CN115216645A - Method for extracting lithium from electrolytic aluminum waste slag by mixed salt calcination method - Google Patents
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Abstract
The invention aims to provide a method for extracting lithium from electrolytic aluminum waste slag by a mixed salt calcination method, which takes the electrolytic aluminum waste slag as a raw material, potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method, adopts the processes of calcification calcination, potassium salt re-calcination, alkaline leaching, solid-liquid separation, freezing impurity removal and purification, has low content of other metal impurity ions in a leaching solution, is easy to separate and extract lithium salt, extracts and separates out industrialized lithium hydroxide and lithium carbonate, has extraction rate of more than 95 percent, is suitable for industrialized and large-scale production, and improves the market competitiveness of products.
Description
The technical field is as follows:
the invention relates to the field of lithium extraction materials of lithium battery new energy technology, mainly relates to a technology for extracting lithium or lithium salt from electrolytic aluminum waste residue raw materials, and particularly relates to a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method.
Background art:
aiming at the situation that new energy is vigorously developed in various countries, a large amount of material resources and financial resources are invested in various countries for developing and utilizing the new energy. The lithium battery new energy technology and the application thereof are a new industry greatly supported by governments of various countries.
Lithium and its compound are used as energy source material for new technology and widely applied in energy source, chemical, metallurgical, ceramic, nuclear 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 the major industries which are preferentially developed by countries in the world. At present, two technologies of extracting lithium from ore and extracting lithium from brine are mainly used for producing lithium carbonate. The ore lithium extraction technology is mature, the recovery rate is high, the process is simple, but the ore lithium extraction technology has the disadvantages of high energy consumption, large material circulation, high cost and the like, and the salt lake brine lithium extraction technology is greatly restricted by resources and technical level. However, the extraction of lithium from lithium-containing solid wastes is particularly important.
Lithium is known as energy metal and white petroleum, and a lithium compound is a basic core raw material of new energy of the lithium battery. Lithium is mainly present in natural ores in the form of spodumene, lepidolite, and xenotime as a lithic ore resource. Technical solutions for extracting lithium or lithium salts from lithium ore resources have become common. However, there are not many other lithium-related materials as raw materials for extracting lithium and salts thereof.
For example, in aluminum electrolysis, in addition to cryolite, some fluoride or chloride and other salts are added to the electrolyte to improve the properties of the electrolyte and achieve the purposes of increasing current efficiency and reducing energy consumption, one of the commonly used additives is lithium fluoride. Lithium-containing anhydrous aluminum fluoride and lithium-containing cryolite have good use effects in electrolytic aluminum enterprises at present, can effectively reduce the initial temperature of electrolyte, reduce the emission of fluorine, and play a role in promoting energy conservation and consumption reduction of the electrolytic aluminum enterprises. With the use of fluoride salt containing lithium, the waste slag of lithium-containing electrolytic aluminum is generated, the lithium content of the waste slag is 1-3% (calculated by Li < + >), and many production enterprises adopt a concentrated sulfuric acid pressure boiling method to extract lithium at present, so that a large amount of hydrofluoric acid overflows, the environment is polluted, and the energy consumption of equipment 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 residues with concentrated sulfuric acid at the temperature of 200-400 ℃ to obtain a mixture A; adding water into the mixture A, leaching, and filtering to obtain a filtrate A and a filter residue A; adding sodium carbonate into the filtrate A to perform alkaline hydrolysis reaction at the temperature of 20-40 ℃, and filtering to obtain filtrate B and filter residue B; adding water into the filter residue B to prepare slurry, adding lime into the slurry for 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 content of impurity ions 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 ores at present; the method opens up a new process for producing high-added-value and high-quality lithium products from low-grade lithium resources, has simple flow, is easy for industrial operation, and has obvious economic and social benefits. According to the technical scheme disclosed by the document, the lithium is extracted by taking the electrolytic aluminum waste residues as raw materials and adopting a concentrated sulfuric acid pressure boiling method, and the method has the disadvantages that firstly, because a large amount of hydrofluoric acid is generated and overflows, the influence on the environment is too large, and the requirement on production equipment is higher; secondly, as a large amount of hydrofluoric acid solution exists in the extracted leachate, other metal chemical elements in the solution are 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 residues by a mixed salt calcination method is to use the electrolytic aluminum waste residues as raw materials and adopt the mixed salt calcination method, and a method which has the advantages of simple technical process, low energy consumption and cost and high product quality and is a comprehensive utilization of lithium solid waste materials in the whole technical treatment process is found. The hydrofluoric acid solution does not cause 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 the electrolytic aluminum waste residues. Greatly reduces the production cost of extracting lithium from the electrolytic aluminum waste residue.
