CN111453748A - Lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate - Google Patents
Lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate Download PDFInfo
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Abstract
The invention discloses a lithium precipitation crystallization method for preparing high-purity lithium carbonate of snowflake monocrystal, which takes a lithium solution generated in the process of lithium extraction as a raw material, and comprises the following steps of 1) preparing a standard sodium carbonate solution, 2) preparing a lithium carbonate adsorption mother nucleus, 3) preparing a lithium carbonate crystal-shaped solution, and 4) preparing the high-purity lithium carbonate of the snowflake monocrystal, wherein the purity of the prepared lithium carbonate is over 99.8 percent, and the prepared lithium carbonate crystal is of a snowflake monocrystal large granular structure; the one-step method for preparing the high-purity lithium carbonate is realized, the process is short, the operation is simple, the continuous production can be realized, and the cost is low. And the production process is simple.
Description
The technical field is as follows:
the invention relates to a lithium precipitation crystallization method of high-purity lithium carbonate, in particular to a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate.
Background art:
with the increasing shortage of world energy, the development and utilization of new energy become common problems in the world, and the new energy of lithium batteries is increasingly regarded by various countries as one of important industries for the development of new energy. "lithium is an energy element in the 21 st century". Lithium carbonate is an important chemical raw material, and with the development and the utilization of new energy in China, the development and the utilization of the new energy are encouraged; lithium carbonate is used as an important basic raw material for the development of new energy of lithium batteries, and is widely applied to the fields of automobiles, industrial production and the like.
Lithium and salts thereof such as lithium carbonate, lithium sulfate and the like are basic raw material products of the lithium new energy industry, and the lepidolite contains lithium metal which is a basic material of the lithium new energy industry, so that the development and application of the lepidolite become a popular problem at present. At present, the treatment of the main lithium-containing ores, namely spodumene and lepidolite, in China adopts dry or wet treatment, mainly destroys the original gangue structure, dissolves lithium oxide in the gangue in a soluble lithium salt form, and then precipitates lithium through carbonization or soda ash to obtain a lithium carbonate product. The preparation method for extracting lithium carbonate by using lepidolite ore as a raw material is mainly divided into a calcination method and an acid leaching method, which are also called a dry method and a wet method. From the existing production process, lithium oxide in the lithium carbonate is mainly dissolved out in the form of soluble lithium salt to form a lithium-containing solution, and then the lithium-containing solution is subjected to treatment processes such as carbonization, lithium precipitation and the like to obtain a lithium carbonate product.
At present, the common methods for extracting high-purity lithium carbonate from lithium solution mainly include solvent extraction and precipitation methods. The extraction method needs repeated extraction and back extraction to achieve the purpose of extracting high-purity lithium carbonate in an enriched manner. However, most of the extracting agents are organic reagents, so that the cost is high, the process is complex, the operation and control are difficult, and the industrial application is restricted.
Precipitation method, adding sodium carbonate solution directly into lithium solution, and performing chemical reaction 2L i++CO3 2-→Li2CO3And producing precipitate to prepare lithium carbonate product. The precipitation method has the advantages of low energy consumption, simple process operation, low production cost and the like, and becomes a mainstream method for industrial production. However, the lithium carbonate product prepared by the existing precipitation method has the problems that the crystal grains are small, the crystal morphology is often columnar or irregular, or the morphology is incomplete even though the crystal morphology is regular. Therefore, the prepared pure lithium carbonate crystal particles are small and difficult to separate, and the flowability of the pure lithium carbonate crystal particles is relatively poor; the shape of the small crystal of the pure lithium carbonate crystal grains is columnar and irregular or incomplete, impurities are easily wrapped, and the purity of the lithium carbonate product is influenced; meanwhile, the lithium carbonate is easy to agglomerate and agglomerate due to the small crystal grains, columnar or irregular crystal appearance or incomplete crystal appearance and extrusion and vibration in the storage or transportation process. The lithium is extracted by precipitation, usually by secondary purification, i.e. by secondary carbonisation, in which carbon dioxide is introduced into an aqueous suspension of lithium carbonate, carbonic acidLithium is converted into acid lithium carbonate to be dissolved, the solution is filtered again to carry out deep impurity removal, and finally the filtered acid lithium carbonate solution is heated, so that carbon dioxide is released and high-purity lithium carbonate is precipitated, thereby prolonging the addition type working procedure and greatly increasing the production cost for preparing the high-purity lithium carbonate.
Meanwhile, the lithium carbonate prepared by the existing process method has the advantages that the prepared lithium carbonate has small crystal lattice particle size, and is easy to agglomerate, agglomerate and agglomerate if the time is long in the storage and stacking links; secondly, the preparation process is longer, the preparation cost is correspondingly increased, the prepared lithium carbonate has low purity, and the crystal structure of the prepared lithium carbonate cannot form a snowflake-shaped single crystal large granular structure.
