CN109052436B - Method for preparing lithium-containing compound from lithium-phosphorus-aluminum - Google Patents
Method for preparing lithium-containing compound from lithium-phosphorus-aluminum Download PDFInfo
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- CN109052436B CN109052436B CN201811110542.9A CN201811110542A CN109052436B CN 109052436 B CN109052436 B CN 109052436B CN 201811110542 A CN201811110542 A CN 201811110542A CN 109052436 B CN109052436 B CN 109052436B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- 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
- C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
- C01B25/306—Preparation from phosphorus-containing compounds by alkaline treatment from phosphates
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- 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
Abstract
The present invention provides a method for preparing a lithium-containing compound from a lithium-phosphorus-aluminum ore, the method comprising the steps of: mixing the lithium-phosphorus-aluminum and acid to obtain a dissolution liquid; adding a pH regulator, regulating the pH of the dissolution liquid, carrying out solid-liquid separation to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding a precipitator into the first lithium-containing solution, and carrying out solid-liquid separation to obtain a lithium salt; or adding an aluminum precipitation agent into the dissolution liquid, carrying out heating reaction, carrying out solid-liquid separation to obtain a second lithium-containing solution and an aluminum-containing solid, adjusting the pH value of the second lithium-containing solution, carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the second lithium-containing solution, carrying out solid-liquid separation to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor to obtain the lithium iron phosphate. The method can synthesize the lithium iron phosphate by one step, greatly reduces the cost, and the prepared lithium iron phosphate has high purity.
Description
Technical Field
The invention belongs to the field of compound preparation, relates to a preparation method of lithium salt, and particularly relates to a method for preparing a lithium-containing compound from lithium phosphosiderite.
Background
Lithium is the lightest metal, and lithium metal and its alloys and compounds have been widely used in many fields such as nuclear power generation, light high specific strength alloys, metallurgy, aluminum production, high-energy batteries, medicine, glass, ceramics, grease, petroleum, chemical engineering, organic synthesis, light metal welding, surface modification of non-metallic minerals, and production of daily necessities. In recent decades, countries such as America, English, Germany, French, Japan, Russia and the like invest a great deal of capital, manpower and material resources in sequence, research on aluminum-lithium alloy and magnesium-lithium alloy and deep development and application research on lithium resources are carried out, the achievement and the success of attention of the world are obtained successively, the development, the application, the production, the consumption and the trade of the world lithium resources are promoted, and the important role is generated on the development of the world lithium industry.
Lithium resources are abundant in the world, and are mainly distributed in south, north america, asia, australia and africa. The Li2O reserve in the virvia only viny salt pot reached 1913.5 kilotons; both Silver Peak (Silver Peak) in Nevada, USA and West lake in California have Li2O reserves in excess of 1000 ten thousand t; in the salt lake of the Chaohan and the salt lake of the Chadan in the Qinghai of China and in a plurality of brine waters in Sichuan province, the reserve of lithium resources is estimated to be about 1000 ten thousand tons. The reserve of lithium resources in the bittern deposits of Argentina catabacea is also considerable, and the reserve of Li2O is estimated to reach millions of t. The reserves calculated according to Li2O in Viagra lithium ore deposit are 634.8 million in the United states, 426 million in Chile, 660 million in Canada, Li2O reserve of Grignard (Greenbushes) spodumene ore in Western Australia reaches 600 million, reserves of Zimbabwe and lithium phosphosiderite Li2O in Nanbia are also larger, and the reserves of lepidolite in ore deposits such as spodumene in Tokkai, northwest of Sichuan and Liantadinium-cesium polymetallic ore in Yichun of China are also abundant.
Many methods for extracting lithium from spodumene, petalite and lepidolite have been reported, but little research has been conducted on extracting lithium from spodumene.
CN107188205A discloses a process for extracting lithium sulfate from lithium-phosphorus-aluminum by an acidification method, which comprises the following steps: (1) grinding raw materials: grinding the raw materials in the lithium-phosphorus-aluminum alloy; (2) preparing materials: mixing the lithium-phosphorus-aluminum milled in the step (1) with concentrated sulfuric acid; (3) roasting: roasting the mixed material obtained in the step (2); (4) slurry mixing and leaching: putting the clinker obtained in the step (3) into a reaction kettle, adding water, heating and stirring; (5) purifying and removing impurities: removing impurities such as aluminum or calcium from the solution leached in the step (4); (6) the solution after the completion of the reaction in step (5) is concentrated by evaporation.
CN107162024A discloses a process for extracting lithium carbonate from lithium-phosphorus-aluminum by an acidification method, which comprises the following steps: the preparation method comprises the following steps of grinding raw materials, batching, mixing the grinded lithium-phosphorus-aluminum and concentrated sulfuric acid, roasting, mixing and leaching, purifying and removing impurities, removing impurities such as aluminum or calcium, evaporating and concentrating, depositing lithium for the first time, stirring and washing for the second time, and drying to obtain a lithium carbonate product.
CN107200338A discloses a process for extracting lithium hydroxide from lithium-phosphorus-aluminum by acidification, which comprises the following steps: the lithium-phosphorus-aluminum is milled and mixed with concentrated sulfuric acid → roasting → milling clinker and leaching → purifying and impurity removing → evaporating and concentrating → causticizing → sodium cryolite → evaporating and crystallizing → recrystallizing → drying and packaging. By applying the process technology of the invention, lithium can be extracted from the lithium-phosphorus-aluminum stone and becomes a lithium hydroxide monohydrate product meeting the standard, and the yield of lithium can reach over 86 percent.
CN107188204A discloses a process for extracting lithium hydroxide from lithium-phosphorus-aluminum by lime method, comprising the following steps: s1, grinding the raw material, and grinding to 100-200 meshes; s2, blending, and uniformly mixing to obtain raw materials; s3, roasting at high temperature to form clinker; s4 leaching and filtering to obtain a lithium hydroxide solution; s5, evaporating and concentrating to obtain lithium hydroxide clear solution; s6 crystallization to obtain lithium hydroxide crystals.