The invention content is as follows:
the invention aims to provide a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which takes the electrolytic aluminum waste residues as raw materials, potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method, adopts the processes of calcification calcination, potassium salt re-calcination, alkaline leaching, solid-liquid separation, freezing impurity removal and purification, has low content of other metal impurity ions in a leaching solution, is easy to separate and extract the lithium salt, and improves the market competitiveness of products.
The invention aims to provide a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which takes the electrolytic aluminum waste residues as raw materials, potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method, adopts the processes of calcification calcination, potassium salt re-calcination, 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 residues into fine feed materials, screening, mixing with calcium salt, and then feeding into a ball milling device for ball milling treatment to obtain ball-milled mixed feed;
2) Pressing and calcified roasting, namely putting the ball-milled and uniformly-mixed material obtained in the step 1) into a press device, pressing the ball-milled and uniformly-mixed material into brick blocks, and then putting the brick blocks into a tunnel kiln device for calcified roasting to obtain a roasted material;
3) Mixing materials and performing secondary ball milling, namely placing the roasted material and the sylvite obtained in the step 2) into a ball milling device for mixing and ball milling until the mixture is 50-100 meshes and is a mixture;
4) Secondary roasting, placing the mixture into a rotary kiln device, roasting by the rotary kiln, controlling the roasting temperature to be 750-900 ℃, roasting heat preservation time to be 0.5-1.0h to obtain secondary roasting material, mechanically crushing and ball-milling the secondary roasting material by clinker, and treating the secondary roasting material to 80-160 meshes to obtain roasted fine powder;
5) Alkali leaching, namely placing the roasted fine powder, alkali liquor and aqueous solution in a stirring device, fully stirring and mixing, and performing leaching treatment to obtain a lithium hydroxide-containing solution leachate;
6) Performing solid-liquid separation and countercurrent washing, namely performing solid-liquid separation on the lithium hydroxide solution leachate through a filtering device to obtain filter residue and filtrate; carrying out countercurrent washing on the filter residue for a plurality of times, and then filtering by using a plate and frame filter to obtain washing liquid and washing residue, wherein the concentration of lithium ions in the washing residue is controlled to be low;
7) Freezing, fully mixing the filtrate prepared in the step 6) with a washing solution to obtain a lithium preparation solution, carrying out freezing process treatment on the lithium preparation solution to obtain aluminum potassium sulfate dodecahydrate mixed salt, and carrying out centrifugal separation treatment to obtain a lithium purification solution;
8) Washing, namely washing the dodecahydrate potassium aluminum sulfate obtained after centrifugal separation in the step 7) with clear water for a plurality of times to obtain washing liquid and washed dodecahydrate potassium aluminum sulfate, wherein the washing liquid is used for alkaline leaching in the next step 5);
9) Deeply purifying to prepare lithium oxide or lithium carbonate, and adsorbing and purifying the purified lithium liquid obtained in the step 7) by using chelate resin of a purifying device to remove Ca in the purified lithium liquid 2+ 、Mg 2+ And then the obtained product is treated by a concentration process to obtain a lithium deep purification solution, and the lithium deep purification solution is treated to prepare battery-grade lithium hydroxide or battery-grade lithium carbonate.
The method for extracting lithium from the electrolytic aluminum waste residue by the mixed salt calcination method comprises the following steps of 1) ball milling, wherein the ball milling time is controlled to be 2-3h, and the rotating speed of a ball mill is controlled to be 200-400 r/min; and simultaneously controlling electrolytic aluminum waste residues: the mass ratio of calcium salts is =100:40-60 parts; the calcium salt is one or more of calcium oxide, calcium carbonate and calcium hydroxide.
Preferably, the pressing in the step 2) is carried out by controlling the pressure of the press to be 6000-8000MPa, the roasting temperature to be 800-950 ℃ and the roasting heat preservation time to be 1-2h.
Preferably, in the step 3), the mass ratio of the calcine to the potassium salt is controlled to be the calcine: potassium salt =100:20-80 parts of; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate.
