CA3054748C - Method for producing lithium hydroxide from lithium-containing ore - Google Patents
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
The invention relates to a method for producing lithium hydroxide, for use in batteries and/or accumulators, from lithium-containing ore, mineral and/or earths.
The aim of the invention is to provide a method by which highly pure lithium hydroxide may be produced using a chlor-alkali electrolysis. In a calcining and leaching step, a lithium chloride solution is produced, the lithium-containing ores, minerals and/or earths first being roasted, one or more metal chlorides and/or a mixture of metal chlorides being used, and then leached out, water being used, then a highly pure lithium chloride solution being produced in a subsequent purification step, the solution being purified by removing cations, such as sodium, potassium, calcium, magnesium, and/or iron, and then lithium hydroxide being produced in a subsequent electrolysis step, the highly pure lithium chloride solution being subjected to a membrane electrolysis process, which produces chlorine gas and hydrogen as byproducts.
The aim of the invention is to provide a method by which highly pure lithium hydroxide may be produced using a chlor-alkali electrolysis. In a calcining and leaching step, a lithium chloride solution is produced, the lithium-containing ores, minerals and/or earths first being roasted, one or more metal chlorides and/or a mixture of metal chlorides being used, and then leached out, water being used, then a highly pure lithium chloride solution being produced in a subsequent purification step, the solution being purified by removing cations, such as sodium, potassium, calcium, magnesium, and/or iron, and then lithium hydroxide being produced in a subsequent electrolysis step, the highly pure lithium chloride solution being subjected to a membrane electrolysis process, which produces chlorine gas and hydrogen as byproducts.
Description
Method for Producing Lithium Hydroxide from Lithium-Containing Ore The invention relates to a method for producing lithium hydroxide, in particular highly pure lithium hydroxide, for use in batteries and/or accumulators, from lithium-containing ore and/or mineral and/or from lithium-containing earths.
For some years, a worldwide increase in demand for the light metal lithium has already been observed. Lithium, for example in the form of lithium hydroxide and lithium carbonate, is mainly used for battery applications, in particular for rechargeable batteries and/or accumulators, so-called lithium-ion batteries, due to its electrochemical properties. These batteries are used in particular in portable electrical devices, such as mobile phones, laptops or the like. Also, in the automotive industry, the lithium-ion battery in electric and hybrid vehicles is becoming increasingly important as an alternative or add-on to the internal combustion engine.
In the future, therefore, a further increase in the demand for lithium hydroxide and highly pure lithium carbonate can be expected.
The extraction of lithium currently takes place predominantly from brines or sols, which are obtained, for example, from salt lakes, by means of an absorption, evaporation, precipitation and/or ion exchange method. However, these sources will not be sufficient for the future demand for lithium. In the article by MESHRAM
et al., Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation, in: Hydrometallurgy 150 (October 2014) 192-208, various natural sources of lithium and methods for its extraction are disclosed. Accordingly, the lithium extraction from ores and minerals, such as pegmatite, spodumene and petalite or clays, such as hectorite, is more expensive than the extraction from brines or sols, but can also be achieved by various methods, such as the sulfate process or alkaline digesting. Usually, the extraction of lithium hydroxide from lithium-containing ores is performed by addition of sulfate salts or sulfuric acid and through the production of lithium carbonate as an intermediate product. The lithium-containing ores are first roasted or calcined, resulting in the leachable lithium mineral spodumene. The 8-spodumene is then leached with sulfuric acid to obtain an aqueous lithium sulfate solution. By adding lime milk and sodium carbonate, =
magnesium, iron and calcium are then gradually removed from the solution. By adding more sodium carbonate to the solution, up to 98% of the lithium contained in the solution can be precipitated as lithium carbonate. In a further step, the resulting lithium carbonate is converted into lithium hydroxide.
Recent developments are aimed at the direct production of lithium hydroxide by the chlor-alkali process without the prior production of lithium carbonate. For example, US 2011/0044882 discloses a process for the preparation of lithium hydroxide from a lithium chloride solution. A solution containing lithium, which can be obtained from sols or ores, is first concentrated and then subjected to various purification steps, such as a pH adjustment for the precipitation of divalent or trivalent ions or an ion exchange to reduce the total concentration of calcium and magnesium.
The concentrated and purified lithium chloride solution is subjected to electrolysis, wherein a semipermeable membrane is permeable to lithium ions, so that a lithium hydroxide solution with chlorine and hydrogen as by-products is obtained.
Chlorine gas is obtained at the anode of the electrolyzer and lithium hydroxide and hydrogen at the cathode. The total amount of calcium and magnesium in the high purity lithium hydroxide solution is less than 150 ppb (parts per billion).
In order to produce the lithium chloride solution, AU 2013 20 18 33 B2 and the parallel application US 2015/152523 propose extracting the lithium contained in the ore by leaching f3-spodumene with hydrochloric acid. In a subsequent purification step, the resulting solution is purified and concentrated to be subsequently supplied to the electrolysis. The lithium extraction rate for the resulting lithium chloride solution according to this production route is less than 84%, according to the article by NOGUEI RA et al., Comparison of Processes for Lithium Recovery from Lepidolite by H2SO4 Digestion or HCI Leaching, Proc. Inter. Con. Min. Mater. and Metal. Eng.
(2014). Further, in the article by YAN et al., Extraction of lithium from lepidolite using chlorination roasting ¨ water leaching process, Trans. Nonferrous Met. Soc.
China 22 (2012), 1753, an alternative method for producing a lithium chloride solution is known. According to the described method, lepidolite is initially crushed and mixed with a mixture of sodium chloride and calcium chloride for chlorination. The resulting lithium chloride solution contains 92% of the lithium portion of the ore.
