CN114934195A - Lithium salt recovery method and recovery equipment for aluminum electrolysis waste - Google Patents
Lithium salt recovery method and recovery equipment for aluminum electrolysis waste Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The application discloses a lithium salt recovery method and recovery equipment for aluminum electrolysis waste, which relate to the technical field of aluminum electrolysis, do not need roasting, acid adding or alkali adding, and can simplify the lithium salt recovery process. A method for recovering lithium salt from aluminum electrolysis waste, comprising the following steps: mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent to dissolve lithium salt to obtain dissolved slurry; and carrying out multi-stage impurity removal on the dissolved slurry to obtain lithium salt.
Description
Technical Field
The application relates to the technical field of aluminum electrolysis, in particular to a lithium salt recovery method and recovery equipment for aluminum electrolysis waste materials.
Background
The aluminum electrolysis waste mainly comprises overhaul residues and electrolyte, wherein the overhaul residues are waste residues generated in the damage maintenance process of the aluminum electrolysis cell, the electrolyte comprises electrolyte fished out of the aluminum electrolysis cell in the electrolysis process, electrolyte obtained after carbon residue flotation and the like, and the electrolyte contains high-content lithium. Along with the improvement of the aluminum yield in China, the production amount of aluminum electrolysis waste materials is increased year by year, and lithium with different proportions mainly exists in the form of lithium fluoride according to different aluminum electrolysis enterprises. Lithium is an important strategic resource and is widely applied to the production and living fields of mobile phones, computers, new energy vehicles, energy storage and the like.
However, most of the existing lithium extraction methods adopt an acid adding method, an alkali adding method or a roasting method to improve the lithium salt conversion rate, but all of the existing lithium extraction methods have the problems of long flow, high dissolved liquid impurity content, complex impurity removal process and the like.
Disclosure of Invention
The embodiment of the application provides a method and equipment for recovering lithium salt from aluminum electrolysis waste, roasting, acid adding or alkali adding is not needed, and the lithium salt recovery process can be simplified.
In a first aspect of an embodiment of the present application, a method for recovering a lithium salt from an aluminum electrolysis waste includes:
mixing powder of aluminum electrolysis waste with water and a lithium extraction agent to dissolve lithium salt to obtain dissolved slurry, wherein the aluminum electrolysis waste comprises aluminum electrolysis overhaul residues and electrolyte;
and carrying out multi-stage impurity removal on the dissolved slurry to obtain lithium salt.
In some embodiments, the lithium extraction agent comprises one of calcium sulfate, magnesium sulfate, calcium chloride, and magnesium chloride;
the granularity of the powder of the aluminum electrolysis waste is less than 0.5 mm.
In some embodiments, in the step of mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent, the solid-to-liquid ratio of the powder of the aluminum electrolysis waste to the water is in a range of 1:3 to 1:5, and the addition amount of the lithium extraction agent is 1.8 to 2.2 times of the theoretical value of the lithium extraction agent required for complete reaction with lithium and fluorine in the powder of the aluminum electrolysis waste.
In some embodiments, in the step of mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent, the dissolution reaction time is 1-2 hours, and the reaction temperature is in the range of 80-95 ℃.
In some embodiments, the removing the impurities from the dissolution slurry in multiple stages to obtain the lithium salt comprises:
carrying out first solid-liquid separation on the dissolved slurry to obtain a first dissolved liquid;
controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide, and precipitating;
carrying out second solid-liquid separation on the mixed solution after precipitation to obtain a second dissolution liquid;
removing impurities from the second dissolution liquid by using a resin adsorption column or a filtering membrane to obtain a third dissolution liquid;
concentrating, crystallizing and removing impurities from the third dissolving liquid to obtain a crystallization mixed liquid;
carrying out solid-liquid separation on the crystallization mixed solution for the third time to obtain a fourth dissolution liquid;
adding a displacement reactant into the fourth dissolution liquid to perform a displacement reaction, and performing evaporation precipitation for 1.5-2.5 hours at the temperature of 90-100 ℃ to obtain a solid crude lithium salt;
and sequentially washing and drying the solid crude lithium salt to obtain the lithium salt.
