Method for enriching zirconium, lithium and titanium elements from coal gangue and / or fly ash and application thereof

Abstract

The invention provides a method for enriching zirconium, lithium and titanium elements from coal gangue and / or fly ash, which comprises the following steps: S1, taking coal gangue and / or fly ash, adding a gelatinizing agent, mixing, roasting, washing with water, and adding dilute acid to prepare gel I; s2, adding a treating agent into coal gangue and / or fly ash, roasting, and adding water for washing to form slurry I; s3, adding the slurry I into the gel I, stirring, reacting, layering and separating to obtain gel II and slurry II; s4, the gel II is subjected to acid pickling with an acid pickling solution and separated, and filtrate containing zirconium, lithium and titanium elements and gel III are obtained; and S5, extracting the filtrate by using an organic solvent, and carrying out back extraction on an organic phase by using an acid solution to obtain a solution containing zirconium, lithium, titanium and other element atoms, thereby realizing enrichment of zirconium, lithium and titanium elements. In the technological process, all raw materials and reagents can be recycled, pollution is avoided, the cost is low, and the separation recovery rate is high.

Description

Technical Field

[0001] This invention belongs to the field of industrial by-product recycling technology, specifically relating to a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash and its application. Background Technology

[0002] Coal gangue and fly ash contain elements such as zirconium, lithium, and titanium. Due to their low content, recycling them requires a large amount of processing agents, significantly increasing energy consumption and costs. Furthermore, the recycled waste is difficult to dispose of. For a long time, these precious metals have been unavailable, and coal gangue and fly ash have been used as filler materials or building blocks for comprehensive utilization. Moreover, due to their complex structure and technological limitations, separating zirconium, lithium, and titanium from coal gangue and fly ash is quite difficult.

[0003] Therefore, developing an economical and efficient method for the green enrichment and recovery of elements such as zirconium, lithium, and titanium from coal gangue or fly ash has become the key to the high-value utilization of coal gangue and fly ash. Summary of the Invention

[0004] In view of this, the present invention provides a method for enriching zirconium, lithium and titanium elements from coal gangue and / or fly ash and its application.

[0005] To achieve the above objectives, the present invention adopts the following technical solution, the technical flowchart of which is shown below. Figure 1 : A method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash, the method comprising the following steps: S1. Take coal gangue and / or fly ash, add a gelling agent and mix, calcine, wash with water and add dilute acid to obtain gel I; S2. Take coal gangue and / or fly ash, add treatment agent, mix, calcine, wash with water to form slurry I; S3. Add the above slurry I to gel I, stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II; S4. The above gel II is acid-washed with acid washing solution and separated to obtain filtrate containing zirconium, lithium and titanium elements and gel III; S5. The above filtrate is extracted with an organic solvent to obtain an inorganic phase and an organic phase. The organic phase is then back-extracted with an acid solution to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements. The gelling agent includes at least one of sodium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, and potassium carbonate. The treatment agent is composed of at least one of treatment agent A and treatment agent B. Treatment agent A includes sodium carbonate, potassium carbonate, sodium acetate, and sodium oxalate. Treatment agent B includes sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, potassium bromide, and sodium bromide. The organic solvent includes at least one of TBP, D2EHPA sulfuric acid, Cyanex 923 hydrochloric acid, Alamine 336 hydrochloric acid, and kerosene. Furthermore, the method also includes the following steps: Gel III and slurry II are mixed, stirred and reacted, allowed to stand and separate into layers, and gel IV and slurry III are obtained. Gel III is then acid-washed with acid washing solution. This step is repeated to increase the enrichment amount. After enrichment, the remaining gel and slurry are mixed and treated with the washing water in step S1 to form the gel material. The inorganic phase is returned to the pickling solution for continued use; The organic phase obtained after back-extraction is returned to the organic solvent for further extraction.

[0006] Furthermore, the mass of the gelling agent mentioned in step S1 accounts for 1 to 100% of the mass of coal gangue and / or fly ash.

[0007] Furthermore, the calcination conditions described in steps S1 and S2 are the same: temperature 500~900℃, time 20~150min; In steps S1 and S2, the solid-liquid ratio of the washing water is less than 1:3; and the washing water in step S1 can be reused.

