CN109628768B - Method for preparing high-purity rare earth by conventional ion adsorption method - Google Patents

Method for preparing high-purity rare earth by conventional ion adsorption method Download PDF

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CN109628768B
CN109628768B CN201811540875.5A CN201811540875A CN109628768B CN 109628768 B CN109628768 B CN 109628768B CN 201811540875 A CN201811540875 A CN 201811540875A CN 109628768 B CN109628768 B CN 109628768B
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CN109628768A (en
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韦世强
娄战荒
吴忠何
莫国荣
张亮玖
周慧荣
龙江志
卢阶主
梁壮
杨金涛
庄辉
羊多彦
李飞龙
马宗云
况涛
许旭升
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Chinalco Guangxi Nonferrous Rare Earth Development Co ltd
Guangxi Guosheng Rare Earth New Material Co ltd
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Chinalco Guangxi Guosheng Rare Earth Development Co ltd
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Abstract

The invention relates to a method for preparing high-purity rare earth by a conventional ion adsorption method, which comprises the steps of preparing an adsorption stock solution, preparing an ion exchange column, adsorbing rare earth ions, washing for the first time, separating the rare earth ions for the first time, washing for the second time, separating the rare earth ions for the second time and the like, and is characterized in that two different eluting agents and eluting processes are adopted to separate and purify the rare earth under the conditions of normal temperature and normal pressure, an effluent liquid containing the rare earth ions obtained by ion exchange is precipitated by a saturated oxalic acid solution to obtain an oxalic acid rare earth precipitate, and the oxalic acid rare earth precipitate is washed, dried and burned to obtain an ultra-pure rare earth oxide with the purity of 99.9999-99.99999%. The invention overcomes the problems of long period, low yield, high cost and relatively low purity of the traditional normal temperature and pressure ion exchange method, the non-rare earth impurities are less than 100 PPM, wherein Fe is less than 1PPM, Ca is less than 3PPM, Si is less than 3PPM, the product quality is very good, and the invention has good production benefit.

Description

Method for preparing high-purity rare earth by conventional ion adsorption method
Technical Field
The invention belongs to the technical field of rare earth material preparation, and particularly relates to a method for preparing high-purity rare earth by a conventional ion adsorption method.
Background
China is a big rare earth resource country, and the yield is the first in the world. The rare earth element has excellent physical, chemical, magnetic, optical and electrical properties due to its special material structure, and has a very wide application, which is called the strategic element of the 21 st century. With the continuous research and understanding of people on the performance and application of rare earth elements and the advantages of rich rare earth resources and low price in China, rare earth is increasingly and widely applied in the fields of domestic appliances, daily chemical industry, ferrous metallurgy, petrochemical industry, laser technology, superconducting materials, medical care, agriculture, forestry, environmental protection and the like in China.
At present, although methods for industrially separating rare earth elements include ion exchange methods, solvent extraction methods, chemical separation methods, and the like, the ion exchange methods have significant advantages in the production of high-purity rare earth elements and the separation of heavy rare earth elements, and are incomparable with other separation methods. However, the traditional ion exchange method at normal temperature and normal pressure has the defects of long period, low yield and the like, so that the rare earth production efficiency is low and the cost is high.
Therefore, the development of a novel ion exchange method for preparing rare earth oxide is beneficial to improving the production efficiency of rare earth and reducing the production cost, and simultaneously, the problem of low purity of rare earth products is solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing high-purity rare earth by using a conventional ion adsorption method.