In some embodiments, before mixing the powder lot of the aluminum electrolysis waste with water and a lithium extracting agent, the method further comprises:
under the condition that the fluorine content of the powder of the aluminum electrolysis waste is more than 5000mg/L, carrying out fluorine extraction and washing on the powder of the aluminum electrolysis waste, and then carrying out solid-liquid separation to obtain a fluorine-containing solution and solid slag, wherein the solid slag is used for mixing with water and the lithium extraction agent;
and carrying out evaporation crystallization on the fluorine-containing solution to obtain the fluorine salt.
In a second aspect of the embodiments of the present application, there is provided an apparatus for recovering lithium salt from aluminum electrolysis waste, which is applied to the method for recovering lithium salt from aluminum electrolysis waste according to the first aspect, the apparatus for recovering lithium salt including:
a crusher;
the material inlet of the flour mill is communicated with the material outlet of the crusher;
the lithium extraction device comprises a dissolving tank, wherein a feed inlet of the dissolving tank is provided with a two-way valve or a three-way valve, one way of the two-way valve or the three-way valve is communicated with a discharge outlet of the pulverizer, and the other way of the two-way valve or the three-way valve is used for injecting a lithium extraction agent;
and the feed inlet of the impurity removal system is communicated with the discharge outlet of the dissolution tank.
In some embodiments, the elution tank comprises:
the digestion reaction cavity is used for accommodating the powder of the aluminum electrolysis waste, the lithium extraction agent and water, and is communicated with a feeding port, a water injection port, a slurry outlet, an overflow port and a liquid level meter port;
the first heating cavity at least partially wraps the dissolution reaction cavity and comprises a first injection port, a first overflow port and a thermometer port;
the stirring paddle is inserted into the digestion reaction cavity, a second heating cavity is arranged in the stirring paddle, the second heating cavity is communicated with a second injection port and a second overflow port, and the stirring paddle comprises a blade and a partition plate;
the first heating cavity and the second heating cavity are used for containing hot water and/or hot steam.
In some embodiments, the edulcoration system includes:
the first solid-liquid separator is communicated with the dissolving tank;
the sedimentation tank is communicated with a liquid outlet of the first solid-liquid separator and is used for controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide for sedimentation;
the second solid-liquid separator is communicated with the liquid outlet of the settling tank;
the filter is communicated with a liquid outlet of the second solid-liquid separator;
a crystallizer in communication with an outlet of the filter;
the third solid-liquid separator is communicated with the liquid outlet of the crystallizer;
the lithium precipitation tank is communicated with a liquid outlet of the third solid-liquid separator and is used for carrying out displacement reaction to obtain solid crude lithium salt;
the fourth solid-liquid separator is communicated with the discharge hole of the lithium precipitation tank;
the washer is communicated with a solid discharge hole of the fourth solid-liquid separator;
and the dryer is communicated with the solid discharge hole of the washer.
In some embodiments, the apparatus for recovering lithium salt from aluminum electrolysis waste further comprises:
the fluorine removal system comprises a reverse scrubber, a fifth solid-liquid separator and an evaporator which are sequentially connected;
the feed inlet of the reverse washer is communicated with the discharge outlet of the flour mill;
and a solid discharge port of the fifth solid-liquid separator is communicated with a feed port of the dissolving tank, and a liquid discharge port of the fifth solid-liquid separator is communicated with the evaporator.
According to the lithium salt recovery method and recovery equipment for the aluminum electrolysis waste, the aluminum electrolysis waste is broken and ground to obtain the powder of the aluminum electrolysis waste, the powder of the aluminum electrolysis waste is mixed with water, then the lithium extracting agent is added, lithium fluoride in the powder of the aluminum electrolysis waste is converted into the lithium salt dissolved in the water, and the lithium salt is obtained through multi-stage impurity removal and purification. The roasting of raw materials is not needed, and the lithium recovery process is simplified. Need not to add acid or add alkali and carry out dissolving out of lithium salt, can avoid the corruption of lithium recovery process to equipment, improve equipment life, can avoid dissolving out of more impurity in addition to reduce the edulcoration flow, further simplify the lithium and retrieve the flow, and can avoid poisonous hydrogen fluoride gas to produce, avoid causing environmental pollution.
Drawings
Fig. 1 is a schematic flow chart of a lithium salt recovery method for aluminum electrolysis waste provided by an embodiment of the present application;
fig. 2 is a schematic structural block diagram of a lithium salt recovery apparatus for aluminum electrolysis waste provided in an embodiment of the present application;
FIG. 3 is a schematic structural view of a dissolution tank provided in an embodiment of the present application;
fig. 4 is a schematic structural diagram of another lithium salt recovery apparatus for aluminum electrolysis waste provided in the embodiments of the present application.
