CN111252749B - Method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum - Google Patents
Method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum Download PDFInfo
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- CN111252749B CN111252749B CN202010072073.7A CN202010072073A CN111252749B CN 111252749 B CN111252749 B CN 111252749B CN 202010072073 A CN202010072073 A CN 202010072073A CN 111252749 B CN111252749 B CN 111252749B
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- 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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Abstract
The invention belongs to the technical field of separation and extraction of metallurgical ores, and particularly relates to a method for preparing iron phosphate and aluminum hydroxide from lithium phospholite. The method comprises the steps of taking the lithium-phosphorus-aluminum-based stone as a raw material, obtaining a mixed solution of phosphate and aluminate through alkaline leaching and dissolving, then obtaining phosphate precipitate and aluminate solution through temperature reduction treatment to precipitate the phosphate, and adding an iron source and an oxidant to react after the phosphate precipitate reacts with acid to obtain iron phosphate; and (4) carrying out seed separation on the aluminate solution to obtain the aluminum hydroxide. According to the method, the lithium phospholite is dissolved in a low-temperature alkaline leaching manner, and then the phosphate is precipitated by utilizing the characteristic that the solubility of the phosphate is greatly changed along with the temperature, so that the phosphorus element and the aluminum element in the low-cost lithium phospholite can be fully dissolved out, the recovery rate of the aluminum element is more than 96%, the purity of the obtained iron phosphate is more than 98%, the purity of the obtained aluminum hydroxide is more than 97%, the production cost of ferric phosphate can be remarkably reduced, a byproduct aluminum hydroxide can be produced, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of separation and extraction of metallurgical ores, and particularly relates to a method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum.
Background
With the development of society, new energy automobiles are continuously developed and applied due to the advantage of environmental protection, and the new energy automobiles can reduce the consumption of petroleum, prolong the service life of the petroleum and relieve the energy crisis on one hand; on the other hand, the new energy automobile is green, non-toxic and pollution-free, and the pollution of waste gas discharged by the fuel automobile to the environment is greatly reduced by replacing part of fuel automobiles with the new energy automobile. As a common lithium ion battery material, the lithium iron phosphate has the characteristics of long service life, large discharge capacity and the like, and the usage amount of the lithium iron phosphate in new energy automobiles is increased continuously. The iron phosphate is used as a common raw material for preparing the lithium iron phosphate, so that the production cost of the iron phosphate is reduced, and the lithium iron phosphate can be better applied.
The existing preparation process of the iron phosphate takes a pure substance containing an iron source and a phosphorus source as a raw material for preparation, and the production cost is generally higher; although there is a process for preparing iron phosphate by recycling waste batteries, the battery components are complex, and the content of valuable elements capable of being recycled in the battery is low, so that the problem of difficulty in separation and purification is high.
Disclosure of Invention
The invention aims to provide a method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum, and aims to solve the requirement that the production cost of the conventional lithium iron phosphate material needs to be reduced.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum ore, comprising the following steps:
crushing the lithium-phosphorus-aluminum to obtain lithium-phosphorus-aluminum powder;
mixing the lithium-phosphorus-aluminum powder with alkali for reaction, and performing solid-liquid separation to obtain a mixed solution of phosphate and aluminate;
cooling the temperature of the mixed solution of the phosphate and the aluminate to room temperature, and performing solid-liquid separation to obtain phosphate precipitate and aluminate solution;
the phosphate precipitate is mixed with acid for dissolution, and a solution containing phosphate radicals is obtained through solid-liquid separation, and the solution containing phosphate radicals reacts with an iron source and an oxidant to obtain iron phosphate;
and carrying out seed separation on the aluminate solution to obtain the aluminum hydroxide.
As a preferable technical scheme of the invention, in the step of mixing and reacting the lithium-phosphorus-aluminum powder and the alkali, the mass ratio of the lithium-phosphorus-aluminum powder to the alkali is 1 (5-16).
In a preferred embodiment of the present invention, in the step of mixing and reacting the lithium-phosphorus-aluminum powder with an alkali, the alkali is at least one selected from sodium hydroxide and potassium hydroxide.
As a preferable technical scheme of the invention, in the step of mixing and reacting the lithium-phosphorus-aluminum powder and the alkali, the mass concentration of the alkali is 10-30%.
