CN108910851B - 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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- C01B25/00—Phosphorus; Compounds thereof
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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 ore with acid and hydrogen fluoride, wherein the acid does not contain hydrofluoric acid, and obtaining mixed solution; adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution; or adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, heating the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution; and adjusting the pH value of the lithium-containing solution, and carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the 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 has 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. 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 a lithium-containing compound, and particularly relates to a method for preparing the 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-containing compound has high purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing a lithium-containing compound from lithium-phosphorus aluminum, which comprises the following steps:
mixing the lithium-phosphorus-aluminum ore with acid and hydrogen fluoride, wherein the acid does not contain hydrofluoric acid, and obtaining mixed solution;
adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution;
or adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, heating the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution;
and adjusting the pH value of the lithium-containing solution, and carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the 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 the method, aluminum element is dissolved by hydrofluoric acid to generate hexafluoroaluminate acid, the pH is adjusted by a pH regulator to generate sodium hexafluoroaluminate or potassium hexafluoroaluminate precipitate, or ammonium hexafluoroaluminate which is easy to dissolve in water is generated, and aluminum fluoride precipitate, ammonia gas and hydrogen fluoride are generated in a heating decomposition mode, so that the aim of separating the aluminum element is fulfilled.
In a preferred embodiment of the present invention, the mass ratio of the above-mentioned lithium-phosphorus-aluminum-fluoride to hydrogen fluoride is 1 (0.8 to 2.0), for example, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.0, but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable, and 1 (1.0 to 1.5) is preferable.
When the mass ratio of the lithium-phosphosiderite to the hydrogen fluoride is more than 1:0.8, aluminum element partially generates tetrafluoro aluminic acid, and cannot be separated from the solution through precipitation; when the mass ratio of the lithium-phosphorus-aluminum alloy to the hydrogen fluoride is less than 1:2.0, fluorine ions can be combined with other impurity elements in the lithium-phosphorus-aluminum alloy, so that the purity of the product is reduced.
In a preferred embodiment of the present invention, the mass ratio of the acid to hydrogen fluoride is (0.1 to 1.0):1, and the acid does not include hydrofluoric acid, and may be, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1.0:1, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
In the present invention, the acid is added to promote the dissolution of lithium, aluminum and phosphate, the mass ratio of the acid to hydrofluoric acid is less than 0.1:1, which results in a decrease in the dissolution of lithium, and when the mass ratio of the acid to hydrogen fluoride is greater than 1.0:1, the acid and fluorine ions act together to promote the dissolution of a large amount of impurity elements.
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 hydrogen fluoride 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.
In a preferred embodiment of the present invention, the pH adjusting agent is added to adjust the pH of the mixed solution to 4 to 6, such as 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8, or 6, but the pH adjusting agent is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
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 the pH regulator is non-liquid ammonia or ammonia water, the solution can generate slightly water-soluble hexafluoroaluminate, aluminum element can be separated through solid-liquid separation, although the solution still contains a small amount of hexafluoroaluminate, the solubility of the hexafluoroaluminate is poor in pH responsiveness in the subsequent process of precipitating lithium phosphate by adjusting pH through precipitation, and the pH is not separated out even when the pH is increased, so that the purity of the product is not influenced.
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.
In a preferred embodiment of the present invention, the temperature for heating the mixed solution is 300 to 500 ℃, for example, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃ or 500 ℃, 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.
In the invention, ammonium hexafluoroaluminate cannot be completely decomposed when the heating temperature is less than 300 ℃, and uncontrollable side reactions can occur in the system when the heating temperature is more than 500 ℃, so that the purity of the product is influenced. It is noted that when the pH is not adjusted within the range of 4 to 6, a large amount of aluminum remains in the solution regardless of the reaction temperature, and thus the pH of the solution and the reaction temperature together determine the degree of aluminum separation.
Preferably, the mixed solution is heated when the pH adjuster is liquid ammonia or ammonia water.
Preferably, the temperature of the mixed solution after the heating is maintained at 80 to 100 ℃, for example, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃ or 100 ℃, 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, ammonium hexafluoroaluminate is heated and decomposed to generate ammonia gas and hydrogen fluoride, in order to reduce excessive impurities caused by the subsequent lithium element precipitation step when the ammonia gas and the hydrogen fluoride are excessively dissolved into the solution, the temperature of the solution is controlled to be 80-100 ℃,
in a preferred embodiment of the present invention, the pH of the 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 within the above-mentioned range are also applicable, preferably 10 to 12.