For some years, a worldwide increase in demand for the light metal lithium has already been observed. Lithium, for example in the form of lithium hydroxide and lithium carbonate, is mainly used for battery applications, in particular for rechargeable batteries and/or accumulators, so-called lithium-ion batteries, due to its electrochemical properties. These batteries are used in particular in portable electrical devices, such as mobile phones, laptops or the like. Also, in the automotive industry, the lithium-ion battery in electric and hybrid vehicles is becoming increasingly important as an alternative or add-on to the internal combustion engine.
In the future, therefore, a further increase in the demand for lithium hydroxide and highly pure lithium carbonate can be expected.
The extraction of lithium currently takes place predominantly from brines or sols, which are obtained, for example, from salt lakes, by means of an absorption, evaporation, precipitation and/or ion exchange method. However, these sources will not be sufficient for the future demand for lithium. In the article by MESHRAM
et al., Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation, in: Hydrometallurgy 150 (October 2014) 192-208, various natural sources of lithium and methods for its extraction are disclosed. Accordingly, the lithium extraction from ores and minerals, such as pegmatite, spodumene and petalite or clays, such as hectorite, is more expensive than the extraction from brines or sols, but can also be achieved by various methods, such as the sulfate process or alkaline digesting. Usually, the extraction of lithium hydroxide from lithium-containing ores is performed by addition of sulfate salts or sulfuric acid and through the production of lithium carbonate as an intermediate product. The lithium-containing ores are first roasted or calcined, resulting in the leachable lithium mineral spodumene. The 8-spodumene is then leached with sulfuric acid to obtain an aqueous lithium sulfate solution. By adding lime milk and sodium carbonate, =
magnesium, iron and calcium are then gradually removed from the solution. By adding more sodium carbonate to the solution, up to 98% of the lithium contained in the solution can be precipitated as lithium carbonate. In a further step, the resulting lithium carbonate is converted into lithium hydroxide.
Recent developments are aimed at the direct production of lithium hydroxide by the chlor-alkali process without the prior production of lithium carbonate. For example, US 2011/0044882 discloses a process for the preparation of lithium hydroxide from a lithium chloride solution. A solution containing lithium, which can be obtained from sols or ores, is first concentrated and then subjected to various purification steps, such as a pH adjustment for the precipitation of divalent or trivalent ions or an ion exchange to reduce the total concentration of calcium and magnesium.
The concentrated and purified lithium chloride solution is subjected to electrolysis, wherein a semipermeable membrane is permeable to lithium ions, so that a lithium hydroxide solution with chlorine and hydrogen as by-products is obtained.
Chlorine gas is obtained at the anode of the electrolyzer and lithium hydroxide and hydrogen at the cathode. The total amount of calcium and magnesium in the high purity lithium hydroxide solution is less than 150 ppb (parts per billion).
In order to produce the lithium chloride solution, AU 2013 20 18 33 B2 and the parallel application US 2015/152523 propose extracting the lithium contained in the ore by leaching f3-spodumene with hydrochloric acid. In a subsequent purification step, the resulting solution is purified and concentrated to be subsequently supplied to the electrolysis. The lithium extraction rate for the resulting lithium chloride solution according to this production route is less than 84%, according to the article by NOGUEI RA et al., Comparison of Processes for Lithium Recovery from Lepidolite by H2SO4 Digestion or HCI Leaching, Proc. Inter. Con. Min. Mater. and Metal. Eng.
(2014). Further, in the article by YAN et al., Extraction of lithium from lepidolite using chlorination roasting ¨ water leaching process, Trans. Nonferrous Met. Soc.
China 22 (2012), 1753, an alternative method for producing a lithium chloride solution is known. According to the described method, lepidolite is initially crushed and mixed with a mixture of sodium chloride and calcium chloride for chlorination. The resulting lithium chloride solution contains 92% of the lithium portion of the ore.
2 Furthermore, in BARBOSA LUCIA I et al.: "Extraction of lithium from [beta]-spodumene using chlorination roasting with calcium chloride," THERMOCHIMICA
ACTA, vol. 605, (2015), a possible process route for the extraction of lithium from lithium-containing ore is known. In particular, the naturally occurring alpha-crystalline form of spodumene is calcined, in order to transfer the spodumene into its beta-crystalline form. In particular, the starting material is roasted with calcium chloride in a fixed bed reactor, wherein subsequently the roasted material is leached out with water.
A disadvantage of the known prior art consists in the high cost and the sometimes low yield of lithium or lithium hydroxide from the lithium-containing ores and/or minerals and/or earths. In particular, in the precipitation of lithium carbonate from a lithium sulfate solution, high amounts of sodium carbonate are consumed. Sodium carbonate, however, is subject to a highly fluctuating price curve in the market, whereby a process for the production of lithium hydroxide via lithium carbonate as an intermediate product is subject to an increased cost risk.
In AU 2013 20 18 33 B2, the production of the intermediate lithium carbonate is circumvented by recovering lithium hydroxide from the lithium chloride solution by means of the chlor-alkali process. The lithium chloride solution is obtained by leaching 8-spodumene with hydrochloric acid. Also in this process route, the yield of lithium through leaching with hydrochloric acid is comparatively low.
Higher lithium extraction rates could be achieved through longer process times and an increase in process temperature, but this results in lower process economic efficiency.
The object of the invention is therefore to provide in a method for producing lithium hydroxide from lithium-containing ore and/or mineral and/or lithium-containing earths, a solution which makes it possible to increase the extraction rate of highly pure lithium hydroxide by applying a chlor-alkali process.
