method of oil shale waste is characterized in that: the method comprises the following steps: treating the oil shale waste sequentially by hydrochloric acid, fluosilicic acid and concentrated sulfuric acid; the processing comprises the following steps: performing first solid-liquid separation on a mixture obtained after the oil shale waste is subjected to hydrochloric acid treatment to obtain a first solid mixture and a first liquid mixture; treating the first solid mixture with fluorosilicic acid to obtain a mixture, and performing second solid-liquid separation to obtain a second solid mixture and a second liquid mixture; carrying out gas-solid separation on a mixture obtained after the second solid mixture is treated by the concentrated sulfuric acid to obtain a first mixed gas and a third solid mixture; separating the first mixed gas into a first liquid product and a first solid product through an absorption process; boiling the third solid mixture in water, and then carrying out third solid-liquid separation to obtain a third liquid mixture and a fourth solid mixture; carrying out first alkali treatment on the third liquid mixture, and then carrying out fourth solid-liquid separation to obtain a fourth liquid mixture and a second solid product; carrying out fifth solid-liquid separation on the fourth solid mixture after carrying out second alkali treatment to obtain a second liquid product and a solid residue; carrying out third alkali treatment on the fourth liquid mixture, and then carrying out sixth solid-liquid separation to obtain a third solid product and a third liquid product; subjecting the first liquid mixture to fourth alkali treatment, then subjecting the first liquid mixture to seventh solid-liquid separation to obtain a fifth liquid mixture and a fourth solid product, subjecting the fifth liquid mixture to fifth alkali treatment, and then subjecting the fifth liquid mixture to eighth solid-liquid separation to obtain a fifth solid product and a fourth liquid product; crystallizing the second liquid product by condensation to obtain a sixth solid product, crystallizing the third liquid product by concentration to obtain a seventh solid product, and crystallizing the fourth liquid product by concentration to obtain an eighth solid product; wherein the pH value of the system in which the first alkali treatment is carried out is adjusted to 3-5, the pH value of the system in which the third alkali treatment is carried out is adjusted to 6-8, the pH value of the system in which the fourth alkali treatment is carried out is adjusted to 2-6, and the pH value of the system in which the fifth alkali treatment is carried out is adjusted to 6-8; an alkaline agent ammonia water is used in the first alkaline treatment and the third alkaline treatment, an alkaline agent sodium hydroxide solution is used in the second alkaline treatment, and an alkaline agent lime emulsion is used in the fourth alkaline treatment and the fifth alkaline treatment; the concentration of the sodium hydroxide solution is 30-53wt%, and the concentration of the lime emulsion is 10-20wt%; the concentration of the hydrochloric acid is 4-30wt%, and the concentration of the fluosilicic acid is 20-45wt%; the treatment of the hydrochloric acid comprises: heating and boiling the oil shale waste and the hydrochloric acid for 0.5-4 hours under normal pressure; the treatment of the fluosilicic acid comprises the following steps: carrying out solid-liquid separation on the oil shale slag treated by the hydrochloric acid, and carrying out heating reaction on the obtained solid and the fluosilicic acid at 130-150 ℃; the treatment of concentrated sulfuric acid comprises: and carrying out solid-liquid separation on the oil shale waste treated by the fluosilicic acid, and reacting the obtained solid with the concentrated sulfuric acid at 100-338 ℃.
2. The processing method according to claim 1, characterized in that: the first liquid product is fluosilicic acid, the second liquid product is a sodium silicate solution, the third liquid product is an ammonium sulfate solution, the fourth liquid product is a mixed solution of calcium chloride and magnesium chloride, the first solid product is hydrated silicon dioxide, the second solid product is ferric hydroxide, the third solid product is aluminum hydroxide, the fourth solid product is ferric hydroxide, the fifth solid product is aluminum hydroxide, the sixth solid product is sodium metasilicate nonahydrate, the seventh solid product is an ammonium sulfate solid, and the eighth solid product is a mixture of calcium chloride and magnesium chloride.
3. The processing method according to claim 1, characterized in that: in the treatment, the mass ratio of the oil shale waste to the hydrochloric acid is 1.5-1:8; and/or the solid-liquid ratio of the solid obtained by solid-liquid separation of the oil shale waste after the hydrochloric acid treatment to the fluosilicic acid is 1: 10-1.
