CN115286019A - Method for producing high-purity lithium carbonate from spodumene - Google Patents
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Abstract
The invention provides a method for producing high-purity lithium carbonate from spodumene ore, belonging to the technical field of recycling of lithium ore; the method comprises the following steps: calcining and ball-milling the spodumene ore, then carrying out secondary reverse leaching by nitric acid, separating the obtained leachate into a high-valence ion solution and a monovalent ion solution by a nanofiltration membrane, evaporating and concentrating the high-valence ion solution, and calcining to obtain a crude alumina byproduct; the monovalent ion liquid is subjected to a two-stage pH regulation impurity removal mode to obtain a cleaner filtrate II and a cleaner filter residue II, the filtrate II is concentrated and crystallized to obtain potassium nitrate and a mother liquor I, and the obtained mother liquor I is subjected to ion exchange and bipolar membrane treatment to respectively obtain a mixed solution of nitric acid, lithium hydroxide, trace sodium hydroxide and trace potassium hydroxide; further preparing lithium hydroxide or lithium carbonate products. The invention aims at preparing a high-purity lithium carbonate product from the spodumene, and the product has high purity and high lithium recovery rate.
Description
Technical Field
The invention relates to the technical field of lithium ore recycling, in particular to a method for producing high-purity lithium carbonate from spodumene.
Background
Since 2011, all countries in the world have introduced new energy strategies in consideration of environmental protection and energy safety, and the wave of new energy industry development is raised in the world. China also develops the new energy industry vigorously, and the fields of energy-saving and new energy automobiles, electric tools, electric bicycles, novel energy storage and the like become the important investment development of China.
Lithium and salts thereof (lithium hydroxide, lithium carbonate and the like) are basic raw materials of the new energy industry, lithium metal which is a basic material of the new energy industry is contained in lithium ore, and the lithium salt industry in China, particularly the lithium extraction industry of the lithium ore, has strong scale and technical advantages all over the world, and is very important for optimizing the development and application of the lithium ore.
At present, lithium ore mainly comprises lepidolite and spodumene, and methods for extracting lithium from the lithium ore mainly comprise a sulfuric acid roasting method, a chloride roasting method, a limestone sintering method, a pressure cooking method and the like. However, the process of extracting lithium from the leachate obtained by leaching after the lithium ore pretreatment is complicated, and the loss of lithium in the recovery process is large.
Therefore, the development of a new process and a new technology for extracting lithium from lithium ore solves the problems in the prior art, and has great significance for development and application of lithium ore in China and promotion of development of new energy lithium battery industry.
For the extraction of lithium from the limonite, a sulfuric acid method is mainly adopted, the limonite is subjected to sulfating roasting after being calcined, sulfur dioxide gas is generated to pollute air, the acidified and roasted limonite is subjected to primary leaching to obtain a leaching solution, the pH value of the leaching solution is less than or equal to 0.5, a large amount of lime milk is needed to neutralize residual acid and soda for adjusting the pH value and removing impurities, the auxiliary material cost is increased, and calcium is introduced to additionally generate a large amount of calcium sulfate precipitation slag. Furthermore, one leaching does not ensure that a large amount of metal in the acidified spodumene ore is leached into solution by one leaching, resulting in a large amount of metal loss. For lithium extraction from salt lake brine, the method usually needs to be different from lake to lake and is suitable according to local conditions, and the method mainly adopts a membrane method, an extraction method and electrodialysis, but the electrodialysis and the front-end solution treatment of the membrane method have high magnesium-lithium ratio and are difficult to separate, so membrane pollution/membrane blockage are easily caused, the price of an extracting agent in the extraction method is high, the extraction process is carried out under a high-acidity condition, equipment corrosion is possibly caused, the environmental protection pressure of an organic solvent is high, and lithium extraction from lithium aurate and lithium extraction from salt lake are carried out according to the advantages and disadvantages of lithium aurate and lithium extraction from salt lake.