Although the method can realize the extraction of lithium from the lithium-phosphorus-aluminum-stone, the process route is long, the extraction rate of lithium is required to be improved, the purity of lithium-containing products is required to be further improved, and iron and phosphorus in the lithium-phosphorus-aluminum-stone are not fully utilized.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the method for preparing the lithium-containing compound from the lithium-phosphorus-aluminum, the method has simple process flow and simple and convenient operation, the lithium element in the lithium-phosphorus-aluminum can be fully extracted, and the prepared lithium salt has high purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a method for preparing a lithium-containing compound from a lithium-phosphorus-aluminum ore, the method comprising the steps of:
mixing the lithium-phosphorus-aluminum and acid to obtain a dissolution liquid;
adding a pH regulator, regulating the pH of the dissolution liquid, carrying out solid-liquid separation to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding a precipitator into the first lithium-containing solution, and carrying out solid-liquid separation to obtain a lithium salt;
or adding an aluminum precipitation agent into the dissolution liquid, carrying out heating reaction, carrying out solid-liquid separation to obtain a second lithium-containing solution and an aluminum-containing precipitate, adjusting the pH value of the second lithium-containing solution, carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the second lithium-containing solution, carrying out solid-liquid separation to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor to obtain the lithium iron phosphate.
In a preferred embodiment of the present invention, the mass ratio of the above-mentioned lithium-phosphorus-aluminum-acid is 1 (1 to 4), for example, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5 or 1:4, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and 1 (1.5 to 3) is preferable.
When the mass ratio of the lithium-phosphorus-aluminum alloy to the acid is higher than 1:1, lithium, aluminum and phosphorus elements in the ore cannot be completely dissolved out, and when the mass ratio of the lithium-phosphorus-aluminum alloy to the acid is lower than 1:4, impurity elements in the lithium-phosphorus-aluminum alloy are dissolved out more, so that the purity of a subsequent prepared product is influenced. In the preferable mass ratio of the lithium-phosphorus-aluminum-oxide to the acid of 1 (1.5-3), the purity of aluminum phosphate precipitated by subsequently adjusting the pH of the dissolution liquid is better, and the aluminum phosphate can be directly used as a product after simple post-treatment such as water washing.
As a preferred embodiment of the present invention, the acid includes an organic acid and/or an inorganic acid.
Preferably, the acid is a pure acid or an acid solution.
Wherein, when the above-mentioned lithionite is mixed with the acid solution in the present invention, the mass ratio of the lithionite to the acid is the ratio of the total mass of the lithionite to the acid contained in the acid solution.
Preferably, the inorganic acid comprises any one of sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid, or a combination of at least two of these, typical but non-limiting examples being: a combination of sulfuric acid and hydrochloric acid, a combination of nitric acid and sulfuric acid, a combination of nitric acid and hydrochloric acid, a combination of hydrochloric acid and phosphoric acid, or a combination of sulfuric acid, nitric acid and hydrochloric acid, and the like.
Wherein, when the acid is an inorganic acid in the present invention, it is mainly mixed with the lithium-phosphorus-aluminum in the form of an acid solution.
Preferably, the organic acid comprises any one of formic acid, acetic acid, oxalic acid or trifluoroacetic acid or a combination of at least two of these, typical but non-limiting examples being: formic acid and acetic acid in combination, acetic acid and oxalic acid in combination, oxalic acid and trifluoroacetic acid in combination, trifluoroacetic acid and additive in combination or acid, acetic acid and oxalic acid in combination, and the like.
Wherein, when the acid is an organic acid in the present invention, it is mainly mixed with the lithium-phosphosiderite in the form of a pure acid.
In a preferred embodiment of the present invention, the above-mentioned lithionite is mixed with an acid and then reacted at 150 to 350 ℃, and the reaction temperature may be 150 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 320 ℃ or 350 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
When the reaction temperature of the lithionite and the acid is lower than 150 ℃, lithium, aluminum and phosphorus elements in the ore cannot be completely dissolved out, and when the reaction temperature of the lithionite and the acid is higher than 350 ℃, more side reactions occur, such as the change of the valence state of the phosphorus element in phosphoric acid, the change of the valence state of a metal element and the like, so that the purity of subsequent products is influenced, and the post-treatment difficulty of the products is increased.
Preferably, the reaction time is 1 to 12 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction is carried out under sealed conditions.
Wherein, the reaction is carried out under sealed conditions, namely the reaction temperature exceeds the boiling point of some acids and the boiling point of water in acid solution, and in order to ensure the stability of the mass ratio of the reactants, the reaction is carried out in a closed reactor which can bear high pressure, such as a high-pressure reaction kettle and the like.
Preferably, the acid is added simultaneously during the temperature rise of the reaction.
In the invention, a mode of simultaneously heating and adding acid is preferably adopted, and the mode can be better matched with the dissolution conditions of the three substances so as to realize better dissolution of different elements. If a feeding hole is formed in the upper end of the high-pressure reaction kettle, and a stirring device is arranged inside the high-pressure reaction kettle, the lithium-phosphorus-aluminum is added into the high-pressure reaction kettle firstly, the reactor is heated, and acid is added from the feeding hole simultaneously, so that the temperature rise of the reaction and the acid addition are carried out simultaneously, the acid addition can adopt a high-pressure conveying device, the feeding pressure is ensured to be greater than the internal pressure of the reactor, and the gasified acid or water and the like in the reaction process can not overflow from the feeding hole and can not be separated from a reaction system.
In a preferred embodiment of the present invention, the pH of the dissolution liquid is adjusted to 2 to 5, for example, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2 or 4.5 by adding the pH adjuster, but the pH is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 3.5 to 4.5.
When the pH is less than 2, namely peracid, aluminum ions and phosphate ions in the dissolution liquid cannot be fully precipitated, and when the pH is more than 5, namely acidity is insufficient, lithium phosphate is co-precipitated together with aluminum phosphate, so that the direct use of the aluminum phosphate as a product is influenced, and the extraction rate of lithium is reduced. The above-mentioned adjustment of pH is limited to the case where the lithium element, phosphorus element and aluminum element are sufficiently eluted in the lithium-phosphorus-aluminum alloy, and when the elution is insufficient in the preceding step, the lithium phosphate and aluminum phosphate are coprecipitated regardless of the pH adjustment.