As a preferred technical scheme of the invention, in the step of mixing and reacting the lithium-phosphorus-aluminum powder and the alkali, the reaction temperature of the mixing reaction is 80-130 ℃.
As a preferable technical scheme of the invention, in the step of mixing and reacting the lithium-phosphorus-aluminum powder and the alkali, the reaction time of the mixing reaction is 1h-3h.
In a preferable technical scheme of the invention, in the step of mixing and dissolving the phosphate precipitate and the acid, the mass ratio of the phosphate precipitate to the acid is 1 (1-5).
In a preferred embodiment of the present invention, in the step of mixing and dissolving the phosphate precipitate with an acid, the acid is at least one selected from nitric acid, hydrochloric acid, sulfuric acid, and oxalic acid.
In a preferable technical scheme of the invention, in the step of mixing and dissolving the phosphate precipitate and the acid, the mass concentration of the acid is 5-15%.
As a preferable technical scheme of the invention, in the step of reacting the solution containing phosphate radicals with the iron source and the oxidizing agent, the mass ratio of the solution containing phosphate radicals to the iron source and the oxidizing agent is (10-60): (3-12): 1.
As a preferable technical solution of the present invention, the iron source is at least one selected from the group consisting of ferrous sulfate, ferric nitrate, red iron oxide, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate, and ferrous carbonate.
As a preferable technical scheme of the invention, the oxidant is at least one selected from hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium persulfate, sodium peroxide and potassium permanganate.
As a preferable technical scheme of the invention, the seed separation is to add aluminum hydroxide seed crystals into the aluminate solution, and obtain the aluminum hydroxide through decomposition, sedimentation and separation.
As a preferable technical scheme of the invention, the particle size of the lithium-phosphorus-aluminum powder is 10-100 μm.
According to the invention, the lithium-phosphorus-aluminum-based aluminum is used as a raw material, the lithium-phosphorus-based aluminum is dissolved by a low-temperature alkaline leaching manner to obtain a lithium phosphate precipitate and a mixed solution of phosphate and aluminate, so that phosphorus and aluminum in the lithium-phosphorus-based aluminum with low cost can be fully dissolved out; and then, by utilizing the characteristic that the solubility of the phosphate greatly changes with the temperature, the phosphate is precipitated by reducing the temperature of the mixed solution of the phosphate and the aluminate, and the phosphate is used for preparing the iron phosphate, wherein the purity of the obtained iron phosphate is more than 98 percent. In addition, the obtained aluminate solution can be subjected to seed precipitation to obtain the aluminum hydroxide. The method can obviously reduce the production cost of ferric phosphate, is simple to operate and easy to implement, can also produce a byproduct aluminum hydroxide, and has good application prospect.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field, such as μ g, mg, g, kg, etc.
In addition, unless the context clearly dictates otherwise, expressions in the singular form of a word should be understood to include plural forms of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum, which comprises the following steps:
s1, crushing the lithium-phosphorus-aluminum to obtain lithium-phosphorus-aluminum powder;
s2, carrying out mixing reaction on lithium-phosphorus-aluminum powder and alkali, and carrying out solid-liquid separation to obtain a mixed solution of phosphate and aluminate;
s3, cooling the temperature of the mixed solution of the phosphate and the aluminate to room temperature, and performing solid-liquid separation to obtain phosphate precipitate and an aluminate solution;
s4, mixing and dissolving the phosphate precipitate and acid, and carrying out solid-liquid separation to obtain a solution containing phosphate radicals, wherein the solution containing phosphate radicals reacts with an iron source and an oxidant to obtain iron phosphate;
s5, carrying out seed separation on the aluminate solution to obtain the aluminum hydroxide.