[0008] Furthermore, the dilute acid mentioned in step S1 includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and oxalic acid, and the concentration of the dilute acid is not higher than 3 mol / L; Dilute acid treatment conditions: temperature 20~95℃, time 20~150min, solid-liquid ratio 1:(1-10).

[0009] Furthermore, the amount of treatment agent used in step S2 is 0.1-1% of the mass of coal gangue and / or fly ash.

[0010] Furthermore, in step S3, the mass ratio of slurry I to gel I is 1:(1-3).

[0011] Furthermore, the pickling solution mentioned in step S4 is composed of pickling solution C and pickling solution D mixed in a volume ratio of (6~9):(1~4); Pickling solution C includes at least one of hydrochloric acid, sulfuric acid, and nitric acid; pickling solution D includes at least one of phosphoric acid, acetic acid, oxalic acid, tartaric acid, and citric acid. The concentration of the pickling solution is not less than 6 mol / L, and the pickling time is 10~200 min.

[0012] Furthermore, the acid solution mentioned in step S5 includes at least one of sulfuric acid and hydrochloric acid, and the concentration of the acid solution is not higher than 1 mol / L.

[0013] Furthermore, when the treatment agent is a mixture of treatment agent A and treatment agent B, the mass ratio of treatment agent A to treatment agent B is (2~5):2.

[0014] The above methods are applied in the recycling of coal gangue and / or fly ash.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention has the following significant features: First, it uses coal gangue and fly ash as raw materials to prepare gels as enrichment and separation agents, which greatly saves costs; second, it uses coal gangue as a raw material or adds it in a certain proportion, utilizing its own energy, which greatly saves energy consumption; third, it obtains precious metals such as zirconium, lithium, and titanium at low cost, making industrialization a reality; fourth, the acid and organic solvents are designed for recycling, greatly reducing production consumption; fifth, the gel and the extracted materials, after processing, can be used as widely applicable gel materials, realizing green environmental protection and large-scale treatment and utilization of coal-based solid waste, and all reagents used can be recycled.

[0016] Furthermore, this invention exhibits high enrichment and recovery rates for zirconium, lithium, and titanium, with zirconium recovery rates reaching 84.8-89.7%, lithium recovery rates reaching 83.2-92.4%, and titanium recovery rates reaching 81.6-87.3%. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the technical solution of the present invention. Detailed Implementation

[0018] The present invention will be further described in detail below with reference to specific embodiments, so that those skilled in the art can more clearly understand the present invention. Unless otherwise specified, the technical means used in the following embodiments are all conventional means well known to those skilled in the art, and all reagents and consumables are commercially available products.

[0019] Key experimental material sources and physicochemical parameters: The coal gangue raw material comes from Shuikuang Group Company in Liupanshui City, Guizhou Province; The fly ash raw material comes from Datang Guizhou Faer Power Generation Co., Ltd.

[0020] The elemental composition of coal gangue and fly ash is shown in Table 1 below.

[0021] Table 1. Elemental composition of coal gangue and fly ash

[0022] Example 1 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash, as detailed below: S1. Take 20% sodium carbonate by mass of coal gangue and add it to the coal gangue. Mix and calcine at 700℃ for 100 min. After calcination, wash with water (solid-liquid ratio 1:1, wash water can be reused). Then add 3 mol / L hydrochloric acid at a solid-liquid ratio of 1:5 and stir at 80℃ for 60 min to form gel I.

[0023] S2. Take 0.5% of potassium carbonate by mass of coal gangue and add it to the coal gangue. Mix and calcine at 700℃ for 70 minutes. After calcination, wash with water (solid-liquid ratio 1:1) to form slurry I.

[0024] S3. Add the above slurry I to gel I (mass ratio 1:2), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0025] S4. The above gel II is acid-washed with a 3 mol / L acid washing solution (made by mixing hydrochloric acid and acetic acid in a volume ratio of 3:2) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0026] S5. The above filtrate is extracted with an organic solvent (tributyl phosphate (TBP)) to separate the inorganic phase and the organic phase. The organic phase is then back-extracted with 1 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0027] Furthermore, to improve enrichment efficiency, in the above steps, gel III is mixed with slurry II to enrich and adsorb elements such as zirconium, lithium, and titanium. After standing and separating the layers, the mixture is separated to obtain gel IV and slurry III. Gel IV is then returned to the acid washing solution for acid washing, and this process is repeated until the content of the desired element atoms in the slurry is reduced to a certain level. The gel can be mixed with the slurry and treated with the previous wash water to become a gel material for soil improvement, medical and health applications, and engineering materials.