Therefore, how to provide a lithium precipitation crystallization method for preparing high-purity snowflake monocrystal lithium carbonate is provided, the prepared lithium-containing solution is used as a raw material to prepare high-purity lithium carbonate with the purity of more than 99.8%, and the prepared lithium carbonate crystals are in a snowflake monocrystal large granular structure; the method can realize one-step preparation of high-purity lithium carbonate single crystal products, has short working procedure and simple operation, and can realize continuous production; compared with the existing extraction method and lithium precipitation method, the method has the advantages of pure product, high efficiency and low cost.
The invention content is as follows:
the invention provides a lithium precipitation crystallization method for preparing high-purity lithium carbonate of snowflake monocrystal, which takes a lithium solution generated in the process of lithium extraction as a raw material, and comprises the following steps of 1) preparing a standard sodium carbonate solution, 2) preparing a lithium carbonate adsorption mother nucleus, 3) preparing a lithium carbonate crystal-shaped solution, and 4) preparing the high-purity lithium carbonate of the snowflake monocrystal, wherein the purity of the prepared lithium carbonate is over 99.8 percent, and the prepared lithium carbonate crystal is in a large granular structure of the snowflake monocrystal; the one-step method for preparing the high-purity lithium carbonate is realized, the process is short, the operation is simple, the continuous production can be realized, and the cost is low.
The invention provides a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which takes a lithium solution generated in the lithium extraction process as a raw material and comprises the following method steps:
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device, heating under continuous stirring, adding sodium carbonate, keeping the temperature constant, and preparing a saturated sodium carbonate solution which is the standard sodium carbonate solution under the constant-temperature condition;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder is uniformly distributed and suspended in the standard sodium carbonate solution, and reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, wherein the lithium carbonate ultrafine powder grows on the surface of the lithium carbonate ultrafine powder to form crystals, and the particle size of the crystals is gradually increased to form lithium carbonate adsorption parent nuclei;
3) preparing a lithium carbonate crystal-shaped solution,
spraying a lithium solution into a reaction device provided with the lithium carbonate adsorption mother nucleus obtained in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature, and fully reacting the lithium ions with carbonate ions to prepare a lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and with gradually increased crystal lattice particle size;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
and (3) placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device, settling to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain the snowflake-shaped single crystal high-purity lithium carbonate.
The lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate preferably comprises the step 1) of controlling the constant temperature to be 65-85 ℃, controlling the stirring speed of a reaction kettle of a reaction device to be 10-100 rpm, and controlling the concentration of the prepared standard sodium carbonate solution to be 200-300 g/L.
The lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate comprises the following steps of 2) controlling the adding amount of lithium carbonate superfine powder to be 2% -10% of the mass fraction of theoretical yield; the particle size of the lithium carbonate superfine powder is controlled to be 20-60 mu m.
The lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate, disclosed by the invention, preferably comprises the step 2) of controlling the adding amount of the surfactant to be 0.5-5 per mill of the mass of the lithium carbonate superfine powder; the surfactant is a nonionic surfactant.
The invention relates to a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which comprises the following steps of 3) controlling the time for preparing lithium carbonate crystal-shaped solution to be 3-4 hours; the stirring speed of the stirring device is controlled to be 10-100 revolutions per minute, and the constant temperature is 40-80 ℃.
Further, the sedimentation treatment time is controlled to be 1-3h in the step 4).
According to the lithium precipitation crystallization method for preparing the snowflake-shaped single crystal high-purity lithium carbonate, the surfactant is preferably alkyl glycoside or polysorbate.
The main process flow of the invention comprises the following steps: preparing a standard carbonic acid solution in a reaction device → preparing lithium carbonate by stirring → reacting → preparing lithium carbonate adsorption mother nucleus by stirring → preparing lithium carbonate crystal-shaped solution by stirring → settling → separating → washing → filtering, removing waste → drying → preparing a snowflake-shaped monocrystal high-purity lithium carbonate product.
The invention relates to a lithium precipitation crystallization method for preparing snowflake-shaped single crystal high-purity lithium carbonate, which has the beneficial effects that a unique lithium precipitation process method is adopted, step-by-step purification is not needed, and the single crystal high-purity lithium carbonate with high purity, large lithium carbonate crystal grains, complete crystal lattices and snowflake-shaped crystal lattices is prepared in one step;
the method for preparing the snowflake monocrystal large-particle high-purity lithium carbonate has the following technical advantages:
firstly, the prepared high-purity lithium carbonate has large crystal lattice particle size, has the characteristic of high purity of snowflake-shaped single crystals, is beneficial to precipitation separation and improvement of product purity, and has better product fluidity and better performance;
secondly, the high-purity lithium carbonate crystal lattice prepared by the method has a single crystal with relatively complete morphology characteristics, is a single crystal and has a snowflake-shaped complete morphology, so that impurities cannot be wrapped and foreign matter molecules cannot be linked, and the lithium carbonate prepared by the one-step method has higher purity;
thirdly, the lithium carbonate product is in a snowflake-shaped complete shape based on large crystal lattice particle size, is not easy to agglomerate, agglomerate and grain in the storage and stacking links, and basically keeps a loose state;
fourthly, the process method of the invention does not need purification step by step, but realizes high-purity lithium carbonate by one step, and has short process flow, simple operation and low cost.