The invention is realized by the following modes:
a method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution;
(2) preparing an ion exchange column: preparing 4 ion exchange columns respectively marked as column A, column B, column C and column D, wherein the ion exchange columns are filled with 732 strong acid styrene cation exchange resins, and the column A and the column B are made of 10-15% NH by mass percentage4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+Molding;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 3-5 cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 5-10 cm/min under normal temperature and pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining the concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, adding eluent 1 at normal temperature and normal pressure from the top end of the column A at linear velocity of 2-3 cm/min, wherein the eluent 1 is NH with pH of 6.0-6.5 and concentration of 0.05-0.3 mol/L4The solution of the AC is added into the solution,when the bottom end of the column C is provided with effluent liquid, impurity ions are firstly eluted due to weak affinity with cation exchange resin, a fine conduit with the aperture of 1mm is used for leading part of the effluent liquid to a saturated oxalic acid solution, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of the eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 5-8 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in the gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.1-0.3 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.005-0.01 mol/L, NH4 + 0.1-0.3 mol/L, pH7.5-8.5, residual impurity ions are eluted first because of weak affinity with cation exchange resin, when Cu with blue color2+When the tape reached the bottom of column D, the line speed of eluent 2 was increased to 1-2 cm/min, when the blue Cu2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluent 2 to 3-5 cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, determining that rare earth ions appear in the effluent liquid, receiving the effluent liquid in batches at the same time interval until the effluent liquid does not contain the rare earth ions any more, stopping adding the eluent 2, detecting the effluent liquid received in batches, and adding the effluent liquid containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 1-2, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 5-6, and adding Al3+Precipitating, preparing eluent 2 from the residual solution, and precipitating the effluent containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitateWashing, drying and firing to obtain the ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to prepare the ultra-pure rare earth oxide in a circulating way.
Preferably, the concentration of the rare earth ions in the adsorption stock solution is 0.5-2 mol/L.
Preferably, the ion exchange column has a column length of 40-400 cm and a diameter of =1: 20-30.
Preferably, the ion exchange column has a column length of 200 cm and a diameter column length =1: 30.
Preferably, the 732 strong-acid styrene cation exchange resin has a particle size of 0.315-0.45 mm.
Preferably, the 732 strong-acid styrene cation exchange resin has a specific surface area of 35-50 m2/g。
Preferably, the retardant is CuSO4:H2SO4A mixed solution of 1:0.5-2 mol ratio of CuSO4The concentration is 80-100 g/L.
Preferably, the eluent 1 is 0.3 mol/L NH with pH6.54And (3) AC solution.
Preferably, the eluent 2 is EDTA 0.01 mol/L, NH4 + 0.3 mol/L, pH8.5 solution.
The invention has the beneficial effects that:
1. the invention adopts two different eluting agents and eluting processes, has high production efficiency and short period, and can obviously reduce the production cost.
2. The rare earth oxide product has the purity of 99.9999-99.99999 percent, the non-rare earth impurities are less than 100 PPM, wherein Fe is less than 1PPM, Ca is less than 3PPM, Si is less than 3PPM, and the product quality is very good.
3. The recovery rate of the rare earth is more than or equal to 90 percent, and the waste of rare earth resources can be effectively avoided.
4. Various solutions of the invention can be recycled and reused, and the resource utilization rate is obviously improved.
5. The invention can produce ultra-pure rare earth chloride products circularly and obviously improve the production efficiency.
Detailed Description
The invention is further described with reference to specific examples, without limiting the scope of protection and the scope of application of the invention.
Example 1
A method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution, wherein the concentration of rare earth ions in the adsorption stock solution is 1.5 mol/L;
(2) preparing an ion exchange column: preparing 4 ion exchange columns with column length of 200 cm and diameter of =1:30, respectively labeled as column A, column B, column C and column D, and filled with 732 strong-acid styrene cation exchange resin with particle diameter of 0.315-0.45 mm and specific surface area of 35-50 m2(g) 12% by mass of NH is used for the columns A and B4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+The retardant is CuSO4:H2SO4Mixed solution of 1:2 mol ratio of CuSO4The concentration is 90 g/L;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 4 cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution once every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 8 cm/min under the conditions of normal temperature and normal pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining a concentrated solution containing rare earth ions with the adsorption stock solution;
(5) rare earth ionFirst separation: connecting the column A and the column B in series, and adding eluent 1 at normal temperature and normal pressure from the top end of the column A at a linear velocity of 2 cm/min, wherein the eluent 1 is 0.3 mol/L NH with pH of 6.54When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 6 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.2 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.01 mol/L, NH4 + 0.3 mol/L solution with pH of 8.5, residual impurity ions are eluted first because of weak affinity with cation exchange resin in the elution process, and when Cu with blue color2+When the tape reached the bottom end of column D, the line speed of eluent 2 was increased to 2 cm/min, when the blue Cu2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluent 2 to 4 cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, determining that rare earth ions appear in the effluent liquid, receiving the effluent liquid in batches at the same time interval until the effluent liquid does not contain the rare earth ions any more, stopping adding the eluent 2, detecting the effluent liquid received in batches, and adding the effluent liquid containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent of rare earth ions to replace the Cu simple substance, filtering, adjusting pH to 1, precipitating rare earth ions with saturated oxalic acid solution, adjusting pH to5 mixing Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide.