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for producing high-purity lithium carbonate from spodumene, which comprises the steps of pretreating (calcining and ball-milling) the spodumene, carrying out secondary reverse leaching by nitric acid, increasing the utilization rate of the nitric acid, fully leaching lithium in the spodumene to obtain a leaching solution, treating the leaching solution by a nanofiltration membrane, and separating the leaching solution into Al (NO) after the leaching solution is treated by the nanofiltration membrane 3 ) 3 High valence ion solution and LiNO 3 A predominantly monovalent ion solution of Al (NO) 3 ) 3 Evaporating, concentrating and calcining the mainly high-valence ion solution to obtain a crude alumina byproduct, namely LiNO 3 The monovalent ion solution mainly is subjected to two-stage pH regulation and impurity removal, so that the use of alkaline compounds can be effectively reduced, the generated precipitation slag is less, the loss of lithium can be reduced, and the production cost is reduced. And the obtained solution (filtrate II) after impurity removal is concentrated and crystallized to obtain a potassium nitrate byproduct, the mother solution I only contains monovalent ions and trace high-valence ions, purer monovalent ion solution can be obtained after ion exchange, the monovalent ion solution can be treated by using a bipolar membrane at the moment, the membrane loss can be reduced, the acid and alkali can be separated by the treatment of the monovalent ion solution by using the bipolar membrane to obtain a mixed solution of nitric acid, lithium hydroxide, trace sodium hydroxide and trace potassium hydroxide, the nitric acid can be recycled to reduce the production cost, and the crude LiOH. H is obtained by concentrating and crystallizing the mixed solution of lithium hydroxide, trace sodium hydroxide and trace potassium hydroxide 2 O, crude LiOH. H 2 The O can be dissolved and carbonized to be converted into a high-purity lithium carbonate product, and the purity of the lithium carbonate product is over 99.5 percent. The whole process has the advantages of low slag yield, low Li loss, good economic value, green and environment-friendly process and easy operationAnd the industrial production is realized.
Specifically, the invention provides the following technical scheme:
a method for producing high-purity lithium carbonate by using spodumene comprises the following steps:
s1: calcining and ball-milling the spodumene ore, and then carrying out secondary reverse leaching by nitric acid to obtain leaching slag and leaching liquid;
s2: treating the leachate obtained in the step S1 by a nanofiltration membrane to obtain Al (NO) 3 ) 3 High valence ion solution mainly and LiNO 3 A solution of predominantly monovalent ions in which Al (NO) is present 3 ) 3 Evaporating and concentrating the mainly high-valence ion solution, and calcining to obtain a rough alumina byproduct;
s3: removing impurities from the monovalent ion solution obtained in the step S2 by primary pH adjustment to obtain a filtrate I and a filter residue I, and removing impurities from the filtrate I by secondary pH adjustment to obtain a filtrate II and a filter residue II;
wherein, the conditions of first-stage pH adjustment and impurity removal comprise: the temperature is 40-90 ℃, the pH value end point is 6-8, and the reaction time is 1-2 h;
the conditions for secondary pH adjustment and impurity removal comprise: the temperature is 60-90 ℃, the pH value end point is 10-13, and the reaction time is 1-2 h;
s4: concentrating and crystallizing the filtrate II obtained in the step S3 to obtain a potassium nitrate product and mother liquor I;
s5: carrying out ion exchange and bipolar membrane treatment on the mother liquor I obtained in the step S4 to obtain HNO 3 And a mixed solution containing LiOH, naOH and KOH, HNO 3 Optionally returning to the step S1 for recycling.
S6: concentrating and crystallizing the mixed solution obtained in the step S5 to obtain crude LiOH & H 2 O and mother liquor II, wherein the mother liquor II is further concentrated and crystallized to obtain a sodium hydroxide byproduct and mother liquor VI, and the mother liquor VI can be selectively recycled to the second stage of pH regulation and impurity removal in the step S3;
s7: subjecting the crude LiOH. H obtained in step S6 to 2 And after dissolving the O, carrying out a carbonization reaction to prepare a lithium carbonate product, and evaporating and concentrating the obtained carbonization mother liquor IV to obtain a mother liquor V and a crude lithium carbonate product.
Preferably, in step S1, the calcination conditions include: the temperature is 900-1200 ℃, and the time is 1-3 h; the ball milling makes the particle size of the material less than 48 μm.