The invention provides a lithium precipitation crystallization process method for preparing snowflake monocrystal high-purity lithium carbonate from a lithium solution, which is characterized in that a monocrystal structure is formed, the particle size is increased, and the complete morphology of crystal lattices is controlled during a lithium precipitation reaction process.
On the other hand, the lithium carbonate prepared by the method has high purity, a secondary purification process is not needed, and the purity of the high-purity lithium carbonate prepared by detection is more than or equal to 99.8 percent; the prepared high-purity lithium carbonate crystal is snowflake-shaped single crystal large particles; the method adopts a one-step method to prepare the high-purity lithium carbonate, has short working procedure and simple operation, and can realize continuous production. Compared with the extraction method in the prior art, the method has the advantages that the production efficiency is improved by more than 20 percent, and the cost of the produced product is reduced by more than 45 percent; compared with the lithium deposition method, the efficiency is improved by more than 25%, and the cost is reduced by more than 30%.
Description of the drawings:
FIG. 1 is a crystal lattice morphology diagram of the snowflake single crystal high-purity lithium carbonate prepared by the method of the present invention observed by a high temperature laser confocal microscope;
the specific implementation mode is as follows:
the following will further describe the specific technical scheme of the present invention in detail with reference to the examples, wherein the components are referred to by mass parts or mass ratios, and the concentrations are mass concentrations.
Explanation of technical terms in the present specification:
(1) lithium solution: refers to a lithium-containing compound solution. Namely lithium-containing solution obtained in the process of extracting lithium, wherein the lithium solution is lithium sulfate, lithium chloride, lithium phosphate or other lithium-containing compound solution;
(2) high-purity lithium carbonate of snowflake monocrystal or large-particle lithium carbonate of snowflake monocrystal: the lithium carbonate is of a single crystal structure, the microstructure of the lithium carbonate is similar to snowflake, and the average grain size of crystal grains is larger than that of the conventional grain size, so that the lithium carbonate is named as snowflake-shaped single crystal large-grain lithium carbonate or snowflake-shaped single crystal high-purity lithium carbonate;
(3) lithium carbonate adsorbs mother nucleus: the superfine powder lithium carbonate is suspended in the solution, so that the lithium carbonate generated by the reaction provides a nucleus which can attach to and surround the crystal growth of the lithium carbonate, and the nucleus is an adsorption parent nucleus for the lithium carbonate.
(3) Theoretical yield: the method is the yield of the quality of the snowflake monocrystal high-purity lithium carbonate product which can be extracted by theoretically calculating by taking a lithium solution as a raw material.
The process comprises the following steps:
firstly, preparing a standard sodium carbonate solution, adding pure water into a reaction kettle device, then adding a proper amount of sodium carbonate under certain constant temperature and slow stirring, wherein the adding amount of the sodium carbonate is limited by no crystallization, namely preparing a saturated solution of the sodium carbonate, and completely melting the prepared sodium carbonate solution in water;
secondly, preparing lithium carbonate adsorption mother nucleus, adding a small amount of lithium carbonate superfine powder into the prepared standard sodium carbonate solution, and uniformly distributing the lithium carbonate superfine powder in a suspension state in the sodium carbonate solution under the action of certain constant temperature and slow stirring of a reaction kettle to form the lithium carbonate adsorption mother nucleus for the subsequent adsorption reaction of new lithium carbonate; the stirring speed of the reaction kettle is based on that suspended lithium carbonate is uniformly distributed and does not precipitate;
thirdly, dispersing and spraying the lithium solution into the reaction kettle device through the spraying device, and reacting lithium ions in the lithium solution with carbonate ions in the sodium carbonate solution to combine lithium carbonate; at this time, the newly generated lithium carbonate grows into crystals attached to the surface of the lithium carbonate ultrafine powder suspended in the solution and gradually increases the crystal lattice particle size. The method adopts a spraying mode, the lithium solution enters a reaction kettle device as uniformly as possible without impact, so that lithium ions and carbonate ions react rapidly, and the newly-generated lithium carbonate can be stably adsorbed on the surface of suspended lithium carbonate ultrafine powder for crystal growth; by controlling the spraying speed and the spraying amount of the lithium solution, the balance state of stirring the sodium carbonate and lithium carbonate suspension solution is preferably not broken;
and finally, transferring the lithium carbonate and the solution in the reaction kettle to a settling tank for settling, and then carrying out solid-liquid separation, washing and drying on the lithium carbonate to obtain the large-particle high-purity lithium carbonate which is uniform in chemical components and is in a snowflake-shaped monocrystal.