Preferably, the temperature of the dissolution liquid when the pH regulator is added is 20 to 100 ℃, such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 60 to 90 ℃.
Preferably, the pH adjusting agent comprises any one or a combination of at least two of liquid ammonia, solid sodium hydroxide or solid potassium hydroxide, or any one or a combination of at least two of aqueous ammonia, solution sodium hydroxide or solution potassium hydroxide, as typical but non-limiting examples: combinations of liquid ammonia and sodium hydroxide solids, sodium hydroxide solids and potassium hydroxide solids, potassium hydroxide solids and liquid ammonia, aqueous ammonia and sodium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution, potassium hydroxide solution and aqueous ammonia, and the like.
In the invention, when pure acid is adopted in the dissolution of the prior-order lithium-phosphorus aluminum, the pH value is adjusted by using alkali solution, otherwise, the water content of the dissolution liquid is lower, and the pH value adjusting significance does not exist; however, when an acid solution is used for the pre-pralidoxime dissolution, liquid ammonia or a solid base can be used for adjusting the pH of the solution. However, in view of the exothermic dissolution of the alkali solid, the pH of the solution is stabilized slowly because the solution has an influence on the ionization balance in the solution, and an alkali solution is preferable for the purpose of improving the production efficiency.
Preferably, a buffer is added to the dissolution liquid after adjusting the pH of the dissolution liquid.
Preferably, the buffer includes any one of sodium dihydrogen phosphate-disodium hydrogen phosphate, citric acid-sodium citrate, potassium hydrogen phthalate-sodium hydroxide, or hexamethylenetetramine-hydrochloric acid.
In the present invention, in order to sufficiently precipitate aluminum phosphate, the dissolution liquid needs to be left to stand for a certain period of time after the pH is adjusted, and in order to ensure the pH value of the dissolution liquid to be stable, a small amount of a buffer is added to the dissolution liquid after the pH of the dissolution liquid is adjusted, and the buffer is not limited to the above-mentioned buffer pair, and any buffer that can be used within the range of pH4 to 6 is suitable for the present invention. The buffer may be added as a solid or as a buffer.
As a preferred embodiment of the present invention, the precipitating agent comprises any one of sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium fluoride or potassium fluoride, or a combination of at least two of them, and typical but non-limiting examples of the combination are: a combination of sodium and potassium carbonate, a combination of sodium and potassium phosphate, or a combination of sodium and potassium fluoride, and the like.
In the invention, after the aluminum phosphate is precipitated, the first lithium-containing solution obtained by filtering mainly comprises lithium ions, cations in a pH regulator and acid radical ions in a dissolving-out step, and the lithium ions and the cations (sodium ions, potassium ions or ammonium ions) in the pH regulator cannot be separated by adopting the steps of evaporating a solvent and the like, so that the lithium ions are precipitated by adding a precipitator into the first lithium-containing solution to achieve the aim of fully separating the lithium ions, and the obtained lithium-containing precipitate has high purity and can be used as a product after simple post-treatment such as crushing, washing and the like.
As a preferable technical scheme of the invention, the aluminum precipitation agent is ammonium sulfate.
In the present invention, ammonium sulfate is preferably added as an aqueous solution for the subsequent sufficient crystallization of lithium ammonium sulfate dodecahydrate.
Preferably, the temperature of the heating reaction is 100 to 300 ℃, such as 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 280 ℃ or 300 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Wherein, the reaction temperature exceeds the boiling point of water in the solution, and in order to ensure the stability of the mass ratio of the reactants, the reaction needs to be carried out in a closed reactor which can bear high pressure, such as a high-pressure reaction kettle and the like.
Preferably, the heating reaction time is 0.5-6 h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, water is added to the digestion solution prior to said heating reaction.
Preferably, after the heating reaction, the reaction system is cooled to 1 to 5 ℃ to crystallize the aluminum-containing solid, and the temperature may be 1 ℃, 1.5 ℃, 2 ℃, 2.5 ℃, 3 ℃, 3.5 ℃, 4 ℃, 4.5 ℃ or 5 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the aluminum element is separated from the lithium element by utilizing the characteristic that the aluminum ammonium sulfate is insoluble in water at low temperature, and the lithium element cannot occupy any position in the crystal lattice of the ammonium aluminum sulfate dodecahydrate in the crystallization process, so that the lithium phosphate and the ammonium aluminum sulfate dodecahydrate cannot be crystallized together, and the extraction rate of the lithium element is ensured.
In a preferred embodiment of the present invention, the pH of the second lithium-containing solution is adjusted to 8 to 14, such as 8, 9, 10, 11, 12, 13, or 14, but the pH is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably 10 to 12.
Preferably, the lithium-containing compound is supplemented to the second lithium-containing solution before said adjusting the pH of the second lithium-containing solution.
Preferably, the lithium-containing compound comprises any one of lithium sulfate, lithium chloride, lithium nitrate or lithium hydroxide, or a combination of at least two of these, typical but non-limiting examples being: a combination of lithium sulfate and lithium chloride, a combination of lithium chloride and lithium nitrate, a combination of lithium nitrate and lithium hydroxide, a combination of lithium sulfate, lithium chloride and lithium nitrate, or the like.
Preferably, a pH adjusting agent is added to the solution while said adjusting the pH of the second lithium-containing solution.
Preferably, the pH adjusting agent comprises any one or a combination of at least two of liquid ammonia, solid sodium hydroxide or solid potassium hydroxide, or any one or a combination of at least two of aqueous ammonia, solution sodium hydroxide or solution potassium hydroxide, as typical but non-limiting examples: combinations of liquid ammonia and sodium hydroxide solids, sodium hydroxide solids and potassium hydroxide solids, potassium hydroxide solids and liquid ammonia, aqueous ammonia and sodium hydroxide solution, sodium hydroxide solution and potassium hydroxide solution, potassium hydroxide solution and aqueous ammonia, and the like.
Preferably, after adjusting the pH of the dissolution liquid, adding a buffer to the dissolution liquid;
preferably, the buffer comprises any one of boric acid-potassium chloride-sodium hydroxide, ammonium chloride-aqueous ammonia, disodium hydrogen phosphate-sodium hydroxide, sodium hydrogen carbonate-sodium hydroxide, or Tris-HCl.