[0028] Furthermore, in order to improve the utilization rate of reagents, the obtained inorganic phase is returned to the washing solution for reuse, and the organic solvent is returned for further extraction.

[0029] Example 2 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 1:1. Then, add potassium hydroxide at 30% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 800℃ for 60 minutes. After calcination, wash with water (solid-liquid ratio 1:1, wash water can be reused). Then, add hydrochloric acid with a concentration of 2mol / L at a solid-liquid ratio of 1:6. Stir and react at 70℃ for 100 minutes to form gel I.

[0030] S2. Weigh coal gangue and fly ash at a mass ratio of 1:1. Then, add sodium acetate and sodium sulfate (sodium acetate and sodium sulfate mass ratio of 1:1) at 0.6% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 800℃ for 70 minutes. After calcination, wash with water (solid-liquid ratio of 1:1) to form slurry I.

[0031] S3. Add the above slurry I to gel I (mass ratio 1:2), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0032] S4. The above gel II is acid-washed with a 3 mol / L acid washing solution (made of sulfuric acid and oxalic acid in a volume ratio of 3:2) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0033] S5. The above filtrate is extracted with an organic solvent (di(2-ethylhexyl) phosphate D2EHPA (P204)) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.5 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0034] The subsequent steps are the same as in Example 1.

[0035] Example 3 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 3:2. Then, add sodium sulfate at 50% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 900℃ for 40 minutes. After calcination, wash with water (solid-liquid ratio 1:2, wash water can be reused). Then, add 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:8. Stir and react at 90℃ for 90 minutes to form gel I.

[0036] S2. Weigh coal gangue and fly ash at a mass ratio of 3:2. Then, add sodium carbonate and potassium chloride (sodium carbonate and potassium chloride mass ratio of 1:1) at 0.3% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 900℃ for 30 minutes. After calcination, wash with water (solid-liquid ratio of 1:1) to form slurry I.

[0037] S3. Add the above slurry I to gel I (mass ratio 1:1), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0038] S4. The above gel II is acid-washed with 1 mol / L acid washing solution (made of sulfuric acid and phosphoric acid mixed in a volume ratio of 4:1) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0039] S5. The above filtrate is extracted with an organic solvent (di(2-ethylhexyl) phosphate D2EHPA (P204)) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.6 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0040] The subsequent steps are the same as in Example 1.

[0041] Example 4 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 3:5. Then, add sodium carbonate at 50% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 750℃ for 90 minutes. After calcination, wash with water (solid-liquid ratio 1:1, wash water can be reused). Then, add hydrochloric acid with a concentration of 2mol / L at a solid-liquid ratio of 1:2. Stir and react at 70℃ for 100 minutes to form gel I.

[0042] S2. Weigh coal gangue and fly ash at a mass ratio of 3:5. Then, add potassium carbonate and sodium bromide (potassium carbonate and sodium bromide mass ratio 5:2) at 0.2% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 750℃ for 110 minutes. After calcination, wash with water (solid-liquid ratio 1:2) to form slurry I.

[0043] S3. Add the above slurry I to gel I (mass ratio 1:2), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0044] S4. The above gel II is acid-washed with 2 mol / L acid washing solution (made by mixing hydrochloric acid and tartaric acid in a volume ratio of 3:1) and separated to obtain filtrate containing zirconium, lithium and titanium elements and gel III.

[0045] S5. The above filtrate is extracted with an organic solvent (Cyanex 923 hydrochloric acid system + kerosene) to separate the inorganic phase and the organic phase. The organic phase is then back-extracted with 0.4 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0046] The subsequent steps are the same as in Example 1.

[0047] Example 5 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 4:3. Then, add sodium hydroxide at 10% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 650℃ for 120 min. After calcination, wash with water (solid-liquid ratio 1:2, wash water can be reused). Then, add hydrochloric acid with a concentration of 2.5 mol / L at a solid-liquid ratio of 1:1. Stir and react at 90℃ for 100 min to form gel I.

[0048] S2. Weigh coal gangue and fly ash at a mass ratio of 4:3. Then, add sodium carbonate and potassium bromide (sodium carbonate and potassium bromide mass ratio 3:2) at 0.1% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 650℃ for 110 minutes. After calcination, wash with water (solid-liquid ratio 1:1) to form slurry I.