The specific process steps and technical parameters are controlled as follows:
the invention discloses a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which takes a lithium solution as a raw material; which comprises the following steps of the method,
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device or a reaction kettle device, wherein the pure water can be deionized water, heating the mixture under continuous stirring, adding sodium carbonate, controlling the constant temperature to be 65-85 ℃, and preferably controlling the constant temperature to be 75 +/-5 ℃, preparing a saturated sodium carbonate solution under the constant temperature condition, controlling the stirring speed of a reaction kettle of the reaction device to be 10-100 r/min, and controlling the concentration of the prepared standard sodium carbonate solution to be 200-300 g/L, wherein the standard sodium carbonate solution is the standard sodium carbonate solution;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder and the surfactant can be uniformly distributed and suspended in the standard sodium carbonate solution, reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, growing into crystals on the surface of the lithium carbonate ultrafine powder, and gradually increasing the particle size of the crystals to obtain lithium carbonate adsorption parent nuclei and corresponding solutions thereof; controlling the adding amount of the lithium carbonate superfine powder to be 2-10% of the mass fraction of the theoretical yield; namely, the adding amount of the lithium carbonate superfine powder is 2-10 Wt% of the mass of the theoretical yield; controlling the particle size of the lithium carbonate superfine powder to be 20-60 mu m; controlling the adding amount of the surfactant to be 0.5-5 per mill of the quality of the lithium carbonate superfine powder; the surfactant is a nonionic surfactant; preferably, the surfactant used in this example is an alkyl glycoside or polysorbate; meanwhile, the stable temperature in the step is controlled to be 80-95 ℃, and the stirring speed in the step is controlled to be 10-100 r/min;
3) preparing a lithium carbonate crystal-shaped solution,
spraying the lithium solution into an anti-device provided with the lithium carbonate adsorption mother nucleus in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature of 40-60 ℃, and fully reacting lithium ions in the lithium solution with carbonate ions to prepare lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and formed with gradually increased crystal lattice particle size; controlling the time for preparing the lithium carbonate crystal-shaped solution in the step to be 3-4 hours; controlling the stirring speed of the stirring device to be 10-90 revolutions per minute;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device such as a settling tank, performing settling treatment to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain snowflake-shaped single crystal high-purity lithium carbonate; controlling the settling treatment time to be 1-3 h.
By utilizing the lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate, the purity of the prepared snowflake monocrystal high-purity lithium carbonate is higher than or equal to 99.8% through detection, the impurity content is low, the purity quality requirement of a lithium battery product is met, meanwhile, the continuous production can be realized, compared with the existing extraction method, the efficiency is improved by 20%, and the cost is reduced by 45%; compared with the lithium deposition method, the efficiency is improved by 25 percent, and the cost is reduced by 30 percent.
Through detection and calculation, the extraction efficiency and the purity percent of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method are shown in the table 1 compared with the conventional extraction method and lithium precipitation method.
TABLE 2
Description of the drawings: table 1 shows the comparison between the extraction efficiency and the purity of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method of the present invention and the conventional extraction method and lithium precipitation method.
In table 1, 1 is the extraction efficiency and purity of the snowflake single crystal high-purity lithium carbonate prepared by the invention compared with the existing extraction method and lithium precipitation method;
reference 2 is a comparative example, which compares the extraction efficiency and purity rate by using the existing extraction method and lithium precipitation method.
This is because the method of the present invention is to control the particle size of lithium carbonate ultrafine powder of 20 to 60 μm to be suspended in sodium carbonate solution, and to carry out 2L i of lithium solution and sodium carbonate++CO3 2-→Li2CO3The reaction is favorable for the new lithium carbonate to be adsorbed on the surface of the superfine lithium carbonate to grow crystal and grow; secondly, the reaction process of the lithium solution and the sodium carbonate is always kept in a stable and uniform state. The reaction kettle is stirred smoothly, so that the chemical reaction is promoted, and the relative stability of the superfine lithium carbonate suspended in the solution can be maintained, thereby being beneficial to the adsorption and the stable growth of the new lithium carbonate; the lithium solution adopts a large-area sprinkling mode, so that the material is uniformly distributed, the corresponding rapid reaction is facilitated, and the stable flow state of the solution can be kept without being impacted. The purity of the lithium carbonate prepared under the same conditions is higher by more than 6%. And step-by-step purification is not needed, the preparation of high-purity lithium carbonate is realized in one step, the process flow is short, the operation is simple, and the cost is low.
Example 1
The parts not described in the following examples are the same as those described above.