Preferably, the alkali leaching treatment in the step 5) is carried out, the concentration of alkali liquor is controlled to be 0.5-0.7mol/L, and the alkali liquor is potassium hydroxide solution or sodium hydroxide solution; controlling the mass ratio of the roasted fine powder to water to be 1:5.5-6.5; the leaching temperature is controlled to be 90-95 ℃ during the alkaline leaching treatment, and the leaching time is controlled to be 2-4 h under the condition of continuous stirring.
Further, step 6) is to control the counter-current washing frequency of the filter residue to be 2-6 times and control the lithium ion concentration in the washing residue to be less than or equal to 0.20wt%.
The method for extracting lithium from electrolytic aluminum waste residues by the mixed salt calcination method comprises the step 7) of freezing treatment, wherein the freezing temperature is controlled to be-5 ℃, and the freezing time is controlled to be 2-3 hours.
Further, 9) deep purification, wherein the concentration content of lithium ions in the deep lithium purification solution is controlled to be 12-18g/L; and controlling Ca in the lithium deep purification liquid 2+ 、Mg 2+ 、P、F - The mass concentration of the ions is less than or equal to 0.06 percent; then filtering and separating to prepare battery-grade lithium hydroxide and battery-grade lithium carbonate.
The invention relates to a method for extracting lithium from electrolytic aluminum waste slag by a mixed salt calcination method, wherein the electrolytic aluminum waste slag 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 residue and the washing residue can be used as raw materials in the carbon industry.
The invention discloses a method for extracting lithium from electrolytic aluminum waste slag by a mixed salt calcination method, which relates to the following main chemical reaction equations: 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 slag by a mixed salt calcination method, which comprises the following chemical processes: the method comprises the following steps of crushing and crushing the raw material of the electrolytic aluminum waste residue, ball-milling by a ball mill, pressing fine powder into powder bricks, roasting in a tunnel kiln, carrying out secondary crushing and secondary ball-milling until the size of the fine powder is about 80 meshes to obtain a mixture, carrying out secondary roasting, secondary crushing and ball-milling on the mixture to obtain roasted fine powder, carrying out alkaline leaching treatment, carrying out solid-liquid separation and countercurrent washing, freezing, washing, and finally carrying out deep purification to prepare battery-grade lithium hydroxide or battery-grade lithium carbonate.
Compared with the prior art and the method for extracting lithium from electrolytic aluminum waste residues by adopting a concentrated sulfuric acid pressure boiling method, the method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method disclosed by the invention has the following outstanding advantages that a large amount of hydrofluoric acid overflows, the environment is polluted, the energy consumption of equipment is high, and the like:
firstly, the invention uses the electrolytic aluminum waste residue as the raw material, adopts the mixed salt calcining method, has simple technical process, low energy consumption cost and high product quality, and the whole technical treatment process is the comprehensive utilization of the lithium solid waste. In the extraction process, hydrofluoric acid solution is less, so that the environment cannot be polluted greatly, and in the subsequent leaching and extraction process, the content of other metal impurity ions in the leaching liquor is low, such as the content of impurity Al (g/L), and is 10.8 when lithium is extracted by using a sulfuric acid pressure boiling method, while the Al (g/L) is 0.5 by adopting the method of the invention; fe (mg/L) is 1.80, whereas the process of the invention is 0.1; namely, the mass concentration of Al, fe and other ions in the leachate is low, which is extremely beneficial to the subsequent extraction of lithium salt, lithium hydroxide or lithium carbonate, namely, the method for easily separating and extracting lithium salt realizes the application of the lithium extraction technology in the industrial and large-scale production from the electrolytic aluminum waste residue. Greatly reducing the production cost of extracting lithium from the electrolytic aluminum waste slag; the lithium leaching yield can reach 95%.
The specific implementation mode is as follows:
the invention is further illustrated by the following specific corresponding examples, wherein the components are commercially available in mass ratios or parts by mass.