Example 2
A method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution, wherein the concentration of rare earth ions in the adsorption stock solution is 2 mol/L;
(2) preparing an ion exchange column: preparing 4 ion exchange columns with column length of 400 cm and diameter of =1:20, respectively labeled as column A, column B, column C and column D, and filled with 732 strong-acid styrene cation exchange resin with particle diameter of 0.315-0.45 mm and specific surface area of 35-50 m2(g) 10% by mass of NH is used for the columns A and B4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+The retardant is CuSO4:H2SO4Mixed solution of 1:1 mol ratio of CuSO4The concentration is 80 g/L;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 5 cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 10 cm/min under normal temperature and pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining the concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, and adding eluent 1 at normal temperature and normal pressure from the top end of the column A at a linear velocity of 3cm/min, wherein the eluent 1 is 0.3 mol/L NH with pH of 6.54When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 8 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.1 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.005 mol/L, NH4 + 0.2 mol/L solution with pH value of 7.5, residual impurity ions are eluted out firstly because of weak affinity with cation exchange resin in the elution process, and when Cu with blue color2+When the tape reached the bottom end of column D, the line speed of eluent 2 was increased to 1 cm/min, when the blue Cu2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluent 2 to 3cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, determining that rare earth ions appear in the effluent liquid, receiving the effluent liquid in batches at the same time interval until the effluent liquid does not contain the rare earth ions any more, stopping adding the eluent 2, detecting the effluent liquid received in batches, and adding the effluent liquid containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+After-reconfigurationPreparing eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 2, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 6, and adding Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide.
Example 3
A method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution, wherein the concentration of rare earth ions in the adsorption stock solution is 0.5 mol/L;
(2) preparing an ion exchange column: preparing 4 ion exchange columns with column length of 40 cm and diameter of =1:25, respectively labeled as column A, column B, column C and column D, and filled with 732 strong-acid styrene cation exchange resin with particle diameter of 0.315-0.45 mm and specific surface area of 35-50 m2(g) 15% by mass of NH is used for the columns A and B4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+The retardant is CuSO4:H2SO4Mixed solution of 1:0.5 mol ratio of CuSO4The concentration is 100 g/L;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 3cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution once every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 5 cm/min under the conditions of normal temperature and normal pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining a concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, and adding eluent 1 at normal temperature and normal pressure from the top end of the column A at a linear velocity of 2 cm/min, wherein the eluent 1 is 0.1 mol/L NH with pH of 6.54When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 5 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series end to end, and adding eluent 2 at the linear velocity of 0.1 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.008 mol/L, NH4 + 0.1 mol/L solution with pH of 8.5, residual impurity ions are eluted first because of weak affinity with cation exchange resin in the elution process, and when Cu with blue color2+When the tape reached the bottom end of column D, the line speed of eluent 2 was increased to 1 cm/min, when the blue Cu2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluting agent 2 to 3cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, obtaining the rare earth ions in the effluent liquid, and taking the effluent liquid in batches at the same time interval until the effluent liquid does not contain rare earth ionsThen rare earth ions are contained, the adding of the eluent 2 is stopped, the effluent liquid obtained in batches is detected, and the eluent contains impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 1.5, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 5.5, and adding Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide.