Preferably, in step S1, the nitric acid secondary reverse leaching process includes: sequentially carrying out primary leaching by nitric acid and secondary leaching by nitric acid, wherein a primary leaching solution obtained by the primary leaching by the nitric acid is used for the secondary leaching by the nitric acid, and secondary leaching residues obtained by the secondary leaching by the nitric acid are used as raw materials and returned to the primary leaching by the nitric acid.
Preferably, the amount of the nitric acid in the nitric acid primary leaching is 100-150 wt% of the theoretical amount required by the calculation of the main elements participating in the leaching reaction, and the amount of the nitric acid in the nitric acid secondary leaching is 20-60 wt% of the theoretical amount required by the calculation of the main elements participating in the leaching reaction, wherein the main elements are Li, na, K, al, fe and Ca; the temperatures of the primary leaching of the nitric acid and the secondary leaching of the nitric acid are respectively and independently 80-180 ℃, and the times are respectively and independently 1-6 h. It is understood that the temperatures of the nitric acid primary leaching and the nitric acid secondary leaching are the same or different, and the time of the nitric acid primary leaching and the nitric acid secondary leaching is the same or different.
Preferably, in the step S2, the pressure of the nanofiltration membrane treatment is 2 to 4MPa.
Preferably, the evaporation concentration temperature of the high valence ion solution is 80-100 ℃, the calcination time is 1-3h, and the calcination temperature is 300-600 ℃.
Preferably, in step S3, the substance for adjusting pH is NaOH, liOH, KOH or Na 2 CO 3 。
Preferably, in step S4, the concentrating conditions include: the temperature is 70-100 ℃ and the time is 4-10h. Preferably, in step S4, the crystallization conditions include: the temperature is 0-40 ℃ and the time is 2-5h.
Preferably, in step S6, the concentration temperature of the mixed solution is 60-100 ℃, the time is 3-10h, the crystallization temperature is 0-40 ℃, and the crystallization time is 1-3h.
Preferably, the mother liquor V in the step S7 is returned to the second stage to adjust pH and remove impurities for recycling.
Preferably, in step S7, the conditions for the concentration and crystallization include: the concentration temperature is 60-100 ℃, the time is 2-6h, the crystallization temperature is 0-40 ℃, and the time is 1-4h.
Preferably, in step S7, the carbonization reaction conditions include: the aeration rate of the carbon dioxide is 0.4-2L/min per liter of solution, the carbonization temperature is 35-85 ℃, and the carbonization time is 15-95 min.
The technical scheme of the invention has the following beneficial effects:
compared with the treatment of lithium extraction liquid of lithium ore leachate and salt lake brine by a sulfuric acid method, the method provided by the invention has the advantages that the lithium ore is directly calcined and then leached, and the leachate obtained by leaching is directly separated by a nanofiltration membrane, so that a large amount of Al (NO) can be separated 3 ) 3 Mainly high valence ion solution, evaporating, concentrating and calcining the high valence ion solution to obtain crude alumina byproduct, so as to obtain LiNO 3 The subsequent impurity removal of the monovalent ion solution mainly consumes less impurity removal reagent, and impurity removal slag amount is reduced through specific two-stage pH impurity removal, so that the loss rate of lithium is reduced to the maximum extent. In addition, while the potassium nitrate byproduct is obtained, the impurity elements in the bipolar membrane pre-solution are low, the service life of the bipolar membrane is prolonged, the bipolar membrane separates acid from alkali, the obtained nitric acid and sodium hydroxide can be recycled, and the process cost is reduced. The obtained crude lithium hydroxide is converted into a product to prepare high-purity lithium carbonate. The invention solves the problems of treatment defects of lithium extraction liquid of lithium ore and brine of salt lake by sulfuric acid method and low utilization rate of value elements.
The materials used in the invention are common industrialized products, are easy to purchase and have low price; the whole process flow is short, the slag yield is low, the environment is friendly, the scale is easy to realize, and the industrialization is easy to realize.
Drawings
FIG. 1 is a process flow diagram of one embodiment of the method of the present invention.
