CN115216645B - Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination - Google Patents
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Abstract
The invention aims to provide a method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method, which takes electrolytic aluminum waste residue as a raw material, takes potassium and calcium salts as auxiliary materials, adopts a mixed salt calcination method and adopts calcification roasting, potassium salt re-roasting, alkaline leaching, solid-liquid separation, freezing impurity removal and purification processes, has low content of other metal impurity ions in leaching liquor, is easy to separate and extract lithium salt, and is suitable for industrial production with the extraction rate of more than 95 percent, and the market competitiveness of products is improved.
Description
Technical field:
the invention relates to the field of lithium extraction materials of new energy technology of lithium batteries, mainly relates to the technology of extracting lithium or lithium salt from electrolytic aluminum waste residue raw materials, and in particular relates to a method for extracting lithium from electrolytic aluminum waste residue by a mixed salt calcination method.
The background technology is as follows:
aiming at the situation of developing new energy resources in various countries, a great deal of material resources and financial resources are invested in developing and utilizing new energy resources in various countries. And the new energy technology and application of the lithium battery are emerging industries supported by various government technologies.
Lithium and its compound as one kind of new technological energy source material are applied widely in energy source, chemical industry, metallurgy, ceramic, nuclear power and other fields. There is an increasing global demand for lithium and its compounds. Therefore, the development of lithium resources and the industrial production thereof are one of important industries which are preferentially developed in countries around the world. At present, the production of lithium carbonate mainly comprises two technologies of ore lithium extraction and brine lithium extraction. The technology of extracting lithium from the ore is mature, the recovery rate is high, the process is simple, but the technology has the adverse factors of high energy consumption, large material flow, high cost and the like, and the technology of extracting lithium from the salt lake brine is greatly restricted by the resource endowment and the technical level. However, the extraction of lithium from solid wastes containing lithium is particularly important.
The lithium is known as "energy metal" and "white petroleum", and the lithium compound is a basic core raw material of new energy of lithium battery. Lithium exists in natural ores mainly in the form of lithium ore resources such as spodumene, lepidolite, spodumene and fluorite. Technological schemes for extracting lithium or lithium salts from lithium ore resources are common. However, other lithium-related materials are not used as raw materials for extracting lithium and salts thereof.
In the electrolytic production of aluminum, besides cryolite, some fluoride or chloride and other salts are added to the electrolyte, so as to improve the property of the electrolyte and achieve the purposes of improving the current efficiency and reducing the energy consumption, one of the common additives is lithium fluoride. The lithium-containing anhydrous aluminum fluoride and the lithium-containing cryolite have good use effects in the aluminum electrolysis enterprises at present, can effectively reduce the initial temperature of the electrolyte, reduce the emission of fluorine, and play a role in promoting the energy conservation and consumption reduction of the aluminum electrolysis enterprises. Along with the use of lithium fluoride, lithium-containing electrolytic aluminum waste residues are generated, the lithium content of the lithium-containing electrolytic aluminum waste residues is 1% -3% (calculated by Li < + >) at present, a plurality of production enterprises adopt a concentrated sulfuric acid autoclaving method to extract lithium, a large amount of hydrofluoric acid overflows, the environment is polluted, and the equipment energy consumption is high.
For example, chinese patent publication No. CNCN105293536A discloses a method for extracting lithium from electrolytic aluminum waste residues, which comprises the following steps: reacting lithium-containing electrolytic aluminum waste residue with concentrated sulfuric acid at 200-400 ℃ to obtain a mixture A; leaching the mixture A with water, and filtering to obtain filtrate A and filter residue A; adding sodium carbonate into the filtrate A to perform alkaline hydrolysis reaction at 20-40 ℃, and filtering to obtain filtrate B and filter residue B; adding water into the filter residue B to prepare slurry, adding lime to perform causticization reaction, and filtering to obtain filtrate C and filter residue C; introducing CO2 into the filtrate C obtained in the step 4) to carry out carbonization reaction, and then filtering, washing and drying to obtain the catalyst. The obtained battery grade lithium carbonate has low impurity ion content and excellent product quality, and solves the problems of low yield, high production cost and weak market competitiveness of the battery grade lithium carbonate prepared by extracting lithium from the ore at present; the new process for producing the lithium products with high added value and high quality by using the low-grade lithium resources is developed, the process is simple, the industrial operation is easy, and the economic and social benefits are obvious. As can be seen from the technical scheme disclosed in the document, the lithium is extracted by adopting the concentrated sulfuric acid digestion method by taking the electrolytic aluminum waste residue as a raw material, and the method has the advantages that a large amount of hydrofluoric acid is generated and overflows, so that the influence on environmental pollution is too large, and the requirement on production equipment is higher; secondly, because a large amount of hydrofluoric acid solution exists in the extracted leaching solution, the existence of other metal chemical elements in the solution is higher, namely the content of aluminum and copper serving as impurity elements for lithium or lithium salt is higher; subsequent processing is more difficult, resulting in higher production costs.