Detailed Description
In order to better understand the technical solutions provided by the embodiments of the present specification, the technical solutions of the embodiments of the present specification are described in detail below with reference to the accompanying drawings and specific embodiments, and it should be understood that the specific features of the embodiments and examples of the present specification are detailed descriptions of the technical solutions of the embodiments of the present specification, and are not limitations on the technical solutions of the embodiments, and the technical features of the embodiments and examples of the present specification may be combined with each other without conflict.
In this document, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. The term "two or more" includes the case of two or more.
The aluminum electrolysis waste mainly comprises overhaul residues and electrolyte, wherein the overhaul residues are waste residues generated in the damage maintenance process of the aluminum electrolysis cell, the electrolyte comprises electrolyte fished out of the aluminum electrolysis cell in the electrolysis process, electrolyte obtained after carbon residue flotation and the like, and the electrolyte contains high-content lithium. Along with the improvement of the aluminum yield in China, the production amount of aluminum electrolysis waste materials is increased year by year, and lithium with different proportions exists mainly in the form of lithium fluoride according to different electrolytic aluminum enterprises. Lithium is an important strategic resource and is widely applied to the production and living fields of mobile phones, computers, new energy vehicles, energy storage and the like. However, most of the existing lithium extraction methods adopt an acid adding method, an alkali adding method or a roasting method to improve the lithium salt conversion rate, but all of the existing lithium extraction methods have the problems of long flow, high dissolved liquid impurity content, complex impurity removal process and the like.
In view of this, the embodiments of the present application provide a method and a device for recovering lithium salts from aluminum electrolysis waste, which do not require calcination, acid addition, or alkali addition, and can simplify the process of recovering lithium salts.
In a first aspect of the embodiments of the present application, a lithium salt recovery method for aluminum electrolysis waste is provided, and fig. 1 is a schematic flow chart of the lithium salt recovery method for aluminum electrolysis waste provided in the embodiments of the present application. As shown in fig. 1, the lithium salt recovery method includes:
s100: mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent to dissolve lithium salt to obtain dissolved slurry, wherein the aluminum electrolysis waste comprises aluminum electrolysis overhaul residues and electrolyte. The electrolyte is in a solid state at normal temperature, for example, the aluminum electrolysis overhaul residue or the electrolyte or the powder of the overhaul residue and electrolyte mixture can be mixed with water, and then a lithium extraction agent is added, wherein the lithium extraction agent can dissolve lithium in the powder of the aluminum electrolysis waste into liquid to obtain dissolution slurry. The lithium extraction agent can comprise salts, such as sulfate or chloride, and can replace lithium of lithium fluoride in the powder of the aluminum electrolysis waste material with lithium salt capable of being dissolved in water, so that subsequent purification and impurity removal of the lithium salt are facilitated.
S200: and carrying out multi-stage impurity removal on the dissolved slurry to obtain lithium salt. The multistage impurity removal can comprise precipitation, solid-liquid conversion or crystallization, solid-liquid separation and the like.
The aluminum electrolysis waste mainly comprises overhaul residues and electrolyte, wherein the overhaul residues are waste residues generated in the damage maintenance process of the aluminum electrolysis cell, the electrolyte comprises electrolyte fished out of the aluminum electrolysis cell in the electrolysis process, electrolyte obtained after carbon residue flotation and the like, and the electrolyte contains high-content lithium. Along with the improvement of the aluminum yield in China, the production amount of aluminum electrolysis waste materials is increased year by year, according to the difference of aluminum electrolysis enterprises, 0.5-2% of lithium is contained, the lithium is mainly in the form of lithium fluoride, and the lithium is an important strategic resource and is widely applied to the production and living fields of mobile phones, computers, new energy automobiles, energy storage and the like. The lithium resource in China is relatively rich, but more than 80 percent of the lithium resource exists in salt lakes, the salt lakes have complex components, and the lithium extraction cost is high. The aluminum electrolysis waste material has relatively simple components, less impurities, higher lithium content and quite high recycling value.
