CN110306045B - Method for removing organic impurities in medium-heavy rare earth chloride solution - Google Patents

Method for removing organic impurities in medium-heavy rare earth chloride solution Download PDF

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CN110306045B
CN110306045B CN201910745527.XA CN201910745527A CN110306045B CN 110306045 B CN110306045 B CN 110306045B CN 201910745527 A CN201910745527 A CN 201910745527A CN 110306045 B CN110306045 B CN 110306045B
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rare earth
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heavy rare
chloride solution
earth chloride
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CN110306045A (en
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马莹
郝先库
张文娟
郝一凡
张瑞祥
斯琴毕力格
刘海旺
王士智
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Baotou Jingrui New Material Co ltd
Baotou Rare Earth Research Institute
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    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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    • C22B59/00—Obtaining rare earth metals
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Abstract

The invention discloses a method for removing organic impurities in a medium-heavy rare earth chloride solution, which comprises the following steps: (1) removing organic impurities from the medium-heavy rare earth chloride solution obtained by the extraction separation process through a resin column to obtain an impurity-removed medium-heavy rare earth chloride solution; (2) mixing the medium-heavy rare earth chloride solution after impurity removal, an extracting agent and a diluting agent, and separating an organic phase and a water phase in an extraction section; the organic phase obtained in the extraction section enters a washing section and a back extraction section in turn. The method can effectively eliminate the phenomenon of organic impurity enrichment in the extraction tanks of the extraction section, the washing section and the back extraction section.

Description

Method for removing organic impurities in medium-heavy rare earth chloride solution
Technical Field
The invention relates to a method for removing organic impurities in a medium-heavy rare earth chloride solution.
Background
The medium-heavy rare earth resources are mainly distributed in China, and the resource amount, the element types and the distribution form of the medium-heavy rare earth resources are incomparable with those of any country in the world. The medium-heavy rare earth resource plays an irreplaceable role in light rare earth and other materials in the metallurgical casting industry, luminescent materials, permanent magnetic materials, environment-friendly materials and other high and new technologies and advanced science fields.
Hydroximic acid type collectors are used in the production process of rare earth concentrates. Hydroximic acid can generate rearrangement reaction under the action of high temperature or strong acid to generate isocyano ester or amine compounds, and the organic impurities can enter the rare earth chloride solution to generate adverse effect on extraction separation, particularly on extraction separation of medium and heavy rare earth. The extraction separation of medium-heavy rare earth is continuously produced for a long time, organic impurities dissolved in an organic phase and a water phase in each extraction tank reach a saturated state, and are continuously separated out in a tank body, asphalt-like organic matters can appear in the tank body in a back extraction section and a washing section with higher equilibrium acidity, black brown solid particles can appear in the extraction tank in the extraction section with lower equilibrium acidity, and the asphalt-like organic matters and the black brown solid particles are easy to block a flow guide pipe of the organic phase and the water phase, so that the extraction separation efficiency of rare earth is influenced.
CN101182597A discloses a method for complexing, extracting and separating rare earth elements by an acidic extracting agent, which comprises the following steps: di (2-ethylhexyl phosphatide) or 2-ethylhexyl phosphoric acid monoethyl hexyl ester is used as acidic phosphorus type extractant, kerosene is diluted to be used as organic phase for extraction separation, and citric acid or citrate is added into rare earth chloride solution to prepare rare earth chloride-hydrochloric acid-citric acid mixed solution to be used as water phase for extraction separation. And (4) extracting and separating an organic phase and an aqueous phase to separate the rare earth elements. The method directly extracts and separates the rare earth chloride solution, and the rare earth chloride is not pretreated, so that the phenomenon of organic impurity enrichment in extraction tanks of an extraction section, a washing section and a back extraction section cannot be eliminated.