The specific process steps and technical parameters are controlled as follows:
the invention discloses a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which takes a lithium solution as a raw material; which comprises the following steps of the method,
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device or a reaction kettle device, wherein the pure water can be deionized water, heating the mixture under continuous stirring, adding sodium carbonate, and keeping the constant temperature at 80 ℃, preparing a saturated sodium carbonate solution under the constant temperature condition, and controlling the stirring speed of a reaction kettle of the reaction device to be 60 r/min;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder and the surfactant can be uniformly distributed and suspended in the standard sodium carbonate solution, reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, growing into crystals on the surface of the lithium carbonate ultrafine powder, and gradually increasing the particle size of the crystals to obtain lithium carbonate adsorption parent nuclei and corresponding solutions thereof; controlling the adding amount of the lithium carbonate superfine powder to be 10% of the theoretical mass fraction of the theoretical yield; controlling the grain diameter of the lithium carbonate superfine powder to be 30 mu m; controlling the adding amount of the surfactant to be 0.8 per mill of the quality of the lithium carbonate superfine powder; the surfactant is a nonionic surfactant; preferably, the surfactant used in this example is an alkyl glycoside; meanwhile, the stable temperature in the step is controlled to be 80 ℃, and the stirring speed in the step is controlled to be 50 r/min;
3) preparing a lithium carbonate crystal-shaped solution,
spraying a lithium solution into an anti-device provided with the lithium carbonate adsorption mother nucleus in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature of 40 ℃, and fully reacting lithium ions and carbonate ions to prepare lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and with gradually increased crystal grain size; controlling the time for preparing the lithium carbonate crystal-shaped solution in the step to be 3 hours; controlling the stirring speed of the stirring device to be 20 revolutions per minute;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device such as a settling tank, performing settling treatment to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain snowflake-shaped single crystal high-purity lithium carbonate; controlling the settling treatment time to be 1-3 h.
By utilizing the lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate, the purity of the prepared snowflake monocrystal high-purity lithium carbonate is higher than or equal to 99.8% through detection, the impurity content is low, the purity quality requirement of a lithium battery product is met, meanwhile, the continuous production can be realized, the efficiency is improved by 20% compared with the existing extraction method, and the cost is reduced by 45%; compared with the lithium deposition method, the efficiency is improved by 25 percent, and the cost is reduced by 30 percent.
Through detection and calculation, the extraction efficiency and the purity of the snowflake single crystal high-purity lithium carbonate prepared by the method are shown in the table 1 compared with the conventional extraction method and lithium precipitation method.
TABLE 1
Description of the drawings: table 1 shows the comparison between the extraction efficiency and the purity of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method of the present invention and the conventional extraction method and lithium precipitation method.
In table 1, 1 is the extraction efficiency and purity of the snowflake single crystal high-purity lithium carbonate prepared by the invention compared with the existing extraction method and lithium precipitation method;
reference 2 is a comparative example, which compares the extraction efficiency and purity rate by using the existing extraction method and lithium precipitation method.
Example 2
Explanation of technical terms in the present specification:
(1) lithium solution: refers to a lithium-containing compound solution. Namely lithium-containing solution obtained in the process of extracting lithium, wherein the lithium solution is lithium sulfate, lithium chloride, lithium phosphate or other lithium-containing compound solution;
(2) high-purity lithium carbonate of snowflake monocrystal or large-particle lithium carbonate of snowflake monocrystal: the lithium carbonate is of a single crystal structure, the microstructure of the lithium carbonate is similar to snowflake, and the average grain size of crystal grains is larger than that of the conventional grain size, so that the lithium carbonate is named as snowflake-shaped single crystal large-grain lithium carbonate or snowflake-shaped single crystal high-purity lithium carbonate;
(3) lithium carbonate adsorbs mother nucleus: the superfine powder lithium carbonate is suspended in the solution, so that the lithium carbonate generated by the reaction provides a nucleus which can attach to and surround the crystal growth of the lithium carbonate, and the nucleus is an adsorption parent nucleus for the lithium carbonate.
(3) Theoretical yield: the method is the yield of the quality of the snowflake monocrystal high-purity lithium carbonate product which can be extracted by theoretically calculating by taking a lithium solution as a raw material.
