WO2023059287A1 - Production method of lithium phosphate from lithium enolate (chelate) structure - Google Patents

Production method of lithium phosphate from lithium enolate (chelate) structure Download PDF

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Publication number
WO2023059287A1
WO2023059287A1 PCT/TR2022/050999 TR2022050999W WO2023059287A1 WO 2023059287 A1 WO2023059287 A1 WO 2023059287A1 TR 2022050999 W TR2022050999 W TR 2022050999W WO 2023059287 A1 WO2023059287 A1 WO 2023059287A1
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Prior art keywords
lithium
aqueous phase
lithium phosphate
salt
enolate
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PCT/TR2022/050999
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French (fr)
Inventor
Emin Ender CELEBI
Mehmet Salim ONCEL
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Gebze Teknik Universitesi
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Publication of WO2023059287A1 publication Critical patent/WO2023059287A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/306—Ketones or aldehydes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the invention relates to the method of obtaining high-purity lithium relatively faster at room temperature without applying thermal process from lithium containing wastewater and brines (salt lakes), which is one of the lithium production resources.
  • Lithium is found in three different resources on Earth: brines, clays, and minerals.
  • thermal treatment applications such as evaporation are quite common in the production of lithium salts.
  • lithium carbonate LizCOa
  • differential crystallization is performed by adding sodium carbonate to the solution containing lithium ions at 80-100°C
  • LizCCL salts are produced by precipitating the same at the bottom.
  • the aqueous lithium reserves in Turkey have been currently reported as Eski ⁇ ehir Kirka Plant waste pond water (-150 mg Li/L) and Lake Salt Yav ⁇ an salt basin ( ⁇ 325 mg Li/L) operated under the responsibility of Eti Maden Operations.
  • the total volume of the wastewater in the Kirka Plant waste ponds is approximately 20 million m 3 today. In this case, it can be said that there are approximately 3 kilotons of Li reserves in Kirka waste ponds.
  • the average water volume of Lake Salt is approximately 600 million m 3 , and it is thought that approximately 195 kilotons of lithium reserve are available based on the data in the literature. These values are serious reserve amounts for lithium, which has very strategic importance at present conditions.
  • Lithium phosphate salts are the final raw material for the production of lithium ferro phosphate (LFP) cathode materials. Due to the regulatory pressure on fire safety in electric vehicles with LFP batteries, which are accepted as the safest form of lithium-ion batteries (LIB), a major expansion is expected in their Europe and North America markets. Currently, LFP as a type of LIB is very common in electric vehicles and heavy haulage applications in China. Due to the aforementioned situations, the interest of Tesla in LFP batteries as a rapidly growing electric vehicle manufacturer has been increasing recently. Similarly, the company named Lithium Australia NL has put the production of lithium phosphate from liquid and solid lithium resources on its agenda seriously.
  • LFP lithium ferro phosphate
  • US8778289B2 in the state of the art relates to a method for extracting lithium from a lithium-containing solution. It describes a method for economically removing lithium from a lithium-containing solution by adding a phosphorus feedstock to the solution for conventional precipitation of lithium phosphate from dissolved lithium.
  • a method for removing lithium from brine is disclosed.
  • Lithium is extracted from the brine with the ferric salt and extraction agents that consist of tributyl phosphate, an amide compound and a solvent.
  • This method can be summed in three steps.
  • the auxiliary extracting agent solution is formulated. This solution is obtained by mixing tributyl phosphate and the solvent.
  • an amide compound, tributyl phosphate, and solvent are added to the organic phase, which was prepared first, in order to obtain a second organic phase.
  • an aqueous phase solution comprising lithium is obtained after the second organic phase is mixed with brine and the organic-aqueous phase is separated.
  • lithium phosphate production method was developed from lithium enolate (chelate) structure.
  • the object of the invention is to perform the production of high-purity lithium phosphate relatively fast, from a lithium enolate (chelate) structure without thermal treatment.