This object is achieved by embodiments of the present invention. In the method according to the invention for producing lithium hydroxide from lithium-containing ore and/or mineral and/or lithium-containing earths, in particular for producing highly pure lithium
ACTA, vol. 605, (2015), a possible process route for the extraction of lithium from lithium-containing ore is known. In particular, the naturally occurring alpha-crystalline form of spodumene is calcined, in order to transfer the spodumene into its beta-crystalline form. In particular, the starting material is roasted with calcium chloride in a fixed bed reactor, wherein subsequently the roasted material is leached out with water.
A disadvantage of the known prior art consists in the high cost and the sometimes low yield of lithium or lithium hydroxide from the lithium-containing ores and/or minerals and/or earths. In particular, in the precipitation of lithium carbonate from a lithium sulfate solution, high amounts of sodium carbonate are consumed. Sodium carbonate, however, is subject to a highly fluctuating price curve in the market, whereby a process for the production of lithium hydroxide via lithium carbonate as an intermediate product is subject to an increased cost risk.
In AU 2013 20 18 33 B2, the production of the intermediate lithium carbonate is circumvented by recovering lithium hydroxide from the lithium chloride solution by means of the chlor-alkali process. The lithium chloride solution is obtained by leaching 8-spodumene with hydrochloric acid. Also in this process route, the yield of lithium through leaching with hydrochloric acid is comparatively low.
Higher lithium extraction rates could be achieved through longer process times and an increase in process temperature, but this results in lower process economic efficiency.
The object of the invention is therefore to provide in a method for producing lithium hydroxide from lithium-containing ore and/or mineral and/or lithium-containing earths, a solution which makes it possible to increase the extraction rate of highly pure lithium hydroxide by applying a chlor-alkali process.
This object is achieved by embodiments of the present invention. In the method according to the invention for producing lithium hydroxide from lithium-containing ore and/or mineral and/or lithium-containing earths, in particular for producing highly pure lithium
3 =
hydroxide for use in batteries and/or accumulators, in a calcining and leaching step, a lithium chloride solution is produced, the lithium-containing ores and/or minerals and/or earths first being roasted by using one or more metal chlorides and/or a mixture of metal chlorides, and then leached out, in particular by using water. In a subsequent purification step a highly pure lithium chloride solution is produced, in particular by removing cations, such as sodium and/or potassium, and/or calcium, and/or magnesium, and/or iron, from the lithium chloride solution. In a subsequent, in particular final, electrolysis step, lithium hydroxide, in particular highly pure lithium hydroxide, is produced, the highly pure lithium chloride solution being subjected to a membrane electrolysis process, which produces chlorine gas and hydrogen as byproducts.
According to the invention, therefore, a direct production of lithium hydroxide from an ore and/or mineral and/or earth is proposed, which can take place without the production of lithium carbonate as an intermediate product, with greatly reduced use of chemicals, in particular with greatly reduced use or even without the use of sodium carbonate and/or without the use of acids, in particular hydrochloric acid or sulfuric acid, in contrast to the known prior art. For this purpose, the lithium-containing ore and/or mineral and/or the lithium-containing earth is initially roasted in a calcining and leaching step by using metal chlorides, preferably by using a mixture of metal chlorides. The roasting with metal chlorides instead of hydrochloric acid or other chlorides improves the extraction rate and/or yield of lithium contained in the produced lithium chloride solution based on the lithium content of the ore and/or the mineral and/or the earth. For leaching the lithium chloride water is preferably used, also in view of the subsequent electrolysis step.
In a purification step, a highly pure lithium chloride solution is obtained from the produced, still contaminated lithium chloride solution. This means, in particular, that the proportion of lithium in the solution is increased compared to other ions.
In particular, cations, such as sodium and/or potassium and/or calcium and/or magnesium and/or iron, are removed from the lithium chloride solution. This is likewise advantageous in view of the electrolysis step to be carried out subsequently, in which unwanted cations are deposited on the cathode in addition to the lithium to
hydroxide for use in batteries and/or accumulators, in a calcining and leaching step, a lithium chloride solution is produced, the lithium-containing ores and/or minerals and/or earths first being roasted by using one or more metal chlorides and/or a mixture of metal chlorides, and then leached out, in particular by using water. In a subsequent purification step a highly pure lithium chloride solution is produced, in particular by removing cations, such as sodium and/or potassium, and/or calcium, and/or magnesium, and/or iron, from the lithium chloride solution. In a subsequent, in particular final, electrolysis step, lithium hydroxide, in particular highly pure lithium hydroxide, is produced, the highly pure lithium chloride solution being subjected to a membrane electrolysis process, which produces chlorine gas and hydrogen as byproducts.
According to the invention, therefore, a direct production of lithium hydroxide from an ore and/or mineral and/or earth is proposed, which can take place without the production of lithium carbonate as an intermediate product, with greatly reduced use of chemicals, in particular with greatly reduced use or even without the use of sodium carbonate and/or without the use of acids, in particular hydrochloric acid or sulfuric acid, in contrast to the known prior art. For this purpose, the lithium-containing ore and/or mineral and/or the lithium-containing earth is initially roasted in a calcining and leaching step by using metal chlorides, preferably by using a mixture of metal chlorides. The roasting with metal chlorides instead of hydrochloric acid or other chlorides improves the extraction rate and/or yield of lithium contained in the produced lithium chloride solution based on the lithium content of the ore and/or the mineral and/or the earth. For leaching the lithium chloride water is preferably used, also in view of the subsequent electrolysis step.
In a purification step, a highly pure lithium chloride solution is obtained from the produced, still contaminated lithium chloride solution. This means, in particular, that the proportion of lithium in the solution is increased compared to other ions.