CN1455009A discloses a process for preparing rare earth chloride by extraction and transformation of long-chain fatty acid and a back extraction process thereof: rare earth chloride is extracted and separated by taking rare earth concentrate roasting water extract or rare earth sulfate as a raw material, taking a long-chain fatty acid as an extracting agent, taking mixed alcohol or petroleum sulfoxide as a cosolvent and taking alkane as a diluent. The method directly extracts and separates the rare earth feed liquid, and the rare earth feed liquid is not pretreated, so that the phenomenon of organic impurity enrichment in extraction tanks of an extraction section, a washing section and a back extraction section cannot be eliminated.
Disclosure of Invention
In view of the above, the present invention provides a method for removing organic impurities from a medium-heavy rare earth chloride solution, which can effectively remove the phenomenon of organic impurity enrichment in extraction tanks of an extraction section, a washing section and a stripping section.
The invention provides a method for removing organic impurities in a medium-heavy rare earth chloride solution, which comprises the following steps:
(1) removing organic impurities from the medium-heavy rare earth chloride solution obtained by the extraction separation process through a resin column to obtain an impurity-removed medium-heavy rare earth chloride solution;
(2) mixing the medium-heavy rare earth chloride solution after impurity removal, an extracting agent and a diluting agent, and separating an organic phase and a water phase in an extraction section; the organic phase obtained in the extraction section sequentially enters a washing section and a back extraction section;
wherein the resin column is filled with a crosslinked styrene-divinylbenzene polymer; the medium-heavy rare earth in the medium-heavy rare earth chloride solution obtained by the extraction separation process is selected from a plurality of samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) or yttrium (Y).
According to the method of the present invention, preferably, the extractant is an acidic extractant.
According to the method of the present invention, preferably, the diluent is selected from one or more of kerosene, cyclohexane and n-hexane.
According to the method of the present invention, preferably, the stripping solution of the stripping section can be selected from aqueous solutions of inorganic acids.
According to the method of the present invention, preferably, the crosslinked styrene-divinylbenzene polymer has a specific surface area of not less than 900m2/g。
According to the method of the present invention, preferably, the crosslinked styrene-divinylbenzene polymer has a wet apparent density of 0.50 to 0.90g/ml and a wet true density of 1.00 to 1.50 g/ml.
According to the method of the present invention, preferably, the crosslinked styrene-divinylbenzene polymer is a resin particle having a particle diameter of 0.2 to 2.00mm in a range of 85 to 100%.
According to the method, the concentration of organic impurities in the medium-heavy rare earth chloride solution obtained by the extraction separation process is preferably 5-35 mg/L.
According to the method, preferably, the flow rate of the medium-heavy rare earth chloride solution obtained by the extraction separation process passing through the resin column is 30-1000L/h.
According to the method of the present invention, the ratio of the diameter to the height of the resin column is preferably 1:3 to 20.
The invention adopts the crosslinked styrene-divinylbenzene polymer as the adsorbent, can effectively remove organic impurities in the medium and heavy rare earth chloride solution, and eliminates the phenomenon of organic impurity enrichment in the extraction tanks of the medium and heavy rare earth extraction section, the washing section and the back extraction section. According to a preferred embodiment of the present invention, the crosslinked styrene-divinylbenzene polymer has a specific surface area of not less than 900m2The/g can ensure the adsorption capacity of the crosslinked styrene-divinylbenzene polymer and enhance the effect of removing organic impurities in the medium and heavy rare earth chloride solution.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The medium-heavy rare earth in the invention is a plurality of samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) and yttrium (Y).
(Eu-Dy)Cl3The solution means a solution possibly containing chlorides of Eu, Gd, Tb and Dy.
(Sm-Lu,Y)Cl3The solution means a solution possibly containing chlorides of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
The method for removing the organic impurities in the heavy rare earth chloride solution comprises the following steps: (1) removing impurities; (2) and (5) extracting and separating. As described in detail below.
