CN109231243B - Method for continuously removing calcium ions from lithium chloride conversion solution - Google Patents
Method for continuously removing calcium ions from lithium chloride conversion solution Download PDFInfo
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- CN109231243B CN109231243B CN201811178444.9A CN201811178444A CN109231243B CN 109231243 B CN109231243 B CN 109231243B CN 201811178444 A CN201811178444 A CN 201811178444A CN 109231243 B CN109231243 B CN 109231243B
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- lithium chloride
- chloride conversion
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
Abstract
The invention discloses a method for continuously removing calcium ions from a lithium chloride conversion solution, which comprises the following steps: the method comprises the steps of feeding lithium chloride conversion liquid into a premixing assembly, quantitatively mixing the lithium chloride conversion liquid with a refining agent, sequentially feeding the lithium chloride conversion liquid into a reaction crystallizer and a continuous liquid-solid separator, wherein the obtained mother liquid is the lithium chloride conversion liquid with the removed calcium ions, the premixing assembly comprises a lithium chloride conversion liquid feeding pipe, a refining agent groove and a pre-reaction crystallizer, an outlet of the lithium chloride conversion liquid feeding pipe is communicated with the lower part of the pre-reaction crystallizer, a throat pipe is arranged between an inlet and an outlet of the lithium chloride conversion liquid feeding pipe, a refining agent feeding hole is formed in the throat pipe, and the refining agent groove is connected with the refining agent feeding hole through a pipeline. The method can realize continuous production, simplify the process flow, improve the separation efficiency and simultaneously realize small occupied area of equipment.
Description
Technical Field
The present invention relates to a method for producing lithium salts.
Background
Lithium is a very important energy metal, with the rapid development of the new energy automobile market, the demand of power lithium batteries is gradually increased year by year, and the requirements on the yield and the quality of lithium products are higher and higher. The lithium products are divided into basic lithium products and high-end lithium products, wherein the basic lithium products refer to three products of industrial-grade lithium carbonate, lithium chloride and industrial-grade lithium hydroxide, and the high-end lithium products comprise battery-grade lithium carbonate, high-purity lithium carbonate, battery-grade metal lithium, butyl lithium, lithium fluoride and the like. Lithium chloride is a basic lithium product with wide application, many lithium deep-processed products pass through a lithium chloride link and are particularly used as a key production raw material of battery-grade lithium metal, and the influence of the purity of the lithium chloride on the quality of a final product is extremely obvious.
Lithium sulfate can be prepared from lithium ore, lithium sulfate reacts with calcium chloride to obtain lithium chloride conversion solution and calcium sulfate slag, and the lithium chloride conversion solution obtained after the calcium sulfate slag is filtered and removed is used for producing lithium chloride. The lithium chloride conversion solution contains calcium ions and sulfate radicals besides lithium chloride, and can be used for producing high-quality lithium chloride products only by purification and purification.
The lithium chloride purification technology disclosed at present mostly adopts a chemical precipitation method to remove calcium ions and sulfate ions, as disclosed in patents CN201610257026.3 and CN201611093934.XThe method adopts barium chloride to precipitate sulfate radicals, not only consumes a large amount of chemical agents, but also generates a large amount of barium sulfate mud solid waste, has large environmental pollution, long precipitation process, large impurity residual quantity and low product quality, and is difficult to meet the production requirements of battery-grade lithium products. Meanwhile, the occupied area of the equipment is large, the equipment is in a clearance mode, a conveying machine is required to convey materials in each process, the energy consumption is high, the efficiency is low, and the lithium chloride conversion solution Ca is used2+The content of (B) is low, and is generally only 2-5 g/L, so that the required alkaline refining agent is quite small, and the method is difficult to effectively mix a small amount of alkaline refining agent with a large amount of lithium chloride conversion solution.
Disclosure of Invention
The invention aims to provide a method for continuously removing calcium ions from a lithium chloride conversion solution so as to overcome the defects in the prior art.
The method for continuously removing calcium ions from the lithium chloride conversion solution comprises the following steps:
and (2) feeding the lithium chloride conversion solution into a premixing component through a conveying device, quantitatively mixing the lithium chloride conversion solution with a refining agent to ensure that the addition amount of the refining agent and the lithium chloride conversion solution keeps a preset ratio, then sequentially feeding the lithium chloride conversion solution into a reaction crystallizer and a continuous liquid-solid separator for liquid-solid separation to obtain mother solution, namely the lithium chloride conversion solution with the calcium ions removed, and feeding the lithium chloride conversion solution to subsequent processes for further treatment.
The pre-mixing assembly comprises: a lithium chloride conversion solution feeding pipe, a refining agent groove and a pre-reaction crystallizer;
the outlet of the lithium chloride conversion liquid feeding pipe is communicated with the lower part of the inner cavity of the pre-reaction crystallizer, a throat pipe is arranged between the inlet and the outlet of the lithium chloride conversion liquid feeding pipe, a refining agent feeding hole is formed in the throat pipe, and the refining agent groove is connected with the refining agent feeding hole through a pipeline.