Therefore, how to provide a method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method, which uses the electrolytic aluminum waste residue as a raw material and adopts the mixed salt calcination method, the method is simple in technology, low in energy consumption cost and high in product quality, and the whole technological treatment process is comprehensive utilization of lithium solid waste. The hydrofluoric acid solution does not have great influence on the environment in the extraction process, the content of other metal impurity ions in the leaching solution is not high, and the lithium salt is easily separated and extracted, so that the lithium extraction technology is applied to industrial and large-scale production from electrolytic aluminum waste residues. The production cost of extracting lithium from the electrolytic aluminum waste residue is greatly reduced.
The invention comprises the following steps:
the invention aims to provide a method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method, which takes electrolytic aluminum waste residue as a raw material, takes potassium and calcium salts as auxiliary materials, adopts a mixed salt calcination method, adopts calcification roasting, potassium salt re-roasting, alkaline leaching, solid-liquid separation, freezing impurity removal and purification processes, has low content of other metal impurity ions in leaching liquor, is easy to separate and extract lithium salt, and improves the market competitiveness of products.
The invention aims to provide a method for extracting lithium from electrolytic aluminum waste residue by a mixed salt calcination method, which takes electrolytic aluminum waste residue as a raw material, takes potassium and calcium salts as auxiliary materials, adopts a mixed salt calcination method and adopts the processes of calcification roasting, potassium salt re-sintering, alkaline leaching, solid-liquid separation, freezing impurity removal and purification, and comprises the following steps:
1) Crushing and ball milling, namely mechanically crushing electrolytic aluminum waste residues into fine materials, sieving, mixing with calcium salt, and then entering a ball milling device for ball milling treatment to obtain ball milling mixed materials;
2) Pressing and calcification roasting, namely placing the ball-milling mixed material obtained in the step 1) into a pressing device, pressing into brick blocks, and then placing into a tunnel kiln device for calcification roasting to obtain a roasting material;
3) Mixing and ball milling for the second time, and placing the roasting material and potassium salt obtained in the step 2) into a ball milling device for mixed ball milling until the particle size reaches 50-100 meshes, so as to obtain a mixture;
4) The mixture is put into a rotary kiln device for secondary roasting, the roasting temperature is controlled to be 750-900 ℃ and the roasting heat preservation time is 0.5-1.0h, the secondary roasting is carried out, the secondary roasting is mechanically crushed and ball-milled by clinker, and the secondary roasting is processed to 80-160 meshes, thus obtaining roasting fine powder;
5) Alkali leaching, namely placing the calcined fine powder, alkali liquor and aqueous solution into a stirring device, fully stirring and mixing, and leaching to obtain a lithium hydroxide-containing solution leaching solution;
6) Solid-liquid separation and countercurrent washing, wherein the lithium hydroxide solution leaching solution is subjected to solid-liquid separation by a filtering device to obtain filter residues and filtrate; countercurrent washing the filter residue for several times, filtering with a plate-and-frame filter to obtain washing liquid and washing residue, and controlling the concentration of lithium ions in the washing residue to be low;
7) Freezing, namely fully mixing the filtrate prepared in the step 6) with the washing liquid to prepare a lithium preparation solution, performing freezing process treatment on the lithium preparation solution to obtain aluminum potassium sulfate dodecahydrate mixed salt, and performing centrifugal separation treatment to obtain a lithium purification solution;
8) Washing, namely washing the aluminum potassium sulfate dodecahydrate obtained after centrifugal separation in the step 7) with clear water for a plurality of times to obtain a washing liquid and washed aluminum potassium sulfate dodecahydrate, wherein the washing liquid is used for the alkaline leaching treatment of the next step 5);
9) Deeply purifying to prepare hydrogen lithium oxide or lithium carbonate salt, and removing Ca in the lithium purifying liquid by using chelating resin adsorption purification treatment of the purifying liquid obtained in the step 7) by using a purifying device 2+ 、Mg 2+ And then the lithium deep purification liquid is treated by a concentration process, and the lithium deep purification liquid is prepared into battery-grade lithium hydroxide or battery-grade lithium carbonate by treatment.
The method for extracting lithium from electrolytic aluminum waste residue by using the mixed salt calcination method comprises the following steps of 1) controlling the ball milling time to be 2-3h and the rotating speed of the ball mill to be 200-400 r/min; simultaneously controlling electrolytic aluminum waste residues: the mass ratio of calcium salt is = 100:40-60; the calcium salt is any one or the mixture of more of calcium oxide, calcium carbonate and calcium hydroxide.