< step of removing impurities >
And removing organic impurities from the medium-heavy rare earth chloride solution obtained by the extraction separation process through a resin column to obtain the medium-heavy rare earth chloride solution after impurity removal. The extraction separation process is an extraction separation process of medium and heavy rare earths, and is carried out by adopting a conventional method in the field to obtain a chloride solution of the medium and heavy rare earths. The invention further processes the medium-heavy rare earth chloride solution obtained by the extraction separation process, thereby removing organic impurities.
The resin column of the present invention is a resin column packed with a crosslinked styrene-divinylbenzene polymer. The crosslinked styrene-divinylbenzene polymer in the present invention can be obtained by a conventional method. For example, styrene, divinylbenzene, are passed through a suspension polymerization process to obtain crosslinked styrene-divinylbenzene polymers. The crosslinked styrene-divinylbenzene polymer of the present invention is not limited to one obtained by suspension polymerization, but may be obtained by a conventional method such as solution polymerization, emulsion polymerization, and the like.
In the present invention, the crosslinked styrene-divinylbenzene polymer has a specific surface area of not less than 900m2(ii) in terms of/g. Preferably, the specific surface area is not less than 1200m2(ii) in terms of/g. More preferably, the specific surface area is not less than 1500m2(ii) in terms of/g. Therefore, the adsorption capacity of the polymer can be ensured, and a better impurity removal effect is achieved, so that the phenomenon of organic impurity enrichment in the extraction tanks of the extraction section, the washing section and the back extraction section is eliminated.
In the present invention, the crosslinked styrene-divinylbenzene polymer has a wet apparent density of 0.50 to 0.90g/ml and a wet true density of 1.00 to 1.50 g/ml. Preferably, the wet apparent density is 0.60-0.80 g/ml. More preferably, the wet apparent density is 0.65 to 0.75 g/ml. Preferably, the wet true density is 1.00-1.30 g/ml. More preferably, the wet true density is 1.05 to 1.15 g/ml. Therefore, the adsorption capacity of the polymer can be ensured, and a better organic impurity removal effect is achieved, so that the phenomenon of organic impurity enrichment in extraction tanks of an extraction section, a washing section and a back extraction section is eliminated.
In the present invention, the crosslinked styrene-divinylbenzene polymer is a resin particle having a particle diameter of 0.2 to 2.00mm and containing 85 to 100%. Preferably, the crosslinked styrene-divinylbenzene polymer is a resin particle having a particle diameter of 0.4 to 1.25mm in a range of 85 to 100%. More preferably, the crosslinked styrene-divinylbenzene polymer is a resin particle having a particle diameter of 0.4 to 1.25mm, which is 95 to 100%. The granular resin has more uniform pore diameter, and is beneficial to the adsorption of organic impurities, thereby eliminating the phenomenon of organic impurity enrichment in extraction tanks of an extraction section, a washing section and a back extraction section.
In the present invention, the ratio of the diameter to the height of the resin column is 1:3 to 20. Preferably, the ratio of the diameter to the height of the resin column is 1:5 to 15. More preferably, the ratio of the diameter to the height of the resin column is 1:7 to 12. According to a specific embodiment of the invention, the ratio of the diameter to the height of the resin column is 1: 10. Thus, the adsorption rate can be ensured, and the resin can be fully utilized to reach the maximum adsorption capacity.
In the invention, the flow of the medium-heavy rare earth chloride solution obtained by the extraction separation process through the resin column is 30-1000L/h. Preferably, the flow rate of the medium-heavy rare earth chloride solution passing through the resin column is 50-800L/h. More preferably, the flow rate of the medium-heavy rare earth chloride solution passing through the resin column is 50-300L/h. Therefore, the organic impurities in the medium and heavy rare earth chloride solution can be fully adsorbed and diffused, and the removal efficiency of the organic impurities in the medium and heavy rare earth chloride solution can be ensured, so that the phenomenon of enrichment of the organic impurities in the extraction tanks of the extraction section, the washing section and the back extraction section is eliminated.