The process comprises the following steps:
firstly, preparing a standard sodium carbonate solution, adding pure water into a reaction kettle device, then adding a proper amount of sodium carbonate under certain constant temperature and slow stirring, wherein the adding amount of the sodium carbonate is limited by no crystallization, namely preparing a saturated solution of the sodium carbonate, and completely melting the prepared sodium carbonate solution in water;
secondly, preparing lithium carbonate adsorption mother nucleus, adding a small amount of lithium carbonate superfine powder into the prepared standard sodium carbonate solution, and uniformly distributing the lithium carbonate superfine powder in a suspension state in the sodium carbonate solution under the action of certain constant temperature and slow stirring of a reaction kettle to form the lithium carbonate adsorption mother nucleus for the subsequent adsorption reaction of new lithium carbonate; the stirring speed of the reaction kettle is based on that suspended lithium carbonate is uniformly distributed and does not precipitate;
thirdly, dispersing and spraying the lithium solution into the reaction kettle device through the spraying device, and reacting lithium ions in the lithium solution with carbonate ions in the sodium carbonate solution to combine lithium carbonate; at this time, the newly generated lithium carbonate grows into crystals attached to the surface of the lithium carbonate ultrafine powder suspended in the solution and gradually increases the crystal lattice particle size. The method adopts a spraying mode, the lithium solution enters a reaction kettle device as uniformly as possible without impact, so that lithium ions and carbonate ions react rapidly, and the newly-generated lithium carbonate can be stably adsorbed on the surface of suspended lithium carbonate ultrafine powder for crystal growth; by controlling the spraying speed and the spraying amount of the lithium solution, the balance state of stirring the sodium carbonate and lithium carbonate suspension solution is preferably not broken;
and finally, transferring the lithium carbonate and the solution in the reaction kettle to a settling tank for settling, and then carrying out solid-liquid separation, washing and drying on the lithium carbonate to obtain the large-particle high-purity lithium carbonate which is uniform in chemical components and is in a snowflake-shaped monocrystal.
The specific process steps and technical parameters are controlled as follows:
the invention discloses a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which takes a lithium solution as a raw material; which comprises the following steps of the method,
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device or a reaction kettle device, wherein the pure water can be deionized water, heating the mixture under continuous stirring, adding sodium carbonate, controlling the constant temperature to be 75 ℃, and preferably controlling the constant temperature to be 75 +/-5 ℃, preparing a saturated sodium carbonate solution under the constant temperature condition, controlling the stirring speed of a reaction kettle of the reaction device to be 100 r/min, and controlling the concentration of the prepared standard sodium carbonate solution to be 300 g/L, namely the standard sodium carbonate solution;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder and the surfactant can be uniformly distributed and suspended in the standard sodium carbonate solution, reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, growing into crystals on the surface of the lithium carbonate ultrafine powder, and gradually increasing the particle size of the crystals to obtain lithium carbonate adsorption parent nuclei and corresponding solutions thereof; controlling the adding amount of the lithium carbonate superfine powder to be 6 percent of the mass fraction of the theoretical yield; namely, the adding amount of the lithium carbonate superfine powder is 6 Wt% of the quality of theoretical yield; controlling the grain diameter of the lithium carbonate superfine powder to be 30 mu m; controlling the adding amount of the surfactant to be 2 per mill of the quality of the lithium carbonate superfine powder; the surfactant is a nonionic surfactant; preferably, the surfactant used in this example is an alkyl glycoside or polysorbate; meanwhile, the stable temperature in the step is controlled to be 80 ℃, and the stirring speed in the step is controlled to be 100 revolutions per minute;
3) preparing a lithium carbonate crystal-shaped solution,
spraying the lithium solution into an anti-device provided with the lithium carbonate adsorption mother nucleus in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature of 40-60 ℃, and fully reacting lithium ions in the lithium solution with carbonate ions to prepare lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and formed with gradually increased crystal lattice particle size; controlling the time for preparing the lithium carbonate crystal-shaped solution in the step to be 3-4 hours; controlling the stirring speed of the stirring device to be 10 revolutions per minute;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device such as a settling tank, performing settling treatment to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain snowflake-shaped single crystal high-purity lithium carbonate; controlling the settling treatment time to be 1-3 h.
By utilizing the lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate, the purity of the prepared snowflake monocrystal high-purity lithium carbonate is higher than or equal to 99.8% through detection, the impurity content is low, the purity quality requirement of a lithium battery product is met, meanwhile, the continuous production can be realized, compared with the existing extraction method, the efficiency is improved by 20%, and the cost is reduced by 45%; compared with the lithium deposition method, the efficiency is improved by 25 percent, and the cost is reduced by 30 percent.
Through detection and calculation, the extraction efficiency and the purity percent of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method are shown in the table 1 compared with the conventional extraction method and lithium precipitation method.
TABLE 1
Description of the drawings: table 1 shows the comparison between the extraction efficiency and the purity of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method of the present invention and the conventional extraction method and lithium precipitation method.
In table 1, 1 is the extraction efficiency and purity of the snowflake single crystal high-purity lithium carbonate prepared by the invention compared with the existing extraction method and lithium precipitation method;
reference 2 is a comparative example, which compares the extraction efficiency and purity rate by using the existing extraction method and lithium precipitation method.
Example 3
Explanation of technical terms in the present specification:
(1) lithium solution: refers to a lithium-containing compound solution. Namely lithium-containing solution obtained in the process of extracting lithium, wherein the lithium solution is lithium sulfate, lithium chloride, lithium phosphate or other lithium-containing compound solution;
(2) high-purity lithium carbonate of snowflake monocrystal or large-particle lithium carbonate of snowflake monocrystal: the lithium carbonate is of a single crystal structure, the microstructure of the lithium carbonate is similar to snowflake, and the average grain size of crystal grains is larger than that of the conventional grain size, so that the lithium carbonate is named as snowflake-shaped single crystal large-grain lithium carbonate or snowflake-shaped single crystal high-purity lithium carbonate;
(3) lithium carbonate adsorbs mother nucleus: the superfine powder lithium carbonate is suspended in the solution, so that the lithium carbonate generated by the reaction provides a nucleus which can attach to and surround the crystal growth of the lithium carbonate, and the nucleus is an adsorption parent nucleus for the lithium carbonate.