The invention discloses a method for extracting lithium from electrolytic aluminum waste residues by a mixed salt calcination method, which takes the electrolytic aluminum waste residues as raw materials, potassium and calcium salts as auxiliary materials, adopts the mixed salt calcination method, and adopts the processes of calcification roasting, potassium salt re-roasting, alkaline leaching, solid-liquid separation, freezing impurity removal and purification, and comprises the following method steps:
1) Crushing and ball milling, namely mechanically crushing the electrolytic aluminum waste residue raw material into fine feed material, screening, fully mixing 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; and meanwhile, controlling electrolytic aluminum waste residues: the mass ratio of calcium salts is =100:40-60 parts; the calcium salt is any one or a mixture of more of calcium oxide, calcium carbonate and calcium hydroxide; the electrolytic aluminum waste slag comprises the following components in percentage by mass, namely the content proportion of the main components: 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 calcifying roasting, namely placing the ball-milled uniform material obtained in the step 1) in a press device, pressing the ball-milled uniform material into brick blocks, controlling the water content in the uniform material or the ball-milled uniform material in the pressing process, namely controlling the ball-milled uniform material to be capable of being pressed into blocky brick blocks, controlling the pressure of the press to be 6000-8000MPa, stacking the blocky brick blocks, placing the blocky brick blocks in a tunnel kiln device for calcifying roasting, controlling the roasting temperature to be 800-950 ℃, and roasting and preserving the heat for 1-2 hours to obtain a roasted material;
3) And (3) burdening and carrying out secondary ball milling, namely stirring and mixing the roasted material obtained in the step 2) and potassium salt, then placing the mixture into a ball milling device for fully mixing and ball milling until the mixture is 50-100 meshes, and controlling the mass ratio of the roasted material to the potassium salt as the roasted material: potassium salt =100:20-80 parts of; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate; after ball milling is finished, a mixture is obtained;
4) Secondary roasting, placing the mixture into a rotary kiln device, roasting by the rotary kiln, controlling the roasting temperature to be 750-900 ℃, roasting and preserving heat for 0.5-1.0h to obtain a secondary roasting material, mechanically crushing the secondary roasting material by clinker, then ball-milling the crushed secondary roasting material, and treating the crushed secondary roasting material to 80-160 meshes to obtain roasted fine powder;
5) Performing alkaline leaching treatment, namely putting the roasted fine powder, alkali liquor and aqueous solution into a stirring device, fully stirring and mixing, and performing leaching treatment, wherein the concentration of the alkali liquor is controlled to be 0.5-0.7mol/L, and the alkali liquor is potassium hydroxide solution or sodium hydroxide solution; controlling the mass ratio of the roasted fine powder to water to be 1:5.5-6.5; controlling the leaching temperature in the alkaline leaching treatment to be 90-95 ℃, and controlling the leaching time to be 2-4 h under the condition of continuous stirring; so that lithium in the roasted fine powder exists in the leaching solution in the form of lithium hydroxide in the alkali leaching treatment process to obtain the leaching solution containing the lithium hydroxide solution;
6) Carrying out solid-liquid separation and countercurrent washing, namely carrying out solid-liquid separation on the lithium hydroxide solution leachate obtained in the step 5) through a filtering device to obtain filter residues and filtrate; carrying out 2-6 times of countercurrent washing on filter residues, and filtering by using a plate and frame filter to obtain washing liquid and washing residues, wherein the concentration of lithium ions in the washing residues is controlled to be less than or equal to 0.20wt%;
7) Freezing, namely fully mixing the filtrate prepared in the step 6) with washing liquid to obtain a lithium preparation solution, freezing the lithium preparation solution by a freezing process to obtain aluminum potassium sulfate dodecahydrate mixed salt, controlling the freezing temperature to be-5 ℃, freezing for 2-3h, and performing centrifugal separation to obtain lithium purified liquid;
8) Washing, namely washing the dodecahydrate potassium aluminum sulfate obtained after centrifugal separation in the step 7) with clear water for a plurality of times to obtain washing liquid and washed dodecahydrate potassium aluminum sulfate, and washing for alkaline leaching in the next step 5);
9) Deeply purifying to prepare lithium oxide or lithium carbonate, and adsorbing and purifying the purified lithium liquid obtained in the step 7) by using chelate resin of a purifying device to remove Ca in the purified lithium liquid 2+ 、Mg 2+ Then the lithium is treated by a concentration process to form a lithium deep purification solution, and the purification is to control the concentration content of lithium ions in the lithium deep purification solution to reach 12-18g/L; and controlling Ca in the purified lithium deep purification solution 2+ 、Mg 2+ 、P、 F - The mass concentration of the ions is less than or equal to 0.06 percent(ii) a Then filtering and separating to prepare raw materials of battery-grade lithium hydroxide and battery-grade lithium carbonate, and further preparing the raw materials of battery-grade lithium hydroxide or battery-grade lithium carbonate.
The filter residue, the washing residue and the like prepared in the step 6) can be used as production raw materials in the carbon industry, and the lithium leaching yield can reach 95%. The following embodiments are the same as the present embodiment except for the points not described.