  • Figure 1 X-Ray Diffraction (a) and 20 thousand times magnification SEM image (b) of the salt crystals obtained with the invention
  • the production method of lithium phosphate from the lithium enolate (chelate) structure of the invention comprises the steps of;
  • Lithium phosphate which has a low solubility product constant, reaches saturation, crystallizes and precipitates to the bottom of the aqueous phase by stripping. Then, separation of the aqueous phase containing lithium phosphate crystals from the organic phase with special filter equipment,
  • lithium is simultaneously stripped from the organic phase with orthophosphoric acid (H3PO4) at room temperature without thermal treatment and precipitated as lithium orthophosphate salt in the aqueous phase under suitable conditions (pH, common ion effect).
  • H3PO4 orthophosphoric acid
  • HC1 acid HBr, Hl, HF, etc.
  • the orthophosphoric acid stripping process formulation is included in equation 1.
  • the processes including the following steps are provided for the precipitation and production of lithium extracted from aqueous phase lithium sources to the enolate anion in the organic system as lithium orthophosphate crystals together with back-extraction (stripping) to the aqueous phase with orthophosphoric acid;
  • the wastewater sample with a lithium content of 150 mg Li/L was extracted with the organic system containing Betadiketone, neutral ligand (phosphine oxide) and kerosene in batch system, and lithium ions were bonded to the enolate anion released as a result of keto-enol tautomerization and the extraction of lithium in the wastewater to the organic system was achieved with an efficiency of 94.2%.
  • the organic system containing lithium enolate and ortho -phosphoric acid was subjected to batch liquid-liquid extraction with the help of a pedal mixer and the lithium bounded to the enolate anion was reextracted (back-extraction or stripping) into the phosphoric acid aqueous phase medium.
  • Lithium phosphate which has gained a low solubility product constant with stripping crystallized and started to settle at the bottom of the aqueous phase.
  • the aqueous phase containing lithium phosphate crystals was separated from the organic phase with a special filter equipment.
  • the separated aqueous phase solution was subjected to centrifuge solidliquid separation (minimum 5000 rpm, 3-10 min).
  • the lithium phosphate crystals with relatively low humidity obtained after centrifugation were rinsed with distilled water.
  • products of desired quality were obtained by applying a drying process at 70-105°C, for 6-24 hours to the rinsed lithium phosphate salt crystals.
  • the optimum refined stripping solution pH value was 7.44
  • the optimum organic/aqueous phase volume ratio (O/A) was 8.2
  • the optimum orthophosphoric acid stripping solution concentration was determined at 1.0 M values, under the condition that the crystallized lithium phosphate salt fractions were kept at the maximum level.
  • the lithium stripping efficiency was provided as 94.2%.
  • lithium orthophosphate salt in water is at the lowest levels (maximum solubility 0.39 g Li/L) at neutral pH levels. Therefore, under the optimum conditions specified in the study, 77 percent mass of the lithium was precipitated as lithium orthophosphate salt crystals with the stripping process.
  • the lithium phosphate purity of the salt which was dried at 105°C for 24 hours, was determined as 92.2% with the acid digestion followed by ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer) measurements.
  • the chemical composition of the salt is given in Table 1.
  • the refined organic system obtained as a result of lithium back-extraction can be regenerated with sodium hydroxide and subsequently lithium extraction can be performed from the aqueous phase lithium sources with the regenerated organic phase. Additionally, the lithium mass of 23% which has not crystallized and remains in the stripping solution can be recycled back to the aqueous phase lithium source and included in the lithium phosphate production system.
  • the production of lithium carbonate is a costly and difficult to control process that requires thermal treatment.
  • the wastewater of Kirka Boraks Plant affiliated with ETI Maden operations in Turkey and the aqueous phase resources of Lake Tuz are the targets that can produce lithium phosphate directly.
  • lithium-containing clays in the Bigadif and Kirka Sankaya boron minerals wall rocks are also secondary targets.
  • the invention may be applied to aqueous phase lithium reserves with commercial potential and to all lithium reserves (clays and salt crystals containing Li) that can be taken into the aqueous phase.
  • lithium phosphate salt can be obtained with the help of this invention.