Preferably, the pressing in the step 2) is performed by controlling the pressure of the pressing machine to 6000-8000MPa, controlling the roasting temperature to 800-950 ℃ and the roasting heat preservation time to 1-2h.
Preferably, the mass ratio of the roasting material to the potassium salt is controlled in the step 3): potassium salt = 100:20-80 parts; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate.
Preferably, the alkaline leaching treatment in the step 5) is carried out, the concentration of the alkaline liquor is controlled to be 0.5-0.7mol/L, and the alkaline liquor is potassium hydroxide solution or sodium hydroxide solution; the mass ratio of the calcined fine powder to the water is controlled to be 1:5.5-6.5; the leaching temperature is controlled to be 90-95 ℃ during alkaline leaching treatment, and the leaching time is controlled to be 2-4 h under the condition of continuous stirring.
Further, in the step 6), the countercurrent washing times of the filter residues are controlled to be 2-6 times, and the concentration of lithium ions in the washing residues is controlled to be less than or equal to 0.20wt%.
The invention relates to a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which comprises the following steps of 7) freezing treatment, wherein the freezing temperature is controlled to be-5 ℃ to 5 ℃, and the freezing time is controlled to be 2-3 hours.
Further, the step 9) of deep purification is performed, and the concentration content of lithium ions in the lithium deep purification liquid is controlled to be 12-18g/L; and control Ca in the lithium deep purification liquid 2+ 、Mg 2+ 、P、F - Ion mass concentration is less than or equal to 0.06%; and then filtering and separating to prepare the battery-grade lithium hydroxide and the battery-grade lithium carbonate.
The invention relates to a method for extracting lithium from electrolytic aluminum waste residue by a mixed salt calcination method, which comprises the following components in percentage by mass: al (Al) 3+ ：12％～18％，Na + ：14％～20％，F - ：30％～54％，Li + ：1.5％～ 3.2％，SiO 2 ：0.05％～1.05％，Fe 2 O 3 ：0.5％～0.20％，SO 4 2— ：0.11％～0.35％。
In the step 6), the filtered filter residues and the washing residues can be applied to raw materials in the carbon industry.
The invention discloses a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which relates to a main chemical reaction equation: 2Na 3 AlF 6 +3CaO＝Al 2 O 3 +6NaF+3CaF 2
3CaO+2AlF 3 ＝Al 2 O 3 +3CaF 2
12CaO+7Al 2 O 3 ＝12CaO·7Al 2 O 3
CaO+6Al 2 O 3 ＝CaO·6Al 2 O 3
CaO+2Al 2 O 3 ＝CaO·2Al 2 O 3 。
The invention discloses a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which comprises the following chemical processes: electrolytic aluminum waste residue raw material, crushing, ball milling by a ball mill, pressing the fine powder into powder bricks, roasting by a tunnel kiln, secondarily crushing, secondarily ball milling to 80 meshes or so to obtain a mixture, secondarily roasting the mixture, secondarily crushing, ball milling to obtain roasted fine powder, performing alkaline leaching treatment, performing solid-liquid separation and countercurrent washing, freezing and flushing, and finally deeply purifying to prepare battery-grade lithium hydroxide or battery-grade lithium carbonate.
Compared with the prior art and the method for extracting lithium by adopting concentrated sulfuric acid autoclaving, the method for extracting lithium from the electrolytic aluminum waste residue by using the mixed salt calcination method disclosed by the invention has the advantages of large amount of overflowed hydrofluoric acid, environmental pollution, high equipment energy consumption and the like, and has the following outstanding advantages:
firstly, the invention takes electrolytic aluminum waste residue as raw material, adopts a method of mixed salt calcination, has simple technical process, low energy consumption cost and high product quality, and the whole process treatment process is comprehensive utilization of lithium solid waste. The hydrofluoric acid solution is less in the extraction process, and the environment is not polluted greatly, and the other metal impurity ions in the leaching solution are low in the subsequent leaching extraction process, for example, the impurity Al (g/L) content is 10.8 when the sulfuric acid autoclaving method is used for extracting lithium, and the Al (g/L) content is 0.5 by adopting the method; fe (mg/L) was 1.80, whereas the method of the present invention was 0.1; the method is a method for extracting lithium salt by easy separation, and realizes the application of the lithium extraction technology in industrial and large-scale production from electrolytic aluminum waste residues. The production cost of extracting lithium from the electrolytic aluminum waste residue is greatly reduced; the lithium leaching yield can reach 95 percent.
The specific embodiment is as follows:
the invention is described in further detail below with reference to specific corresponding examples, wherein the components according to the invention are commercially available in the form of mass ratios or parts by mass.