Example 1
The technical content is further illustrated below by means of specific examples, which, however, should be understood by the skilled person, do not in any way limit the scope of protection of the present patent. Modifications and equivalents of the above would be suggested to those skilled in the art and are included within the scope of this 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 electrolytic aluminum waste residues of an aluminum industry company in Tianshan of Xinjiang as raw materials of the embodiment, and comprises the following main components shown in Table 1.
In the context of Table 1, the following examples are,
| 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 of the drawings: the contents in the compositions of the components in the table are mass ratios.
Mechanically crushing the raw material electrolytic aluminum waste residues into fine materials, adding a certain amount of calcium oxide after screening, grinding for 2 hours in a ball mill at the rotating speed of 250r/min, and fully stirring and mixing to obtain a mixed material or a ball-milled mixed material; controlling electrolytic aluminum waste slag: the mass ratio of calcium oxide is =100:40; grinding fine powder, namely ball-milling and mixing refining materials, controlling the humidity of the ball-milling and mixing refining materials, pressing the materials into bricks, namely brick blocks, by using a press device, controlling the pressure of the press to be 6000-8000MPa, stacking the brick blocks to be capable of entering a tunnel kiln device for roasting, controlling the calcification high-temperature roasting transformation of the tunnel kiln, controlling the roasting temperature to be 900-950 ℃, and roasting and preserving the heat for 1-2 hours; calcified and roasted clinker, namely roasted material; then placing the mixture into a ball milling device for ball milling to 70 meshes, wherein fine powder is a roasting material, and the weight ratio of the fine powder is as follows: potassium sulfate: potassium carbonate =100:30:10 Proportioning (mass ratio); uniformly mixing the materials to obtain a mixture, roasting the mixture in a rotary kiln, controlling the roasting temperature of the rotary kiln to 880 ℃, roasting at a high temperature and keeping the temperature for 1 hour, grinding the mixture to 100 meshes, and treating the mixture to obtain roasted sand, namely roasted fine powder; deep alkali leaching or alkali leaching treatment, namely stirring and mixing the roasted fine powder, 0.6mol/L potassium hydroxide solution and water, controlling the mass ratio of the clinker roasted fine powder to the water to be 1:6, wherein the leaching treatment temperature is 90-95 ℃, and the stirring leaching time is 4 hours, so that the clinker fine powder, namely lithium in the roasted fine powder enters the leaching solution as lithium hydroxide liquid; and (3) performing solid-liquid separation and countercurrent washing, and performing 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 the filter residue for 4 times, wherein the filter device is a plate and frame filter, and the concentration of lithium ions in the filter residue is controlled to be less than or equal to 0.20wt%; preparing purified lithium solution, and filteringMixing the solution and the washing solution to prepare a lithium preparation solution, generating potassium, sodium and aluminum in the solution into aluminum potassium sulfate dodecahydrate mixed salt by a freezing process, and centrifugally separating to prepare a lithium purification solution; controlling the freezing temperature to be between 5 ℃ below zero and 5 ℃ and the freezing time to be between 2 and 3 hours; washing the aluminum sulfate potassium salt dodecahydrate after centrifugal separation twice to obtain washing liquid, namely washing liquid, and storing the washing liquid as next alkaline leaching for use; purifying the lithium purified solution by chelating resin adsorption to obtain Ca 2+ 、Mg 2+ The concentration process is carried out to obtain concentrated solution with the concentration content of lithium ions of 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 - The mass concentration of the ions is less than or equal to 0.06 percent, and the mixture is filtered and separated; that is, 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 embodiment 1 are shown in table 2 below.
The following examples are not described in the same manner as in example 1 or the description of the specific embodiment.
