CN116162811A - Method for removing impurities from sulfuric acid rare earth leaching solution - Google Patents

Method for removing impurities from sulfuric acid rare earth leaching solution Download PDF

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CN116162811A
CN116162811A CN202310182633.8A CN202310182633A CN116162811A CN 116162811 A CN116162811 A CN 116162811A CN 202310182633 A CN202310182633 A CN 202310182633A CN 116162811 A CN116162811 A CN 116162811A
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rare earth
solution
content
leaching solution
magnesium oxide
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郭文亮
周建国
郝晓燕
刘旭
石鑫
周晶
董利军
吴建仁
阮爱
张柏林
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Inner Mongolia Baotou Steel Hefa Rare Earth Co ltd
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Inner Mongolia Baotou Steel Hefa Rare Earth Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Environmental & Geological Engineering (AREA)
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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for removing impurities from a rare earth sulfate leaching solution. The method comprises the following steps: (1) Adding ammonium bicarbonate solution with the concentration of 2-3.6 mol/L into rare earth sulfate leaching solution at the flow rate of 3-5.5 mL/min until the pH value of a reaction system is 3.7-4.5, so as to form a first mixed solution; (2) Adding magnesium oxide into the first mixed solution to form a second mixed solution; and (3) reacting the second mixed solution to obtain the leaching solution after impurity removal. The method can effectively reduce the contents of iron element and aluminum element in the rare earth sulfate leaching solution.