The invention discloses a method for extracting lithium from electrolytic aluminum waste residue by a mixed salt calcination method, which takes the electrolytic aluminum waste residue as a raw material, takes potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method and adopts the processes of calcification roasting, potassium salt re-sintering, alkaline leaching, solid-liquid separation, freezing impurity removal and purification, and comprises the following steps:
1) Crushing and ball milling, namely mechanically crushing the electrolytic aluminum waste residue raw material into fine materials, sieving, fully mixing the fine materials with calcium salt, and then entering a ball milling device for ball milling treatment, wherein the ball milling treatment time is controlled to be 2-3h, and the rotating speed of the ball mill during ball milling is controlled to be 200-400 r/min; simultaneously controlling electrolytic aluminum waste residues: the mass ratio of calcium salt is = 100:40-60; the calcium salt is any one or the mixture of more of calcium oxide, calcium carbonate and calcium hydroxide; the electrolytic aluminum waste residue comprises the following components in percentage by mass: al (Al) 3+ ：12％～18％，Na + ：14％～25％， F - ：30％～54％，Li + ：1.5％～3.2％，SiO 2 ：0.05％～1.05％，Fe 2 O 3 ：0.5％～0.20％，SO 4 2— : 0.11 to 0.35 percent; ball milling and mixing;
2) Pressing and calcification roasting, namely placing the ball-milling mixed material obtained in the step 1) into a pressing device to be pressed into brick blocks, controlling the water content in the mixed material or the ball-milling mixed material in the pressing process, namely controlling the water content in the mixed material or the ball-milling mixed material to be capable of being pressed into block-shaped brick materials, controlling the pressing pressure of the pressing device to be 6000-8000MPa, stacking the block-shaped brick blocks, and then placing the stacked block-shaped brick blocks into a tunnel kiln device to be subjected to calcification roasting, wherein the roasting temperature is controlled to be 800-950 ℃, and the roasting and heat preservation time is controlled to be 1-2 hours, so that the block-shaped brick materials are roasted;
3) Mixing the roasting material and the potassium salt in the step 2), stirring and mixing, and then placing in a ball milling device for full mixing and ball milling until the particle size reaches 50-100 meshes, wherein the mass ratio of the roasting material to the potassium salt is controlled as follows: potassium salt = 100:20-80 parts; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate; after ball milling, the mixture is obtained;
4) The secondary roasting is carried out, the mixture is placed in a rotary kiln device, the roasting temperature is controlled to be 750-900 ℃ and the roasting heat preservation time is 0.5-1.0h, the secondary roasting is carried out, the secondary roasting is mechanically crushed by clinker and then ball-milled, and the mixture is processed to 80-160 meshes, thus obtaining roasting fine powder;
5) Alkali leaching, namely placing the calcined fine powder, alkali liquor and aqueous solution into a stirring device, fully stirring and mixing, leaching, and controlling the concentration of the alkali liquor to be 0.5-0.7mol/L, wherein the alkali liquor is potassium hydroxide solution or sodium hydroxide solution; the mass ratio of the calcined fine powder to the water is controlled to be 1:5.5-6.5; controlling the leaching temperature at 90-95 ℃ in the alkaline leaching treatment, and controlling the leaching time at 2-4 h under the condition of continuous stirring; the lithium in the roasting fine powder exists in the leaching solution in the form of lithium hydroxide in the alkaline leaching treatment process, so that the lithium hydroxide-containing solution leaching solution is obtained;
6) Solid-liquid separation and countercurrent washing, wherein the lithium hydroxide solution leaching liquid obtained in the step 5) is subjected to solid-liquid separation by a filtering device to obtain filter residues and filtrate; countercurrent washing the filter residue for 2-6 times, filtering with a plate-frame filter to obtain washing liquid and washing residue, and controlling the concentration of lithium ions in the washing residue to be less than or equal to 0.20wt%;
7) Freezing, namely fully mixing the filtrate prepared in the step 6) with the washing liquid to prepare a lithium preparation solution, carrying out freezing process treatment on the lithium preparation solution, freezing potassium, aluminum and the like in the solution to prepare aluminum potassium sulfate dodecahydrate mixed salt, controlling the freezing temperature to be minus 5 ℃ to 5 ℃, freezing time to be 2 to 3 hours, and carrying out centrifugal separation treatment to obtain a lithium purification solution;
8) Washing treatment, namely washing the aluminum potassium sulfate dodecahydrate obtained in the step 7) by using clear water for a plurality of times to obtain a washing liquid and the aluminum potassium sulfate dodecahydrate, wherein washing is the alkaline leaching treatment of the next step 5);
9) Deeply purifying to prepare hydrogen lithium oxide or lithium carbonate salt, and removing Ca in the lithium purifying liquid by using chelating resin adsorption purification treatment of the purifying liquid obtained in the step 7) by using a purifying device 2+ 、Mg 2+ Then the concentrated working procedure is carried out to obtain the lithium deep purification liquid, and the purification is to control the concentration content of lithium ions in the lithium deep purification liquid to reach 12-18g/L; and controlling Ca in the purified lithium deep purification liquid 2+ 、Mg 2+ 、P、 F - Ion mass concentration is less than or equal to 0.06%; and then filtering and separating to prepare the raw materials of the battery-grade lithium hydroxide and the battery-grade lithium carbonate, and further preparing the battery-grade lithium hydroxide or the battery-grade lithium carbonate.