In particular, cations, such as sodium and/or potassium and/or calcium and/or magnesium and/or iron, are removed from the lithium chloride solution. This is likewise advantageous in view of the electrolysis step to be carried out subsequently, in which unwanted cations are deposited on the cathode in addition to the lithium to
4 be extracted.
The invention thus combines the advantages of two methods known in the art for the production of lithium hydroxide, by adopting individual steps of a production method using the extraction of lithium carbonate as an intermediate product in a chlor-alkali production route and/or by replacing and/or adapting individual steps of the chlor-alkali production route to the same.
In an advantageous embodiment, the method according to the invention is characterized in that the one or more metal chlorides or the mixture of metal chlorides used in the calcining and leaching step comprises/comprise at least sodium chloride and/or potassium chloride and/or lithium chloride and/or magnesium chloride and/or calcium chloride. Preferably, a mixture of sodium chloride and calcium chloride is used for roasting, because the melting temperature of the mixture is well below the melting temperature of the other metal chlorides. Due to the increased fluidity of the melt obtained at a lower temperature, the chlorides more readily diffuse to the surface of the lithium-containing ore and/or mineral and/or the lithium-containing earth, thereby improving lithium extraction. In comparison to the sulfate process, in which the lithium-containing ore and/or mineral and/or the lithium-containing earth, in particular lepidolite, is roasted and the resulting P-spodumene is digested by means of sulfuric acid, roasting with salts, in particular with metal chlorides, provides an increased lithium yield and improved roasting properties. The excess salts contained in the lithium chloride solution are usually removed with soda ash, i.e. with sodium carbonate. The leaching of the solution is advantageously carried out with water, so that lithium hydroxide and HCI can then be obtained from the prepared lithium chloride solution by means of the chlor-alkali process.
Advantageously, before the electrolysis step, cations contained in the lithium chloride solution and affecting the electrolysis, in particular iron and/or calcium and/or magnesium, should be reduced to very low concentrations. In an advantageous embodiment, the invention therefore provides that the lithium chloride solution is purified in the purification step by adjusting the pH of the lithium chloride solution, in particular to a pH higher than 8, wherein the pH is preferably increased by adding a =
lye containing in particular hydroxides and/or carbonates and/or an alkaline solution.
By increasing the pH, in particular to a pH greater than 8, undesirable ions, such as aluminum, iron, magnesium and manganese, can be precipitated as corresponding hydroxides from the lithium chloride solution and then removed. Another possibility is provided, for example, by the oxidation of iron contained in the lithium chloride solution, wherein chemical substances, which are suitable for the oxidation of iron, are added to the lithium chloride solution. Expediently, calcium can be removed from the lithium chloride solution in the purification step by adding alkali carbonate, in particular lithium carbonate and/or sodium carbonate. The invention therefore provides in a further embodiment that the lithium chloride solution is purified in the purification step by adding alkali carbonate, in particular lithium carbonate and/or sodium carbonate, wherein, in particular, calcium is removed from the lithium chloride solution. The resulting calcium carbonate can be separated from the lithium chloride solution, whereas the added lithium is extracted in the electrolysis step.
Furthermore, the prepared lithium chloride solution may also be subject to ion exchange, in particular cation exchange, to further reduce the cations contained in the lithium chloride solution. The invention therefore also provides that the lithium chloride solution in the purification step is subject to an ion exchange, in particular a cation exchange, for further reduction of the cations contained in the lithium chloride solution.
Likewise useful is an optional purification of the lithium chloride solution in the purification step by fractional crystallization, wherein lithium and/or sodium and/or potassium are separated from each other and the sodium and/or potassium precipitate in the form of sodium chloride or potassium chloride, as provided by a further development of the invention.
The lithium chloride solution can also be further purified by solvent extraction. In this case, the lithium to be extracted is separated from other alkali metal salts, in particular sodium chloride. The invention is therefore further characterized in that the lithium chloride solution is purified in the purification step by solvent extraction, wherein lithium is separated from other alkali salts, in particular sodium chloride.
=
According to the invention, sodium chloride obtained during the purification step, in particular by fractional crystallization or solvent extraction, is used for roasting the lithium-containing ores and/or minerals and/or earths and is fed to the calcining and leaching step. In the invention, it is therefore also provided that the sodium chloride obtained in the purification step is used in the calcining and leaching step for roasting the lithium-containing ores and/or minerals and/or the lithium-containing earths.
In this way, the need for sodium chloride for the method according to the invention can be further reduced.
Further possible solutions known from the prior art for the purification of the lithium chloride solution can alternatively or optionally be applied in the previously described purification solutions during the purification step of the production method according to the invention.
To increase the efficiency of the method according to the invention it is finally provided, in a further development of the invention, that the chlorine gas generated in the electrolysis step is recombined with the hydrogen also generated in the electrolysis step, in particular by means of an HCI producer, in order to form hydrochloric acid. The hydrochloric acid produced thereby can be removed as a by-product of the lithium hydroxide production process.
The invention is explained in more detail below by way of an example with reference to a drawing. In particular The Figure shows a flow diagram of an exemplary method according to the invention for the production of lithium hydroxide from lithium-containing ore and/or mineral and/or a lithium-containing earth.