Detailed Description
At present, the lithium carbonate is prepared from the major lithiumite by using a sulfuric acid process, lime milk is used for removing impurities, calcium ions are additionally introduced to generate a large amount of calcium sulfate precipitation slag, a large amount of lithium is lost, and the recovery rate of the lithium in the whole process is reduced. In addition, the front-end treatment of lithium extraction from salt lake brine adopts an extraction technology, lithium hydroxide is mainly prepared, an extracting agent is expensive, the extraction process is carried out under a high-acidity condition, equipment corrosion is possibly caused, the environmental protection pressure of an organic solvent is high, and continuous production cannot be realized. Aiming at the advantages and disadvantages of lithium extraction from spodumene ore and lithium extraction from salt lake brine, the invention provides a method for producing a high-purity lithium carbonate product from spodumene ore, wherein nitric acid is used for secondary reverse leaching, the nitric acid is fully utilized to minimize lithium in leaching residues, a nanofiltration membrane is directly adopted to separate the leaching solution into high-valence ionic liquid and monovalent ionic liquid, the monovalent ionic liquid is subjected to multi-stage impurity removal, fewer alkaline compounds are required, and fewer precipitation residues are generated, so that the loss of lithium is reduced.
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The analysis results of the components of the leachate obtained by leaching lithium ore with nitric acid in the examples are shown in table 1.
TABLE 1 analysis results of respective components of leachate obtained by leaching lithium ore with nitric acid
Example 1
As shown in fig. 1, a method for producing high-purity lithium carbonate by spodumene includes the following steps:
step S1: calcining lithium ore at 1000 ℃ for 3h, ball-milling until the particle size is below 41 mu m, and carrying out secondary reverse leaching on the pretreated lithium ore by nitric acid to obtain leaching residue and leaching solution (the composition of which is shown in Table 1);
the secondary reverse leaching process of the nitric acid comprises the following steps: sequentially carrying out primary leaching by nitric acid and secondary leaching by nitric acid, wherein a primary leaching solution obtained by the primary leaching by the nitric acid is used for the secondary leaching by the nitric acid, and secondary leaching residues obtained by the secondary leaching by the nitric acid are used as raw materials and returned to the primary leaching by the nitric acid. The dosage of the nitric acid in the primary nitric acid leaching is calculated according to 120wt% of the theoretical amount required by the calculation of the main elements participating in the leaching reaction, and the dosage of the nitric acid in the secondary nitric acid leaching is calculated according to 40wt% of the theoretical amount required by the calculation of the main elements participating in the leaching reaction, wherein the main elements are Li, na, K, al, fe and Ca; the temperatures of the nitric acid primary leaching and the nitric acid secondary leaching are respectively 150 ℃ and 120 ℃, and the time is respectively 4h and 2h.
Step S2: treating the leachate obtained in the step S1 by a nanofiltration membrane to obtain Al (NO) 3 ) 3 High valence ion solution mainly and LiNO 3 The pressure of the nanofiltration membrane is 3Mpa, and Al (NO) is used 3 ) 3 Evaporating and concentrating the mainly high valence ion solution at the temperature of 100 ℃, and calcining for 1h at the temperature of 400 ℃ to obtain crude alumina;
and step S3: liNO obtained in the step S2 3 Adjusting the pH of the solution to 7 at 50 ℃ for the first time to remove trace Fe, al and other ions, and reacting for 2 hours to obtain a filtrate I and a filter residue I, wherein the pH of the filtrate I is adjusted to 10 at 60 ℃ for the second time to further remove trace Ca, mg and other ions, and reacting for 1 hour to obtain a filtrate II and a filter residue II;
and step S4: and (4) concentrating the filtrate II obtained in the step (S3) at 100 ℃ for 5h, and crystallizing at 0 ℃ for 3h to obtain a potassium nitrate product and mother liquor I.
Step S5: subjecting the mother liquor I to ion exchange and bipolar membrane treatment to obtain HNO 3 Mixing with LiOH, a trace of NaOH and a trace of KOH.
Step S6: carrying out negative pressure concentration on the LiOH obtained in the step S5, a trace amount of NaOH and a trace amount of KOH mixed solution at the temperature of 90 ℃ for 6H, and crystallizing at the temperature of 0 ℃ for 2H to obtain crude LiOH & H 2 O and mother liquor II, the mother liquor II is concentrated under negative pressure at the temperature of 80 ℃ for 6 hours, sodium hydroxide products and mother liquor IV are obtained after crystallization is carried out for 2 hours at the temperature of 10 ℃, and the mother liquor IV can be recycled to the step S3 for secondary impurity removal.