The filter residue and washing slag prepared in the step 6) can be used as raw materials for production in the carbon industry, and the lithium leaching yield can reach 95%. The following specific examples are the same as those of the present embodiment, but are not described.
Example 1
The technical content is further illustrated below by means of specific examples, which should not be interpreted in any way as limiting the scope of protection of the patent. Modifications and equivalents thereof by those skilled in the art are intended to be included in the scope of the present patent.
The embodiment of the invention discloses a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which uses the electrolytic aluminum waste residues of certain aluminum industry company of Xinjiang Tianshan as the raw materials of the embodiment, and the main components are shown in the following table 1.
In the table 1 of the description,
| Wt(F) | Wt(Na) | Wt(Al) | Wt(Ca) | Wt(Li) | wt (others) |
| 53.10 | 24.89 | 12.73 | 1.90 | 2.12 | 3.75 |
Description: the contents of the components in the table are mass ratios.
Mechanically crushing raw material electrolytic aluminum waste residues into fine materials, sieving, adding a certain amount of calcium oxide, grinding in a ball mill for 2 hours at the rotating speed of 250r/min, and fully stirring and mixing to obtain a mixed material or ball milling mixed material; controlling electrolytic aluminum waste residues: the mass ratio of calcium oxide is = 100:40, a step of performing a; the fine powder material ground by the method, namely ball milling and mixing materials, is controlled to control the humidity of the ball milling and mixing materials, is pressed into brick blocks by a pressing machine, namely brick blocks, the pressing pressure of the pressing machine is controlled to be 6000-8000MPa, the brick blocks are stacked to be capable of being put into a tunnel kiln device for roasting, the calcification high-temperature roasting transformation of the tunnel kiln is controlled, the roasting temperature is controlled to be 900-950 ℃, and the roasting heat preservation time is controlled to be1-2h; the calcified and roasted clinker is the roasting material; then placing the mixture into a ball milling device for ball milling to 70 meshes, wherein the fine powder material is the roasting material according to the following fine powder materials: potassium sulfate: potassium carbonate = 100:30:10 (mass ratio) batching; the evenly mixed materials are mixed materials, the mixed materials are roasted by a rotary kiln, the roasting temperature of the rotary kiln is controlled to be 880 ℃, the high-temperature roasting and heat preservation time is controlled to be 1h, the powder is grinded to 100 meshes, and the roasted materials are roasted fine powder; deep alkaline leaching or alkaline leaching treatment, namely stirring and mixing the calcined fine powder, 0.6mol/L potassium hydroxide solution and water, controlling the mass ratio of the clinker calcined fine powder to the water to be 1:6, leaching treatment temperature to be 90-95 ℃, and stirring and leaching for 4 hours, so that the clinker fine powder, namely lithium in the calcined fine powder, enters the leaching solution as lithium hydroxide liquid; and (3) carrying out solid-liquid separation and countercurrent washing, and carrying out solid-liquid separation on the lithium hydroxide solution solid-liquid mixture through a filtering device to obtain filter residues and filtrate. Carrying out countercurrent washing on filter residues for 4 times, wherein a filtering device is a plate-frame filter, and controlling the concentration of lithium ions in the filter residues to be less than or equal to 0.20wt%; mixing the filtrate and the washing solution to obtain a lithium preparation solution, generating potassium, sodium and aluminum in the solution into aluminum potassium sulfate dodecahydrate mixed salt by using a freezing process, and centrifugally separating to obtain the lithium purification solution; controlling the freezing temperature to be between minus 5 ℃ and the freezing time to be between 2 and 3 hours; washing the centrifugally separated aluminum potassium sulfate dodecahydrate twice, and storing the obtained washing liquid, namely flushing liquid, as the next alkaline leaching; purifying the lithium purified solution by chelating resin to adsorb and purify Ca 2+ 、Mg 2+ The concentration process is carried out to obtain concentrated solution, the lithium ion concentration content is about 15g/L, namely the lithium deep purification solution, and Ca in the purified solution, namely the lithium deep purification solution, is controlled 2+ 、Mg 2+ 、P、F - Ion mass concentration is less than or equal to 0.06%, and filtering and separating; namely, the solution for preparing the battery grade lithium hydroxide or the battery grade lithium carbonate is further prepared to obtain the battery grade lithium hydroxide or the lithium carbonate, and the detection results of the battery grade lithium hydroxide or the lithium carbonate prepared in the embodiment 1 are shown in the following table 2.