In the invention, if the process is carried out under the supercooling condition, the impurity content of the precipitated lithium phosphate is too high, so that the control of the solution temperature has important influence on the lithium precipitation step.
Preferably, the lithium-containing compound is supplemented to the lithium-containing solution before said adjusting the pH of the 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 when said adjusting the pH of the 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-oxide with acid and hydrogen fluoride, wherein the acid does not contain hydrofluoric acid, the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1 (0.8-2), and the mass ratio of the acid to the hydrogen fluoride is (0.1-1): 1, so as to obtain a mixed solution;
adding a pH regulator into the mixed solution, regulating the pH of the mixed solution to 4-6, and carrying out solid-liquid separation to obtain a lithium-containing solution;
or adding a pH regulator into the mixed solution, regulating the pH of the mixed solution to 4-6, heating the mixed solution to 300-500 ℃ when the pH regulator is liquid ammonia or ammonia water, keeping the temperature of the mixed solution at 80-100 ℃ after heating, and performing solid-liquid separation to obtain a lithium-containing solution;
adjusting the pH value of the lithium-containing solution to 8-14, and carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the 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.
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 lithium-phosphorus-aluminum, acid and hydrofluoric acid, improves the dissolving-out rate of lithium element in the lithium-phosphorus-aluminum and is beneficial to the separation of subsequent lithium element;
(2) the invention provides a method for preparing a lithium-containing compound from lithium-phosphorus-aluminum, which separates aluminum elements in a mixed solution by means of hexafluoroaluminate generated by hydrofluoric acid and the aluminum elements in a mode of adjusting pH, reduces the loss of the lithium elements in the separation process, and improves the separation rate of the aluminum elements;
(3) the invention provides a method for preparing a lithium-containing compound from the lithium-phosphorus-aluminum-stone, which can also adopt liquid ammonia and ammonia water to adjust the pH value of the mixed solution, generate aluminum fluoride by means of heating, remove the aluminum element in the mixed solution, reduce the loss of the lithium element in the separation process and improve the separation rate of the aluminum element;
(4) the invention provides a method for preparing a lithium-containing compound from lithium-phosphosiderite, which comprises the step of separating aluminum element, so that the lithium element is fully separated from the aluminum element, 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 salt has high purity. The extraction rate of lithium of the lithium phosphate product can reach more than 95 percent, and the product purity 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%.
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:0.8, and the mass ratio of the hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.1:1 to obtain a mixed solution;
adding sodium hydroxide solid into the mixed solution, adjusting the pH value of the mixed solution to 4, and filtering to obtain a lithium-containing solution and sodium hexafluoroaluminate solid;
and (3) adjusting the pH value of the lithium-containing solution to 8 by using sodium hydroxide solid, adding lithium chloride until no precipitate is generated in the solution, filtering, and washing filter residue for 3 times by using deionized water to obtain lithium phosphate.
The extraction rate of the lithium element is 95.2%, and the purity of the prepared lithium phosphate is 99.1%.
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-oxide with concentrated nitric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:2, and the mass ratio of the nitric acid to the hydrogen fluoride in the concentrated nitric acid is 1:1 to obtain a mixed solution;
adding a potassium hydroxide solid into the mixed solution, adjusting the pH value of the mixed solution to 6, and filtering to obtain a lithium-containing solution and a potassium hexafluoroaluminate solid;
and (3) adjusting the pH value of the lithium-containing solution to 14 by using a potassium hydroxide solid, adding lithium chloride until no precipitate is generated in the solution, filtering, washing the filter residue for 3 times by using a phosphoric acid solution, and then washing the filter residue for 3 times by using deionized water to obtain the lithium phosphate.
The extraction rate of the lithium element is 95.9%, and the purity of the prepared lithium phosphate is 99.3%.
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.5:1 to obtain a mixed solution;
adding 1mol/L sodium hydroxide solution into the mixed solution, adjusting the pH value of the mixed solution to 5, and filtering to obtain a lithium-containing solution and sodium hexafluoroaluminate solid;
and (3) adjusting the pH value of the lithium-containing solution to 10 by using 1mol/L sodium hydroxide solution, adding lithium chloride until no precipitate is generated in the solution, filtering, and washing filter residue for 3 times by using deionized water to obtain the lithium phosphate.