Example 2
The method comprises the steps of taking electrolytic aluminum waste residues of a company desiring certain aluminum industry in the east as raw materials, mechanically crushing the electrolytic aluminum waste residues of the company desiring certain aluminum industry in the east into fine materials, sieving, adding a certain amount of calcium oxide and calcium hydroxide, mixing according to any proportion, grinding in a ball mill for 3 hours at a rotating speed of 280r/min, and fully mixing uniformly; electrolytic aluminum waste residue: calcium oxide and calcium hydroxide mix =100:45 (mass ratio); pressing the ground fine powder into bricks by a press, calcifying and carrying out high-temperature roasting and transformation in a tunnel kiln, controlling the temperature to be 900 ℃, and keeping the high-temperature roasting temperature for 2 hours; and (3) carrying out ball milling on the calcified and roasted clinker to 70 meshes, wherein the mass ratio of the calcified and roasted clinker is as follows: potassium sulfate: potassium carbonate =100: 40:10 (mass ratio) batching. Roasting the uniformly mixed materials in a rotary kiln, controlling the temperature at 880 ℃, keeping the temperature at high temperature for 1h, grinding the materials to 100 meshes, and processing the ground materials into roasted sand crushed fine powder; deep alkali leaching, namely stirring and mixing the roasted fine powder with 0.6mol/L potassium hydroxide solution, controlling the mass ratio of the clinker fine powder to water to be 1:6, leaching at 90 ℃, and stirring and leaching for 4 hours to ensure that clinker is leached outLithium in the fine powder enters the leaching solution as lithium hydroxide liquid; and (3) performing solid-liquid separation and countercurrent washing, namely performing solid-liquid separation on the lithium hydroxide solution solid-liquid mixture through a filtering device to obtain filter residue and filtrate. Carrying out countercurrent washing on the filter residue for 4 times, wherein the filter device is a plate and frame filter, and the concentration of lithium ions in the filter residue is controlled to be 0.150wt%; preparing lithium purifying solution, mixing the filtrate and the washing solution to obtain the lithium preparing solution, freezing potassium, sodium and aluminum in the solution to produce aluminum potassium sulfate dodecahydrate mixed salt, and centrifuging to obtain the lithium purifying solution. The freezing temperature is-5 ℃ to 5 ℃, and the freezing time is 3 hours. Washing the aluminum sulfate potassium salt dodecahydrate after centrifugal separation twice, and storing the washing liquid for next alkali leaching; purifying the lithium purified solution by using chelating resin to adsorb Ca 2+ 、 Mg 2+ After the concentration process, the concentration of lithium ion in the concentrated solution is about 17g/L, and Ca in the purified solution is controlled 2+ 、Mg 2+ 、P、 F - And filtering and separating the lithium hydroxide with the ion mass concentration of 0.05 percent to prepare 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 the analysis report is shown in the following table 2.
Table 2:
the product name is as follows: a lithium carbonate of a battery grade is added,
the product appearance is as follows: micro powder, white powder, no agglomeration,
granularity: the D50 particle size diameter is used as detection data to show that the standard is controlled to be about 6 μm.
Description of the drawings: as can be seen from the above report sheet of the detection results, the process technical route disclosed by the invention can realize industrialization. The content of the prepared lithium hydroxide reaches more than 99.5 percent, and the detection results all meet the quality standard requirements of battery-grade lithium carbonate.
Comparative examples
The comparative examples, which use the same raw materials as in the examples, are currently generalExtracting electrolytic aluminum waste residues by a sulfuric acid method; at present, most of the methods for extracting lithium from electrolytic aluminum waste residues by using a sulfuric acid method comprise the steps of (1) reacting electrolytic aluminum waste residues of a certain aluminum industry company in Henan of Li-containing with concentrated sulfuric acid at 200-400 ℃ for 2-3h to obtain hydrogen fluoride gas generated by reaction of a mixture containing sodium, aluminum and lithium sulfate, absorbing the hydrogen fluoride gas by water to obtain hydrofluoric acid (2) containing water, dissolving the mixture containing sodium, aluminum and lithium sulfate by adding water to prepare a 25-35% concentration solution, filtering to remove unreacted carbon residue (3), adding sodium carbonate into the filtrate, performing alkaline hydrolysis reaction at 20-40 ℃ to obtain aluminum hydroxide and lithium carbonate (4), adding lithium carbonate precipitate into decarbonization mother liquor to prepare slurry, preferably 3-4% lithium