  • Multivalent cations must be removed from the system with an effective pre-treatment in order to apply the invention to the areas that have the mentioned characteristics.
  • the presence of multivalent cations is at the minimum level particularly Kirka waste ponds and borax production process dilute solutions of Eti Maden operations. In this respect, the invention could be applied effectively in the wastewater of the Kirka Plant.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the method of obtaining high-purity lithium relatively faster at room temperature without applying thermal process from lithium containing wastewater and brines (salt lakes), which is one of the lithium production resources. Obtaining lithium salt in solid form is much less costly and is performed in a shorter period of time compared to the salt extraction processes to be applied after stripping with other acid agents (HBr, Hl, HF, etc.) such as HCl acid.

Description

PRODUCTION METHOD OF LITHIUM PHOSPHATE FROM LITHIUM ENOLATE (CHELATE) STRUCTURE
Technical Field
The invention relates to the method of obtaining high-purity lithium relatively faster at room temperature without applying thermal process from lithium containing wastewater and brines (salt lakes), which is one of the lithium production resources.
Prior Art
Lithium is found in three different resources on Earth: brines, clays, and minerals. Today, it can be said that lithium mining is shifting towards liquid phase resources (brines, geothermal waters and wastewaters) with the emerging strict environmental policies, high production costs of clays and reduction of lithium mineral resources. Therefore, lithium production from aqueous phase sources is preferred because it is found at higher concentrations, can be easily treated, and the cost factors, compared to clays and mineral sources. Commercially, thermal treatment applications such as evaporation are quite common in the production of lithium salts. Particularly in the production of lithium carbonate (LizCOa ), differential crystallization is performed by adding sodium carbonate to the solution containing lithium ions at 80-100°C, and LizCCL salts are produced by precipitating the same at the bottom.
On the other hand, since the solubility of lithium hydroxide (LiOH) and lithium chloride (LiCl) salts in binary systems with water is quite high, the concentration of the said salts should be brought to a certain saturation by evaporation. The solubility of lithium carbonate salt in water decreases with increasing temperature. The solubility of the LiCl salt decreases significantly in the presence of other salts (NaCl, KC1, etc.) that can form a common ion effect in the water. Therefore, a thermal process is needed in the production of both salts.
The aqueous lithium reserves in Turkey have been currently reported as Eski§ehir Kirka Plant waste pond water (-150 mg Li/L) and Lake Salt Yav§an salt basin (~325 mg Li/L) operated under the responsibility of Eti Maden Operations. The total volume of the wastewater in the Kirka Plant waste ponds is approximately 20 million m3 today. In this case, it can be said that there are approximately 3 kilotons of Li reserves in Kirka waste ponds. On the other hand, the average water volume of Lake Salt is approximately 600 million m3, and it is thought that approximately 195 kilotons of lithium reserve are available based on the data in the literature. These values are serious reserve amounts for lithium, which has very strategic importance at present conditions.
Lithium phosphate salts are the final raw material for the production of lithium ferro phosphate (LFP) cathode materials. Due to the regulatory pressure on fire safety in electric vehicles with LFP batteries, which are accepted as the safest form of lithium-ion batteries (LIB), a major expansion is expected in their Europe and North America markets. Currently, LFP as a type of LIB is very common in electric vehicles and heavy haulage applications in China. Due to the aforementioned situations, the interest of Tesla in LFP batteries as a rapidly growing electric vehicle manufacturer has been increasing recently. Similarly, the company named Lithium Australia NL has put the production of lithium phosphate from liquid and solid lithium resources on its agenda seriously.
Globally, lithium production is currently made from brines in the form of lithium carbonate salt. The most important brine fields commercially operated are known as Salar de UyunL Bolivia (250 mg Li/L), Salar de Atacama-Chile (1,250 mg Li/L), Salton Sea- California-USA (220 mg Li/L), Silver Peak-Nevada-USA (300 mg Li/L), Searles Lake-Calif ornia-US A (83 mg Li/L), Great Salt Lake-Utah -USA (60 mg Li/L) and the lowest point of the earth, Dead Sea-Israel/Jordan (20 mg Li/L). One of the most important problems in lithium production in these areas is the presence of multivalent cations such as Ca2+ and Mg2+ in very high concentrations.