Example 4
A method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution, wherein the concentration of rare earth ions in the adsorption stock solution is 1.2 mol/L;
(2) preparing an ion exchange column: preparing 4 ion exchange columns with column length of 300 cm and diameter of =1:25, respectively labeled as column A, column B, column C and column D, and filled with 732 strong-acid styrene cation exchange resin with particle diameter of 0.315-0.45 mm and specific surface area of 35-50 m2(g) 15% by mass of NH is used for the columns A and B4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+The retardant is CuSO4:H2SO4Mixed solution of 1:2 mol ratio of CuSO4The concentration is 80 g/L;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 5 cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 6 cm/min under the conditions of normal temperature and normal pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining a concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, and adding eluent 1 at normal temperature and normal pressure from the top end of the column A at a linear velocity of 2.5 cm/min, wherein the eluent 1 is 0.25 mol/L NH with pH of 6.54When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 5 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.15 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.01 mol/L, NH4 + 0.3 mol/L solution with pH value of 7.5, residual impurity ions are eluted out firstly because of weak affinity with cation exchange resin in the elution process, and when Cu with blue color2+When the tape reached the bottom end of column D, the line speed of eluent 2 was increased to 2 cm/min, when the blue Cu2+When the tape reached the bottom end of column E, the linear velocity of eluent 2 was increased to 5 cm/min while usingIntroducing part of the effluent into saturated oxalic acid solution via a fine conduit with a pore diameter of 1mm, collecting the effluent at the same time intervals when precipitation occurs, stopping adding eluent 2, detecting the effluent, and collecting the effluent containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 1, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 5, and adding Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide.
Example 5
A method for preparing high-purity rare earth by a conventional ion adsorption method comprises the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution, wherein the concentration of rare earth ions in the adsorption stock solution is 1.2 mol/L;
(2) preparing an ion exchange column: preparing 4 ion exchange columns with column length of 100 cm and diameter of =1:22, respectively labeled as column A, column B, column C and column D, and filled with 732 strong-acid styrene cation exchange resin with particle diameter of 0.315-0.45 mm and specific surface area of 35-50 m2(g) 10% by mass of NH is used for the columns A and B4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+The retardant is CuSO4:H2SO4Mixed solution of 1:2 mol ratio of CuSO4The concentration is 90 g/L;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 3cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution once every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 5 cm/min under the conditions of normal temperature and normal pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining a concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, and adding eluent 1 at normal temperature and normal pressure from the top end of the column A at a linear velocity of 2 cm/min, wherein the eluent 1 is 0.2 mol/L NH with pH of 6.54When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 5 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.1 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.005 mol/L, NH4 + 0.1 mol/L solution with pH value of 7.5, residual impurity ions are eluted out firstly because of weak affinity with cation exchange resin in the elution process, and when Cu with blue color2+When the tape reached the bottom end of column D, the line speed of eluent 2 was increased to 2 cm/min, when the blue Cu2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluent 2 to 5 cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, determining that rare earth ions appear in the effluent liquid, receiving the effluent liquid in batches at the same time interval until the effluent liquid does not contain the rare earth ions any more, stopping adding the eluent 2, detecting the effluent liquid received in batches, and adding the effluent liquid containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 1, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 5, and adding Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions with refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide.

Claims (1)

1. A method for preparing high-purity rare earth by a conventional ion adsorption method is characterized by comprising the following steps:
(1) preparing an adsorption stock solution: extracting and separating the ionic rare earth ore feed liquid by a P507-kerosene-HCl solvent system to obtain a single rare earth chloride solution, namely an adsorption stock solution;
(2) preparing an ion exchange column: preparing 4 ion exchange columns respectively marked as column A, column B, column C and column D, wherein the ion exchange columns are filled with 732 strong acid styrene cation exchange resins, and the column A and the column B are made of 10-15% NH by mass percentage4Elution conversion of AC solution to NH4 +Type, elution of column C and column D with retarder to form Cu2+-H+Molding;