The extraction rate of the lithium element is 96.1%, and the purity of the prepared lithium phosphate 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-oxide with concentrated nitric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1.5, and the mass ratio of the nitric acid to the hydrogen fluoride in the concentrated nitric acid is 1:0.8 to obtain a mixed solution;
adding 1mol/L potassium hydroxide solution into the mixed solution, adjusting the pH value of the mixed solution to 6, and carrying out solid-liquid separation to obtain a lithium-containing solution and potassium hexafluoroaluminate solid;
and (3) adjusting the pH value of the lithium-containing solution to 12 by using 1mol/L potassium hydroxide solution, adding lithium chloride until no precipitate is generated in the solution, filtering, washing the filter residue for 3 times by using phosphoric acid solution, and then washing the filter residue for 3 times by using deionized water to obtain the lithium phosphate.
The extraction rate of the lithium element is 95.7%, and the purity of the prepared lithium phosphate 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:
mixing the lithium-phosphorus-aluminum-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.5:1 to obtain a mixed solution;
adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 5, placing the solution into a high-pressure reaction kettle, heating the solution to 300 ℃, keeping the solution to 80 ℃ after the reaction is finished, and filtering to obtain a lithium-containing solution and an aluminum fluoride solid;
and (3) adjusting the pH value of the lithium-containing solution to 10 by using 1mol/L sodium hydroxide solution, adding lithium chloride until no precipitate is generated in the solution, filtering, and washing filter residue for 3 times by using deionized water to obtain the lithium phosphate.
The extraction rate of lithium element is 96.5%, and the purity of the prepared lithium phosphate is 99.1%.
Example 6
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1.5, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.8:1 to obtain a mixed solution;
adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 5, placing the solution into a high-pressure reaction kettle, heating the solution to 500 ℃, keeping the solution to 100 ℃ after the reaction is finished, and filtering to obtain a lithium-containing solution and an aluminum fluoride solid;
and (3) adjusting the pH value of the lithium-containing solution to 12 by using 1mol/L sodium hydroxide solution, adding lithium chloride until no precipitate is generated in the solution, filtering, washing the filter residue for 3 times by using phosphoric acid solution, and then washing the filter residue for 3 times by using deionized water to obtain the lithium phosphate.
The extraction rate of the lithium element is 96.1%, and the purity of the prepared lithium phosphate is 99.3%.
Example 7
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.5:1 to obtain a mixed solution;
adding 1mol/L sodium hydroxide solution into the mixed solution, adjusting the pH value of the mixed solution to 5, and filtering to obtain a lithium-containing solution and sodium hexafluoroaluminate solid;
adding ferrous chloride into the 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 30 hours at 500 ℃ under the protection of nitrogen to obtain the lithium iron phosphate. .
The extraction rate of lithium element is 96.6%, and the purity of the prepared lithium iron phosphate 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:
mixing the lithium-phosphorus-aluminum-oxide with concentrated nitric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1.5, and the mass ratio of the nitric acid to the hydrogen fluoride in the concentrated nitric acid is 1:0.8 to obtain a mixed solution;
adding 1mol/L potassium hydroxide solution into the mixed solution, adjusting the pH value of the mixed solution to 6, and carrying out solid-liquid separation to obtain a lithium-containing solution and potassium hexafluoroaluminate solid;
adding ferrous sulfate into the 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 10 hours at 900 ℃ under the protection of nitrogen to obtain the lithium iron phosphate.
The extraction rate of lithium element is 96.9%, and the purity of the prepared lithium iron phosphate is 99.6%.
Example 9
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.5:1 to obtain a mixed solution;
adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 5, placing the solution into a high-pressure reaction kettle, heating the solution to 300 ℃, keeping the solution to 80 ℃ after the reaction is finished, and filtering to obtain a lithium-containing solution and an aluminum fluoride solid;
adding ferric chloride and iron powder (the molar ratio is 1.1:1) into a 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 24 hours at 600 ℃ under the protection of nitrogen to obtain the lithium iron phosphate.