The invention reacts with crushed lithium-phosphorus-aluminum by low-temperature alkaline leaching to generate a mixture of lithium phosphate, phosphate and aluminate, so that phosphorus and aluminum are fully dissolved; secondly, the invention utilizes the characteristic that lithium phosphate is difficult to dissolve in alkali liquor, and can separate the lithium phosphate from the mixture of lithium phosphate, phosphate and aluminate through solid-liquid separation to obtain a lithium phosphate solid and a mixed solution of the phosphate and the aluminate; thirdly, the invention also utilizes the characteristics that the solubility of the phosphate is small at low temperature and the solubility of the aluminate does not change much along with the temperature, the phosphate is separated out by reducing the temperature of the mixed solution of the phosphate and the aluminate, and the aluminate still exists in the form of solution, thereby realizing the separation of the phosphate and the aluminate; the separated phosphate is used for preparing the iron phosphate, and the purity of the obtained iron phosphate is more than 98%; and finally, after the phosphate in the mixed solution of the phosphate and the aluminate is separated out, the obtained aluminate solution can also be used for preparing aluminum hydroxide, the purity of the obtained aluminum hydroxide is more than 97%, and the recovery rate of the aluminum element is more than 96%. In conclusion, the method for preparing the iron phosphate and the aluminum hydroxide from the lithium-phosphorus-aluminum-based material has the advantages of low production cost, simple operation, easy industrial production and good application prospect.
It should be noted that, although the steps S1 to S5 describe the processes for preparing iron phosphate and aluminum hydroxide in a specific order, it is not required that the steps are performed in the specific order, and the steps may be performed simultaneously or sequentially according to actual situations.
In the step S1, the reaction contact area of the lithium-phosphorus-aluminum and the alkali can be increased by crushing the lithium-phosphorus-aluminum, so that the mixing reaction time of the lithium-phosphorus-aluminum and the alkali is shortened, and the dissolution rate and the recovery rate of lithium are improved. In some embodiments, the lithium phosphoaluminum powder is crushed to a particle size of 10 μm to 100 μm.
In S2, the lithium-phosphorus-aluminum powder and alkali are mixed and react to generate a mixture of lithium phosphate, phosphate and aluminate. Wherein, because the lithium phosphate is difficult to dissolve in the alkali liquor, the lithium phosphate is separated from the aluminate mixed solution in a solid-liquid separation mode to obtain a solid substance with the main component of the lithium phosphate. Wherein, the alkali is mainly mixed with the lithium phosphorus aluminum powder in the form of solution for reaction. The reaction equation of the mixing reaction of the lithium-phosphorus-aluminum powder and the alkali is as follows:
LiAl(F，OH)PO 4 +OH-→Li 3 PO 4 ↓+AlO 2 - +PO 4 3- +AlF 3 ↓。
in the mixing reaction of the lithium phosphorus aluminum powder and the alkali, the ratio of the lithium phosphorus aluminum powder to the alkali is optimized, so that the alkali leaching reaction rate can be accelerated, and the cost increase caused by adding excessive alkali can be avoided. In some embodiments, the mass ratio of the lithium-phosphorus-aluminum powder to the alkali is controlled to be 1 (5-16), so that the lithium-phosphorus-aluminum powder and the alkali can be quickly and completely reacted. Specifically, the typical but not limiting mass ratio of lithium-phosphorus-aluminum powder to alkali is 1:5, 1:6, 1:7, 1:8, 1:9, 1.
In the mixing reaction of the lithium-phosphorus-aluminum powder and the alkali, the alkali leaching reaction rate can be accelerated by selecting the proper alkali and the proper alkali concentration, and the influence of introducing redundant impurities on the subsequent treatment process is avoided. In some embodiments, sodium hydroxide and/or potassium hydroxide is selected to be mixed and reacted with the lithium-phosphorus-aluminum powder, and the mass concentration of the sodium hydroxide and/or potassium hydroxide is 10% -30%. In particular, typical, but not limiting, mass concentrations of sodium hydroxide and/or potassium hydroxide are 10%, 15%, 20%, 25%, 30%.
In the mixing reaction of the lithium-phosphorus-aluminum powder and the alkali, the alkali leaching reaction rate can be further accelerated by optimizing the mixing reaction conditions, so that the lithium element is fully dissolved out, and the recovery rate of the lithium phosphate is improved. In some embodiments, the reaction temperature of the mixing reaction is 80 ℃ to 130 ℃ and the reaction time of the mixing reaction is 1h to 3h. Specifically, typical but not limiting reaction temperatures are 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃; typical but not limiting reaction times are 1h, 1.5h, 2h, 2.5h, 3h.