The invention has the beneficial effects that:
the method can ensure that the refining agent added quantitatively fully reacts with calcium ions in the raw material lithium chloride conversion solution, reduces the consumption of the refining agent, accelerates the reaction speed, can realize continuous production, has little pollution to the environment, simplifies the process flow, improves the separation efficiency, and simultaneously has small floor area of equipment.
Drawings
FIG. 1 is a schematic flow diagram of a process for continuously removing calcium ions from a lithium chloride conversion solution.
FIG. 2 is a schematic diagram of a pre-mix assembly configuration.
FIG. 3 is a schematic diagram of a reactive crystallizer.
Detailed Description
Referring to fig. 1, the method for continuously removing calcium ions from a lithium chloride conversion solution according to the present invention comprises the following steps:
the lithium chloride conversion solution is sent into a premixing component 1 through a conveying device and is quantitatively mixed with a refining agent, the addition amount of the refining agent and the lithium chloride conversion solution keeps a preset proportion, then the lithium chloride conversion solution is sent into a reaction crystallizer 2 and a continuous liquid-solid separator 3 in sequence for liquid-solid separation, and the obtained mother solution is the lithium chloride conversion solution with calcium ions removed, and is sent to the subsequent working procedures for further treatment.
Referring to fig. 2, the pre-mixing assembly 1 comprises: a lithium chloride conversion solution feeding pipe 4, a refining agent groove 5 and a pre-reaction crystallizer 6;
an outlet 401 of the lithium chloride conversion liquid feeding pipe 4 is communicated with the lower part of the inner cavity of the pre-reaction crystallizer 6, a throat pipe 402 is arranged between an inlet 4011 and the outlet 401 of the lithium chloride conversion liquid feeding pipe 4, a refining agent feeding hole 501 is arranged at the position of the throat pipe 402, and the refining agent groove 5 is connected with the refining agent feeding hole 501 through a pipeline;
preferably, the diameter of the throat pipe 402 is 30-40% of the diameter of the lithium chloride conversion solution feeding pipe 4;
preferably, a quantitative feeder 502 is arranged in the refining agent tank 5, and the quantitative feeder 502 is preferably a screw;
referring to fig. 3, preferably, the reactive crystallizer 2 comprises a spiral pipe 201 and a cooling outer cylinder 202, the spiral pipe 201 is arranged in the cooling outer cylinder 202, an upper end inlet 203 of the spiral pipe 201 is communicated with a pre-reaction crystal outlet 601 of the pre-reaction crystallizer 6 through a pipeline, and a lower end outlet 204 of the spiral pipe 201 is connected with the continuous liquid-solid separator 3;
preferably, the continuous liquid-solid separator 3 comprises more than 2 centrifugal separators, the centrifugal separators are connected with a power assembly such as an electric motor through a rotating member and are arranged on the frame, when one centrifugal separator is filled with materials to be separated, the centrifugal separator is shifted and rotated to start centrifugal separation, and the other centrifugal separator is in place to continue to be filled with separated liquid, so that the purpose of continuous separation is achieved;
preferably, the flow speed of the lithium chloride conversion solution in the lithium chloride conversion solution feeding pipe 4 is 10-20 m/s;
preferably, the retention time of the materials in the reaction crystallizer 2 is 30-60 minutes;
the temperature of the reaction crystallizer 2 is 5-10 ℃;
the refining agent is one or a mixture of more of sodium carbonate, sodium oxalate, sodium fluoride or sodium phosphate, and the addition amount is 2-7 times of the weight of calcium ions in the lithium chloride conversion solution;
in the lithium chloride conversion solution, the content of each component is as follows:
LiCl (in Li)2And (C) calculated by O): 10-40 g/L;
Ca2+：2～5g/L；
SO4 2-：2～5g/L；
in the obtained lithium chloride conversion solution with the calcium ions removed, the contents of all components are as follows:
LiCl (in Li)2And (C) calculated by O): 10-40 g/L;
Ca2+：0.01mg/L～2mg/L；
SO4 2-：2～5g/L；
the invention operates as follows:
the lithium chloride conversion solution is sent into a lithium chloride conversion solution feeding pipe 4 through a conveying device, a quantitative feeder 501 is started, the rotating speed is set, the adding amount of the refining agent and the lithium chloride conversion solution keep a preset proportion, and a continuous liquid-solid separator 3 is started;
in the lithium chloride conversion liquid feeding pipe 4, the flow speed of the lithium chloride conversion liquid is accelerated after passing through the throat pipe 402, the lithium chloride conversion liquid is quickly mixed with a quantitative refining agent entering the lithium chloride conversion liquid feeding pipe 4, the dissolution and mass transfer speeds are accelerated due to the sudden change of the pipe diameter at the outlet of the throat pipe, so that the reaction speed is accelerated, the lithium chloride conversion liquid enters the pre-reaction crystallizer 6 for pre-reaction crystallization, then enters the reaction crystallizer 2 for reaction crystallization, and finally is sent into the continuous liquid-solid separator 3 for liquid-solid separation, and the obtained mother liquid is the lithium chloride conversion liquid with the calcium ions removed, and is sent to the subsequent process for further treatment;
in said reactive crystallizer 2, the main crystallization, the reaction process, is actually already completed in the premixing assembly 1, and therefore, it is necessary to operate at a lower temperature.