[0049] S3. Add the above slurry I to gel I (mass ratio 1:2), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0050] S4. The above gel II is acid-washed with 1.5 mol / L acid washing solution (made of sulfuric acid and citric acid in a volume ratio of 13:7) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0051] S5. The above filtrate is extracted with an organic solvent (tributyl phosphate (TBP) + D2EHPA (P2O4)) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.8 mol / L sulfuric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0052] The subsequent steps are the same as in Example 1.

[0053] Example 6 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 5:6. Then, add potassium sulfate at 35% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcine at 850℃ for 50 minutes. After calcination, wash with water (solid-liquid ratio 1:2, wash water can be reused). Then, add hydrochloric acid with a concentration of 1.5 mol / L at a solid-liquid ratio of 1:2. Stir and react at 50℃ for 100 minutes to form gel I.

[0054] S2. Weigh coal gangue and fly ash at a mass ratio of 5:6. Then, add sodium oxalate and potassium sulfate (sodium oxalate to potassium sulfate mass ratio of 3:2) at 0.25% of the total mass of coal gangue and fly ash to the coal gangue and mix. Calcine at 850℃ for 40 minutes. After calcination, wash with water (solid-liquid ratio of 1:2) to form slurry I.

[0055] S3. Add the above slurry I to gel I (mass ratio 1:3), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0056] S4. The above gel II is acid-washed with 2 mol / L acid washing solution (made by mixing sulfuric acid and acetic acid in a volume ratio of 3:2) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0057] S5. The above filtrate is extracted with an organic solvent (di(2-ethylhexyl) phosphate D2EHPA (P204)) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.6 mol / L sulfuric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0058] The subsequent steps are the same as in Example 1.

[0059] Example 7 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 3:4. Then, add sodium carbonate at 5% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 650℃ for 120 min. After calcination, wash with water (solid-liquid ratio 1:1, wash water can be reused). Then, add hydrochloric acid with a concentration of 2 mol / L at a solid-liquid ratio of 1:2. Stir and react at 40℃ for 50 min to form gel I.

[0060] S2. Weigh coal gangue and fly ash at a mass ratio of 1:1. Then, add sodium carbonate and potassium bromide (sodium carbonate and potassium bromide mass ratio 4:3) at 0.15% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 650℃ for 100 min. After calcination, wash with water (solid-liquid ratio 1:1) to form slurry I.

[0061] S3. Add the above slurry I to gel I (mass ratio 1:1), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0062] S4. The above gel II is acid-washed with 1 mol / L acid washing solution (made of hydrochloric acid and phosphoric acid in a volume ratio of 13:7) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0063] S5. The above filtrate is extracted with an organic solvent (tributyl phosphate (TBP) + Alamine 336) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.5 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0064] The subsequent steps are the same as in Example 1.

[0065] Example 8 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Weigh coal gangue and fly ash at a mass ratio of 3:5. Then, add potassium carbonate at 8% of the total mass of coal gangue and fly ash to the coal gangue and fly ash mixture. Calcinate at 600℃ for 120 min. After calcination, wash with water (solid-liquid ratio 1:2, wash water can be reused). Then, add hydrochloric acid with a concentration of 1.5 mol / L at a solid-liquid ratio of 1:1. Stir and react at 90℃ for 120 min to form gel I.

[0066] S2. Weigh coal gangue and fly ash at a mass ratio of 3:5. Then, add sodium carbonate and potassium chloride (sodium carbonate to potassium chloride mass ratio of 7:3) at 0.1% of the total mass of coal gangue and fly ash and mix them with the coal gangue. Calcine at 600℃ for 120 minutes. After calcination, wash with water (solid-liquid ratio of 1:1) to form slurry I.

[0067] S3. Add the above slurry I to gel I (mass ratio 1:1), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0068] S4. The above gel II is acid-washed with a 3 mol / L acid washing solution (made of hydrochloric acid and oxalic acid in a volume ratio of 17:3) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0069] S5. The above filtrate is extracted with an organic solvent (tributyl phosphate (TBP) + kerosene) to separate the inorganic phase and the organic phase. The organic phase is then back-extracted with 0.3 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0070] The subsequent steps are the same as in Example 1.