(3) Theoretical yield: the method is the yield of the quality of the snowflake monocrystal high-purity lithium carbonate product which can be extracted by theoretically calculating by taking a lithium solution as a raw material.
The process comprises the following steps:
firstly, preparing a standard sodium carbonate solution, adding pure water into a reaction kettle device, then adding a proper amount of sodium carbonate under certain constant temperature and slow stirring, wherein the adding amount of the sodium carbonate is limited by no crystallization, namely preparing a saturated solution of the sodium carbonate, and completely melting the prepared sodium carbonate solution in water;
secondly, preparing lithium carbonate adsorption mother nucleus, adding a small amount of lithium carbonate superfine powder into the prepared standard sodium carbonate solution, and uniformly distributing the lithium carbonate superfine powder in a suspension state in the sodium carbonate solution under the action of certain constant temperature and slow stirring of a reaction kettle to form the lithium carbonate adsorption mother nucleus for the subsequent adsorption reaction of new lithium carbonate; the stirring speed of the reaction kettle is based on that suspended lithium carbonate is uniformly distributed and does not precipitate;
thirdly, dispersing and spraying the lithium solution into the reaction kettle device through the spraying device, and reacting lithium ions in the lithium solution with carbonate ions in the sodium carbonate solution to combine lithium carbonate; at this time, the newly generated lithium carbonate grows into crystals attached to the surface of the lithium carbonate ultrafine powder suspended in the solution and gradually increases the crystal lattice particle size. The method adopts a spraying mode, the lithium solution enters a reaction kettle device as uniformly as possible without impact, so that lithium ions and carbonate ions react rapidly, and the newly-generated lithium carbonate can be stably adsorbed on the surface of suspended lithium carbonate ultrafine powder for crystal growth; by controlling the spraying speed and the spraying amount of the lithium solution, the balance state of stirring the sodium carbonate and lithium carbonate suspension solution is preferably not broken;
and finally, transferring the lithium carbonate and the solution in the reaction kettle to a settling tank for settling, and then carrying out solid-liquid separation, washing and drying on the lithium carbonate to obtain the large-particle high-purity lithium carbonate which is uniform in chemical components and is in a snowflake-shaped monocrystal.
The specific process steps and technical parameters are controlled as follows:
the invention discloses a lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate, which takes a lithium solution as a raw material; which comprises the following steps of the method,
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device or a reaction kettle device, wherein the pure water can be deionized water, heating the mixture under continuous stirring, adding sodium carbonate, controlling the constant temperature to be 85 ℃, and preferably controlling the constant temperature to be 75 +/-5 ℃, preparing a saturated sodium carbonate solution under the constant temperature condition, controlling the stirring speed of a reaction kettle of the reaction device to be 80 r/min, controlling the concentration of the prepared standard sodium carbonate solution to be 200 g/L, and obtaining the standard sodium carbonate solution;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder and the surfactant can be uniformly distributed and suspended in the standard sodium carbonate solution, reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, growing into crystals on the surface of the lithium carbonate ultrafine powder, and gradually increasing the particle size of the crystals to obtain lithium carbonate adsorption parent nuclei and corresponding solutions thereof; controlling the adding amount of the lithium carbonate superfine powder to be 10 percent of the mass fraction of the theoretical yield; namely, the adding amount of the lithium carbonate superfine powder is 10 Wt% of the mass of the theoretical yield; controlling the particle size of the lithium carbonate superfine powder to be 20 mu m; controlling the adding amount of the surfactant to be 1 per mill of the quality of the lithium carbonate superfine powder; the surfactant is sodium dodecyl sulfate; meanwhile, the stable temperature in the step is controlled to be 80-95 ℃, and the stirring speed in the step is controlled to be 10 r/min;
3) preparing a lithium carbonate crystal-shaped solution,
spraying the lithium solution into an anti-device provided with the lithium carbonate adsorption mother nucleus in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature of 40-60 ℃, and fully reacting lithium ions in the lithium solution with carbonate ions to prepare lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and formed with gradually increased crystal lattice particle size; controlling the time for preparing the lithium carbonate crystal-shaped solution in the step to be 3-4 hours; controlling the stirring speed of the stirring device to be 40 revolutions per minute;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device such as a settling tank, performing settling treatment to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain snowflake-shaped single crystal high-purity lithium carbonate; controlling the settling treatment time to be 1-3 h.