Example 1
The continuous removal of calcium ions from the lithium chloride conversion liquor was carried out using the scheme of figure 1, the premixing assembly of figure 2 and the reactive crystallizer of figure 3.
Wherein: the flow speed of the lithium chloride conversion solution in the lithium chloride conversion solution feeding pipe 4 is 10 m/s, and the retention time of the material in the reaction crystallizer 2 is 60 minutes;
the temperature of the reaction crystallizer 2 is 5 ℃;
the refining agent is sodium carbonate, and the adding amount of the sodium carbonate is 2 times of the weight of calcium ions in the lithium chloride conversion solution;
in the lithium chloride conversion solution, the content of each component is as follows:
LiCl (in Li)2And (C) calculated by O): 10 g/L;
Ca2+：5g/L；
SO4 2-：2～5g/L；
in the obtained lithium chloride conversion solution with the calcium ions removed, the contents of all components are as follows:
LiCl (in Li)2And (C) calculated by O): 10 g/L;
Ca2+：2mg/L；
SO4 2-：2g/L；
the removal rate was (5000-2)/5000 was 99.96%.
Example 2
The continuous removal of calcium ions from the lithium chloride conversion liquor was carried out using the scheme of figure 1, the premixing assembly of figure 2 and the reactive crystallizer of figure 3.
Wherein: the flow speed of the lithium chloride conversion solution in the lithium chloride conversion solution feeding pipe 4 is 20 m/s, and the retention time of the material in the reaction crystallizer 2 is 30 minutes;
the temperature of the reaction crystallizer 2 is 10 ℃;
the refining agent is sodium phosphate, and the addition amount of the refining agent is 7 times of the weight of calcium ions in the lithium chloride conversion solution;
in the lithium chloride conversion solution, the content of each component is as follows:
LiCl (in Li)2And (C) calculated by O): 40 g/L;
Ca2+：2g/L；
SO4 2-：5g/L；
in the obtained lithium chloride conversion solution with the calcium ions removed, the contents of all components are as follows:
LiCl (in Li)2And (C) calculated by O): 40 g/L;
Ca2+：0.01mg/L；
SO4 2-：5g/L；
the removal rate was (2000-2)/5000 was 99.999%.
Claims (8)
1. A method for continuously removing calcium ions from a lithium chloride conversion solution, which is characterized by comprising the following steps: the lithium chloride conversion solution is sent into a premixing component (1) through a conveying device and is quantitatively mixed with a refining agent, the addition amount of the refining agent and the lithium chloride conversion solution keeps a preset proportion, then the lithium chloride conversion solution is sequentially sent into a reaction crystallizer (2) and a continuous liquid-solid separator (3) for liquid-solid separation, and the obtained mother solution is the lithium chloride conversion solution with calcium ions removed and is sent to the subsequent working procedures for further treatment;
the premixing assembly (1) comprising: a lithium chloride conversion liquid feeding pipe (4), a refining agent groove (5) and a pre-reaction crystallizer (6);
an outlet (401) of the lithium chloride conversion liquid feeding pipe (4) is communicated with the lower part of an inner cavity of the pre-reaction crystallizer (6), a throat pipe (402) is arranged between an inlet (4011) and the outlet (401) of the lithium chloride conversion liquid feeding pipe (4), a refining agent feeding hole (501) is formed in the throat pipe (402), and the refining agent groove (5) is connected with the refining agent feeding hole (501) through a pipeline.
2. The method according to claim 1, characterized in that the throat (402) has a diameter of 30-40% of the diameter of the lithium chloride conversion solution feed pipe.
3. The method according to claim 1, wherein a quantitative feeder is provided in the refining agent tank.
4. The method of claim 3, wherein the doser is a screw.
5. The method according to claim 1, wherein the reaction crystallizer (2) comprises a spiral pipe and a cooling outer cylinder, the spiral pipe is arranged in the cooling outer cylinder, an upper end inlet of the spiral pipe is communicated with a pre-reaction crystal outlet of the pre-reaction crystallizer through a pipeline, and a lower end outlet of the spiral pipe is connected with the continuous liquid-solid separator.
6. A method according to claim 1, characterized in that the continuous liquid-solid separator (3) comprises more than two centrifugal separators, which are connected to the power pack motor via rotating members and mounted on the frame.
7. The method according to any one of claims 1 to 6, wherein the flow speed of the lithium chloride conversion solution in the lithium chloride conversion solution feeding pipe is 10-20 m/s, the residence time of the material in the reaction crystallizer (2) is 30-60 min, and the temperature of the reaction crystallizer is 5-10 ℃.
8. The method according to claim 7, wherein the refining agent is one or more of sodium carbonate, sodium oxalate, sodium fluoride and sodium phosphate, and the addition amount is 2-7 times of the weight of calcium ions in the lithium chloride conversion solution, and the content of each component in the lithium chloride conversion solution is as follows:
calculated as Li2O, LiCl: 10-40 g/L; ca2+：2～5g/L；SO4 2-：2～5g/L。
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