In the present invention, since lithium phosphate is sufficiently precipitated, the dissolution liquid needs to be left to stand for a certain period of time after the pH is adjusted, and in order to ensure a stable pH value of the dissolution liquid, a small amount of a buffer is added to the dissolution liquid after the pH of the dissolution liquid is adjusted, and the buffer is not limited to the above-mentioned buffer pair, and any buffer that can be used within a range of pH8 to 14 is suitable for the present invention. The buffer may be added as a solid or as a buffer.
As a preferred embodiment of the present invention, the iron source comprises any one of ferrous sulfate, ferrous chloride, ferrous nitrate, ferric sulfate, ferric chloride or ferric nitrate, or at least a combination thereof, and typical but non-limiting examples of the combination are: combinations of ferrous sulfate and ferrous chloride, ferrous chloride and ferrous nitrate, ferrous nitrate and ferrous sulfate, ferric sulfate and ferric chloride, ferric chloride and ferric nitrate, ferric nitrate and ferric sulfate, and the like.
Preferably, when the iron element in the iron source is trivalent positive, the reducing agent is added at the same time.
Preferably, the reducing agent comprises any one of iron powder, potassium borohydride, sodium borohydride, hypophosphorous acid or sodium hypophosphite, or a combination of at least two of them, as typical but non-limiting examples: a combination of iron powder and potassium borohydride, a combination of potassium borohydride and sodium borohydride, a combination of sodium borohydride and hypophosphorous acid, a combination of hypophosphorous acid and sodium hypophosphite, or a combination of iron powder, potassium borohydride and sodium borohydride, and the like.
In the invention, because the ferrous ions can be obtained by reducing the ferric ions, the ferrous ions can be replaced by the form of adding the ferric ion salts and the reducing agent together in principle, but in order to improve the production efficiency, the method of obtaining the corresponding ferrous ion salts by reacting the reducing agent and the ferric ion salts in advance is more applicable.
Preferably, the sintering is performed under a protective atmosphere.
Preferably, the protective atmosphere comprises any one of nitrogen, helium, neon or argon, or a combination of at least two of these, typical but non-limiting examples being: a combination of nitrogen and helium, a combination of helium and neon, a combination of neon and argon, a combination of argon and nitrogen, or a combination of nitrogen, helium and argon, and the like.
Preferably, the sintering temperature is 500 to 900 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the sintering time is 10-30 h, such as 10h, 12h, 15h, 18h, 20h, 22h, 25h, 28h or 30h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the lithium iron phosphate is carbon-coated to obtain lithium iron phosphate containing a carbon coating layer.
The carbon coating of the lithium iron phosphate can be performed by a ball milling method, a vapor deposition method, an organic carbon source sintering method or the like, which are conventional operations in the field, and thus, the description is omitted.
As a preferred embodiment of the present invention, the method for preparing a lithium-containing compound from the lithium-phosphorus-aluminum ore comprises the following steps:
mixing the lithium-phosphorus-aluminum alloy with acid, wherein the mass ratio of the lithium-phosphorus-aluminum alloy to the acid is 1 (1-4), and reacting at 150-350 ℃ to obtain a dissolution liquid;
adding a pH regulator at 20-100 ℃, regulating the pH of a dissolution liquid to 2-5, carrying out solid-liquid separation to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding a precipitator into the first lithium-containing solution, and carrying out solid-liquid separation to obtain a lithium salt;
or adding ammonium sulfate into the dissolution liquid, heating to react at 100-300 ℃, cooling the reaction system to 1-5 ℃, crystallizing to obtain an aluminum-containing solid, performing solid-liquid separation to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adjusting the pH of the second lithium-containing solution to 8-14, performing solid-liquid separation to obtain lithium phosphate, or adding an iron source into the second lithium-containing solution, performing solid-liquid separation to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor to obtain the lithium iron phosphate.
In the present invention, the solid-liquid separation is independently selected from any one or a combination of at least two of filtration, centrifugation, evaporation, or sedimentation. And the corresponding operation method is well known in the art, and thus is not described in detail.
In the invention, when the pH is adjusted, a pH test paper can be used for testing or a pH instrument can be used for real-time measurement, and when the pH reaches the corresponding range defined by the invention, the addition of the pH regulator can be stopped, so that the addition amount of the pH regulator is not specifically defined by the invention.
In the invention, the obtained product needs to be subjected to purification treatment such as crushing, recrystallization or water washing to remove a small amount of impurities in the product, the methods are all conventional operations in the field, and detailed description is omitted.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a method for preparing a lithium-containing compound from lithium-phosphorus-aluminum, which adopts a dissolving-out mode of mixing and heating lithium-phosphorus-aluminum and acid to improve the dissolving-out rate of lithium in the lithium-phosphorus-aluminum;
(2) the invention provides a method for preparing a lithium-containing compound from lithium-phosphosiderite, which separates aluminum element and phosphorus element in a stripping solution by adjusting pH, and reduces the loss of lithium element in the separation process;
(3) the invention provides a method for preparing a lithium-containing compound from the lithium-phosphorus-aluminum-stone, which can also remove aluminum element by adding an aluminum precipitation agent into a dissolution liquid and adjusting the pH value, so that the lithium element and the phosphorus element are jointly utilized, the loss of the lithium element in the separation process is reduced, the phosphorus element in the lithium-phosphorus-aluminum-stone is fully utilized, and the production process is simplified;
(4) the invention provides a method for preparing a lithium-containing compound from lithium-phosphosiderite, which comprises the step of separating an aluminum element and/or a phosphorus element, so that the lithium element is fully separated from the two elements, and the purity of the lithium-containing compound in a product is improved;
(5) the invention provides a method for preparing a lithium-containing compound from the lithium-phosphorus-aluminum, which has the advantages of simple process flow and simple and convenient operation, can fully extract the lithium element in the lithium-phosphorus-aluminum, and the prepared lithium-containing compound has high purity. When the lithium salt product is insoluble in water, the extraction rate of lithium can reach more than 95%, and the product purity can reach more than 99%; when the lithium salt product is slightly soluble in water, the extraction rate of lithium can reach more than 90%, and the purity of the product can reach more than 99%; the extraction rate of lithium of the lithium iron phosphate product can reach more than 95%, and the product purity can reach more than 99%.