The organic impurities in the present invention comprise hydroxamic acid-forming isocyanamides or amines. The concentration of organic impurities in the medium-heavy rare earth chloride solution obtained by the extraction separation process is 5-35 mg/L. Preferably, the concentration of the organic impurities is 10-30 mg/L. More preferably, the concentration of the organic impurities is 10-25 mg/L. Thus, the removal effect of organic impurities can be ensured, and the phenomenon of organic impurity enrichment in the extraction tanks of the extraction section, the washing section and the back extraction section is eliminated.
In the invention, the hydrogen ion concentration of the medium-heavy rare earth chloride solution obtained by the extraction separation process is 0.05-0.9 mg/L. Preferably, the hydrogen ion concentration of the medium-heavy rare earth chloride solution obtained by the extraction separation process is 0.1-0.8 mg/L. More preferably, the hydrogen ion concentration of the medium-heavy rare earth chloride solution obtained by the extraction separation process is 0.2-0.5 mol/L.
In the invention, the concentration of the medium-heavy rare earth chloride in the medium-heavy rare earth chloride solution obtained by the extraction separation process is 0.05-4 mol/L. Preferably, the concentration of the medium-heavy rare earth chloride is 0.05-3 mol/L. More preferably, the concentration of the medium-heavy rare earth chloride is 1-2 mol/L. Thus, the removal effect of organic impurities in the medium-heavy rare earth chloride solution can be ensured, and the phenomenon of organic impurity enrichment in the extraction tanks of the extraction section, the washing section and the back extraction section is eliminated.
< step of extraction separation >
Mixing the medium-heavy rare earth chloride solution after impurity removal, an extracting agent and a diluting agent, and separating an organic phase and a water phase in an extraction section; the organic phase obtained in the extraction section enters a washing section and a back extraction section in turn.
In the present invention, the extractant is an acidic extractant. Preferably, the extractant is 2-ethylhexyl phosphate mono 2-ethylhexyl ester or bis (2-ethylhexyl) phosphate. More preferably, the extractant is 2-ethylhexyl phosphate mono 2-ethylhexyl ester.
In the invention, the diluent is selected from one or more of kerosene, cyclohexane and n-hexane. Preferably, the diluent is selected from one or more of kerosene or cyclohexane. More preferably, the diluent is kerosene.
In the present invention, the washing liquid used in the washing stage is water or an aqueous solution of an inorganic acid. The aqueous solution of the inorganic acid may be one selected from an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, or an aqueous solution of nitric acid. Preferably, the washing liquid is water or an aqueous solution of hydrochloric acid. More preferably, the washing liquid is water.
In the present invention, the stripping solution used in the stripping section may be an aqueous solution of a mineral acid. The aqueous solution of the inorganic acid may be one selected from an aqueous solution of hydrochloric acid, an aqueous solution of nitric acid, or an aqueous solution of sulfuric acid. Preferably, the aqueous solution of the inorganic acid is selected from one of aqueous solution of hydrochloric acid or aqueous solution of sulfuric acid. More preferably, the aqueous solution of inorganic water is an aqueous solution of hydrochloric acid.
The properties of the crosslinked styrene-divinyl polymers used in the examples below are seen in the following table.
TABLE 1
Figure BDA0002165423970000071
The concentrations of organic impurities in the medium and heavy rare earth chloride solutions of the following examples were tested using the following method:
the total oil content in water is determined by infrared spectrophotometry for determining water quality of petroleum and animal and vegetable oils (HJ 637-2012). Total oil means, under the conditions specified in this standard, that it can be extracted by carbon tetrachloride and has a wavenumber of 2930cm-1、2960cm-1、3030cm-1Substances with characteristic absorption at all or part of the spectral band mainly comprise petroleum and animal and vegetable oils.
The HCl concentration in the aqueous hydrochloric acid solutions of the following examples and comparative examples was 18 to 19 wt%.