The Figure shows a flow diagram of an exemplary method according to the invention for the production of lithium hydroxide from lithium-containing ore and/or mineral and/or a lithium-containing earth (1). According to the exemplary embodiment, the lithium-containing mineral or earth (1) spodumene (LiAl[Si206]) serves as a starting material for the production of lithium hydroxide (4), which is extracted as the end product of the production method according to the invention for further use for battery applications, in particular for rechargeable lithium-ion batteries. In particular, by means of the production method according to the invention, it is possible to obtain highly pure lithium hydroxide, whose total content of disturbing foreign cations, such as calcium and magnesium, is less than 150 ppb (parts per billion). Spodumene is found in lithium-containing ores (1), in particular in lepidolite. The preparation of the lithium-containing ore and/or mineral (1) for further processing according to the invention can be carried out in the usual way by crushing and grinding the rocks. The following is the overall reaction of the inventive embodiment for the production of lithium hydroxide (4) from the lithium-containing mineral (1) spodumene:
2 LiAlSi206 + 2 H20 + CaCl2 -> 2 LiOH + CaA12514012 In a calcining and leaching step (A), the lithium-containing mineral (1) spodumene is initially roasted at a temperature of 880 C for 30 minutes with the addition of a mixture of metal chlorides (5). In the exemplary embodiment, since the melting point of a mixture with lepidolite, depending on the respective mixing proportions, is below the melting point of mixtures with other metal chlorides, the mixture is composed of sodium and calcium chloride, and thus an extraction of the lithium is favored.
The leaching is then carried out with water at a temperature of 90 C. Compared with leaching with acid, for example hydrochloric acid or sulfuric acid, the use of water is safer, less expensive and advantageous for a subsequent chlor-alkali process.
The yield, i.e. the extracted amount of lithium relative to the total amount of lithium contained in the starting product is at least 92% in the exemplary embodiment.
The proportion of excess salts in the still contaminated lithium chloride solution (2) is about 31%. The excretion of the excess salts can be carried out by addition of alkali carbonate, wherein expediently sodium carbonate or alternatively lithium carbonate is added. A precipitation reaction for calcium chloride by addition of sodium carbonate is as follows:
-CaCl2 + Na2003-> CaCO3 + 2 NaCI
In a purification step (B), the lithium chloride solution (2) is further purified in order to obtain a highly pure lithium chloride solution (3). A highly pure lithium chloride solution (3) is characterized in particular by a very low proportion of disturbing foreign cations, such as sodium, potassium, magnesium, calcium and iron. In particular, the total amount of magnesium and calcium is less than 150 ppb (parts per billion) based on the total amount of ions. As described above, the removal of the foreign cations and other purification can be carried out by adjusting the pH to pH > 8 of the lithium chloride solution (2) by adding chemicals for oxidizing iron, by fractional crystallization separation, solvent extraction and/or by ion exchange. If a separation between lithium and sodium or lithium and other alkali metal salts is carried out by means of fractional crystallization and/or solvent extraction, separated sodium chloride and/or if appropriate calcium chloride can be used for roasting the lithium-containing mineral (1) spodumene in the calcining and leaching step (A). In this way, waste products obtained in the purification step (B) can be supplied to the calcining and leaching step (A) in order to reduce the requirement for substances required for the production process according to the invention, in particular sodium chloride and/or calcium chloride.
The highly pure lithium chloride solution (3) obtained by the purification step (B) is subjected to an electrolysis step (C) to obtain lithium hydroxide (4). By means of a membrane electrolyzing device having a semipermeable membrane, a chlor-alkali process is carried out in the electrolysis step (C). An anode and a cathode of the electrolyzer are separated by the semipermeable membrane. By applying a voltage, the ions contained in the highly pure lithium chloride solution (3) are separated from each other, wherein lithium hydroxide (4) is obtained as the main product and hydrogen as a by-product of the electrolysis at the cathode and chlorine gas is extracted as a by-product at the anode. Since disturbing foreign cations have already been removed from the lithium chloride solution (2) in the purification step (B) to obtain a highly pure lithium chloride solution (3), the lithium hydroxide (4) accumulating at the cathode can also be extracted in a highly pure state, i.e.
almost free of interfering cations.
The extracted by-products, hydrogen and chlorine gas, can be recombined by an HCI
producer (6) with hydrochloric acid. By producing a readily available by-product, such as hydrochloric acid, the cost-effectiveness of the process according to the invention can be further increased.
The extracted, in particular highly pure lithium hydroxide is suitable for use in battery applications, in particular for use in rechargeable lithium-ion batteries or for further processing, for example to obtain lithium carbonate, in particular highly pure lithium carbonate.
List of reference numerals:
1 lithium-containing ores and/or minerals and/or earths 2 lithium chloride solution 3 highly pure lithium chloride solution 4 lithium hydroxide metal chlorides 6 HCI producer A calcining and leaching step B purification step C electrolysis step
The invention thus combines the advantages of two methods known in the art for the production of lithium hydroxide, by adopting individual steps of a production method using the extraction of lithium carbonate as an intermediate product in a chlor-alkali production route and/or by replacing and/or adapting individual steps of the chlor-alkali production route to the same.
In an advantageous embodiment, the method according to the invention is characterized in that the one or more metal chlorides or the mixture of metal chlorides used in the calcining and leaching step comprises/comprise at least sodium chloride and/or potassium chloride and/or lithium chloride and/or magnesium chloride and/or calcium chloride. Preferably, a mixture of sodium chloride and calcium chloride is used for roasting, because the melting temperature of the mixture is well below the melting temperature of the other metal chlorides. Due to the increased fluidity of the melt obtained at a lower temperature, the chlorides more readily diffuse to the surface of the lithium-containing ore and/or mineral and/or the lithium-containing earth, thereby improving lithium extraction. In comparison to the sulfate process, in which the lithium-containing ore and/or mineral and/or the lithium-containing earth, in particular lepidolite, is roasted and the resulting P-spodumene is digested by means of sulfuric acid, roasting with salts, in particular with metal chlorides, provides an increased lithium yield and improved roasting properties. The excess salts contained in the lithium chloride solution are usually removed with soda ash, i.e. with sodium carbonate. The leaching of the solution is advantageously carried out with water, so that lithium hydroxide and HCI can then be obtained from the prepared lithium chloride solution by means of the chlor-alkali process.