Drawings
Fig. 1 is a flow chart of a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum according to the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
mixing the lithium-phosphorus-aluminum ore and concentrated sulfuric acid according to the mass ratio of 1:1, and reacting for 1h at 350 ℃ to obtain a dissolution liquid;
adding ammonia water at 20 ℃, adjusting the pH value of the dissolution liquid to 2, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium carbonate into the first lithium-containing solution until no precipitate is generated, filtering, and washing the solid obtained by filtering with deionized water for 3 times to obtain lithium carbonate.
According to the method, the extraction rate of the lithium element is 95.2%, and the purity of the prepared lithium carbonate is 99.0%.
Example 2
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
mixing the lithium-phosphorus-aluminum ore and concentrated hydrochloric acid according to the mass ratio of 1:4, and reacting at 150 ℃ for 12 hours to obtain a dissolution liquid;
adding solid sodium hydroxide at 100 ℃, adjusting the pH value of a dissolution liquid to 5, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium phosphate into the first lithium-containing solution, concentrating, crystallizing, filtering, and recrystallizing the obtained solid for 3 times to obtain lithium phosphate.
The extraction rate of lithium element is 93.1%, and the purity of the prepared lithium phosphate is 99.2%.
Example 3
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
mixing the lithium-phosphorus-aluminum ore and concentrated nitric acid according to the mass ratio of 1:2, and reacting for 5 hours at 200 ℃ to obtain a dissolution liquid;
adding potassium hydroxide solid at 50 ℃, adjusting the pH value of a dissolution liquid to 3, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium fluoride into the first lithium-containing solution until no precipitate is generated, filtering, and recrystallizing the obtained solid for 3 times to obtain lithium fluoride.
The extraction rate of lithium element is 92.5%, and the purity of the prepared lithium fluoride is 99.0%.
Example 4
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
mixing the lithium-phosphorus-aluminum and trifluoroacetic acid solution according to the mass ratio of 1:3, and reacting for 3 hours at 300 ℃ to obtain a dissolution liquid;
adding 1mol/L sodium hydroxide solution at 80 ℃, adjusting the pH value of a dissolution liquid to 4, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium carbonate into the first lithium-containing solution until no precipitate is generated, filtering, and washing the solid obtained by filtering with deionized water for 3 times to obtain lithium carbonate.
According to the method, the extraction rate of lithium element is 96.1%, and the purity of the prepared lithium carbonate is 99.2%.
Example 5
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
raising the reaction temperature to 350 ℃ at the speed of 2 ℃/min, adding concentrated sulfuric acid into the lithium-phosphorus-aluminum-stone in the temperature raising process, reacting for 1h to obtain a dissolution liquid, wherein the mass ratio of the lithium-phosphorus-aluminum-stone to the concentrated sulfuric acid is 1: 1;
adding ammonia water at 20 ℃, adjusting the pH value of the dissolution liquid to 2, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium carbonate into the first lithium-containing solution until no precipitate is generated, filtering, and washing the solid obtained by filtering with deionized water for 3 times to obtain lithium carbonate.
According to the method, the extraction rate of the lithium element is 97.8%, and the purity of the prepared lithium carbonate is 99.5%.
Example 6
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
raising the reaction temperature to 150 ℃ at a speed of 1 ℃/min, simultaneously adding concentrated hydrochloric acid into the lithium-phosphorus-aluminum-based material in the temperature raising process, reacting the lithium-phosphorus-based material and the concentrated hydrochloric acid according to a mass ratio of 1:4 for 12h to obtain a dissolution liquid;
adding solid sodium hydroxide at 100 ℃, adjusting the pH value of a dissolution liquid to 5, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium phosphate into the first lithium-containing solution, concentrating, crystallizing, filtering, and recrystallizing the obtained solid for 3 times to obtain lithium phosphate.
The extraction rate of the lithium element is 98.1%, and the purity of the prepared lithium phosphate is 99.6%.
Example 7
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
raising the reaction temperature to 200 ℃ at the speed of 2 ℃/min, simultaneously adding concentrated nitric acid into the lithium-phosphorus-aluminum-based powder in the temperature raising process, reacting the lithium-phosphorus-based powder and the concentrated nitric acid for 5 hours to obtain a dissolution liquid, wherein the mass ratio of the lithium-phosphorus-based powder to the concentrated nitric acid is 1: 2;
adding potassium hydroxide solid at 50 ℃, adjusting the pH value of a dissolution liquid to 3, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium fluoride into the first lithium-containing solution until no precipitate is generated, filtering, and recrystallizing the obtained solid for 3 times to obtain lithium fluoride.
The extraction rate of the lithium element is 97.3%, and the purity of the prepared lithium fluoride is 99.5%.
Example 8
This example provides a method for preparing a lithium-containing compound from a lithium-phosphor-aluminum comprising the steps of:
raising the reaction temperature to 300 ℃ at the speed of 2 ℃/min, adding a saturated trifluoroacetic acid solution into the lithium-phosphorus aluminum in the process of raising the temperature, reacting for 3 hours to obtain a dissolution liquid, wherein the mass ratio of the lithium-phosphorus aluminum to the saturated trifluoroacetic acid solution is 1: 3;
adding 1mol/L sodium hydroxide solution at 80 ℃, adjusting the pH value of a dissolution liquid to 4, filtering to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding sodium carbonate into the first lithium-containing solution until no precipitate is generated, filtering, and washing the solid obtained by filtering with deionized water for 3 times to obtain lithium carbonate.
According to the method, the extraction rate of the lithium element is 97.5%, and the purity of the prepared lithium carbonate is 99.5%.
Example 9
Mixing the lithium-phosphorus-aluminum ore and concentrated sulfuric acid according to the mass ratio of 1:1, and reacting at 350 ℃ for 1h to obtain a dissolution liquid;
adding 0.1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating the ammonium sulfate and aluminum element in the dissolution liquid at a molar ratio of 1.05:1, reacting for 6h at 100 ℃, cooling a reaction system to 1 ℃ after the reaction is finished to crystallize an aluminum-containing solid, filtering to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding ammonia water into the second lithium-containing solution, adjusting the pH value of the second lithium-containing solution to 8, filtering, and washing the filtered solid with deionized water for 3 times to obtain lithium phosphate.