The patent document numbered WO2021053514A1 in the state of the art mentions a method of selectively recovering lithium from brine using aqueous redox reactions involving lithium extraction into ferric phosphate solid. Brine is heated to separate solids, and the brine is exposed to ferric phosphate for lithium extraction. Then, a solid/liquid separation is performed to separate lithium from the brine. Finally, the final product is obtained by purification of lithium chloride.
The patent document numbered US8778289B2 in the state of the art relates to a method for extracting lithium from a lithium-containing solution. It describes a method for economically removing lithium from a lithium-containing solution by adding a phosphorus feedstock to the solution for conventional precipitation of lithium phosphate from dissolved lithium.
In the patent document numbered CN112063857A in the state of the art, a method for removing lithium from brine is disclosed. Lithium is extracted from the brine with the ferric salt and extraction agents that consist of tributyl phosphate, an amide compound and a solvent. This method can be summed in three steps. First, the auxiliary extracting agent solution is formulated. This solution is obtained by mixing tributyl phosphate and the solvent. Then, an amide compound, tributyl phosphate, and solvent are added to the organic phase, which was prepared first, in order to obtain a second organic phase. Lastly, an aqueous phase solution comprising lithium is obtained after the second organic phase is mixed with brine and the organic-aqueous phase is separated.
When the present methods in the art were examined, a need emerged for the production of high purity and strategically important lithium salt with a low cost and fast applicable method without thermal treatment. Due to this requirement, the lithium phosphate production method was developed from lithium enolate (chelate) structure.
The Object of the Invention
The object of the invention is to perform the production of high-purity lithium phosphate relatively fast, from a lithium enolate (chelate) structure without thermal treatment.
Detailed Description of the Invention
The method of lithium phosphate production from the lithium enolate (chelate) structure realized to achieve the purposes of this invention is shown in the attached figure.
In this figure,
Figure 1: X-Ray Diffraction (a) and 20 thousand times magnification SEM image (b) of the salt crystals obtained with the invention The production method of lithium phosphate from the lithium enolate (chelate) structure of the invention comprises the steps of;
Agitation of wastewater sample containing lithium with the organic system containing beta-diketone, neutral ligand (phosphine oxide) and kerosene in batch system.
Subjecting the organic system containing lithium enolate and ortho -phosphoric acid to a batch liquid-liquid extraction process with the help of a pedal mixer,
Extraction of lithium bound to the enolate anion back into the aqueous phase medium consisting of ortho-phosphoric acid (stripping),
Lithium phosphate, which has a low solubility product constant, reaches saturation, crystallizes and precipitates to the bottom of the aqueous phase by stripping. Then, separation of the aqueous phase containing lithium phosphate crystals from the organic phase with special filter equipment,
Subjecting the separated aqueous phase solution to the centrifugal solid-liquid separation process at a minimum speed of 5000 RPM for 3-10 minutes, Rinsing the obtained lithium phosphate crystals with distilled water,
Obtaining the lithium phosphate salt crystals that have the desired quality by drying the rinsed lithium phosphate salt crystals at 70-105°C for 6-24 hours.
With the subject method of the invention, lithium is simultaneously stripped from the organic phase with orthophosphoric acid (H3PO4) at room temperature without thermal treatment and precipitated as lithium orthophosphate salt in the aqueous phase under suitable conditions (pH, common ion effect). Thereby, lithium recovered as organolithium chelate by solvent extraction from aqueous phase lithium resources (brines and wastewater) is obtained in solid form after stripping with H3PO4 acid; it is much less costly and takes less time than the salt extraction processes to be applied after stripping with other acid agents such as HC1 acid (HBr, Hl, HF, etc.). The invention significantly reduces the lithium production costs from aqueous phase resources and provides faster and higher purity lithium production.
The orthophosphoric acid stripping process formulation is included in equation 1.