The following examples are not described in detail in the same manner as in example 1 or the description of the specific embodiments.
Example 2
In the embodiment, the electrolytic aluminum waste residue of the Oriental hope certain aluminum industry company is taken as a raw material, the electrolytic aluminum waste residue of the Oriental hope certain aluminum industry is mechanically crushed into fine materials, a certain amount of calcium oxide and calcium hydroxide are added after sieving and mixed according to any proportion, and the mixture is ground in a ball mill for 3 hours at the rotating speed of 280r/min, so that the materials are fully and uniformly mixed; electrolytic aluminum waste residue: mix of calcium oxide and calcium hydroxide = 100:45 (mass ratio); pressing the ground fine powder material into bricks by a press, calcification high-temperature roasting and transformation of a tunnel kiln, controlling the temperature to 900 ℃, and keeping the temperature for 2 hours; the calcified and roasted clinker is ball-milled to 70 meshes and is prepared according to the following fine powder: potassium sulfate: potassium carbonate = 100: 40:10 (mass ratio) ingredients. Roasting the uniformly mixed materials in a rotary kiln, controlling the temperature to 880 ℃, preserving heat for 1h at a high temperature, grinding the materials to 100 meshes, and processing the materials into calcine crushing fine powder; deep alkaline leaching, namely stirring and mixing the calcined fine powder and 0.6mol/L potassium hydroxide solution, controlling the mass ratio of the clinker fine powder to water to be 1:6, leaching at 90 ℃ for 4 hours, and enabling lithium in the clinker fine powder to enter the leaching solution as lithium hydroxide liquid; and (3) carrying out solid-liquid separation and countercurrent washing, and carrying out solid-liquid separation on the lithium hydroxide solution solid-liquid mixture through a filtering device to obtain filter residues and filtrate. Carrying out countercurrent washing on filter residues for 4 times, wherein a filtering device is a plate-frame filter, and controlling the concentration of lithium ions in the filter residues to be 0.150wt%; and (3) preparing a lithium purifying solution, mixing the prepared filtrate and the washing solution to obtain the lithium preparing solution, generating potassium aluminum sulfate dodecahydrate potassium aluminum sulfate mixed salt by using a freezing process from potassium, sodium and aluminum in the solution, and centrifugally separating to obtain the lithium purifying solution. Freezing temperature is-5 ℃ to 5 ℃ and freezing time is 3 hours. Washing the centrifugally separated aluminum potassium sulfate dodecahydrate twice, and storing the washing liquid as the next alkali leaching; purifying Ca by adsorption of lithium purifying liquid with chelating resin 2+ 、 Mg 2+ The concentration process is carried out to obtain a concentrated solution with the lithium ion concentration content of about 17g/L, and Ca in the purified solution is controlled 2+ 、Mg 2+ 、P、 F - Filtering and separating the lithium hydroxide with the ion mass concentration of 0.05%, and preparing the battery-grade lithium hydroxide and the battery-grade lithium carbonate. The quality index of the battery grade lithium carbonate is detected by related departments and analyzedThe following table 2 shows the results.
Table 2:
product name: the lithium carbonate of the battery grade is used for preparing the lithium carbonate,
product appearance: micropowder, white powder, no caking,
particle size: the particle size diameter of D50 was used as the measurement data, and the standard was controlled to about 6. Mu.m.
Description: from the report of the detection result, the technical route of the process disclosed by the invention can realize industrialization. The content of lithium hydroxide prepared by the method reaches more than 99.5%, and the detection results all meet the quality standard requirements of battery-grade lithium carbonate.