Most of the existing lithium extraction methods adopt an acid adding method, an alkali adding method or a roasting method to improve the conversion rate of lithium salt, but all have the problems of long flow, high impurity content of a dissolution liquid, complex impurity removal process, high equipment requirement and the like, sulfuric acid and alkali liquor not only belong to hazardous wastes, but also have strong reactivity, can dissolve various impurities in raw materials together in the dissolution process, are difficult to remove subsequent impurities, and have the environmental protection problems of toxic hydrogen fluoride gas generation and the like in the acid adding and roasting processes, so that the working environment is poor and the environmental pollution is serious. In addition, the corrosion of acid or alkali to the equipment is serious, the maintenance period of the equipment is shortened, and the equipment loss is increased.
The lithium salt recovery method of aluminium electroloysis waste material that this application embodiment provided carries out broken grinding to aluminium electroloysis waste material and obtains the powder of aluminium electroloysis waste material, mixes the powder of aluminium electroloysis waste material with water, adds the lithium-extracting agent again, converts the lithium fluoride in the powder of aluminium electroloysis waste material into the lithium salt that dissolves in water, obtains the lithium salt through multistage edulcoration purification again. The roasting of raw materials is not needed, and the lithium recovery process is simplified. Need not to add acid or add alkali and carry out dissolving out of lithium salt, can avoid the corruption of lithium recovery process to equipment, improve equipment life, can avoid dissolving out of more impurity in addition to reduce the edulcoration flow, further simplify the lithium and retrieve the flow, and can avoid poisonous hydrogen fluoride gas to produce, avoid causing environmental pollution.
In some embodiments, before step S100, the method may further include:
and (3) crushing and grinding the aluminum electrolysis waste to obtain powder of the aluminum electrolysis waste. The method specifically comprises two steps, namely, primary crushing is firstly carried out, and then powder making is carried out, so that the powder of the aluminum electrolysis waste is obtained.
In some embodiments, the lithium extraction agent comprises one of calcium sulfate, magnesium sulfate, calcium chloride, and magnesium chloride. Only one of calcium sulfate, magnesium sulfate, calcium chloride and magnesium chloride is adopted, so that the dissolution of redundant impurities can be reduced, the addition of impurity removal processes is avoided, the lithium recovery process is further simplified, and the recovery cost can be reduced.
In some embodiments, in the step of mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent, the solid-to-liquid ratio of the powder of the aluminum electrolysis waste to the water is 1:3 to 1:5, and the addition amount of the lithium extraction agent is 1.8 to 2.2 times of the theoretical value of the lithium extraction agent required for complete reaction with lithium and fluorine in the powder of the aluminum electrolysis waste. The dissolution reaction time is 1-2 hours, and the reaction temperature range is 80-95 ℃.
Illustratively, the aluminum electrolysis waste can be aluminum electrolysis overhaul slag raw materials, electrolyte raw materials, mixed raw materials of aluminum electrolysis overhaul slag and electrolyte, the aluminum electrolysis waste is crushed by a crusher and then discharged, the crushed materials are added into a pulverizer to be pulverized by a conveying device, and the particle size of the discharged materials of the pulverizer is controlled to be below 0.5 mm. Adding water into the dissolution tank through a water injection port, adding the powder of the aluminum electrolysis waste into the dissolution tank through a feeding port, controlling the solid-to-liquid ratio to be 1: 3-1: 5, wherein the solid-to-liquid ratio can be 1:3, 1:4 and 1:5, adjusting according to the content of lithium salt in overhaul residues, adding the calculated lithium extraction agent into the dissolution tank through the feeding port, wherein the lithium extraction agent can be one of calcium sulfate, magnesium sulfate, calcium chloride and magnesium chloride, and the feeding ports of the powder of the aluminum electrolysis waste and the lithium extraction agent can be realized through conversion of a two-way valve or a three-way valve. The adding amount of the lithium extracting agent takes the sum of the lithium content and the fluorine content in the overhaul slag as a base number, the theoretical value is calculated according to the complete reaction of the molar ratio of 1:1, the adding amount is 1.8-2.2 times of the theoretical value, and can be 1.8 times, 1.9 times, 2.0 times, 2.1 times or 2.2 times, the dissolution reaction time range is 1-2 hours, and can be 1.0 hour, 1.5 hours or 2.0 hours, the dissolution reaction temperature range is 80-95 ℃, and can be 80 ℃, 85 ℃, 90 ℃ or 95 ℃, and the adding amount of the lithium extracting agent, the reaction time and the reaction temperature can be adjusted according to the lithium salt content in the overhaul slag. The material inlet and the water filling port of the dissolving-out groove can be provided with one-way valves, and can only flow in one way, and each material is automatically closed after being added.