The solubility of phosphate has a significant correlation with the solution temperature. When the temperature of the solution is higher than 90 ℃, the phosphate is completely dissolved in the alkaline solution or the aqueous solution; when the temperature of the solution is lower than 90 ℃, phosphate can be gradually separated out of the solution to be precipitate. Therefore, S3 utilizes the characteristic, the temperature of the mixed solution of the phosphate and the aluminate is reduced to room temperature, the phosphate is precipitated, and then the phosphate precipitate and the aluminate solution can be obtained through solid-liquid separation.
The term "room temperature" used in the present invention means that the temperature of the mixed solution of phosphate and aluminate is 20 ℃ to 30 ℃. Specifically, typical but non-limiting temperatures are 20 ℃, 22 ℃, 24 ℃, 25 ℃, 26 ℃, 28 ℃, 30 ℃.
And S4, mixing the phosphate precipitate with acid, wherein the acid can dissolve the phosphate precipitate, removing insoluble impurities through solid-liquid separation, and obtaining a filtrate which is a solution containing phosphate radicals, wherein the solution containing phosphate radicals is used as a phosphorus source and reacts with an iron source and an oxidant to obtain an iron phosphate product.
In the mixing and dissolving of the phosphate precipitate and the acid, the rate of dissolving the phosphate precipitate by the acid can be accelerated by adjusting the addition amount of the acid, and the proper pH environment for reaction can be maintained. In some embodiments, the mass ratio of phosphate precipitate to acid is controlled to be (1-5): 1, phosphate precipitation can be rapidly dissolved by acid. Specifically, typical but non-limiting mass ratios of phosphate precipitate to acid are 1:1, 2:1, 3:1, 4:1, 5:1.
In the process of mixing and dissolving the phosphate precipitate and the acid, the mixing reaction rate can be accelerated by selecting a proper acid and a proper acid concentration, and the influence of introducing redundant impurities on the subsequent treatment process is avoided. In some embodiments, the acid is selected from at least one of nitric acid, hydrochloric acid, sulfuric acid, and oxalic acid, and the mass concentration of the acid is 5% -15%. In particular, typical, but not limiting, acid concentrations by mass are 5%, 7%, 9%, 10%, 13%, 15%.
When the solution containing phosphate radicals is used as a phosphorus source and reacts with an iron source and an oxidant, the reaction rate can be increased and the production time can be shortened on the premise of ensuring the full reaction of the phosphorus source, the iron source and the oxidant by optimizing the proportion of the phosphorus source, the iron source and the oxidant. In some embodiments, the mass ratio of the phosphate-containing solution to the iron source and the oxidizing agent is (10-60): (3-12): 1.
The solution containing phosphate radical is used as phosphorus source, and when reacting with iron source and oxidant, the iron source can be at least one selected from ferrous sulfate, ferric nitrate, iron oxide red, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate and ferrous carbonate. Preferably, ferrous sulfate with low cost and rich sources is selected as an iron source; the oxidant is at least one selected from hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium persulfate, sodium peroxide and potassium permanganate. Preferably, the hydrogen peroxide with strong oxidizability is selected as the oxidant, so that the method has the advantages of small using amount, low cost and no introduction of impurity ions.
And S5, separating and extracting aluminum from the aluminate solution obtained in the S3 to obtain an aluminum hydroxide product. Specifically, the seed separation is to add aluminum hydroxide seed crystals into an aluminate solution, and obtain aluminum hydroxide through decomposition, sedimentation and separation, wherein the related chemical reaction formula is as follows:
AlO 2 - +2H 2 O→Al(OH) 3 +OH - 。
it is understood that after the aluminum hydroxide is obtained by the above method of the present invention, it may be further calcined to produce alumina. The conditions for the calcination in the present invention are not particularly limited, and may be those conventionally used in the art. Accordingly, in the method for preparing iron phosphate and aluminum hydroxide from the lithium-phosphorus-aluminum ore according to the present invention, a by-product of aluminum oxide may be also produced.
In the embodiment of the present invention, solid-liquid separation may be performed by at least one of filtration, centrifugation, evaporation, sedimentation, and the like, and the corresponding operation method is a method commonly used in the art and will not be described herein again.
In order to make the above-mentioned details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the method for preparing iron phosphate and aluminum hydroxide from the lithium-containing bauxite more obvious, the above-mentioned technical solution is illustrated by the following examples, wherein the results of measuring the composition of the lithium-containing bauxite used in each example are shown in table 1.