Comparative examples
In the comparative example, the raw materials are the same as those in the example, and the electrolytic aluminum waste residue is extracted by the current general sulfuric acid method; the current method is mainly a method for extracting lithium from electrolytic aluminum waste residue by sulfuric acid method, the process (1) is that electrolytic aluminum waste residue of certain aluminum industry company in Henan containing lithium is reacted with concentrated sulfuric acid for 2-3 hours at 200-400 ℃ to obtain hydrogen fluoride gas generated by the reaction of sodium, aluminum and lithium sulfate mixture, the hydrogen fluoride gas is absorbed by water to obtain aqueous hydrofluoric acid (2) which is prepared by dissolving the sodium, aluminum and lithium sulfate mixture into 25-35% concentration solution, filtering to remove unreacted carbon residue (3) and adding sodium carbonate into the filtrate to respectively obtain aluminum hydroxide and lithium carbonate (4) which is precipitated into decarbonizing mother solution to prepare slurry, water is added to prepare 3-4% lithium carbonate slurry, and then CO is introduced 2 Performing carbonization reaction to control the pH value of a carbonization end point to be 6-6.5, and filtering to obtain lithium bicarbonate solution filter residues for cryolite synthesis; (5) and heating the lithium bicarbonate solution to 90-100 ℃ for decarburization and recrystallization to obtain the battery grade lithium carbonate. The method of the invention is that the electrolytic aluminum waste residue of certain aluminum industry in Henan Kaman is crushed into fine powder by machinery, and is added with a certain amount of calcium oxide after sieving, and the powder is put into a ball mill to be ground for 2.5h at the rotating speed of 260r/min, and fully mixedAnd the materials are uniform. Electrolytic aluminum waste residue: calcium oxide = 100:47 (mass ratio). Pressing the ground fine powder material into bricks by a press, calcification high-temperature roasting and transformation of a tunnel kiln, controlling the temperature to 920 ℃, and keeping the temperature for 2 hours. The calcified and roasted clinker is ball-milled to 70 meshes and is prepared according to the following fine powder: potassium sulfate: potassium carbonate = 100: 42:10 (mass ratio) ingredients. Roasting the uniformly mixed materials in a rotary kiln, controlling the temperature to 890 ℃, preserving heat for 1h at a high temperature, grinding the materials to 100 meshes, and processing the materials into calcine crushing fine powder; deep alkaline leaching, namely stirring and mixing the calcined fine powder and 0.6mol/L potassium hydroxide solution, controlling the mass ratio of the clinker fine powder to water to be 1:6, leaching at 90 ℃ for 4 hours, and enabling lithium in the clinker fine powder to enter the leaching solution as lithium hydroxide liquid; and (3) carrying out solid-liquid separation and countercurrent washing, and carrying out solid-liquid separation on the lithium hydroxide solution solid-liquid mixture through a filtering device to obtain filter residues and filtrate. Carrying out countercurrent washing on filter residues for 4 times, wherein a filtering device is a plate-frame filter, and controlling the concentration of lithium ions in the filter residues to be 0.150wt%; and (3) preparing a lithium purifying solution, mixing the prepared filtrate and the washing solution to obtain the lithium preparing solution, generating potassium aluminum sulfate dodecahydrate potassium aluminum sulfate mixed salt by using a freezing process from potassium, sodium and aluminum in the solution, and centrifugally separating to obtain the lithium purifying solution. Freezing temperature is-5 ℃ to 5 ℃ and freezing time is 3 hours. Washing the centrifugally separated aluminum potassium sulfate dodecahydrate twice, and storing the washing liquid as the next alkali leaching; purifying Ca by adsorption with chelating resin 2+ 、Mg 2+ The concentration process is carried out to obtain a concentrated solution with the lithium ion concentration content of about 17g/L, and Ca in the solution is controlled 2+ 、Mg 2+ 、P、F - And filtering and separating the mixture with ion mass concentration of 0.05%. And precipitating lithium with sodium carbonate solution to prepare lithium carbonate. However, the main difference between the patent and the sulfuric acid method is that fluoride ions are stabilized in slag by calcium fluoride compounds, rather than a large amount of F ions entering the leaching solution, and other metal ions in the leaching solution, such as iron, aluminum, copper and the like, and the content of fluorine are extremely low. Table 3 below also shows the comparison of the process route according to the invention and the content of the main impurity ions in the leachate according to the comparative example.
The leachate impurity detection analysis results are compared with the following table 3,
| F(g/L) | Al(g/L) | Fe(mg/L) | Si(mg/L) | Cu(mg/L) | |
| concentrated sulfuric acid process | 15.12 | 10.8 | 1.80 | 2.70 | 0.70 |
| The method of the invention | 0.20 | 0.50 | 0.10 | 0.60 | 0.20 |
From the detection results, the mass concentration of impurity ions of the primary leaching solution is obviously lower than that of the ions in the sulfuric acid method by adopting the method for the same raw materials; the invention can be applied to large-scale industrialized production and greatly reduce the production cost. The method of the comparative example has obviously higher content of main impurity ions than the method of the invention.
The description is only an overview of the technical solution of the present invention, but can be implemented according to the content of the specification, which is merely a preferred embodiment of the present invention, and is not limited in any way. Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art, or equivalent embodiments with equivalent variations can be made, without departing from the scope of the disclosed technology. Therefore, any modification, equivalent variation and modification of the above embodiments according to the technology of the present invention fall within the protection scope of the present invention.