4. The processing method according to claim 1, characterized in that: it comprises the following steps:
(1) Drying and crushing the oil shale waste to obtain oil shale waste to be comprehensively treated;
(2) Uniformly mixing the oil shale waste obtained in the step (1) with hydrochloric acid with the concentration of 4-30wt% according to the mass ratio of 1;
(3) Adding a solid-liquid ratio of 1:10-1 g/ml, 20-45wt% fluosilicic acid, reacting at 130-150 ℃, and after the reaction is finished, carrying out solid-liquid separation;
(4) Adding concentrated sulfuric acid into the solid separated in the step (3), reacting at 100-338 ℃, absorbing the gas generated in the reaction by using an absorption tower to obtain liquid and white precipitate, wherein the liquid obtained by absorption is fluosilicic acid, and the white precipitate obtained by absorption is hydrated silicon dioxide; adding water into the residual solid after gas absorption, boiling, and performing centrifugal separation to obtain solid and liquid;
(5) Adding 30-53wt% sodium hydroxide into the solid obtained by separation in the step (4) for alkali dissolution, reacting for 0.5-4 hours under 0.2-0.6MPa, carrying out solid-liquid separation, and then crystallizing and condensing the obtained liquid to obtain sodium metasilicate nonahydrate; and (5) adding ammonia water into the liquid obtained by separation in the step (4) to adjust the pH value to 3-5, then carrying out solid-liquid separation to obtain ferric hydroxide, continuously adding ammonia water to adjust the pH value to 7, then carrying out solid-liquid separation to obtain aluminum hydroxide, and concentrating and crystallizing the residual liquid to obtain ammonium sulfate.
5. The processing method according to claim 1, characterized in that: it includes:
(1) Firstly, drying oil shale slag and crushing the oil shale slag into 80-200 meshes;
(2) And (3) hydrochloric acid treatment:
uniformly mixing the oil shale residue obtained in the step (1) with hydrochloric acid with the concentration of 4-30wt% according to the mass ratio of 1:0.5-1:8, heating and boiling at normal pressure to react for 0.5-4 hours, filtering and separating solid and liquid, allowing the solid to remain in the step (3) for treatment, adding one or more of alkaline reagent lime emulsion, ammonia water, sodium hydroxide and potassium hydroxide into the filtrate to adjust the pH to 2-6, further performing solid-liquid separation to obtain solid precipitated iron hydroxide, continuously adding one or more of alkaline reagent lime emulsion, ammonia water, sodium hydroxide and potassium hydroxide into the residual filtrate to adjust the pH to 6-8, further performing solid-liquid separation to obtain solid precipitated aluminum hydroxide, and performing multi-effect concentration treatment on the residual filtrate to obtain a calcium chloride and magnesium chloride crystal mixture;
(3) And (3) treating fluosilicic acid:
adding fluosilicic acid with the concentration of 20-45wt% into the solid obtained by the first solid-liquid separation in the step (2) to ensure that the solid-liquid ratio of the two is 1:10-1 g/ml, reacting at the temperature of 130-150 ℃, performing solid-liquid separation by using a filter press after the reaction is finished, recovering the separated liquid for use as fluosilicic acid, adding concentrated sulfuric acid into the separated solid, heating for reaction at the temperature of 100-338 ℃, absorbing gas containing silicon tetrafluoride and hydrofluoric acid generated by the reaction by using an absorption tower to obtain liquid and white precipitate, wherein the liquid obtained by absorption is fluosilicic acid, concentrating the fluosilicic acid to 30-45%, returning the concentrated liquid to the fluosilicic acid treatment for recycling, and the white precipitate obtained by absorption is hydrated silicon dioxide which is further washed by water and dried to obtain a finished product; adding water into the residual solid after concentrated sulfuric acid treatment, boiling, performing centrifugal separation to obtain liquid, adding an alkaline reagent ammonia water to adjust the pH value to 3-5, performing solid-liquid separation to obtain ferric hydroxide solid, continuously adjusting the pH value to 6-8, performing solid-liquid separation to obtain aluminum hydroxide solid, and performing multi-effect concentration and crystallization on the residual liquid to obtain ammonium sulfate; and (2) adding 40-53wt% of sodium hydroxide into the solid after water boiling separation for alkali dissolution, reacting for 0.5-2 hours under 0.2-0.6MPa, separating to obtain solid residue which is the final residual insoluble residue, returning to the step (1) for continuous treatment, and pumping the obtained liquid into a settling tank for condensation and crystallization to obtain the sodium metasilicate nonahydrate.
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