In some embodiments, step S200 may include:
and carrying out first solid-liquid separation on the dissolved slurry to obtain a first dissolved liquid. The liquid for solid-liquid separation contains a lithium salt, and when the lithium extracting agent is calcium sulfate, the lithium salt eluted is lithium sulfate.
And (3) controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide, and precipitating. Impurities such as magnesium, calcium, aluminum, iron and the like can be removed in a solid form through precipitation.
And carrying out second solid-liquid separation on the precipitated mixed solution to obtain a second dissolution liquid.
And removing impurities from the second dissolution liquid by using a resin adsorption column or a filtering membrane to obtain a third dissolution liquid. The resin adsorption column or the filter membrane can adsorb calcium salt and magnesium salt, and further remove impurities and purify.
And concentrating, crystallizing and removing impurities from the third dissolution liquid to obtain a crystallization mixed liquid. The concentration can be membrane concentration or evaporation concentration, the crystallization can be freezing crystallization, the temperature can be controlled below zero, sodium sulfate crystallization can be obtained under the condition that the lithium extracting agent is calcium sulfate, the sodium sulfate crystallization can be used as a byproduct of lithium recovery, and the purification of lithium salt is also realized.
And carrying out solid-liquid separation on the crystallized mixed solution for the third time to obtain a fourth dissolved solution.
And adding a displacement reactant into the fourth dissolution liquid to perform a displacement reaction, and performing evaporation precipitation for 1.5-2.5 hours at the temperature of 90-100 ℃ to obtain a solid crude lithium salt. The displacer can be sodium carbonate solution, which is subjected to displacement reaction with lithium sulfate to obtain lithium carbonate, and the lithium carbonate is solid lithium salt, and is subjected to evaporation precipitation to obtain solid crude lithium salt.
And (3) sequentially washing and drying the solid crude lithium salt to obtain the lithium salt. And (3) washing and drying to further remove impurities on the surface of the solid crude lithium salt, and further purifying to obtain the pure lithium salt.
In some embodiments, before step S100, the method further includes:
under the condition that the fluorine content of the powder of the aluminum electrolysis waste is more than 5000mg/L, carrying out fluorine extraction and washing on the powder of the aluminum electrolysis waste, and then carrying out solid-liquid separation to obtain a fluorine-containing solution and solid slag, wherein the solid slag is used for mixing with water and a lithium extraction agent;
and (4) carrying out evaporation crystallization on the fluorine-containing solution to obtain the fluorine salt. The villiaumite can be used as a byproduct of lithium recovery, and the utilization rate of the aluminum electrolysis waste is improved.
In a second aspect of the embodiments of the present application, there is provided an apparatus for recovering lithium salt from aluminum electrolysis waste, which is applied to the method for recovering lithium salt from aluminum electrolysis waste in the first aspect, and fig. 2 is a schematic structural block diagram of the apparatus for recovering lithium salt from aluminum electrolysis waste provided in the embodiments of the present application. As shown in fig. 2, the lithium salt recovering apparatus includes: a crusher 101; a mill 102, a feeding port of which is communicated with a discharging port of the crusher; the dissolving-out groove 103 is provided with a two-way valve or a three-way valve at a feeding port, one way of the two-way valve or the three-way valve is communicated with a discharging port of the powder making machine, and the other way is used for injecting a lithium extracting agent; impurity removal system 400, impurity removal system's pan feeding mouth and the discharge gate intercommunication that dissolves out the groove.
The lithium salt recovery plant of aluminium electroloysis waste material that this application embodiment provided breaks the powder that grinds the system appearance and obtain aluminium electroloysis waste material to aluminium electroloysis waste material, mixes the powder and the water of aluminium electroloysis waste material, adds and carries the lithium agent again, converts the lithium fluoride in the powder of aluminium electroloysis waste material into the lithium salt that dissolves in water, obtains the lithium salt through multistage edulcoration purification again. The roasting of raw materials is not needed, and the lithium recovery process is simplified. Need not to add acid or add alkali and carry out dissolving out of lithium salt, can avoid the corruption of lithium recovery process to equipment, improve equipment life, can avoid dissolving out of more impurity in addition to reduce the edulcoration flow, further simplify the lithium and retrieve the flow, and can avoid poisonous hydrogen fluoride gas to produce, avoid causing environmental pollution.