Description

Method for removing impurities from sulfuric acid rare earth leaching solution
Technical Field
The invention relates to a method for removing impurities from rare earth sulfate leaching liquid, in particular to a method for reducing iron and aluminum content in rare earth sulfate leaching liquid.
Background
In the rare earth wet smelting process, concentrated sulfuric acid and a small amount of iron powder are added into rare earth concentrate to be roasted at high temperature to form rare earth roasted ore; leaching the rare earth roasting ore with water, and filtering to obtain rare earth sulfate leaching liquid. The rare earth sulfate leaching solution contains impurities such as iron, aluminum and the like, and influences the quality of products in subsequent procedures. Therefore, it is necessary to remove impurities in the rare earth sulfate leaching solution.
CN112281003B discloses a method for removing impurities from low-grade rare earth sulfate leaching liquid. Lime powder is added into rare earth sulfate leaching solution to enable the pH value of the leaching solution to reach 1.5-2.5, then magnesia slurry is added to enable the pH value of the rare earth sulfate leaching solution to reach 4.5-5.5, and the mixture is settled and clarified to obtain precipitation liquid. The method is suitable for low-grade rare earth sulfate leaching solution, and has low impurity removal effect on iron element and aluminum element in the rare earth sulfate leaching solution.
CN114293012a discloses a method for reducing iron and aluminium content in rare earth sulphate leaching solutions. Introducing lime milk into rare earth sulfuric acid leaching solution containing iron element and aluminum element to obtain a first mixed solution; introducing the magnesium oxide slurry into the first mixed solution to obtain a second mixed solution; and (3) reacting the second mixed solution, and then carrying out solid-liquid separation to obtain a rare earth sulfate solution. The method has improved impurity removing effect on iron and aluminum elements.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for removing impurities from a rare earth sulfate leaching solution, which can effectively reduce the contents of iron and aluminum elements in the rare earth sulfate leaching solution. Further, it can reduce the loss of rare earth elements in the sulfuric acid rare earth leaching solution. The above object is achieved by the following technical scheme.
The invention provides a method for removing impurities from a sulfuric acid rare earth leaching solution, which comprises the following steps:
(1) Adding ammonium bicarbonate solution with the concentration of 2-3.6 mol/L into rare earth sulfate leaching solution at the flow rate of 3-5.5 mL/min until the pH value of a reaction system is 3.7-4.5, so as to form a first mixed solution;
(2) Adding magnesium oxide into the first mixed solution to form a second mixed solution; and (3) reacting the second mixed solution to obtain the leaching solution after impurity removal.
According to the method of the present invention, preferably, the ammonium bicarbonate solution is added to the rare earth sulfate leach solution at 15-30 ℃.
According to the method of the present invention, preferably, the magnesium oxide is added to the first mixed liquid in the form of powder or slurry.
According to the method of the present invention, preferably, the magnesium oxide is added to the first mixed liquid in the form of a slurry, and the flow rate of the magnesium oxide slurry is 0.2 to 2.0mL/min.
According to the method of the present invention, preferably, the magnesium oxide slurry is formed of magnesium oxide and water in a mass-to-volume ratio of 1 (3-5) kg/L.
According to the method of the present invention, preferably, magnesium oxide is added to the first mixed liquor to a pH of 4.8 to 5.5 to form a second mixed liquor.
According to the method of the present invention, preferably, the pH of the rare earth sulfate leaching solution is 0.5 to 2.5.
According to the method of the present invention, preferably, the rare earth element content in the rare earth sulfate leaching solution is 30 to 37g/L, the iron element content is 10 to 12g/L, and the aluminum element content is 1 to 2g/L;
wherein the content of rare earth element is calculated by rare earth oxide, and the content of iron element is calculated by Fe 2 O 3 Calculated by Al content 2 O 3 And (5) counting.
According to the method of the invention, preferably, the content of iron element in the leaching solution after impurity removal is less than or equal to 0.0013g/L, and the content of aluminum element is less than or equal to 0.0012g/L.
According to the method of the present invention, preferably, the second mixed liquor is reacted for 1 to 5 hours.
The method can effectively reduce the contents of iron and aluminum in the rare earth sulfate leaching solution. Further, the method can reduce the loss of rare earth elements in the sulfuric acid rare earth leaching solution.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
Adding ammonium bicarbonate solution with specific concentration into rare earth sulfuric acid leaching solution at a certain flow rate to form first mixed solution with specific pH value; and adding magnesium oxide into the first mixed solution. Therefore, the contents of iron element and aluminum element in the rare earth sulfuric acid leaching solution can be effectively reduced, and the loss rate of the rare earth elements is small.
The method for removing impurities from the rare earth sulfate leaching solution comprises the following steps: (1) adding an ammonium bicarbonate solution; and (2) a step of adding magnesium oxide and reacting. The following is a detailed description.
Step of adding ammonium bicarbonate solution
And adding the ammonium bicarbonate solution into the rare earth sulfate leaching solution to form a first mixed solution.
The rare earth sulfate leaching liquid is a liquid substance obtained by leaching rare earth roasting ore formed by adding concentrated sulfuric acid into rare earth concentrate and roasting iron powder at high temperature, filtering and the like. Methods of forming the rare earth sulfate leach solution are conventional in the art. For example, rare earth concentrate, concentrated sulfuric acid and iron powder are fully mixed, added into a rotary kiln and roasted at 700-900 ℃ to obtain rare earth roasting ore. Soaking the rare earth roasting ore in water to obtain rare earth roasting ore slurry with rare earth element content (calculated by rare earth oxide) of 30-40 g/L. And (3) filtering the rare earth roasting ore slurry mixture through a plate filter to obtain rare earth sulfate leaching liquid.
The pH value of the sulfuric acid rare earth leaching solution can be 0.5-2.5; preferably 0.5 to 2.0; more preferably 1.0 to 2.0.
The content of rare earth elements in the sulfuric acid rare earth leaching solution is 30-37 g/L; preferably 30-36 g/L; more preferably 32 to 36g/L. The content of rare earth elements is calculated by rare earth oxidation.
The content of iron element in the sulfuric acid rare earth leaching solution is 10-12 g/L; preferably 10.5 to 12g/L; more preferably 10.5 to 11.6g/L. Iron content in terms of Fe 2 O 3 And (5) counting.