carbonate slurry, then introducing CO to prepare slurry, preferably 3-4% lithium carbonate slurry, and introducing CO to prepare the slurry 2 Carrying out carbonization reaction to control the pH value of the carbonization end point to be 6-6.5, and filtering to obtain lithium bicarbonate solution filter residue for synthesizing cryolite; (5) and heating the lithium bicarbonate solution to 90-100 ℃, decarbonizing and recrystallizing to obtain the battery-grade lithium carbonate. The method comprises the steps of mechanically crushing electrolytic aluminum waste residues of certain aluminum industry in Karman in Henan, screening, adding a certain amount of calcium oxide, grinding in a ball mill for 2.5h at a rotating speed of 260r/min, and mixing uniformly. Electrolytic aluminum waste residue: calcium oxide =100:47 (mass ratio). Pressing the ground fine powder into bricks by a press, and carrying out calcification high-temperature roasting and transformation by a tunnel kiln, wherein the temperature is controlled to be 920 ℃, and the high-temperature roasting heat preservation time is 2 hours. And (3) carrying out ball milling on the calcified and roasted clinker to 70 meshes, and mixing the fine powder: potassium sulfate: potassium carbonate =100: 42:10 (mass ratio) batching. Roasting the uniformly mixed materials in a rotary kiln, controlling the temperature to 890 ℃, keeping the temperature at high temperature for 1h, grinding the materials to 100 meshes, and treating the ground materials into roasted sand crushed fine powder; deep alkaline leaching, namely stirring and mixing the roasted 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 ℃, and stirring and leaching for 4 hours to ensure that lithium in the clinker fine powder enters the leaching solution as lithium hydroxide liquid; and (3) performing solid-liquid separation and countercurrent washing, namely performing solid-liquid separation on the lithium hydroxide solution solid-liquid mixture through a filtering device to obtain filter residue and filtrate. Carrying out countercurrent washing on the filter residue for 4 times, wherein the filter device is a plate and frame filter, and the concentration of lithium ions in the filter residue is controlled to be 0.150wt%; lithium-making purifying solutionMixing the filtrate and the washing liquid to obtain lithium solution, freezing potassium, sodium and aluminum to produce potassium aluminum sulfate dodecahydrate salt, and centrifuging to obtain purified lithium liquid. The freezing temperature is-5 ℃ to 5 ℃, and the freezing time is 3 hours. Washing the aluminum sulfate potassium salt dodecahydrate after centrifugal separation twice, and storing the washing liquid for next alkali leaching; then the Ca is adsorbed and purified by chelating resin 2+ 、Mg 2+ The concentration procedure is carried out to ensure that the concentration content of lithium ions in the concentrated solution is about 17g/L, and Ca in the solution is controlled 2+ 、Mg 2+ 、P、F - And the ion mass concentration is 0.05 percent. And precipitating lithium by using a sodium carbonate solution to prepare lithium carbonate. However, the main difference between the patent of the invention 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 leachate, and the content of other metal ions such as iron, aluminum, copper and the like and fluorine in the leachate is extremely low. See table 3 below, which is a comparison of the contents of the main impurity ions in the leachate according to the process scheme of the present invention and the comparative examples.
The results of the leachate impurity detection and analysis are compared as follows, 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 above detection results, it can be seen that, by adopting the method of the present invention for the same raw material, the mass concentration of impurity ions in the primary leachate is obviously lower than that of ions in the sulfuric acid process; in order to reduce the burden of subsequent deep purification and impurity removal, the process method can be applied to large-scale industrial production and greatly reduce the production cost. The content of main impurity ions is obviously higher than that of the method of the invention by adopting the method of the comparative example.
The description is only an overview of the invention, and can be implemented according to the content of the description, which is only a preferred embodiment of the invention, and not to limit the invention in any way. Those skilled in the art can make numerous possible variations and modifications to the described embodiments, or modify equivalent embodiments, without departing from the scope of the invention. Therefore, any modification, equivalent change and modification made to the above embodiments according to the technology of the present invention are within the protection scope of the present invention, unless the content of the technical solution of the present invention is departed from.