In some embodiments, figure 3 is a schematic block diagram of a dissolution tank as provided in the examples of the present application. As shown in fig. 3, the dissolution tank includes: the leaching reaction chamber 210 is used for accommodating powder of the aluminum electrolysis waste, a lithium extraction agent and water, and the leaching reaction chamber 210 is communicated with a feed inlet 202, a water injection port 203, a slurry outlet 208, an overflow port 205 and a liquid level meter port 204. The first heating chamber 220 at least partially encloses the elution reaction chamber 210, and the first heating chamber 220 comprises a first injection port 207, a first overflow port 201, and a temperature metering port 206. The stirring paddle 301 is inserted into the dissolution reaction chamber 210, a second heating chamber 230 is arranged in the stirring paddle 301, the second heating chamber 230 is communicated with a second inlet 302 and a second outlet 303, and the stirring paddle 301 comprises a blade 304 and a partition plate 305. The first heating cavity 220 and the second heating cavity 230 are used for containing hot water and/or hot steam, and the first heating cavity 220 and the second heating cavity 230 containing hot water and/or hot steam can provide a temperature environment of 80 ℃ to 95 ℃ for the dissolution reaction cavity 210.
Illustratively, the entire lithium salt dissolution process is performed in the dissolution tank 103, and the dissolution tank 103 may be a vertical tank; the second heating cavity 230 is disposed on the outer wall of the heating chamber, so as to realize jacket type indirect heating, steam or hot water can be injected from the first injection port 207 and overflow from the first overflow port 201, the first injection port 207 is located at the bottom end, the first overflow port 201 is located at the top end, and the steam or hot water flows in from the first injection port 207 after heat exchange is completed in the outside. The stirring paddle 301 is hollow and is provided with a partition plate 305, a heat source is introduced for auxiliary heating, the heat source is steam or hot water, the paddle 304 is arc-shaped, the heat source has no dead angle when flowing, the steam or the hot water flows in the whole stirring paddle 301 along the partition plate 305, so that the internal temperature of the stirring paddle 301 is uniform, the slurry in the dissolution tank 103 is uniformly heated by the rotation of the stirring paddle 301, the stirring paddle 301 is provided with a second injection port 302 and a second overflow port 303 which are both positioned at the upper part of the stirring paddle 301, the steam or the hot water flows in through the second injection port 302, the second overflow port 303 flows out, and the steam or the hot water flows in from the second injection port 302 after external heat exchange. The material of the lining of the dissolution tank 103 and the stirring paddle 301 is steel lining anti-corrosion tetrafluoroethylene. In the dissolution reaction process, the stirring paddle 301 continuously works to ensure that the overhaul slag raw material and the lithium extraction agent fully react, and the reaction temperature and the liquid level in the dissolution tank 103 are monitored through the thermometer port 206 and the liquid level meter port 204 in the reaction process.
In some embodiments, fig. 4 is a schematic structural diagram of another lithium salt recovery apparatus for aluminum electrolysis waste provided in the examples of the present application. As shown in FIG. 4, the purge system 400 includes: a first solid-liquid separator 104 communicating with the elution tank 103; a precipitation tank 105 which is communicated with a liquid outlet of the first solid-liquid separator 104 and is used for controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide to carry out precipitation; a second solid-liquid separator 106 communicated with the liquid outlet of the precipitation tank 105; a filter 107 communicated with a liquid outlet of the second solid-liquid separator 106; the filter can be a resin adsorption column or a filter membrane. A crystallizer 108 communicating with the outlet of the filter 107; a third solid-liquid separator 109 communicated with the liquid outlet of the crystallizer 108; a lithium precipitation tank 110, which is communicated with a liquid outlet of the third solid-liquid separator 109 and is used for carrying out a displacement reaction to obtain solid crude lithium salt; a fourth solid-liquid separator 111 communicated with the discharge port of the lithium precipitation tank 110; a scrubber 112 communicated with a solid discharge port of the fourth solid-liquid separator 111; and a dryer 113 communicated with the solid discharge port of the washer 112. And (3) carrying out multistage reverse washing and purification on the crude lithium carbonate by using a washer 112 to obtain an industrial-grade lithium carbonate product, wherein the washing liquid is recycled.