3(RLi)org + [3H+ + PO4’3]aq 3(RH)org + [3Li+ + PO4’3]aq (1)
Within the scope of the present invention, the processes including the following steps are provided for the precipitation and production of lithium extracted from aqueous phase lithium sources to the enolate anion in the organic system as lithium orthophosphate crystals together with back-extraction (stripping) to the aqueous phase with orthophosphoric acid;
Back-extraction of lithium extracted into the organic phase as lithium enolate to the aqueous phase with orthophosphoric acid, and simultaneously formation of lithium phosphate crystals in the aqueous phase,
Separation of the refined organic phase with the stripping solution containing lithium phosphate crystals,
Separation of lithium phosphate crystals from the separated stripping solution by centrifugation,
Rinsing the relatively low moisture lithium phosphate crystals separated from the stripping solution,
Drying of the rinsed lithium phosphate crystals.
In the assays carried out to obtain the lithium enolate organic system, the wastewater sample with a lithium content of 150 mg Li/L was extracted with the organic system containing Betadiketone, neutral ligand (phosphine oxide) and kerosene in batch system, and lithium ions were bonded to the enolate anion released as a result of keto-enol tautomerization and the extraction of lithium in the wastewater to the organic system was achieved with an efficiency of 94.2%. Then, in the assays carried out within the scope of the invention, the organic system containing lithium enolate and ortho -phosphoric acid was subjected to batch liquid-liquid extraction with the help of a pedal mixer and the lithium bounded to the enolate anion was reextracted (back-extraction or stripping) into the phosphoric acid aqueous phase medium. Lithium phosphate which has gained a low solubility product constant with stripping crystallized and started to settle at the bottom of the aqueous phase. Then, the aqueous phase containing lithium phosphate crystals was separated from the organic phase with a special filter equipment. The separated aqueous phase solution was subjected to centrifuge solidliquid separation (minimum 5000 rpm, 3-10 min). The lithium phosphate crystals with relatively low humidity obtained after centrifugation were rinsed with distilled water. Finally, products of desired quality (different relative water content) were obtained by applying a drying process at 70-105°C, for 6-24 hours to the rinsed lithium phosphate salt crystals.
As a result of a set of assays carried out with the surface reaction method D-optimal plan, the optimum refined stripping solution pH value was 7.44, the optimum organic/aqueous phase volume ratio (O/A) was 8.2 and the optimum orthophosphoric acid stripping solution concentration was determined at 1.0 M values, under the condition that the crystallized lithium phosphate salt fractions were kept at the maximum level. Under the optimum conditions, the lithium stripping efficiency was provided as 94.2%.
The solubility of lithium orthophosphate salt in water is at the lowest levels (maximum solubility 0.39 g Li/L) at neutral pH levels. Therefore, under the optimum conditions specified in the study, 77 percent mass of the lithium was precipitated as lithium orthophosphate salt crystals with the stripping process. The lithium phosphate purity of the salt which was dried at 105°C for 24 hours, was determined as 92.2% with the acid digestion followed by ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer) measurements. The chemical composition of the salt is given in Table 1.
Table 1. Composition of the obtained salt
Figure imgf000008_0001
As a result of the chemical analysis of the salt, it was determined that Mg+2, Ca+2, Na+ and K+ ions interfered the crystal structure of the salt as well, and somewhat reduced the purity of the lithium phosphate salt. In order to prevent this situation, it is recommended to remove the multivalent cations (such as Mg+2, Ca+2, Al+2) in the raw wastewater content with the most appropriate process before the liquid-liquid extraction process is carried out within the scope of obtaining the organic system containing lithium enolate. Thereby, the purity of the lithium phosphate salt crystals to be obtained with the method of the invention will reach the maximum level. On the other hand, the result of the mineralogical analysis of the obtained salt is included in Figure 1 (b) as an X-Ray Pattern and 20 thousand times magnification scanning electron microscope (SEM) image.
Another proof of the high-purity lithium orthophosphate salt obtained with the invention is the result of the mineralogical analysis. When the mineralogical analysis is examined over Figure 1 (b), only lithium orthophosphate salt peaks are seen as the major and minor. In this case, it is understood that the impurities in the obtained lithium orthophosphate salt could not have been detected and therefore, they were at very low levels.