Step S7: will be provided withCrude LiOH. H obtained in step S6 2 Dissolving O, carrying out carbonization reaction at the carbon dioxide aeration rate of 1L/min per liter of solution, the carbonization temperature of 40 ℃ for 40min, and filtering and washing after the reaction is finished to obtain Li 2 CO 3 The product, the obtained carbonization mother liquor IV is evaporated and concentrated under negative pressure at the temperature of 90 ℃ and trace Li is recycled in one step 2 CO 3 And (3) returning the obtained mother liquor V to the second stage for pH adjustment and impurity removal.
Obtained Li 2 CO 3 The purity of (2) was 99.5%, and the yield of lithium was 91%.
Example 2
A process for producing high purity lithium carbonate from spodumene was carried out as described in example 1, except that:
in the step S2, the pressure of the nanofiltration membrane is 2.5Mpa.
In the step S3, the pH is adjusted to 55 ℃ for the first time, and the reaction time is 2h; the temperature of the secondary pH adjustment is 70 ℃, the end point of the pH value is 11, and the reaction time is 1h.
In the step S7, the crude LiOH. H obtained in the step S6 2 And after O is dissolved, carrying out carbon dioxide carbonization reaction, wherein the aeration rate is 0.6L/min per liter of solution, the carbonization temperature is 45 ℃, and the carbonization time is 60min.
Obtained Li 2 CO 3 The purity of (D) was 99.6%, and the lithium yield was 92.6%.
Example 3
A process for producing high purity lithium carbonate from spodumene was carried out as described in example 1, except that:
in the step S2, the pressure of the nanofiltration membrane is 2Mpa.
In the step S3, the pH is adjusted to 60 ℃ for the first time, and the reaction time is 1.5h; the temperature of the second stage of pH adjustment is 75 ℃, and the reaction time is 1.5h.
In the step S7, the crude LiOH. H obtained in the step S6 2 And after O is dissolved, carrying out carbon dioxide carbonization reaction, wherein the aeration rate is 0.7L/min per liter of solution, the carbonization temperature is 50 ℃, and the carbonization time is 50min.
Obtained Li 2 CO 3 The purity of (D) was 99.56%, and the yield was 91.8%.
Example 4
A process for producing high purity lithium carbonate from spodumene was carried out as described in example 1, except that:
in the step S2, the pressure of the nanofiltration membrane is 1Mpa.
The Li of the present example 2 CO 3 The purity of (D) was 99.58% and the yield was 82%.
Further, as can be seen from the comparison between example 1 and example 4, when the pressure of the nanofiltration membrane is low, the lithium content in the monovalent ion liquid is low, and the recovery rate of lithium is low.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for producing high-purity lithium carbonate from spodumene is characterized by comprising the following steps of:
s1: calcining the spodumene ore, carrying out ball milling, and carrying out secondary reverse leaching by nitric acid to obtain leaching slag and leaching liquid;
s2: treating the leachate obtained in the step S1 by a nanofiltration membrane to obtain Al (NO) 3 ) 3 High valence ion solution mainly and LiNO 3 A main monovalent ion solution, wherein the high valence ion solution is evaporated and concentrated and then calcined to obtain a crude alumina byproduct;
s3: carrying out primary pH adjustment and impurity removal on the monovalent ion solution obtained in the step S2 to obtain a filtrate I and a filter residue I, and carrying out secondary pH adjustment and impurity removal on the filtrate I to obtain a filtrate II and a filter residue II;
s4: concentrating and crystallizing the filtrate II obtained in the step S3 to obtain a potassium nitrate product and a mother solution I;
s5: carrying out ion exchange and bipolar membrane treatment on the mother liquor I obtained in the step S4 to obtain HNO 3 And a mixed solution containing LiOH, naOH and KOH, HNO 3 Optional Return to step S1Recycling;
s6: concentrating and crystallizing the mixed solution obtained in the step S5 to obtain crude LiOH & H 2 O and mother liquor II, wherein the mother liquor II is further concentrated and crystallized to obtain a sodium hydroxide byproduct and mother liquor VI, and the mother liquor VI can be optionally recycled to the step S3 for secondary pH regulation and impurity removal;
s7: subjecting the crude LiOH. H obtained in step S6 to 2 And after dissolving the O, carrying out a carbonization reaction to prepare a lithium carbonate product, and evaporating and concentrating the obtained carbonization mother liquor IV to obtain a mother liquor V and a crude lithium carbonate product.