TABLE 1 detection results of the Lifoenite component
Example 1
A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum ore comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to obtain lithium-phosphorus-aluminum powder with the particle size of 30 mu m;
(2) Taking 100g of lithium-phosphorus-aluminum powder, adding 550mL of 23% sodium hydroxide solution at 90 ℃, heating and reacting for 1.2h, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 200mL of sulfuric acid with the mass concentration of 10% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 120g of ferrous sulfate and 20mL of hydrogen peroxide into the filtrate C for reacting for 3 hours, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) Adding 3g of aluminum hydroxide seed crystal into the filtrate B for 30 hours, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
Example 2
A method for preparing iron phosphate and aluminum hydroxide from lithium phosphoaluminate comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to obtain lithium-phosphorus-aluminum powder with the particle size of 50 mu m;
(2) Taking 120g of lithium-phosphorus-aluminum powder, adding 800mL of 15% sodium hydroxide solution at 100 ℃, heating for reaction for 3h, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 150mL of sulfuric acid with the mass concentration of 13% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 140g of ferrous sulfate and 18mL of hydrogen peroxide into the filtrate C for reacting for 2.1h, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) Adding 2g of aluminum hydroxide seed crystal into the filtrate B for 36 hours, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
Example 3
A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum ore comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to obtain lithium-phosphorus-aluminum powder with the particle size of 10 mu m;
(2) Taking 70g of lithium-phosphorus-aluminum powder, adding 500mL of 20% sodium hydroxide solution at 130 ℃, heating and reacting for 1h, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 120mL of sulfuric acid with the mass concentration of 15% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 100g of ferrous sulfate and 30mL of hydrogen peroxide into the filtrate C for reacting for 1.5h, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) Adding 2.5g of aluminum hydroxide seed crystal into the filtrate B for 20 hours, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
Example 4
A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum ore comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to 80 mu m of particle size;
(2) Taking 50g of lithium-phosphorus-aluminum powder, adding 750mL of 10% sodium hydroxide solution at the mass concentration, heating and reacting for 1.8h at 110 ℃, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 100mL of sulfuric acid with the mass concentration of 9% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 150g of ferrous sulfate and 25mL of hydrogen peroxide into the filtrate C for reacting for 3 hours, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) Adding 3.5g of aluminum hydroxide seed crystal into the filtrate B for 50 hours, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
Example 5
A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum ore comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to obtain lithium-phosphorus-aluminum powder with the particle size of 100 mu m;
(2) Taking 150g of lithium-phosphorus-aluminum powder, adding 650mL of 30% sodium hydroxide solution at 80 ℃, heating and reacting for 2.2h, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 280mL of sulfuric acid with the mass concentration of 5% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 130g of ferrous sulfate and 14mL of hydrogen peroxide into the filtrate C for reacting for 1h, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) And adding 5g of aluminum hydroxide seed crystal into the filtrate B for 48 hours, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
Example 6
A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum ore comprises the following steps:
(1) Crushing the lithium-phosphorus-aluminum powder to obtain lithium-phosphorus-aluminum powder with the particle size of 20 mu m;
(2) Taking 140g of lithium-phosphorus-aluminum powder, adding 600mL of 28% sodium hydroxide solution at 120 ℃, heating and reacting for 1.8h, and filtering to obtain filter residue A and filtrate A, wherein the filtrate A is a mixed solution of phosphate and aluminate;
(3) Cooling the filtrate A to room temperature, and filtering to obtain filter residue B and filtrate B;
(4) Adding 300mL of sulfuric acid with the mass concentration of 12% into the filter residue B for dissolving, filtering to obtain a filter residue C and a filtrate C, adding 120g of ferrous sulfate and 10mL of hydrogen peroxide into the filtrate C for reacting for 2.6h, filtering, and carrying out countercurrent washing for 3 times to obtain an iron phosphate product;
(5) Adding 4g of aluminum hydroxide seed crystal into the filtrate B for 40h, sieving, washing for 3 times, and filtering to obtain an aluminum hydroxide product.
The recovery of aluminum element and the purity of the iron phosphate and aluminum hydroxide products obtained from examples 1-6 are shown in table 2.