Claims (9)
1. A mixed salt calcining method for extracting lithium from electrolytic aluminum waste residues is characterized by comprising the following steps of:
1) Crushing and ball milling, namely mechanically crushing the electrolytic aluminum waste residues into fine materials, screening, and then feeding the fine materials and calcium salt into a ball milling device for ball milling treatment to obtain ball-milled and uniform materials;
2) Pressing and calcified roasting, namely putting the ball-milled and uniformly-mixed material obtained in the step 1) into a press device, pressing the ball-milled and uniformly-mixed material into brick blocks, and then putting the brick blocks into a tunnel kiln device for calcified roasting to obtain a roasted material;
3) Performing secondary ball milling on the ingredients, namely placing the calcined material and the potassium salt obtained in the step 2) into a ball milling device for mixing and ball milling until the granularity is 50-100 meshes, thus obtaining a mixture;
4) Secondary roasting, namely placing the mixture into a rotary kiln device, roasting the mixture by using the rotary kiln, controlling the roasting temperature to be 750-900 ℃, keeping the roasting temperature for 0.5-1.0h to obtain a secondary roasting material, mechanically crushing and ball-milling the secondary roasting material by using clinker, and treating the secondary roasting material to 80-160 meshes to obtain roasted fine powder;
5) Alkali leaching, namely placing the roasted fine powder, alkali liquor and aqueous solution in a stirring device, fully stirring and mixing, and performing leaching treatment to obtain a lithium hydroxide-containing solution leachate;
6) Performing solid-liquid separation and countercurrent washing, namely performing solid-liquid separation on the lithium hydroxide solution leachate through a filtering device to obtain filter residue and filtrate; carrying out countercurrent washing on the filter residue for a plurality of times, and then filtering by using a plate and frame filter to obtain washing liquid and washing residue, wherein the concentration of lithium ions in the washing residue is controlled to be low;
7) Freezing, fully mixing the filtrate prepared in the step 6) with a washing solution to obtain a lithium preparation solution, carrying out freezing process treatment on the lithium preparation solution to obtain aluminum potassium sulfate dodecahydrate mixed salt, and carrying out centrifugal separation treatment to obtain a lithium purified solution;
8) Washing, namely washing the dodecahydrate potassium aluminum sulfate obtained after centrifugal separation in the step 7) with clear water for a plurality of times to obtain washing liquid and washed dodecahydrate potassium aluminum sulfate, wherein the washing liquid is used for alkaline leaching in the next step 5);
9) Deeply purifying to prepare lithium oxide or lithium carbonate, and adsorbing and purifying the purified lithium liquid obtained in the step 7) by using chelate resin of a purifying device to remove Ca in the purified lithium liquid 2+ 、Mg 2+ And then the obtained product is treated by a concentration process to obtain a lithium deep purification solution, and the lithium deep purification solution is treated to prepare battery-grade lithium hydroxide or battery-grade lithium carbonate.
2. The method for extracting lithium from electrolytic aluminum waste residues by the mixed salt calcination method according to claim 1, wherein the ball milling in the step 1) is carried out for 2h to 3h, and the rotating speed of a ball mill is controlled to be 200r/min to 400r/min; and simultaneously controlling electrolytic aluminum waste residues: the mass ratio of calcium salts is =100:40-60 parts; the calcium salt is one or more of calcium oxide, calcium carbonate and calcium hydroxide.
3. The method for extracting lithium from electrolytic aluminum waste residues by the mixed salt calcination method according to claim 1, wherein the pressing in the step 2) is carried out by controlling the pressure of a pressing machine to be 6000-8000MPa, the roasting temperature to be 800-950 ℃ and the roasting heat preservation time to be 1-2h.
4. The method for extracting lithium from the electrolytic aluminum waste residue by the mixed salt calcination method as claimed in claim 1, wherein the mass ratio of the calcine to the potassium salt in the step 3) is controlled as the calcine: potassium salt =100:20-80 parts of; the potassium salt is a mixture of potassium sulfate and/or potassium carbonate.
5. The method for extracting lithium from the electrolytic aluminum waste residue by the mixed salt calcination method according to claim 1, wherein in the step 5), the alkali leaching treatment is performed, the concentration of alkali liquor is controlled to be 0.5-0.7mol/L, and the alkali liquor is potassium hydroxide solution or sodium hydroxide solution; controlling the mass ratio of the roasted fine powder to water 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.
6. The method for extracting lithium from electrolytic aluminum waste residue by the mixed salt calcination method as claimed in claim 1, wherein the step 6) is to control the counter-current washing frequency of the filter residue to be 2-6 times, and the lithium ion concentration in the washing residue to be less than or equal to 0.20wt%.
7. The method for extracting lithium from electrolytic aluminum waste residues by the mixed salt calcination method as claimed in claim 1, wherein 7) freezing treatment is carried out, the freezing temperature is controlled to be-5 ℃, and the freezing time is 2-3h.
8. The method for extracting lithium from the electrolytic aluminum waste residue by the mixed salt calcination method as claimed in claim 1, wherein in the step 9), deep purification is performed, and the concentration of lithium ions in the deep lithium-purified solution is controlled to be 12-18g/L; and controlling Ca in the lithium deep purification liquid 2+ 、Mg 2+ 、P、F - The mass concentration of the ions is less than or equal to 0.06 percent; then filtering and separating to prepare battery-grade lithium hydroxide and battery-grade lithium carbonate.
9. The method for extracting lithium from electrolytic aluminum waste residues by 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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