The content of aluminum element in the sulfuric acid rare earth leaching solution is 1-2 g/L; preferably 1 to 1.8g/L; more preferably 1 to 1.5g/L. The content of the aluminum element is Al 2 O 3 And (5) counting.
The concentration of the ammonium bicarbonate solution is 2-3.6 mol/L; preferably 2.1 to 3.55mol/L; more preferably 2.2 to 3.5mol/L. Therefore, the contents of iron element and aluminum element in the leaching solution after impurity removal can be reduced, and the loss rate of rare earth elements can be reduced.
The flow rate of adding the ammonium bicarbonate solution into the rare earth sulfate leaching solution is 3-5.5 mL/min; preferably 3-5 mL/min; more preferably 3.3 to 4mL/min. Thus being beneficial to reducing the content of iron element and aluminum element in the leaching liquid after impurity removal and reducing the loss rate of rare earth elements.
At 15-30 deg.c, ammonium bicarbonate solution is added into the rare earth sulfate leaching solution. Preferably, the ammonium bicarbonate solution is added to the rare earth sulfate leach solution at 20-25 ℃.
In the invention, ammonium bicarbonate solution is added into rare earth sulfate leaching solution until the pH value is 3.7-4.5, so as to form first mixed solution. Preferably, the pH is 3.8 to 4.2. More preferably, the pH is 3.8 to 4. Thus being beneficial to reducing the content of iron element and aluminum element in the leaching liquid after impurity removal and reducing the loss rate of rare earth elements.
Step of adding magnesium oxide and reacting
Adding magnesium oxide into the first mixed solution to form a second mixed solution; and (3) reacting the second mixed solution to obtain the leaching solution after impurity removal. Preferably, the magnesium oxide is added to the first mixed solution under stirring.
The magnesium oxide may be used in the form of powder or slurry. In certain embodiments, the magnesium oxide powder is added to the first mixed liquor. In other embodiments, the magnesium oxide slurry is added to the first mixed liquor.
The magnesium oxide slurry may be formed from the reaction of magnesium oxide and water. The mass volume ratio of the magnesium oxide to the water is 1 (3-5) kg/L; preferably 1 (3.3-4.8) kg/L; more preferably 1 (3.5-4.5) kg/L.
The flow rate of the magnesium oxide slurry added into the first mixed solution is 0.2-2.0 mL/min; preferably 0.5-1.5 mL/min; more preferably 0.8 to 1mL/min.
In the present invention, magnesium oxide is added to the first mixed solution to a pH of 4.8 to 5.5 to form a second mixed solution. Preferably, the pH is from 5 to 5.5. More preferably, the pH is from 5.3 to 5.4.
The reaction time of the second mixed solution is 1-5 h; preferably 1.5 to 4 hours; more preferably 2 to 3 hours.
And (3) carrying out solid-liquid separation on a reaction product obtained by the reaction of the second mixed solution to obtain leaching solution after impurity removal.
The content of iron element in the leaching solution after impurity removal is less than or equal to 0.0013g/L; preferably, the content of the iron element is less than or equal to 0.0011g/L. Iron content in terms of Fe 2 O 3 And (5) counting.
The content of aluminum element in the leaching solution after impurity removal is less than or equal to 0.0012g/L; preferably, the content of aluminum element is less than or equal to 0.0009g/L. The content of the aluminum element is Al 2 O 3 And (5) counting.
The loss rate of rare earth elements is less than or equal to 1.5%; preferably, the loss rate of the rare earth element is 1.2% or less; more preferably, the loss rate of the rare earth element is 0.8 to 1.1%.
The test method is described as follows:
the content of iron element is measured by atomic absorption method.
The content of aluminum element is measured by adopting a plasma spectrometry method.
The rare earth element content is determined by EDTA titration.
In the following examples and comparative examples, the pH of the rare earth sulfate leaching solution was 1.5, the rare earth content (in terms of rare earth oxide) was 35.3g/L, and the iron element content (in terms of Fe 2 O 3 Meter) was 11.58g/L, aluminum element content (in terms of Al 2 O 3 Calculated as 1.06 g/L).
The magnesium oxide slurries in the following examples and comparative examples were formed by reacting magnesium oxide and water in a mass to volume ratio of 1:4 kg/L.
Example 1
(1) At 25 ℃, adding ammonium bicarbonate solution with the concentration of 2.5mol/L into rare earth sulfate leaching solution at the flow rate of 3.3mL/min until the pH value is 3.8, and forming a first mixed solution.
(2) The magnesium oxide slurry was added to the first mixed solution at a flow rate of 0.8mL/min to a pH of 5.3 with stirring to form a second mixed solution. And (3) reacting the second mixed solution for 2 hours, and then carrying out solid-liquid separation to obtain the leaching solution after impurity removal.
The contents of partial elements in the leachate after impurity removal are shown in table 1.
Comparative example 1
Example 1 was repeated except that the concentration of the ammonium bicarbonate solution was 1.5 mol/L. The contents of partial elements in the leachate after impurity removal are shown in table 1.
Comparative example 2
Example 1 was repeated except that the flow rate of the ammonium bicarbonate solution was 7 mL/min. The contents of partial elements in the leachate after impurity removal are shown in table 1.
Comparative example 3
Example 1 was repeated except that the step (1) was performed in the same manner as example 1. The step (1) is specifically as follows:
(1) At 25 ℃, adding ammonium bicarbonate solution with the concentration of 2.5mol/L into rare earth sulfate leaching solution at the flow rate of 3.3mL/min until the pH value is 3.5, and forming a first mixed solution.
The contents of partial elements in the leachate after impurity removal are shown in table 1.
Comparative example 4
Example 1 was repeated except that the ammonium bicarbonate solution was replaced with lime milk. Lime milk with mass-volume ratio of 1:8t/m 3 Is obtained by reacting quicklime of (2) with water. The contents of partial elements in the leachate after impurity removal are shown in Table 1As shown.
TABLE 1
Figure BDA0004102732240000071
Note that: content of aluminum element in Al 2 O 3 Calculated according to Fe content 2 O 3 The rare earth element content is calculated by rare earth oxide.
From the above table, the concentration and flow rate of ammonium bicarbonate solution and the pH value of the reaction system have important influence on the content of iron element and aluminum element in the leaching solution after impurity removal, and also have certain influence on the loss rate of rare earth element, so that the method does not belong to the conventional selection in the field. In addition, the ammonium bicarbonate solution and the lime milk have great difference in chemical components, and the ammonium bicarbonate solution is adopted to replace the lime milk, so that the content of iron element and aluminum element in the leachate after impurity removal can be obviously reduced, and the conventional selection in the field is not included.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.