The extraction rate of lithium element is 96.2%, and the purity of the prepared lithium iron phosphate is 99.3%.
Example 10
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-oxide with concentrated hydrochloric acid and hydrogen fluoride, wherein the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1:1.5, and the mass ratio of hydrogen chloride to the hydrogen fluoride in the concentrated hydrochloric acid is 0.8:1 to obtain a mixed solution;
adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 5, placing the solution into a high-pressure reaction kettle, heating the solution to 500 ℃, keeping the solution to 100 ℃ after the reaction is finished, and filtering to obtain a lithium-containing solution and an aluminum fluoride solid;
adding ferric nitrate and sodium hypophosphite (the molar ratio is 4.1:1) into a 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 800 ℃ for 12 hours under the protection of nitrogen to obtain lithium iron phosphate.
The extraction rate of lithium element is 96.6%, and the purity of the prepared lithium iron phosphate is 99.5%.
Comparative example 1
In this comparative example, the conditions were the same as in example 6 except that the mass ratio of the lithium-phosphosiderite to the hydrogen fluoride was 1: 0.5.
The extraction rate of the lithium element is 75.2%, and the purity of the prepared lithium phosphate is 81.3%.
Comparative example 2
In this comparative example, the conditions were the same as in example 6 except that the mass ratio of the lithium-phosphosiderite to the hydrogen fluoride was 1: 3.
The extraction rate of lithium element is 72.3%, and the purity of the prepared lithium phosphate is 79.6%.
Comparative example 3
In this comparative example, the conditions were the same as in example 6 except that concentrated hydrochloric acid was not added.
The extraction rate of the lithium element is 39.5%, and the purity of the prepared lithium phosphate is 91.2%.
Comparative example 4
In this comparative example, the conditions were the same as in example 6 except that the mass ratio of hydrogen chloride to hydrogen fluoride in concentrated hydrochloric acid was 2: 1.
The extraction rate of the lithium element is 89.6%, and the purity of the prepared lithium phosphate is 51.2%.
Comparative example 5
In this comparative example, the conditions were the same as in example 6 except that the pH adjusting agent was added to adjust the pH of the mixed solution to 2.
The extraction rate of the lithium element is 77.7%, and the purity of the prepared lithium phosphate is 84.6%.
Comparative example 6
In this comparative example, the conditions were the same as in example 6 except that the pH adjusting agent was added to adjust the pH of the mixed solution to 8.
The extraction rate of the lithium element is 82.8%, and the purity of the prepared lithium phosphate is 71.5%.
Comparative example 7
In this comparative example, the conditions were the same as in example 6 except that the heating temperature of the mixed solution was 150 ℃.
The extraction rate of the lithium element is 81.6%, and the purity of the prepared lithium phosphate is 54.6%.
Comparative example 8
In this comparative example, the conditions were the same as in example 6 except that the heating temperature of the mixed solution was 700 ℃.
The extraction rate of the lithium element is 85.2%, and the purity of the prepared lithium phosphate is 66.3%.
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 (28)
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 ore with acid and hydrogen fluoride, wherein the acid does not contain hydrofluoric acid, and obtaining mixed solution;
adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution;
or adding a pH regulator into the mixed solution, regulating the pH of the mixed solution, heating the mixed solution, and carrying out solid-liquid separation to obtain a lithium-containing solution;
adjusting the pH value of the lithium-containing solution, carrying out solid-liquid separation to obtain lithium phosphate, or adding an iron source into the 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 hydrogen fluoride is 1 (0.8-2);
adding a pH regulator, and regulating the pH of the mixed solution to 4-6; the pH regulator comprises any one or the combination of at least two of liquid ammonia, sodium hydroxide solid or potassium hydroxide solid, or any one or the combination of at least two of ammonia water, sodium hydroxide solution or potassium hydroxide solution;
and when the pH regulator is liquid ammonia or ammonia water, heating the mixed solution.
2. The method according to claim 1, wherein the mass ratio of the lithium-phosphorus-aluminum alloy to the hydrogen fluoride is 1 (1-1.5).
3. The method according to claim 1, wherein the mass ratio of the acid to the hydrogen fluoride is (0.1-1): 1, and the acid does not include hydrofluoric acid.