Table 2 aluminum recovery and purity results for iron phosphate and aluminum hydroxide products
| Examples | Recovery rate of aluminium element | Purity of iron phosphate | Purity of aluminum hydroxide |
| Example 1 | 97.32 | 98.73 | 98.15 |
| Example 2 | 97.54 | 98.82 | 97.89 |
| Example 3 | 97.14 | 98.59 | 98.35 |
| Example 4 | 96.86 | 98.31 | 98.11 |
| Example 5 | 96.93 | 98.67 | 97.96 |
| Example 6 | 97.05 | 98.54 | 98.02 |
It can be seen from table 2 that the iron phosphate and aluminum hydroxide products prepared by using the lithium phosphoaluminate as the raw material have the advantages of high recovery rate of aluminum elements and high purity of the obtained iron phosphate and aluminum hydroxide, and the iron phosphate can be used as the raw material to prepare the lithium iron phosphate with excellent performance.
Claims (8)
1. A method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus aluminum is characterized by comprising the following steps:
crushing the lithium-phosphorus-aluminum to obtain lithium-phosphorus-aluminum powder;
mixing the lithium-phosphorus-aluminum powder with alkali for reaction, and performing solid-liquid separation to obtain a mixed solution of phosphate and aluminate; wherein the mass ratio of the lithium-phosphorus-aluminum powder to the alkali is 1 (5-16);
cooling the temperature of the mixed solution of the phosphate and the aluminate to room temperature, and performing solid-liquid separation to obtain phosphate precipitate and aluminate solution;
mixing and dissolving the phosphate precipitate with acid, wherein the acid is used for dissolving the phosphate precipitate, and performing solid-liquid separation to obtain a solution containing phosphate radicals to remove insoluble impurities, and reacting the solution containing phosphate radicals with an iron source and an oxidant to obtain iron phosphate; wherein the mass ratio of the phosphate precipitate to the acid is 1 (1-5), and the mass concentration of the acid is 5-15%;
and carrying out seed separation on the aluminate solution to obtain the aluminum hydroxide.
2. The method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum stone according to claim 1, wherein in the step of mixing and reacting the lithium-phosphorus-aluminum powder with a base, the base is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide; and/or
The mass concentration of the alkali is 10-30%.
3. The method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum powder according to claim 1, wherein in the step of mixing and reacting the lithium-phosphorus-aluminum powder with alkali, the reaction temperature of the mixing and reacting is 80 ℃ to 130 ℃; and/or
The reaction time of the mixing reaction is 1h-3h.
4. The method for preparing iron phosphate and aluminum hydroxide from lithium-phosphorus-aluminum-stone according to any one of claims 1 to 3, wherein the step of dissolving the phosphate precipitate in a mixture with an acid selected from at least one of nitric acid, hydrochloric acid, sulfuric acid and oxalic acid.
5. The method for producing iron phosphate and aluminum hydroxide from lithium-phosphosiderite according to any one of claims 1 to 3, wherein in the step of reacting the phosphate-containing solution with an iron source and an oxidizing agent, the mass ratio of the phosphate-containing solution to the iron source and the oxidizing agent is (10-60): (3-12): 1.
6. The method for preparing iron phosphate and aluminum hydroxide from the lithium-phosphorus-aluminum-stone according to any one of claims 1 to 3, wherein the iron source is at least one selected from the group consisting of ferrous sulfate, ferric nitrate, red iron oxide, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate, and ferrous carbonate; and/or
The oxidant is at least one selected from hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium superphosphate, sodium peroxide and potassium permanganate.
7. The method for preparing iron phosphate and aluminum hydroxide from the lithium-phosphorus-aluminum ore according to any one of claims 1 to 3, wherein the seed precipitation is to add aluminum hydroxide seed crystals to the aluminate solution, and obtain the aluminum hydroxide through decomposition, sedimentation and separation.
8. The method for preparing iron phosphate and aluminum hydroxide from lithium phosphoaluminate according to any one of claims 1 to 3, characterized in that the particle size of the lithium phosphoaluminate powder is 10 μm to 100 μm.
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| PT2971252T (en) * | 2013-03-15 | 2021-04-06 | Nemaska Lithium Inc | Processes for preparing lithium hydroxide |
| ES2893498T3 (en) * | 2016-02-09 | 2022-02-09 | Lithium Australia Nl | Procedures for extracting and recovering lithium values from lithium-bearing materials |
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