Advantageously, before the electrolysis step, cations contained in the lithium chloride solution and affecting the electrolysis, in particular iron and/or calcium and/or magnesium, should be reduced to very low concentrations. In an advantageous embodiment, the invention therefore provides that the lithium chloride solution is purified in the purification step by adjusting the pH of the lithium chloride solution, in particular to a pH higher than 8, wherein the pH is preferably increased by adding a =
lye containing in particular hydroxides and/or carbonates and/or an alkaline solution.
By increasing the pH, in particular to a pH greater than 8, undesirable ions, such as aluminum, iron, magnesium and manganese, can be precipitated as corresponding hydroxides from the lithium chloride solution and then removed. Another possibility is provided, for example, by the oxidation of iron contained in the lithium chloride solution, wherein chemical substances, which are suitable for the oxidation of iron, are added to the lithium chloride solution. Expediently, calcium can be removed from the lithium chloride solution in the purification step by adding alkali carbonate, in particular lithium carbonate and/or sodium carbonate. The invention therefore provides in a further embodiment that the lithium chloride solution is purified in the purification step by adding alkali carbonate, in particular lithium carbonate and/or sodium carbonate, wherein, in particular, calcium is removed from the lithium chloride solution. The resulting calcium carbonate can be separated from the lithium chloride solution, whereas the added lithium is extracted in the electrolysis step.
Furthermore, the prepared lithium chloride solution may also be subject to ion exchange, in particular cation exchange, to further reduce the cations contained in the lithium chloride solution. The invention therefore also provides that the lithium chloride solution in the purification step is subject to an ion exchange, in particular a cation exchange, for further reduction of the cations contained in the lithium chloride solution.
Likewise useful is an optional purification of the lithium chloride solution in the purification step by fractional crystallization, wherein lithium and/or sodium and/or potassium are separated from each other and the sodium and/or potassium precipitate in the form of sodium chloride or potassium chloride, as provided by a further development of the invention.
The lithium chloride solution can also be further purified by solvent extraction. In this case, the lithium to be extracted is separated from other alkali metal salts, in particular sodium chloride. The invention is therefore further characterized in that the lithium chloride solution is purified in the purification step by solvent extraction, wherein lithium is separated from other alkali salts, in particular sodium chloride.
=
According to the invention, sodium chloride obtained during the purification step, in particular by fractional crystallization or solvent extraction, is used for roasting the lithium-containing ores and/or minerals and/or earths and is fed to the calcining and leaching step. In the invention, it is therefore also provided that the sodium chloride obtained in the purification step is used in the calcining and leaching step for roasting the lithium-containing ores and/or minerals and/or the lithium-containing earths.
In this way, the need for sodium chloride for the method according to the invention can be further reduced.
Further possible solutions known from the prior art for the purification of the lithium chloride solution can alternatively or optionally be applied in the previously described purification solutions during the purification step of the production method according to the invention.
To increase the efficiency of the method according to the invention it is finally provided, in a further development of the invention, that the chlorine gas generated in the electrolysis step is recombined with the hydrogen also generated in the electrolysis step, in particular by means of an HCI producer, in order to form hydrochloric acid. The hydrochloric acid produced thereby can be removed as a by-product of the lithium hydroxide production process.
The invention is explained in more detail below by way of an example with reference to a drawing. In particular The Figure shows a flow diagram of an exemplary method according to the invention for the production of lithium hydroxide from lithium-containing ore and/or mineral and/or a lithium-containing earth.
The Figure shows a flow diagram of an exemplary method according to the invention for the production of lithium hydroxide from lithium-containing ore and/or mineral and/or a lithium-containing earth (1). According to the exemplary embodiment, the lithium-containing mineral or earth (1) spodumene (LiAl[Si206]) serves as a starting material for the production of lithium hydroxide (4), which is extracted as the end product of the production method according to the invention for further use for battery applications, in particular for rechargeable lithium-ion batteries. In particular, by means of the production method according to the invention, it is possible to obtain highly pure lithium hydroxide, whose total content of disturbing foreign cations, such as calcium and magnesium, is less than 150 ppb (parts per billion). Spodumene is found in lithium-containing ores (1), in particular in lepidolite. The preparation of the lithium-containing ore and/or mineral (1) for further processing according to the invention can be carried out in the usual way by crushing and grinding the rocks. The following is the overall reaction of the inventive embodiment for the production of lithium hydroxide (4) from the lithium-containing mineral (1) spodumene:
2 LiAlSi206 + 2 H20 + CaCl2 -> 2 LiOH + CaA12514012 In a calcining and leaching step (A), the lithium-containing mineral (1) spodumene is initially roasted at a temperature of 880 C for 30 minutes with the addition of a mixture of metal chlorides (5). In the exemplary embodiment, since the melting point of a mixture with lepidolite, depending on the respective mixing proportions, is below the melting point of mixtures with other metal chlorides, the mixture is composed of sodium and calcium chloride, and thus an extraction of the lithium is favored.
The leaching is then carried out with water at a temperature of 90 C. Compared with leaching with acid, for example hydrochloric acid or sulfuric acid, the use of water is safer, less expensive and advantageous for a subsequent chlor-alkali process.
The yield, i.e. the extracted amount of lithium relative to the total amount of lithium contained in the starting product is at least 92% in the exemplary embodiment.