4. The method of claim 1, wherein the acid comprises an organic acid and/or an inorganic acid.
5. The method of claim 1, wherein the acid is a pure acid or an acid solution.
6. The method of claim 4, wherein the inorganic acid comprises any one of sulfuric acid, nitric acid, hydrochloric acid, or phosphoric acid, or a combination of at least two thereof.
7. The method of claim 4, wherein the organic acid comprises any one of formic acid, acetic acid, oxalic acid, or trifluoroacetic acid, or a combination of at least two thereof.
8. The method of claim 1, wherein a buffer is added to the dissolution solution after adjusting the pH of the dissolution solution.
9. The method of claim 8, 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.
10. The method according to claim 1, wherein the temperature of the heating of the mixed solution is 300 to 500 ℃.
11. The method according to claim 1, wherein the temperature of the mixed solution is maintained at 80 to 100 ℃ after the heating.
12. The method according to claim 1, wherein the pH of the lithium-containing solution is adjusted to 8 to 14.
13. The method according to claim 12, wherein the pH of the lithium-containing solution is adjusted to 10 to 12.
14. The method of claim 1, wherein the lithium-containing compound is supplemented to the lithium-containing solution prior to said adjusting the pH of the lithium-containing solution.
15. The method of claim 14, 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.
16. The method of claim 1, wherein a buffer is added to the dissolution solution after adjusting the pH of the dissolution solution.
17. The method of claim 16, wherein the buffer comprises any one of boric acid-potassium chloride-sodium hydroxide, ammonium chloride-ammonia, disodium hydrogen phosphate-sodium hydroxide, sodium hydrogen carbonate-sodium hydroxide, or Tris-HCl.
18. The method of claim 1, wherein a pH adjusting agent is added to the lithium-containing solution during said adjusting the pH of the solution.
19. The method of claim 18, 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.
20. The method of claim 1, 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.
21. The method of claim 1, wherein the reducing agent is added simultaneously when the iron element in the iron source is trivalent.
22. The method of claim 21, 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.
23. The method of claim 1, wherein the sintering is performed under a protective atmosphere.
24. The method of claim 23, wherein the protective atmosphere comprises any one of nitrogen, helium, neon, or argon, or a combination of at least two thereof.
25. The method of claim 1, wherein the sintering temperature is 500-900 ℃.
26. The method according to claim 1, wherein the sintering time is 10-30 h.
27. The method according to claim 1, wherein the lithium iron phosphate is carbon-coated to obtain lithium iron phosphate containing a carbon-coated layer.
28. Method according to claim 1, characterized in that it comprises the following steps:
mixing the lithium-phosphorus-aluminum-oxide with acid and hydrogen fluoride, wherein the acid does not contain hydrofluoric acid, the mass ratio of the lithium-phosphorus-aluminum-oxide to the hydrogen fluoride is 1 (0.8-2), and the mass ratio of the acid to the hydrogen fluoride is (0.1-1): 1, so as to obtain a mixed solution;
adding a pH regulator into the mixed solution, regulating the pH of the mixed solution to 4-6, and carrying out solid-liquid separation to obtain a lithium-containing solution;
or adding a pH regulator into the mixed solution, regulating the pH of the mixed solution to 4-6, heating the mixed solution to 300-500 ℃ when the pH regulator is liquid ammonia or ammonia water, keeping the temperature of the mixed solution at 80-100 ℃ after heating, and performing solid-liquid separation to obtain a lithium-containing solution;
adjusting the pH value of the lithium-containing solution to 8-14, and 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.
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| CN111204726B (en) * | 2020-01-21 | 2022-11-08 | 曲靖市德方纳米科技有限公司 | Method for preparing lithium phosphate from lithium phosphoaluminate |
| CN111137868A (en) * | 2020-01-21 | 2020-05-12 | 曲靖市德方纳米科技有限公司 | Preparation method of lithium phosphate |
| 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 |
| CN112626357B (en) * | 2020-12-14 | 2022-09-27 | 赣州有色冶金研究所有限公司 | Method for extracting lithium from waste lithium iron phosphate powder |
| CN114455569B (en) * | 2022-02-11 | 2023-05-02 | 齐鲁工业大学 | Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof |
| CN114735670B (en) * | 2022-04-12 | 2023-11-03 | 宜昌邦普时代新能源有限公司 | Preparation method and application of high-performance lithium iron phosphate |
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