Example 1
The crosslinked styrene-divinylbenzene polymer was loaded into a resin column. The diameter of the resin column was 0.3 m and the height was 3 m.
Will contain (TbDy) Cl3The solution (organic impurity concentration: 30mg/L, hydrogen ion concentration: 0.8mol/L, (TbDy) Cl)3Concentration of 1.2mol/L) at room temperature, removing organic impurities through a resin column at a flow rate of 50L/h to obtain (TbDy) Cl after impurity removal3And (3) solution. (TbDy) Cl after impurity removal3The solution properties are shown in Table 2.
Removing impurities from (TbDy) Cl3Mixing the solution, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and kerosene in a mixing chamber of an extraction section, and separating an organic phase and a water phase in the extraction section; the organic phase obtained in the extraction section firstly enters a washing section, the washing liquid used in the washing section is water, and then the organic phase enters a back extraction section, and the back extraction liquid used in the back extraction section is the aqueous solution of hydrochloric acid. Continuously running for 90 days, observing the extraction sectionWhether black brown solid particles appear in the extraction tank or not and whether asphalt-like organic matters appear in the extraction tanks of the washing section and the back-extraction section are observed, and the observation results are shown in table 2.
Example 2
The crosslinked styrene-divinylbenzene polymer was loaded into a resin column. The diameter of the resin column was 0.3 m and the height was 3 m.
Containing (Eu-Dy) Cl3(organic impurity concentration: 29.46mg/L, hydrogen ion concentration: 0.2mol/L, (Eu-Dy) Cl)3Concentration of 1.5mol/L) at room temperature, removing organic impurities through a resin column at a flow rate of 270L/h to obtain (Eu-Dy) Cl after impurity removal3And (3) solution. (Eu-Dy) Cl after impurity removal3The solution properties are shown in Table 2.
Removing impurities from (Eu-Dy) Cl3Mixing the solution, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and kerosene in a mixing chamber of an extraction section, and separating an organic phase and a water phase in the extraction section; the organic phase obtained in the extraction section firstly enters a washing section, the washing liquid used in the washing section is water, and then the organic phase enters a back extraction section, and the back extraction liquid used in the back extraction section is the aqueous solution of hydrochloric acid. Continuously operating for 90 days, observing whether black brown solid particles appear in the extraction tank of the extraction section, and observing whether asphalt-like organic matters appear in the extraction tanks of the washing section and the back-extraction section, wherein the observation results are shown in a table 2.
Example 3
The crosslinked styrene-divinylbenzene polymer was loaded into a resin column. The diameter of the resin column was 0.3 m and the height was 3 m.
Will contain (EuGd) Cl3The solution (organic impurity concentration: 10.18mg/L, hydrogen ion concentration: 0.15mol/L, (EuGd) Cl)3Concentration of 1.5mol/L) at room temperature, removing organic impurities through a resin column according to the flow rate of 210L/h to obtain (EuGd) Cl after impurity removal3And (3) solution. (EuGd) Cl after impurity removal3The solution properties are shown in Table 2.
Removing impurities from the (EuGd) Cl3Mixing the solution, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and kerosene in a mixing chamber of an extraction section, and separating an organic phase and a water phase in the extraction section; organic matter obtained in the extraction sectionThe phase firstly enters a washing section, the washing liquid used in the washing section is water, and then the phase enters a back extraction section, and the back extraction liquid used in the back extraction section is the aqueous solution of hydrochloric acid. Continuously operating for 90 days, observing whether black brown solid particles appear in the extraction tank of the extraction section, and observing whether asphalt-like organic matters appear in the extraction tanks of the washing section and the back-extraction section, wherein the observation results are shown in a table 2.
Example 4
The crosslinked styrene-divinylbenzene polymer was loaded into a resin column. The diameter of the resin column was 0.3 m and the height was 3 m.