The proportion of excess salts in the still contaminated lithium chloride solution (2) is about 31%. The excretion of the excess salts can be carried out by addition of alkali carbonate, wherein expediently sodium carbonate or alternatively lithium carbonate is added. A precipitation reaction for calcium chloride by addition of sodium carbonate is as follows:
-CaCl2 + Na2003-> CaCO3 + 2 NaCI
In a purification step (B), the lithium chloride solution (2) is further purified in order to obtain a highly pure lithium chloride solution (3). A highly pure lithium chloride solution (3) is characterized in particular by a very low proportion of disturbing foreign cations, such as sodium, potassium, magnesium, calcium and iron. In particular, the total amount of magnesium and calcium is less than 150 ppb (parts per billion) based on the total amount of ions. As described above, the removal of the foreign cations and other purification can be carried out by adjusting the pH to pH > 8 of the lithium chloride solution (2) by adding chemicals for oxidizing iron, by fractional crystallization separation, solvent extraction and/or by ion exchange. If a separation between lithium and sodium or lithium and other alkali metal salts is carried out by means of fractional crystallization and/or solvent extraction, separated sodium chloride and/or if appropriate calcium chloride can be used for roasting the lithium-containing mineral (1) spodumene in the calcining and leaching step (A). In this way, waste products obtained in the purification step (B) can be supplied to the calcining and leaching step (A) in order to reduce the requirement for substances required for the production process according to the invention, in particular sodium chloride and/or calcium chloride.
The highly pure lithium chloride solution (3) obtained by the purification step (B) is subjected to an electrolysis step (C) to obtain lithium hydroxide (4). By means of a membrane electrolyzing device having a semipermeable membrane, a chlor-alkali process is carried out in the electrolysis step (C). An anode and a cathode of the electrolyzer are separated by the semipermeable membrane. By applying a voltage, the ions contained in the highly pure lithium chloride solution (3) are separated from each other, wherein lithium hydroxide (4) is obtained as the main product and hydrogen as a by-product of the electrolysis at the cathode and chlorine gas is extracted as a by-product at the anode. Since disturbing foreign cations have already been removed from the lithium chloride solution (2) in the purification step (B) to obtain a highly pure lithium chloride solution (3), the lithium hydroxide (4) accumulating at the cathode can also be extracted in a highly pure state, i.e.
almost free of interfering cations.
The extracted by-products, hydrogen and chlorine gas, can be recombined by an HCI
producer (6) with hydrochloric acid. By producing a readily available by-product, such as hydrochloric acid, the cost-effectiveness of the process according to the invention can be further increased.
The extracted, in particular highly pure lithium hydroxide is suitable for use in battery applications, in particular for use in rechargeable lithium-ion batteries or for further processing, for example to obtain lithium carbonate, in particular highly pure lithium carbonate.
List of reference numerals:
1 lithium-containing ores and/or minerals and/or earths 2 lithium chloride solution 3 highly pure lithium chloride solution 4 lithium hydroxide metal chlorides 6 HCI producer A calcining and leaching step B purification step C electrolysis step
Claims (23)
1. A method for producing lithium hydroxide (4), for use in at least one of batteries and accumulators, from at least one of lithium-containing ore, lithium-containing mineral and lithium-containing earth (1) by means of a chlor-alkali process, wherein - in a calcining and leaching step (A), a lithium chloride solution (2) is produced, wherein the at least one of said lithium-containing ore, lithium-containing mineral and lithium-containing earth (1) is initially roasted by using a metal chloride (5) or a mixture of metal chlorides (5), and is then leached out, wherein the metal chloride (5) or the mixture of metal chlorides (5) comprises at least sodium chloride, - wherein, in a subsequent purification step (B), a highly pure lithium chloride solution (3) is produced, wherein the lithium chloride solution (2) is purified by removing cations from the lithium chloride solution (2), said cations comprising a sodium cation, and - wherein, in a subsequent electrolysis step (C), lithium hydroxide (4) is produced, wherein the highly pure lithium chloride solution (3) is subjected to a membrane electrolysis process, which produces chlorine gas and hydrogen as byproducts, - wherein, sodium chloride obtained in the purification step (B) is used for roasting the at least one of said lithium-containing ore, lithium-containing mineral = and lithium-containing earth (1) and is supplied to the calcining and leaching step (A).
2. The method according to claim 1, wherein the cations removed in the purification step (B) further cOmprise one or more selected from the group =
consisting of potassium, calcium, magnesium and iron.
consisting of potassium, calcium, magnesium and iron.
3. The method according to claim 1 or claim 2, wherein in the calcining and leaching step (A), the at least one of said lithium-containing ore, lithium-containing mineral and lithium-containing earth (1) is leached out by using water.
1 l
1 l
4. The method according to any one of claims 1 to 3, wherein the sodium chloride obtained in the purification step (B) is obtained by fractional crystallization or solvent extraction.
5. The method according to any one of claims 1 to 4, characterized in that the metal chloride (5) or the mixture of metal chlorides (5) used in the calcining and leaching step (A) comprises at least one selected from the group consisting of potassium chloride, lithium chloride, magnesium chloride and calcium chloride.
6. The method according to any one of claims 1 to 5, characterized in that the lithium chloride solution (2) is purified in the purification step (B) by adjusting the pH.
7. The method according to any one of claims 1 to 5, wherein the lithium chloride solution (2) is purified in the purification step (B) by adjusting the pH to a pH higher than 8.
8. The method according to claim 6 or claim 7, wherein the lithium chloride solution (2) is purified in the purification step (B) by increasing the pH by adding a lye containing at least one of hydroxides, carbonates and an alkaline solution.