Claims (10)

1. The method for removing impurities from the rare earth sulfate leaching solution is characterized by comprising the following steps of:
(1) Adding ammonium bicarbonate solution with the concentration of 2-3.6 mol/L into rare earth sulfate leaching solution at the flow rate of 3-5.5 mL/min until the pH value of a reaction system is 3.7-4.5, so as to form a first mixed solution;
(2) Adding magnesium oxide into the first mixed solution to form a second mixed solution; and (3) reacting the second mixed solution to obtain the leaching solution after impurity removal.
2. The method according to claim 1, wherein the ammonium bicarbonate solution is added to the rare earth sulphate leaching solution at 15-30 ℃.
3. The method of claim 1, wherein the magnesium oxide is added to the first mixed liquor in the form of a powder or slurry.
4. A method according to claim 3, wherein the magnesium oxide is added to the first mixed liquor in the form of a slurry, the flow rate of the magnesium oxide slurry being in the range of 0.2 to 2.0mL/min.
5. The method according to claim 4, wherein the magnesium oxide slurry is formed of magnesium oxide and water in a mass-to-volume ratio of 1 (3-5) kg/L.
6. The method of claim 1, wherein magnesium oxide is added to the first mixed liquor to a pH of 4.8 to 5.5 to form the second mixed liquor.
7. The method according to claim 1, wherein the pH of the rare earth sulphate leaching solution is between 0.5 and 2.5.
8. The method according to claim 1, wherein the rare earth element content in the rare earth sulfate leaching solution is 30-37 g/L, the iron element content is 10-12 g/L, and the aluminum element content is 1-2 g/L;
wherein the content of rare earth element is calculated by rare earth oxide, and the content of iron element is calculated by Fe 2 O 3 Calculated by Al content 2 O 3 And (5) counting.
9. The method according to claim 1, wherein the content of iron element in the leachate after impurity removal is less than or equal to 0.0013g/L and the content of aluminum element is less than or equal to 0.0012g/L.
10. The method according to any one of claims 1 to 9, wherein the second mixed liquor is reacted for a period of time of 1 to 5 hours.
CN202310182633.8A 2023-03-01 2023-03-01 Method for removing impurities from sulfuric acid rare earth leaching solution Pending CN116162811A (en)

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