In some embodiments, referring to fig. 4, the lithium salt recovery apparatus for aluminum electrolysis waste provided in the examples of the present application further includes: the fluorine removal system comprises a reverse scrubber 401, a fifth solid-liquid separator 402 and an evaporator 403 which are sequentially connected; a feed inlet of the reverse washer 401 is communicated with a discharge outlet of the flour mill 102; a solid discharge port of the fifth solid-liquid separator 402 is communicated with a feed port of the dissolution tank 103, and a liquid discharge port of the fifth solid-liquid separator 402 is communicated with the evaporator 403.
If the fluorine content in the overhaul residue raw material is too high and exceeds 5000mg/L, the overhaul residue can be firstly prepared into a sample by a crusher 101 and a pulverizer 102, fluorine is extracted by a reverse washer 401, then solid-liquid separation is carried out by a fifth solid-liquid separator 402, the filter residue is added into a dissolving tank 103 for lithium extraction and dissolution, and the filtrate is crystallized by an evaporator 403 to obtain a fluorine salt product.
It should be noted that, in the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and reference may be made to relevant descriptions of other embodiments for parts that are not described in detail in a certain embodiment.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
While preferred embodiments of the present specification have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all changes and modifications that fall within the scope of the specification.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present specification without departing from the spirit and scope of the specification. Thus, if such modifications and variations of the present specification fall within the scope of the claims of the present specification and their equivalents, then such modifications and variations are also intended to be included in the present specification.
Claims (10)
1. A method for recovering lithium salt from aluminum electrolysis waste is characterized by comprising the following steps:
mixing powder of aluminum electrolysis waste with water and a lithium extraction agent to dissolve lithium salt to obtain dissolved slurry, wherein the aluminum electrolysis waste comprises aluminum electrolysis overhaul residues and electrolyte;
and carrying out multi-stage impurity removal on the dissolved slurry to obtain lithium salt.
2. The method for recovering lithium salt from aluminum electrolysis waste according to claim 1, wherein the lithium extraction agent comprises one of calcium sulfate, magnesium sulfate, calcium chloride and magnesium chloride;
the granularity of the powder of the aluminum electrolysis waste is less than 0.5 mm.
3. The method for recovering lithium salt from aluminum electrolysis waste according to claim 1, wherein in the step of mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent, the solid-to-liquid ratio of the powder of the aluminum electrolysis waste to the water is in the range of 1:3 to 1:5, and the amount of the lithium extraction agent added is 1.8 to 2.2 times of the theoretical value of the lithium extraction agent required for complete reaction with lithium and fluorine in the powder of the aluminum electrolysis waste.
4. The method for recovering lithium salt from aluminum electrolysis waste according to claim 3, wherein in the step of mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent, the dissolution reaction time is 1 to 2 hours, and the reaction temperature is 80 to 95 ℃.
5. The method for recovering lithium salt from aluminum electrolysis scrap according to claim 1, wherein the step of removing impurities from the dissolution slurry in multiple stages to obtain lithium salt comprises the following steps:
carrying out first solid-liquid separation on the dissolved slurry to obtain a first dissolved liquid;
controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide, and precipitating;
carrying out second solid-liquid separation on the mixed solution after precipitation to obtain a second dissolution liquid;
removing impurities from the second dissolution liquid by using a resin adsorption column or a filtering membrane to obtain a third dissolution liquid;
concentrating, crystallizing and removing impurities from the third dissolving liquid to obtain a crystallization mixed liquid;
carrying out solid-liquid separation on the crystallization mixed liquor for the third time to obtain a fourth dissolving liquor;
adding a displacement reactant into the fourth dissolution liquid to perform a displacement reaction, and performing evaporation precipitation for 1.5-2.5 hours at the temperature of 90-100 ℃ to obtain a solid crude lithium salt;
and sequentially washing and drying the solid crude lithium salt to obtain the lithium salt.
6. The method for recovering lithium salt from aluminum electrolysis waste according to claim 1, further comprising, before mixing the powder of the aluminum electrolysis waste with water and a lithium extraction agent:
under the condition that the fluorine content of the powder of the aluminum electrolysis waste is more than 5000mg/L, carrying out fluorine extraction and washing on the powder of the aluminum electrolysis waste, and then carrying out solid-liquid separation to obtain a fluorine-containing solution and solid slag, wherein the solid slag is used for mixing with water and the lithium extraction agent;
and carrying out evaporation crystallization on the fluorine-containing solution to obtain the fluorine salt.