[0071] Example 9 This embodiment provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Embodiment 1, with the main differences as follows: S1. Take 30% sodium carbonate by weight of fly ash and add it to the fly ash. Mix and calcine at 750℃ for 80 minutes. After calcination, wash with water (solid-liquid ratio 1:1, wash water can be reused). Then add hydrochloric acid with a concentration of 1.5 mol / L at a solid-liquid ratio of 1:2 and stir at 60℃ for 100 minutes to form gel I.

[0072] S2. Take 0.6% of potassium carbonate by weight of fly ash, add it to coal gangue and mix. Calcine at 700℃ for 90 minutes. After calcination, wash with water (solid-liquid ratio 1:2) to form slurry I.

[0073] S3. Add the above slurry I to gel I (mass ratio 1:1), stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II.

[0074] S4. The above gel II is acid-washed with 2.5 mol / L acid washing solution (made by mixing hydrochloric acid and oxalic acid in a volume ratio of 3:2) and separated to obtain a filtrate containing zirconium, lithium and titanium elements and gel III.

[0075] S5. The above filtrate is extracted with an organic solvent (tributyl phosphate (TBP) + Alamine 336) to separate the inorganic and organic phases. The organic phase is then back-extracted with 0.8 mol / L hydrochloric acid to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements.

[0076] The subsequent steps are the same as in Example 1.

[0077] Comparative Example 1 This comparative example provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Example 1, with the following main differences: in step S1, the gelling agent is changed from sodium carbonate to sodium chloride; in step S2, the treatment agent is changed from potassium carbonate to potassium chloride; the rest remain unchanged.

[0078] The experimental results showed that the quality of the formed gel was very poor, and it was even difficult to obtain a gel. Furthermore, the slurry treated with the treatment agent did not separate into layers when mixed with it. After extraction with organic solvent, the solution containing elements such as zirconium, lithium, and titanium was obtained by back-extraction. The recovery rates were calculated to be 48.7%, 53.3%, and 41.6%, respectively.

[0079] Comparative Example 2 This comparative example provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Example 1, with the following main differences: the roasting temperature in step S1 is changed to 400℃; the roasting temperature in step S2 is changed to 400℃; all other steps remain unchanged.

[0080] The experimental results showed that the quality of the formed gel was poor, and the stratification effect of mixing with the slurry treated by the treatment agent was not good. After extraction with organic solvent, the solution containing elements such as zirconium, lithium, and titanium was obtained by back-extraction. The recovery rates were calculated to be 56.4%, 58.1%, and 52.3%, respectively.

[0081] Comparative Example 3 This comparative example provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Example 1, with the main differences being: the content of the treatment agent in step S2 is increased to 2%; all other steps remain unchanged.

[0082] Experimental results showed that the slurry treated with the treatment agent did not have a good stratification effect when mixed with it. After extraction with organic solvent, the solution containing zirconium, lithium, titanium and other elements was obtained by back-extraction. The recovery rates were calculated to be 64.5%, 61.7% and 59.8%, respectively.

[0083] Comparative Example 4 This comparative example provides a method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash. The specific process is basically the same as that in Example 1, with the main differences being: in step S1, the concentration of hydrochloric acid is increased to 4 mol / L; all other steps remain unchanged.

[0084] Experimental results showed that the gelling agent treatment resulted in poor gel formation. After organic solvent extraction and back-extraction, a solution containing zirconium, lithium, and titanium atoms was obtained. The recovery rates were calculated to be 69.2%, 72.7%, and 63.6%, respectively.

[0085] As for the solid-liquid ratio, adopting it within a reasonable range is conducive to the rapid separation of solids and liquids, which helps with recycling and plays an important role in reducing production costs and improving economic efficiency.

[0086] Furthermore, to understand the final enrichment effect of the above embodiments on zirconium, lithium, and titanium, their separation efficiency was tested, and the specific results are shown in Table 2 below: Table 2. Specific enrichment effect data for each embodiment.

[0087] As shown in Table 2, except for the comparative examples, the enrichment and recovery rates of zirconium, lithium, and titanium were all above 80%, demonstrating good results. Furthermore, all raw materials and reagents were fully utilized, reducing resource waste. Example 4 showed the best results, with enrichment and recovery rates of 89.7%, 92.4%, and 87.3% for zirconium, lithium, and titanium, respectively.