By utilizing the lithium precipitation crystallization method for preparing the snowflake monocrystal high-purity lithium carbonate, the purity of the prepared snowflake monocrystal high-purity lithium carbonate is higher than or equal to 99.8% through detection, the impurity content is low, the purity quality requirement of a lithium battery product is met, meanwhile, the continuous production can be realized, compared with the existing extraction method, the efficiency is improved by 20%, and the cost is reduced by 45%; compared with the lithium deposition method, the efficiency is improved by 25 percent, and the cost is reduced by 30 percent.
Through detection and calculation, the extraction efficiency and the purity percent of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method are shown in the table 1 compared with the conventional extraction method and lithium precipitation method.
TABLE 1
Description of the drawings: table 1 shows the comparison between the extraction efficiency and the purity of the snowflake-shaped single crystal high-purity lithium carbonate prepared by the method of the present invention and the conventional extraction method and lithium precipitation method.
In table 1, 1 is the extraction efficiency and purity of the snowflake single crystal high-purity lithium carbonate prepared by the invention compared with the existing extraction method and lithium precipitation method;
reference 2 is a comparative example, which compares the extraction efficiency and purity rate by using the existing extraction method and lithium precipitation method.
Technical features not described in the present invention may be implemented by or using the prior art, and are not described herein again. It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above embodiments, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (7)
1. A lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate takes a lithium solution as a raw material; the method is characterized by comprising the following steps:
1) preparing a standard sodium carbonate solution, adding pure water into a reaction device, heating under continuous stirring, adding sodium carbonate, keeping the temperature constant, and preparing a saturated sodium carbonate solution which is the standard sodium carbonate solution under the constant-temperature condition;
2) preparing an adsorption mother nucleus of lithium carbonate,
adding lithium carbonate ultrafine powder and a surfactant into the standard sodium carbonate solution obtained in the step 1) in a reaction device under the condition of continuous stirring, so that the lithium carbonate ultrafine powder is uniformly distributed and suspended in the standard sodium carbonate solution, and reacting under the conditions of stable temperature and slow stirring to form lithium carbonate ultrafine powder, wherein the lithium carbonate ultrafine powder grows on the surface of the lithium carbonate ultrafine powder to form crystals, and the particle size of the crystals is gradually increased to form lithium carbonate adsorption parent nuclei;
3) preparing a lithium carbonate crystal-shaped solution,
spraying a lithium solution into a reaction device provided with the lithium carbonate adsorption mother nucleus obtained in the step 2) by using a spraying device, carrying out mixing reaction under the condition of continuous stirring, controlling the stirring device to be carried out under the conditions of continuous slow stirring and constant temperature, and fully reacting the lithium ions with carbonate ions to prepare a lithium carbonate crystal-shaped solution with lithium carbonate attached to the surface of the lithium carbonate superfine powder mother nucleus suspended in the solution and with gradually increased crystal lattice particle size;
4) preparing high-purity lithium carbonate of snowflake monocrystal,
and (3) placing the lithium carbonate crystal-shaped solution obtained in the step 3) into a settling device, settling to obtain a lithium carbonate settling solution, and then separating, washing and drying the lithium carbonate settling solution to obtain the snowflake-shaped single crystal high-purity lithium carbonate.
2. The lithium precipitating and crystallizing method for preparing high purity lithium carbonate of snowflake monocrystal as claimed in claim 1, wherein the step 1) is to control the constant temperature at 65-85 ℃, the stirring speed of the reaction kettle of the reaction device at 10-100 rpm, and the concentration of the prepared standard sodium carbonate solution at 200-300 g/L.
3. The lithium precipitation crystallization method for preparing snowflake monocrystal high-purity lithium carbonate according to claim 1, characterized in that the adding amount of lithium carbonate superfine powder in the step 2) is controlled to be 2% -10% of the mass fraction of theoretical yield; controlling the particle size of the lithium carbonate superfine powder to be 20-60 mu m.
4. The lithium deposition and crystallization method for preparing snowflake monocrystal high-purity lithium carbonate according to claim 1, wherein in the step 2), the addition amount of the surfactant is controlled to be 0.5-5 per mill of the mass of the lithium carbonate superfine powder; the surfactant is a nonionic surfactant.
5. The lithium deposition and crystallization method for preparing snowflake monocrystal high-purity lithium carbonate according to claim 1, characterized in that the time for preparing lithium carbonate crystal-forming solution in the step 3) is controlled to be 3-4 hours; the stirring speed of the stirring device is controlled to be 10-100 revolutions per minute, and the constant temperature is 40-80 ℃.
6. The lithium precipitating and crystallizing method for preparing snowflake monocrystal high-purity lithium carbonate according to claim 1, wherein the precipitation treatment time in the step 4) is controlled to be 1-3 h.
7. The lithium precipitating and crystallizing method for preparing snowflake single crystal high purity lithium carbonate as claimed in claim 1 or 4, wherein the surfactant is alkyl glycoside or polysorbate.
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