7. A lithium salt recovery apparatus of aluminum electrolysis scraps, applied to the lithium salt recovery method of aluminum electrolysis scraps as recited in any one of claims 1 to 6, the lithium salt recovery apparatus comprising:
a crusher;
the material inlet of the flour mill is communicated with the material outlet of the crusher;
the lithium extraction device comprises a dissolving tank, wherein a feed inlet of the dissolving tank is provided with a two-way valve or a three-way valve, one way of the two-way valve or the three-way valve is communicated with a discharge outlet of the pulverizer, and the other way of the two-way valve or the three-way valve is used for injecting a lithium extraction agent;
and the feeding port of the impurity removal system is communicated with the discharge port of the dissolution tank.
8. The apparatus for recovering lithium salt from aluminum electrolysis scrap according to claim 7, wherein the dissolution tank comprises:
the digestion reaction cavity is used for accommodating the powder of the aluminum electrolysis waste, the lithium extraction agent and water, and is communicated with a feeding port, a water injection port, a slurry outlet, an overflow port and a liquid level meter port;
the first heating cavity at least partially wraps the digestion reaction cavity, and comprises a first injection port, a first overflow port and a thermometer port;
the stirring paddle is inserted into the digestion reaction cavity, a second heating cavity is arranged in the stirring paddle, the second heating cavity is communicated with a second injection port and a second overflow port, and the stirring paddle comprises a blade and a partition plate;
the first heating cavity and the second heating cavity are used for containing hot water and/or hot steam.
9. The apparatus for recovering lithium salt from aluminum electrolysis waste according to claim 7, wherein the impurity removing system comprises:
the first solid-liquid separator is communicated with the dissolving tank;
the sedimentation tank is communicated with a liquid outlet of the first solid-liquid separator and is used for controlling the pH value of the first dissolution liquid to be 11-12 by using sodium hydroxide to carry out sedimentation;
the second solid-liquid separator is communicated with the liquid outlet of the settling tank;
the filter is communicated with a liquid outlet of the second solid-liquid separator;
a crystallizer in communication with an outlet of the filter;
the third solid-liquid separator is communicated with the liquid outlet of the crystallizer;
the lithium precipitation tank is communicated with a liquid outlet of the third solid-liquid separator and is used for carrying out displacement reaction to obtain solid crude lithium salt;
the fourth solid-liquid separator is communicated with the discharge hole of the lithium precipitation tank;
the washer is communicated with a solid discharge hole of the fourth solid-liquid separator;
and the dryer is communicated with the solid discharge hole of the washer.
10. The apparatus for recovering lithium salt from aluminum electrolysis waste according to claim 7, further comprising:
the fluorine removal system comprises a reverse scrubber, a fifth solid-liquid separator and an evaporator which are sequentially connected;
the feed inlet of the reverse washer is communicated with the discharge outlet of the flour mill;
and a solid discharge port of the fifth solid-liquid separator is communicated with a feed port of the dissolving tank, and a liquid discharge port of the fifth solid-liquid separator is communicated with the evaporator.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210722725.6A CN114934195A (en) | 2022-06-20 | 2022-06-20 | Lithium salt recovery method and recovery equipment for aluminum electrolysis waste |
| PCT/CN2023/098544 WO2023246500A1 (en) | 2022-06-20 | 2023-06-06 | Lithium salt recovery method and recovery device for aluminum electrolysis waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210722725.6A CN114934195A (en) | 2022-06-20 | 2022-06-20 | Lithium salt recovery method and recovery equipment for aluminum electrolysis waste |
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| CN114934195A true CN114934195A (en) | 2022-08-23 |
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| CN202210722725.6A Pending CN114934195A (en) | 2022-06-20 | 2022-06-20 | Lithium salt recovery method and recovery equipment for aluminum electrolysis waste |
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| CN (1) | CN114934195A (en) |
| WO (1) | WO2023246500A1 (en) |
Cited By (3)
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| CN116426758A (en) * | 2023-05-12 | 2023-07-14 | 中铝郑州有色金属研究院有限公司 | Purification method and system for lithium extraction solution of aluminum electrolysis waste |
| WO2023246500A1 (en) * | 2022-06-20 | 2023-12-28 | 中国铝业股份有限公司 | Lithium salt recovery method and recovery device for aluminum electrolysis waste |
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| CN117585700A (en) * | 2024-01-17 | 2024-02-23 | 中国科学院过程工程研究所 | Method for denitrification, defluorination and quality-classifying utilization of secondary aluminum ash |
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| WO2023246500A1 (en) | 2023-12-28 |
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