(3) rare earth ion adsorption: adding an adsorption stock solution from the top end of a column A at a linear speed of 3-5 cm/min under the conditions of normal temperature and normal pressure, introducing a residual absorption solution to the top end of the column A after the residual absorption solution flows out from the bottom end of the column A, adding the residual absorption solution and the adsorption stock solution together, detecting the concentration of rare earth ions in the residual absorption solution every 5 min, and stopping adding the adsorption stock solution when the concentration of the rare earth ions in the residual absorption solution is the same as that of the rare earth ions in the adsorption stock solution, namely the column A adsorbs the rare earth ions to reach a saturated state;
(4) primary washing: adding ultrapure water from the top end of the column A at a linear speed of 5-10 cm/min under normal temperature and pressure, washing away adsorption stock solution and part of adsorbed impurity ions in gaps of the column A, taking an effluent liquid as a washing solution 1, precipitating the impurity ions in the washing solution 1, concentrating, and combining the concentrated solution containing rare earth ions with the adsorption stock solution;
(5) first separation of rare earth ions: connecting the column A and the column B in series, adding eluent 1 at normal temperature and normal pressure from the top end of the column A at linear velocity of 2-3 cm/min, wherein the eluent 1 is NH with pH of 6.0-6.5 and concentration of 0.05-0.3 mol/L4When the bottom end of the column C is provided with an effluent liquid, impurity ions are firstly eluted due to weaker affinity with cation exchange resin, a part of the effluent liquid is led out to a saturated oxalic acid solution by a thin conduit with the aperture of 1mm, when precipitation occurs, namely rare earth ions reach the bottom end of the column C, the addition of eluent 1 is stopped, and in the step, the effluent liquid containing the impurity ions but not containing the rare earth ions is prepared into the eluent 1 again after the impurity ions are chemically precipitated;
(6) and (3) secondary washing: adding ultrapure water from the top end of the column A at a linear speed of 5-8 cm/min under normal temperature and pressure, washing the eluent 1 and part of adsorbed impurity ions in the gaps in the column A, wherein the effluent is a washing solution 2, and concentrating the washing solution 2 after precipitating the impurity ions to prepare the eluent 1 again;
(7) and (3) secondary separation of rare earth ions: connecting the column A, the column B, the column C and the column D in series, and adding eluent 2 at the linear velocity of 0.1-0.3 cm/min from the top end of the column A under the conditions of normal temperature and normal pressure, wherein the eluent 2 is EDTA 0.005-0.01 mol/L, NH4 + 0.1-0.3 mol/L, pH7.5-8.5, residual impurity ions are eluted first because of weak affinity with cation exchange resin, when Cu with blue color2+When the belt reaches the bottom end of the column D, the linear velocity of the eluting agent is 2Increasing to 1-2 cm/min when the Cu is blue2+When the strip reaches the bottom end of the column E, increasing the linear velocity of the eluent 2 to 3-5 cm/min, simultaneously leading out part of the effluent liquid into a saturated oxalic acid solution by using a thin conduit with the aperture of 1mm, when precipitation occurs, determining that rare earth ions appear in the effluent liquid, receiving the effluent liquid in batches at the same time interval until the effluent liquid does not contain the rare earth ions any more, stopping adding the eluent 2, detecting the effluent liquid received in batches, and adding the effluent liquid containing impurity ions and Cu2+Precipitating the complete impurity ions and Cu in the effluent of2+Then re-formulating into eluent 2 containing Cu2+Adding aluminum scrap into the effluent liquid of rare earth ions to replace the Cu simple substance, filtering, adjusting the pH to 1-2, precipitating the rare earth ions by using saturated oxalic acid solution, adjusting the pH to 5-6, and adding Al3+Precipitating, preparing eluent 2 from the residual liquid, precipitating the effluent liquid containing rare earth ions by using refined saturated oxalic acid solution to obtain rare earth oxalate precipitate, washing, drying and firing to obtain ultra-pure rare earth oxide with the purity of 99.9999-99.99999%, and finally regenerating and transforming each ion exchange column to circularly prepare the ultra-pure rare earth oxide;
the concentration of rare earth ions in the adsorption stock solution is 0.5-2 mol/L;
the length of the ion exchange column is 200 cm, and the diameter of the ion exchange column is that the length of the ion exchange column is =1: 30;
the particle size of the 732 strong-acid styrene cation exchange resin is 0.315-0.45 mm;
the specific surface area of the 732 strong-acid styrene cation exchange resin is 35-50 m2/g；
The retardant is CuSO4:H2SO4A mixed solution of 1:0.5-2 mol ratio of CuSO4The concentration is 80-100 g/L;
the eluent 1 is 0.3 mol/L NH with pH of 6.54An AC solution;
the eluent 2 is EDTA 0.01 mol/L, NH4 + 0.3 mol/L, pH8.5 solution.
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