2. The method according to claim 1, wherein in step S1, the calcining conditions comprise: the temperature is 900-1200 ℃, and the time is 1-3 h; the ball milling makes the particle size of the material less than 48 μm.
3. The method according to claim 1, wherein in step S1, the nitric acid secondary reverse leaching process comprises: sequentially carrying out primary leaching by nitric acid and secondary leaching by nitric acid, wherein a primary leaching solution obtained by the primary leaching by the nitric acid is used for the secondary leaching by the nitric acid, and secondary leaching residues obtained by the secondary leaching by the nitric acid are used as raw materials and returned to the primary leaching by the nitric acid.
4. The method according to claim 1, wherein the amount of nitric acid used in the primary nitric acid leach is 100-150 wt% of the theoretical amount required by the calculation of the main elements involved in the leaching reaction, and the amount of nitric acid used in the secondary nitric acid leach is 20-60 wt% of the theoretical amount required by the calculation of the main elements involved in the leaching reaction, wherein the main elements are Li, na, K, al, fe and Ca; the temperatures of the primary nitric acid leaching and the secondary nitric acid leaching are respectively and independently 80-180 ℃, and the time is respectively and independently 1-6 h.
5. The method according to claim 1, wherein in step S2, the pressure of the nanofiltration membrane treatment is 2-4 MPa; the evaporation concentration temperature of the high valence ion solution is 80-100 ℃, the calcination time is 1-3h, and the calcination temperature is 300-600 ℃.
6. The method according to claim 1, wherein in step S3, the conditions for adjusting pH and removing impurities comprise: the temperature is 40-90 ℃, the pH value end point is 6-8, and the reaction time is 1-2 h; the conditions for secondary pH regulation and impurity removal comprise: the temperature is 60-90 ℃, the pH value end point is 10-13, and the reaction time is 1-2 h.
7. The method according to claim 1, wherein, in step S4, the concentration conditions comprise: the temperature is 70-100 ℃, and the time is 4-10h; the crystallization conditions include: the temperature is 0-40 ℃ and the time is 2-5h.
8. The method according to claim 1, wherein in step S6, the concentration temperature of the mixed solution is 60-100 ℃ and the time is 3-10h, and the crystallization temperature is 0-40 ℃ and the time is 1-3h.
9. The method according to claim 1, wherein the mother liquor V is returned to step S3 for secondary pH adjustment and impurity removal for recycling.
10. The method according to claim 1, wherein in step S7, the conditions for the concentration and crystallization comprise: the concentration temperature is 60-100 ℃, the time is 2-6h, the crystallization temperature is 0-40 ℃, and the time is 1-4h; the carbonization reaction conditions include: the aeration rate of the carbon dioxide is 0.4-2L/min per liter of solution, the carbonization temperature is 35-85 ℃, and the carbonization time is 15-95 min.
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| CN115893455A (en) * | 2022-11-16 | 2023-04-04 | 四川顺应锂材料科技有限公司 | Method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid |
| CN116495712A (en) * | 2023-05-08 | 2023-07-28 | 四川顺应锂材料科技有限公司 | Method for producing lithium phosphate from phosphorus lithium aluminum ore |
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| CN114318008A (en) * | 2021-12-27 | 2022-04-12 | 四川顺应锂材料科技有限公司 | Method for extracting lithium by secondary reverse leaching of spodumene with nitric acid |
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| CN115583662A (en) * | 2022-11-15 | 2023-01-10 | 四川顺应锂材料科技有限公司 | Method for producing high-purity lithium carbonate by membrane treatment of sulfuric acid leaching solution of spodumene |
| CN115893455A (en) * | 2022-11-16 | 2023-04-04 | 四川顺应锂材料科技有限公司 | Method for producing battery-grade lithium carbonate by carrying out pressurized secondary reverse leaching on spodumene sulfuric acid |
| CN116495712A (en) * | 2023-05-08 | 2023-07-28 | 四川顺应锂材料科技有限公司 | Method for producing lithium phosphate from phosphorus lithium aluminum ore |
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