It is thought that it will be possible to apply the invention which has emerged with batch reactors in the laboratory with cross -flow continuous reactors on an industrial scale as well.
The refined organic system obtained as a result of lithium back-extraction can be regenerated with sodium hydroxide and subsequently lithium extraction can be performed from the aqueous phase lithium sources with the regenerated organic phase. Additionally, the lithium mass of 23% which has not crystallized and remains in the stripping solution can be recycled back to the aqueous phase lithium source and included in the lithium phosphate production system.
In addition, the production of lithium carbonate is a costly and difficult to control process that requires thermal treatment. With the method as the subject of the invention, the wastewater of Kirka Boraks Plant affiliated with ETI Maden operations in Turkey and the aqueous phase resources of Lake Tuz are the targets that can produce lithium phosphate directly. In addition, lithium-containing clays in the Bigadif and Kirka Sankaya boron minerals wall rocks are also secondary targets.
The invention may be applied to aqueous phase lithium reserves with commercial potential and to all lithium reserves (clays and salt crystals containing Li) that can be taken into the aqueous phase.
In addition, significant lithium (1500- 2500 mg/ kg) is found in the boron wall rock clays of the Kirka Sankaya region belonging to Eti Maden operations. Following the aqueous phase extraction of lithium from these solid sources with optimum hydrometallurgical methods, lithium phosphate salt can be obtained with the help of this invention.
Multivalent cations must be removed from the system with an effective pre-treatment in order to apply the invention to the areas that have the mentioned characteristics. The presence of multivalent cations is at the minimum level particularly Kirka waste ponds and borax production process dilute solutions of Eti Maden operations. In this respect, the invention could be applied effectively in the wastewater of the Kirka Plant.

Claims

CLAIMS A method of producing lithium phosphate from the lithium enolate (chelate) structure, characterized in that it comprises the steps of
Batch extraction of lithium from wastewater sample with the organic system containing beta-diketone, neutral ligand (phosphine oxide) and kerosene,
Subjecting the organic system containing lithium enolate and ortho-phosphoric acid to a batch liquid-liquid extraction process by means of a pedal mixer,
Extraction of lithium bound to the enolate anion back into the aqueous phase medium consisting of phosphoric acid,
Crystallization and subsequently precipitation of lithium phosphate, which has a low solubility product constant, to the bottom of the aqueous phase by stripping. Then, separation of the aqueous phase containing lithium phosphate crystals from the organic phase with special filter equipment,
Subjecting the separated aqueous phase solution to the centrifugal solid-liquid separation process at a minimum speed of 5000 RPM for 3-10 minutes,
Rinsing the obtained lithium phosphate crystals with distilled water, Obtaining the lithium phosphate salt crystals by drying the rinsed lithium phosphate salt crystals at 70-105°C for 6-24 hours.
9
PCT/TR2022/050999 2021-10-04 2022-09-16 Production method of lithium phosphate from lithium enolate (chelate) structure WO2023059287A1 (en)

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TR2021/015422A TR2021015422A2 (en) 2021-10-04 2021-10-04 Lithium Phosphate Production Method from Lithium Enolate (Chelate) Structure
TR2021/015422 2021-10-04

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180170763A1 (en) * 2016-12-20 2018-06-21 Sungeel Hitech Co., Ltd. Method for preparing solid lithium salt from lithium solution
CN112919440A (en) * 2021-01-21 2021-06-08 南昌航空大学 Method for extracting lithium from retired lithium battery
KR20210080088A (en) * 2019-12-20 2021-06-30 주식회사 포스코 Lithium phosphates and method of preparing thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180170763A1 (en) * 2016-12-20 2018-06-21 Sungeel Hitech Co., Ltd. Method for preparing solid lithium salt from lithium solution
KR20210080088A (en) * 2019-12-20 2021-06-30 주식회사 포스코 Lithium phosphates and method of preparing thereof
CN112919440A (en) * 2021-01-21 2021-06-08 南昌航空大学 Method for extracting lithium from retired lithium battery

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