9. The method according to any one of claims 1 to 8, wherein the cations removed in the purification step (B) further comprise iron, and the iron contained in the lithium chloride solution (2) is oxidized, wherein chemical substances selected to oxidize the iron are added to the lithium chloride solution (2).
10. The method according to any one of claims 1 to 9, characterized in that the lithium chloride solution (2) is purified in the purification step (B) by adding alkali carbonate.
11. The method according to claim 10, wherein the alkali carbonate added in the purification step (B) comprises at least one of lithium carbonate and sodium carbonate.
12. The method according to claim 10 or claim 11, wherein the cations removed in the purification step (B) further comprise calcium.
1 3. The method according to any one of claims 1 to 12, characterized in that the lithium chloride solution (2) is subject, in the purification step (B), to an ion exchange for further reducing the cations, which are contained in the lithium chloride solution (2).
14. The method according to claim 13, wherein the ion exchange comprises a cation exchange.
15. The method according to any one of claims 1 to 14, wherein the cations removed in the purification step (B) further comprise potassium, and the lithium chloride solution (2) is purified in the purification step (B) by fractional crystallization, wherein lithium, the sodium and the potassium are separated from =
each other, and the sodium and the potassium precipitate in the form of sodium chloride and potassium chloride.
each other, and the sodium and the potassium precipitate in the form of sodium chloride and potassium chloride.
16. The method according to any one of claims 1 to 15, characterized in that the lithium chloride solution (2) is purified in the purification step (B) by solvent extraction, wherein lithium is separated from other alkali salts.
17. The method according to claim 16, wherein the alkali salts comprises sodium chloride.
18. The method according to any one of claims 1 to 17, characterized in that the chlorine gas produced in the electrolysis step (C) is recombined with the hydrogen produced in the electrolysis step (C) in order to form hydrochloric acid.
19. The method according to claim 18, wherein the chlorine gas produced in the electrolysis step (C) is recombined with the hydrogen produced in the electrolysis step (C) by means of an HCI producer (6).
20. The method according to any one of claims 1 to 19, wherein the lithium hydroxide (4) is purified lithium hydroxide.
21. The method according to claim 20, wherein the lithium hydroxide (4) is highly pure lithium hydroxide having, based on a total amount of ions, less than 150 ppb (parts per billion) foreign cations.
22. The method according to claim 21, wherein the foreign cations comprise at least one of calcium and magnesium.
23. The method according to any one of claims 1 to 14, wherein the lithium chloride solution (2) is purified in the purification step (B) by fractional crystallization, wherein lithium and sodium are separated from each other, and sodium precipitates in the form of sodium chloride.
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| Application Number | Priority Date | Filing Date | Title |
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| DE102017203265 | 2017-02-28 | ||
| DE102017203265.0 | 2017-02-28 | ||
| DE102017221288.8A DE102017221288A1 (en) | 2017-02-28 | 2017-11-28 | Process for producing lithium hydroxide from lithiated ore |
| DE102017221288.8 | 2017-11-28 | ||
| PCT/EP2018/052759 WO2018158041A1 (en) | 2017-02-28 | 2018-02-05 | Method for producing lithium hydroxide from lithium-containing ore |
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| EP (1) | EP3589763B1 (en) |
| CN (1) | CN110494573A (en) |
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| CN110029354B (en) * | 2019-05-08 | 2020-10-13 | 蓝星(北京)化工机械有限公司 | Method for preparing battery-grade lithium hydroxide by direct electrolysis of lithium chloride |
| RU2713360C2 (en) * | 2019-09-25 | 2020-02-04 | Общество с ограниченной ответственностью "Экостар-Наутех" | Method of producing lithium hydroxide monohydrate from brines |
| US20240011123A1 (en) * | 2020-12-01 | 2024-01-11 | Basf Corporation | Methods for regenerating li and ni from a solution |
| EP4373981A1 (en) * | 2021-07-23 | 2024-05-29 | Basf Se | Process for recycling lithium ion battery materials |
| CN114959254A (en) * | 2022-04-24 | 2022-08-30 | 山东大学 | Method for separating and recovering cobalt and lithium in lithium cobaltate |
| CN114804955A (en) * | 2022-05-04 | 2022-07-29 | 田美生态农业科技(连云港)有限公司 | Soluble slow-release type soil improvement and conditioning multielement fertilizer and preparation process thereof |
| US20230392233A1 (en) * | 2022-06-03 | 2023-12-07 | Schlumberger Technology Corporation | Target ion recovery from earth material |
| CN115286014A (en) * | 2022-08-15 | 2022-11-04 | 江苏昌吉利新能源科技有限公司 | Method for preparing high-purity lithium hydroxide by recycling waste lithium-based lubricating grease |
| GB2623593A (en) * | 2022-10-21 | 2024-04-24 | Res By British Lithium Limited | Impurity removal and leaching of lithium material |
| CN116154348B (en) * | 2023-04-25 | 2023-07-11 | 赣州市力道新能源有限公司 | Method for preparing lithium iron phosphate positive electrode material by scrapping lithium battery pole piece |
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| AU2013201833B2 (en) * | 2012-08-13 | 2014-07-17 | Reed Advanced Materials Pty Ltd | Processing of Lithium Containing Ore |
| CN105907943B (en) * | 2015-12-15 | 2018-12-18 | 葛新芳 | Lithium ore chlorinating agent inorganic base roasts organic solvent leaching and extracts lithium technique |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
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| WO2018158041A1 (en) | 2018-09-07 |
| AU2018227891B2 (en) | 2020-08-27 |
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| CA3054748A1 (en) | 2018-09-07 |
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