The extraction rate of the lithium element is 92.5%, and the purity of the prepared lithium phosphate is 99.0%.
Example 10
Mixing the lithium-phosphorus-aluminum ore and concentrated hydrochloric acid according to the mass ratio of 1:4, and reacting at 150 ℃ for 12 hours to obtain a dissolution liquid;
adding 1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating the ammonium sulfate and aluminum element in the dissolution liquid at the molar ratio of 1.1:1, reacting at 300 ℃ for 0.5h, cooling the reaction system to 5 ℃ after the reaction is finished, crystallizing out an aluminum-containing solid, filtering to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding sodium hydroxide solid into the second lithium-containing solution, adjusting the pH value of the second lithium-containing solution to 14, filtering, and washing the filtered solid with deionized water for 3 times to obtain lithium phosphate.
The extraction rate of lithium element is 93.0%, and the purity of the prepared lithium phosphate is 99.1%.
Example 11
Mixing the lithium-phosphorus-aluminum ore and concentrated nitric acid according to the mass ratio of 1:2, and reacting for 5 hours at 200 ℃ to obtain a dissolution liquid;
adding 0.5mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating the ammonium sulfate and aluminum element in the dissolution liquid at a molar ratio of 1.1:1, reacting for 3h at 150 ℃, cooling a reaction system to 2 ℃ after the reaction is finished to crystallize an aluminum-containing solid, performing solid-liquid separation to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding 1mol/L potassium hydroxide solution into the second lithium-containing solution, adjusting the pH value of the second lithium-containing solution to 12, filtering, washing the filtered solid with deionized water for 3 times to obtain lithium phosphate.
The extraction rate of the lithium element is 92.7%, and the purity of the prepared lithium phosphate is 99.1%.
Example 12
Mixing the lithium-phosphorus-aluminum ore and concentrated hydrochloric acid according to the mass ratio of 1:4, and reacting for 3 hours at 300 ℃ to obtain a dissolution liquid;
adding 1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating the ammonium sulfate and aluminum element in the dissolution liquid at a molar ratio of 1.1:1, reacting for 1h at 200 ℃, cooling a reaction system to 3 ℃ after the reaction is finished, crystallizing out an aluminum-containing solid, filtering to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding sodium hydroxide solid into the second lithium-containing solution, adjusting the pH value of the second lithium-containing solution to 10, filtering, and washing the filtered solid with deionized water for 3 times to obtain lithium phosphate.
The extraction rate of the lithium element is 92.6%, and the purity of the prepared lithium phosphate is 99.2%.
Example 13
Mixing the lithium-phosphorus-aluminum ore and concentrated sulfuric acid according to the mass ratio of 1:1, and reacting for 1h at 350 ℃ to obtain a dissolution liquid;
adding 0.1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating and reacting the ammonium sulfate and aluminum element in the dissolution liquid at the molar ratio of 1.05:1 at 100 ℃, reacting for 6h, cooling a reaction system to 1 ℃ after the reaction is finished to crystallize an aluminum-containing solid, filtering to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding ferrous chloride into the second lithium-containing solution until no precipitate is generated, filtering, washing the filtered solid with deionized water for 3 times to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor for 30h under the protection of nitrogen at the temperature of 500 ℃ to obtain the lithium iron phosphate.
The extraction rate of lithium element is 94.5%, and the purity of the prepared lithium iron phosphate is 99.5%.
Example 14
Mixing the lithium-phosphorus-aluminum ore and concentrated hydrochloric acid according to the mass ratio of 1:4, and reacting at 150 ℃ for 12 hours to obtain a dissolution liquid;
adding 1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating and reacting at 300 ℃ for 0.5h, cooling a reaction system to 5 ℃ after the reaction is finished to crystallize an aluminum-containing solid, filtering to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding ferrous sulfate into the second lithium-containing solution until no precipitate is generated, filtering, washing the filtered solid with deionized water for 3 times to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor at 900 ℃ for 10h under the protection of nitrogen to obtain the lithium iron phosphate.
The extraction rate of lithium element is 94.1%, and the purity of the prepared lithium iron phosphate is 99.2%.
Example 15
Mixing the lithium-phosphorus-aluminum ore and concentrated nitric acid according to the mass ratio of 1:2, and reacting for 5 hours at 200 ℃ to obtain a dissolution liquid;
adding 0.5mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating and reacting the ammonium sulfate and aluminum element in the dissolution liquid at the molar ratio of 1.1:1 at 150 ℃, reacting for 3h, cooling a reaction system to 2 ℃ after the reaction is finished to crystallize aluminum-containing solid, performing solid-liquid separation to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adding ferric chloride and iron powder (the molar ratio of 1.1:1) into the second lithium-containing solution until no precipitate is generated, filtering, washing the filtered solid with deionized water for 3 times to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor for 24h under the protection of nitrogen at the temperature of 600 ℃ to obtain the lithium iron phosphate.
The extraction rate of lithium element is 94.2%, and the purity of the prepared lithium iron phosphate is 99.1%.
Example 16
Mixing the lithium-phosphorus-aluminum ore and concentrated hydrochloric acid according to the mass ratio of 1:4, and reacting for 3 hours at 300 ℃ to obtain a dissolution liquid;
adding 1mol/L ammonium sulfate aqueous solution into the dissolution liquid, heating the ammonium sulfate and aluminum element in the dissolution liquid at a molar ratio of 1.1:1, reacting for 1h at 200 ℃, cooling a reaction system to 3 ℃ after the reaction is finished to crystallize an aluminum-containing solid, filtering to obtain a second lithium-containing solution and aluminum ammonium sulfate dodecahydrate, adding ferric nitrate and sodium hypophosphite (the molar ratio is 4.1:1) into the second lithium-containing solution until no precipitate is generated, filtering, washing the filtered solid with deionized water for 3 times to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor for 12h under the protection of nitrogen at 800 ℃ to obtain lithium iron phosphate.
The extraction rate of lithium element is 94.5%, and the purity of the prepared lithium iron phosphate is 99.1%.