Will contain (Sm-Lu, Y) Cl3(Sm-Lu, Y) Cl in a solution of (1) (organic impurity concentration 23.44mg/L, hydrogen ion concentration 0.4 mol/L)3Concentration of 1.7mol/L) at room temperature, removing organic impurities through a resin column according to the flow of 800L/h to obtain (Sm-Lu, Y) Cl after impurity removal3The solution of (1). (Sm-Lu, Y) Cl after impurity removal3The solution properties are shown in Table 2.
Removing impurities from (Sm-Lu, Y) Cl3Mixing the solution, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and kerosene in a mixing chamber of an extraction section, and separating an organic phase and a water phase in the extraction section; the organic phase obtained in the extraction section firstly enters a washing section, the washing liquid used in the washing section is water, and then the organic phase enters a back extraction section, and the back extraction liquid used in the back extraction section is the aqueous solution of hydrochloric acid. Continuously operating for 90 days, observing whether black brown solid particles appear in the extraction tank of the extraction section, and observing whether asphalt-like organic matters appear in the extraction tanks of the washing section and the back-extraction section, wherein the observation results are shown in a table 2.
Comparative example
Will contain (TbDy) Cl3The solution (organic impurity concentration: 30mg/L, hydrogen ion concentration: 0.8mol/L, (TbDy) Cl)3Concentration of 1.2mol/L), 2-ethylhexyl phosphate mono 2-ethylhexyl ester and kerosene are mixed in a mixing chamber of an extraction section, and an organic phase and a water phase are separated in the extraction section; the organic phase obtained in the extraction section firstly enters a washing section, the washing liquid used in the washing section is water, and then the organic phase enters a back extraction section, and the back extraction liquid used in the back extraction section is the aqueous solution of hydrochloric acid. Continuously running for 90 days, and observing whether black brown solid appears in the extraction tank of the extraction sectionIf the asphalt-like organic matters appear in the extraction tanks of the granule, washing section and back-extraction section, the observation results are shown in Table 2.
TABLE 2
Figure BDA0002165423970000101
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims (8)

1. A method for removing organic impurities in a medium-heavy rare earth chloride solution is characterized by comprising the following steps:
(1) removing organic impurities from the medium-heavy rare earth chloride solution obtained by the extraction separation process through a resin column to obtain an impurity-removed medium-heavy rare earth chloride solution; the flow speed of the medium-heavy rare earth chloride solution passing through the resin column is 50-300L/h;
(2) mixing the medium-heavy rare earth chloride solution after impurity removal, an extracting agent and a diluting agent, and separating an organic phase and a water phase in an extraction section; the organic phase obtained in the extraction section sequentially enters a washing section and a back extraction section;
wherein the resin column is filled with a crosslinked styrene-divinylbenzene polymer having a specific surface area of not less than 1200m2The wet apparent density is 0.50-0.90 g/ml, and the wet true density is 1.00-1.50 g/ml; the medium-heavy rare earth in the medium-heavy rare earth chloride solution obtained by the extraction separation process is selected from a plurality of samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) or yttrium (Y).
2. The method of claim 1, wherein the extractant is an acidic extractant.
3. The method of claim 1, wherein the diluent is selected from one or more of kerosene, cyclohexane, and n-hexane.
4. The process according to claim 1, characterized in that the stripping solution of the stripping section is selected from aqueous solutions of mineral acids.
5. The method of claim 1, wherein the crosslinked styrene-divinylbenzene polymer has a wet apparent density of 0.60 to 0.80g/ml and a wet true density of 1.00 to 1.30 g/ml.
6. The method as claimed in claim 1, wherein the crosslinked styrene-divinylbenzene polymer is resin particles having a particle size of 0.2 to 2.00mm in a range of 85 to 100%.
7. The method according to claim 1, wherein the concentration of organic impurities in the medium-heavy rare earth chloride solution obtained by the extraction separation process is 5-35 mg/L.
8. The method according to any one of claims 1 to 7, wherein the ratio of the diameter to the height of the resin column is 1:3 to 20.
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