[0088] The above series of studies have shown that this application uses coal gangue or fly ash as raw materials to prepare gels, uses gel adsorption to treat and separate the adsorption of noble metals, and then elutes in acid. After repeated operation, the noble metal ions in the eluent are enriched to a certain concentration, and then extracted and separated by organic extractant to obtain the noble metals. The eluted solid can be used as a gel material after treatment.

[0089] Unless otherwise specified, all raw materials used in this invention are existing substances that can be purchased directly from the market.

[0090] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for enriching zirconium, lithium, and titanium elements from coal gangue and / or fly ash, characterized in that, The method includes the following steps: S1. Take coal gangue and / or fly ash, add a gelling agent and mix, calcine, wash with water and add dilute acid to obtain gel I; S2. Take coal gangue and / or fly ash, add treatment agent, mix, calcine, wash with water to form slurry I; S3. Add the above slurry I to gel I, stir to react, let stand to separate into layers, and separate to obtain gel II and slurry II; S4. The above gel II is acid-washed with acid washing solution and separated to obtain filtrate containing zirconium, lithium and titanium elements and gel III; S5. The above filtrate is extracted with an organic solvent to obtain an inorganic phase and an organic phase. The organic phase is then back-extracted with an acid solution to obtain a solution containing zirconium, lithium, titanium and other element atoms, thus achieving the enrichment of zirconium, lithium and titanium elements. The gelling agent includes at least one of sodium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, and potassium carbonate. The treatment agent is composed of at least one of treatment agent A and treatment agent B. Treatment agent A includes sodium carbonate, potassium carbonate, sodium acetate, and sodium oxalate; treatment agent B includes sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, potassium bromide, and sodium bromide. The organic solvent includes at least one of TBP, D2EHPA (sulfuric acid), Cyanex 923 (hydrochloric acid), Alamine 336 (hydrochloric acid), and kerosene.

2. The method according to claim 1, characterized in that, The method further includes the following steps: Gel III and slurry II are mixed, stirred and reacted, allowed to stand and separate into layers, and gel IV and slurry III are obtained. Gel III is then acid-washed with acid washing solution. This step is repeated to increase the enrichment amount. After enrichment, the remaining gel and slurry are mixed and treated with the washing water in step S1 to form the gel material. The inorganic phase is returned to the pickling solution for continued use; The organic phase obtained after back-extraction is returned to the organic solvent for further extraction.

3. The method according to any one of claims 1 or 2, characterized in that, The mass of the gelling agent mentioned in step S1 accounts for 1 to 100% of the mass of coal gangue and / or fly ash.

4. The method according to any one of claims 1 or 2, characterized in that, The roasting conditions described in steps S1 and S2 are the same: temperature 500-900℃, time 20-150min; In steps S1 and S2, the solid-liquid ratio of the water used for washing is less than 1:

3.

5. The method according to any one of claims 1 or 2, characterized in that, The dilute acid mentioned in step S1 includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and oxalic acid, and the concentration of the dilute acid is not higher than 3 mol / L; Dilute acid treatment conditions: temperature 20-95℃, time 20-150 min, solid-liquid ratio 1:(1-10).

6. The method according to any one of claims 1 or 2, characterized in that, The amount of treatment agent used in step S2 is 0.1% to 1% of the mass of coal gangue and / or fly ash.

7. The method according to any one of claims 1 or 2, characterized in that, In step S3, the mass ratio of slurry I to gel I is 1:(1-3).

8. The method according to any one of claims 1 or 2, characterized in that, The pickling solution mentioned in step S4 is prepared by mixing pickling solution C and pickling solution D in a volume ratio of (6-9):(1-4); Pickling solution C includes at least one of hydrochloric acid, sulfuric acid, and nitric acid; pickling solution D includes at least one of phosphoric acid, acetic acid, oxalic acid, tartaric acid, and citric acid. The concentration of the pickling solution is not less than 6 mol / L, and the pickling time is 10 to 200 min.

9. The method according to any one of claims 1 or 2, characterized in that, The acid solution mentioned in step S5 includes at least one of sulfuric acid and hydrochloric acid, and the concentration of the acid solution is not higher than 1 mol / L.

10. The method according to claim 1, characterized in that, When the treatment agent is a mixture of treatment agent A and treatment agent B, the mass ratio of treatment agent A to treatment agent B is (2-5):2.

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