Comparative example 1
In this comparative example, the conditions were the same as in example 4 except that the mass ratio of the phosphoric acid aluminum stone to the sulfuric acid was 1: 0.8.
According to the method, the extraction rate of the lithium element is 82.5%, and the purity of the prepared lithium carbonate is 73.1%.
Comparative example 2
In this comparative example, the conditions were the same as in example 4 except that the mass ratio of the phosphoric acid aluminum stone to the sulfuric acid was 1: 5.
According to the method, the extraction rate of the lithium element is 87.3%, and the purity of the prepared lithium carbonate is 75.2%.
Comparative example 3
In this comparative example, the conditions were the same as in example 4 except that the reaction temperature of the lithium-phosphosiderite with the acid was 80 ℃.
The extraction rate of lithium element is 86.7%, and the purity of the prepared lithium carbonate is 82.9%.
Comparative example 4
In this comparative example, the conditions were the same as in example 4 except that the reaction temperature of the lithium-phosphosiderite with the acid was 500 ℃.
The extraction rate of the lithium element is 83.1%, and the purity of the prepared lithium carbonate is 80.4%.
Comparative example 5
In this comparative example, the conditions were the same as in example 4 except that a pH adjuster was added to adjust the pH to 1.
According to the method, the extraction rate of the lithium element is 91.3%, and the purity of the prepared lithium carbonate is 65.1%.
Comparative example 6
In this comparative example, the conditions were the same as in example 4 except that a pH adjusting agent was added to adjust the pH to 7.
According to the method, the extraction rate of lithium element is 56.5%, and the purity of the prepared lithium carbonate is 92.7%.
Comparative example 7
In this comparative example, the conditions were the same as in example 8 except that evaporative crystallization was used instead of cooling crystallization.
The extraction rate of the lithium element is 83.7%, and the purity of the prepared lithium phosphate is 84.9%.
Comparative example 8
In this comparative example, the conditions were the same as in example 8 except that sodium fluoride was used as an aluminum precipitating agent.
The extraction rate of the lithium element is 81.2%, and the purity of the prepared lithium phosphate is 43.5%. The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (26)
1. A method for preparing a lithium-containing compound from a lithium-phosphosiderite, characterized in that the method comprises the steps of:
mixing the lithium-phosphorus-aluminum and acid to obtain a dissolution liquid; adding the acid simultaneously during the reaction temperature rise; the reaction is carried out under a sealed condition; the reaction temperature rise process comprises rising the reaction temperature at 1 ℃/min or 2 ℃/min; the acid comprises organic acid and/or inorganic acid, and the inorganic acid comprises any one or the combination of at least two of sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the organic acid comprises trifluoroacetic acid; the sulfuric acid is concentrated sulfuric acid, the nitric acid is concentrated nitric acid, the hydrochloric acid is concentrated hydrochloric acid, and the trifluoroacetic acid is saturated trifluoroacetic acid;
adding a pH regulator, regulating the pH of the dissolution liquid, carrying out solid-liquid separation to obtain a first lithium-containing solution and aluminum phosphate precipitate, adding a precipitator into the first lithium-containing solution, and carrying out solid-liquid separation to obtain a lithium salt;
or adding an aluminum precipitation agent into the dissolution liquid, carrying out solid-liquid separation after heating reaction to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adjusting the pH value of the second lithium-containing solution, carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the second lithium-containing solution, carrying out solid-liquid separation to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor to obtain lithium iron phosphate;
the mass ratio of the lithium-phosphorus-aluminum to the acid is 1 (1-4);
mixing the lithium-phosphorus-aluminum and acid, and reacting at 150-350 ℃;
adding a pH regulator, and regulating the pH of the dissolution liquid to 3.5-4.5;
after adjusting the pH of the dissolution liquid, adding a buffering agent into the dissolution liquid and standing;
the aluminum precipitation agent is ammonium sulfate;
the temperature of the heating reaction is 100-300 ℃;
cooling the reaction system to 1-5 ℃ after the heating reaction to crystallize an aluminum-containing solid;
when the lithium salt is insoluble in water, the extraction rate of lithium can reach more than 95%, and the product purity can reach more than 99%; when the lithium salt is slightly soluble in water, the extraction rate of the lithium can reach more than 90 percent, and the purity of the product can reach more than 99 percent; the extraction rate of lithium of the lithium iron phosphate product can reach more than 95%, and the product purity can reach more than 99%.
2. The method of claim 1, wherein the mass ratio of the lithium-phosphorus-aluminum to the acid is 1 (1.5-3).
3. The method according to claim 1 or 2, wherein the reaction time is 1 to 12 hours.
4. The method according to claim 1 or 2, wherein the temperature of the dissolution liquid when the pH regulator is added is 20 to 100 ℃.
5. The method according to claim 4, wherein the temperature of the dissolution liquid when the pH regulator is added is 60 to 90 ℃.
6. The method of claim 1 or 2, wherein the pH adjusting agent comprises any one or a combination of at least two of liquid ammonia, solid sodium hydroxide, or solid potassium hydroxide, or any one or a combination of at least two of aqueous ammonia, solution sodium hydroxide, or solution potassium hydroxide.
7. The method of claim 1 or 2, wherein the buffer comprises any one of sodium dihydrogen phosphate-disodium hydrogen phosphate, citric acid-sodium citrate, potassium hydrogen phthalate-sodium hydroxide, or hexamethylenetetramine-hydrochloric acid.
8. The method of claim 1, wherein the precipitating agent comprises any one of sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium fluoride, or potassium fluoride, or a combination of at least two thereof.
9. The method according to claim 1 or 2, wherein the heating reaction time is 0.5-6 h.
10. A process according to claim 1 or 2, characterized in that water is added to the digestion solution before the heating reaction.
11. The method of claim 1 or 2, wherein the adjusting the pH of the second lithium-containing solution is to 8 to 14.
12. The method of claim 11, wherein the adjusting the pH of the second lithium-containing solution is between 10 and 12.
13. The method of claim 1 or 2, wherein the lithium-containing compound is supplemented to the second lithium-containing solution prior to said adjusting the pH of the second lithium-containing solution.