Claims (5)
1. A method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method takes the electrolytic aluminum waste residue as a raw material, takes potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method, and adopts the processes of calcification calcination, potassium salt re-calcination, alkaline leaching, solid-liquid separation, freezing and impurity removal and purification, and is characterized by comprising the following steps:
1) Crushing and ball milling, namely mechanically crushing electrolytic aluminum waste residues into fine materials, sieving, and then enabling the fine materials and calcium salt to enter a ball milling device for ball milling treatment to obtain ball milling mixed materials;
2) Pressing and calcified roasting, namely placing the ball-milling mixed material obtained in the step 1) into a pressing device, pressing into brick blocks, and then placing the brick blocks into a tunnel kiln device for middle calcified roasting to obtain a roasted material;
3) Mixing and ball milling for the second time, and placing the roasting material and potassium salt obtained in the step 2) into a ball milling device for mixed ball milling until the particle size reaches 50-100 meshes, so as to obtain a mixture;
4) The mixture is put into a rotary kiln device for secondary roasting, the roasting temperature is controlled to be 750-900 ℃ and the roasting heat preservation time is 0.5-1.0h, the secondary roasting is carried out, the secondary roasting is mechanically crushed and ball-milled by clinker, and the secondary roasting is processed to 80-160 meshes, thus obtaining roasting fine powder;
5) Alkali leaching, namely placing the calcined fine powder, alkali liquor and aqueous solution into a stirring device, fully stirring and mixing, and leaching to obtain a lithium hydroxide-containing solution leaching solution;
6) Solid-liquid separation and countercurrent washing, wherein the lithium hydroxide solution leaching solution is subjected to solid-liquid separation by a filtering device to obtain filter residues and filtrate; countercurrent washing the filter residue for several times, filtering with a plate-and-frame filter to obtain washing liquid and washing residue, and controlling the concentration of lithium ions in the washing residue to be low;
7) Freezing, namely fully mixing the filtrate prepared in the step 6) with the washing liquid to prepare a lithium preparation solution, performing freezing process treatment on the lithium preparation solution to obtain aluminum potassium sulfate dodecahydrate mixed salt, and performing centrifugal separation treatment to obtain a lithium purification solution;
8) Washing, namely washing the aluminum potassium sulfate dodecahydrate obtained after centrifugal separation in the step 7) with clear water for a plurality of times to obtain a washing liquid and washed aluminum potassium sulfate dodecahydrate, wherein the washing liquid is used for the alkaline leaching treatment of the next step 5);
9) Deeply purifying to prepare hydrogen lithium oxide or lithium carbonate salt, and removing Ca in the lithium purifying liquid by using chelating resin adsorption purification treatment of the purifying liquid obtained in the step 7) by using a purifying device 2+ 、Mg 2+ Then the lithium deep purification liquid is treated by a concentration process, and is prepared into battery-grade lithium hydroxide or battery-grade lithium carbonate by treatment;
the ball milling step 1) is to control the ball milling time to be 2-3h and the rotating speed of the ball mill to be 200-400 r/min; simultaneously controlling electrolytic aluminum waste residues: the mass ratio of calcium salt is = 100:40-60; the calcium salt is any one or the mixture of more of calcium oxide, calcium carbonate and calcium hydroxide;
step 2) pressing, namely controlling the pressure of the pressing machine to be 6000-8000MPa, controlling the roasting temperature to be 800-950 ℃ and the roasting heat preservation time to be 1-2h;
and 3) controlling the mass ratio of the roasting material to the potassium salt to be as follows: potassium salt = 100:20-80 parts; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate.
Step 5), alkaline leaching treatment, wherein the concentration of alkaline liquor is controlled to be 0.5-0.7mol/L, and the alkaline liquor is potassium hydroxide solution or sodium hydroxide solution; the mass ratio of the calcined fine powder to the water is controlled to be 1:5.5-6.5; the leaching temperature is controlled to be 90-95 ℃ during alkaline leaching treatment, and the leaching time is controlled to be 2-4 h under the condition of continuous stirring.
2. The method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method according to claim 1, wherein the step 6) is to control the countercurrent washing times of the filter residue to be 2-6 times, and the concentration of lithium ions in the washing residue to be less than or equal to 0.20wt%.
3. The method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method according to claim 1, wherein 7) the freezing treatment is performed, the freezing temperature is controlled to be-5 ℃ to 5 ℃, and the freezing time is controlled to be 2 to 3 hours.
4. The method for extracting lithium from electrolytic aluminum waste residue by using a mixed salt calcination method according to claim 1, wherein the step 9) is deep purification, and the concentration content of lithium ions in the lithium deep purification liquid is controlled to be 12-18g/L; and control Ca in the lithium deep purification liquid 2+ 、Mg 2+ 、P、F - Ion mass concentration is less than or equal to 0.06%; and then filtering and separating to prepare the battery-grade lithium hydroxide and the battery-grade lithium carbonate.
5. The method for extracting lithium from electrolytic aluminum waste residues by using the mixed salt calcination method as claimed in claim 1, wherein the electrolytic aluminum waste residues comprise the following components in percentage by mass: al (Al) 3+ ：12％～18％，Na + ：14％～25％，F - ：30％～54％，Li + ：1.5％～3.2％，SiO 2 ：0.05％～1.05％，Fe 2 O 3 ：0.5％～0.20％，SO 4 2— ：0.11％～0.35％。
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