14. The method of claim 13, wherein the lithium-containing compound comprises any one of lithium sulfate, lithium chloride, lithium nitrate, or lithium hydroxide, or a combination of at least two thereof.
15. The method of claim 1 or 2, wherein a pH adjusting agent is added to the solution while said adjusting the pH of the second lithium-containing solution.
16. The method of claim 15, wherein the pH adjusting agent comprises any one or a combination of at least two of liquid ammonia, solid sodium hydroxide, or solid potassium hydroxide, or any one or a combination of at least two of aqueous ammonia, solution sodium hydroxide, or solution potassium hydroxide.
17. The method of claim 1 or 2, wherein the buffer comprises any one of boric acid-potassium chloride-sodium hydroxide, ammonium chloride-ammonia, disodium hydrogen phosphate-sodium hydroxide, sodium bicarbonate-sodium hydroxide, or Tris-HCl.
18. The method of claim 1 or 2, wherein the iron source comprises any one of ferrous sulfate, ferrous chloride, ferrous nitrate, ferric sulfate, ferric chloride, or ferric nitrate, or a combination of at least two thereof.
19. A method according to claim 1 or 2, characterized in that the reducing agent is added simultaneously when the iron element in the iron source is trivalent positive.
20. The method of claim 19, wherein the reducing agent comprises any one of iron powder, potassium borohydride, sodium borohydride, hypophosphorous acid, or sodium hypophosphite, or a combination of at least two thereof.
21. The method according to claim 1 or 2, characterized in that the sintering is carried out under a protective atmosphere.
22. The method of claim 21, wherein the protective atmosphere comprises any one of nitrogen, helium, neon, or argon, or a combination of at least two thereof.
23. The method according to claim 1 or 2, wherein the sintering temperature is 500 to 900 ℃.
24. The method of claim 23, wherein the sintering time is 10-30 hours.
25. The method according to claim 1 or 2, wherein the lithium iron phosphate is carbon-coated to obtain lithium iron phosphate containing a carbon-coated layer.
26. Method according to claim 1, characterized in that it comprises the following steps:
mixing the lithium-phosphorus-aluminum alloy with acid, wherein the mass ratio of the lithium-phosphorus-aluminum alloy to the acid is 1 (1-4), and reacting at 150-350 ℃ to obtain a dissolution liquid;
adding a pH regulator at 20-100 ℃, regulating the pH of a dissolution liquid to 3.5-4.5, performing solid-liquid separation to obtain a first lithium-containing solution and an aluminum phosphate precipitate, adding a precipitator into the first lithium-containing solution, and performing solid-liquid separation to obtain a lithium salt;
or adding ammonium sulfate into the dissolution liquid, heating to react at 100-300 ℃, cooling the reaction system to 1-5 ℃, crystallizing to obtain an aluminum-containing solid, performing solid-liquid separation to obtain a second lithium-containing solution and ammonium aluminum sulfate dodecahydrate, adjusting the pH of the second lithium-containing solution to 8-14, performing solid-liquid separation to obtain lithium phosphate, or adding an iron source into the second lithium-containing solution, performing solid-liquid separation to obtain a lithium iron phosphate precursor, and sintering the lithium iron phosphate precursor to obtain the lithium iron phosphate.
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| CN110357055B (en) * | 2019-08-09 | 2022-07-15 | 深圳市德方纳米科技股份有限公司 | Method for extracting lithium from salt lake brine and preparing lithium phosphate and application thereof |
| CN110817829A (en) * | 2019-12-13 | 2020-02-21 | 九江天赐高新材料有限公司 | Method for preparing high-purity anhydrous aluminum orthophosphate from solid raw material containing aluminum and phosphorus |
| CN111252749B (en) * | 2020-01-21 | 2022-11-22 | 曲靖市德方纳米科技有限公司 | Method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum |
| CN111252750A (en) * | 2020-01-21 | 2020-06-09 | 曲靖市德方纳米科技有限公司 | Method for preparing iron phosphate and aluminum oxide from phosphorus aluminum slag |
| JP7166653B2 (en) * | 2020-10-02 | 2022-11-08 | 株式会社アサカ理研 | Method for producing high-purity lithium salt aqueous solution |
| CN114620704B (en) * | 2022-03-14 | 2023-06-06 | 湖州南木纳米科技有限公司 | Material for improving safety of battery and preparation method and application thereof |
| CN114572955B (en) * | 2022-03-24 | 2023-06-13 | 广东光华科技股份有限公司 | Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159308A (en) * | 1975-06-30 | 1979-06-26 | The University Of Melbourne | Mineral treatment |
| WO2017139852A1 (en) * | 2016-02-18 | 2017-08-24 | Li-Technology Pty Ltd | Lithium recovery from phosphate minerals |
| CN107265425A (en) * | 2017-07-28 | 2017-10-20 | 贵州大学 | The method that lithium phosphate is prepared using pelite containing lithium |
| CN108277367A (en) * | 2017-01-06 | 2018-07-13 | 中国科学院过程工程研究所 | A method of carrying lithium from containing lithium ore |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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-
2018
- 2018-09-21 CN CN201811110542.9A patent/CN109052436B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159308A (en) * | 1975-06-30 | 1979-06-26 | The University Of Melbourne | Mineral treatment |
| WO2017139852A1 (en) * | 2016-02-18 | 2017-08-24 | Li-Technology Pty Ltd | Lithium recovery from phosphate minerals |
| CN108277367A (en) * | 2017-01-06 | 2018-07-13 | 中国科学院过程工程研究所 | A method of carrying lithium from containing lithium ore |
| CN107265425A (en) * | 2017-07-28 | 2017-10-20 | 贵州大学 | The method that lithium phosphate is prepared using pelite containing lithium |
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Address after: 518000 1001, building 1, Chongwen Park, Nanshan Zhiyuan garden, no.3370 Liuxian Avenue, Fuguang community, Taoyuan Street, Nanshan District, Shenzhen City, Guangdong Province Applicant after: SHENZHEN DYNANONIC Co.,Ltd. Address before: 518000 223, kanghesheng building, No. 1, ChuangSheng Road, Nanshan District, Shenzhen, Guangdong (West of Baisha Logistics Park) Applicant before: SHENZHEN DYNANONIC Co.,Ltd. |
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