WO2013143271A1 - 一种稀土元素的萃取分离方法 - Google Patents
一种稀土元素的萃取分离方法 Download PDFInfo
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- WO2013143271A1 WO2013143271A1 PCT/CN2012/082448 CN2012082448W WO2013143271A1 WO 2013143271 A1 WO2013143271 A1 WO 2013143271A1 CN 2012082448 W CN2012082448 W CN 2012082448W WO 2013143271 A1 WO2013143271 A1 WO 2013143271A1
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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
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
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- 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
Definitions
- the present invention is in the field of extraction technology, and more particularly, relates to a method for extracting and separating rare earth elements.
- Rare earth elements include lanthanides with an atomic number of 57 to 71 and lanthanum with an atomic number of 39. Due to their unique physical and chemical properties, rare earth elements are often used as additives in metallurgy, glass, and chemical industries. , nuclear industry, electronics, agriculture and medicine, and various functional materials. Solvent extraction and separation method is the main method for separating and purifying rare earth elements in rare earth industrial production at home and abroad, and is also the main method for separating high-purity rare earth compounds. It has the advantages of large processing capacity, fast reaction speed and good separation effect. In recent years, the efficient clean separation of rare earths has become the research direction of rare earth separation. In 2011, China issued the “Rare Earth Industrial Pollutant Emission Standards”, which required the greener and more efficient separation of rare earths.
- the separation process between single rare earths is mainly realized by a process of separating rare earth by grouping agent P507 (2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester) (Li Deqian et al., phosphonate liquid solution - Liquid extraction for the separation of rare earth elements. 1985, CN85102244.).
- grouping agent P507 (2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester)
- the separation coefficient of P507 for heavy rare earth is small, and in the process of extraction and separation, there is a problem that the stripping acidity is high, the stripping is not thorough, and the extraction equilibrium time is long.
- the acid phosphine extractant Cyanex272 bis(2,4,4-tridecylpentyl)phosphinic acid can be used to separate the rare earth to improve the separation factor.
- Cyanex272 system extractant is expensive, and the reagents and equipment are expensive.
- the quality of the liquid is high, the separation system is easy to emulsify, and the production process is difficult to control. Liao Chunsheng et al. (Extraction and separation of high purity cerium oxide.
- acidic organic phosphonic acid such as P507, bis-(2-ethylhexyl)phosphoric acid (P204), etc., or organic carboxylic acid, for example, naphthenic acid, CA-12, etc.
- P507 bis-(2-ethylhexyl)phosphoric acid (P204), etc.
- organic carboxylic acid for example, naphthenic acid, CA-12, etc.
- the sub-exchanger needs to strengthen the extraction of rare earth ions by saponification (ammonia soap, sodium soap, magnesium or rare earth soap, etc.), in addition to introducing corresponding metal ions such as ammonia or sodium or magnesium to produce corresponding ammonia nitrogen or salinization.
- Contamination also requires the consumption of high concentrations of acid and alkali to complete a series of processes of extraction, washing and stripping.
- P204 is easy to produce emulsification when the acidity of the feed liquid is low, and it is difficult to carry out the counter-extraction of the medium-heavy rare earth, the residual acid of the stripping solution is high, and the consumption of s-base is large (Chinese patent ZL85102210).
- the Chinese patent document CN100352954C reports a process for extracting and separating heavy rare earth elements by adding a modifier, which separates a single rare earth with a P507 plus alcohol system, which may result in a long-term operation due to the difference in solubility of each component of the mixed system.
- the composition of the extractant changes, which affects the extraction effect of the system.
- the present inventors considered to provide a method for extracting and separating rare earth elements, which does not require saponification and has a high separation factor for rare earth elements.
- the technical problem to be solved by the present invention is to provide a method for extracting and separating rare earth elements, which does not require saponification and has a high separation coefficient for rare earth elements.
- the present invention provides a method for extracting and separating rare earth elements, comprising the following steps:
- the extraction temperature is 20 to 50 °C.
- a NaN0 3 solution having a concentration of 0.2 to 1.5 mol/L is further included as a salting-out agent.
- the extracting the rare earth element in the rare earth nitrate aqueous solution into the n-heptane is specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extractant, the salting-out agent and the rare earth nitrate aqueous solution to the rare earth nitric acid
- the rare earth element in the brine solution is extracted into n-heptane, and the quaternary ammonium salt ionic liquid extractant is 2-ethylhexylphosphonic acid mono 2-ethylhexyl trialkyl decyl ammonium or phosphonic acid di(2- Ethylhexyl) ester trialkyl decyl ammonium.
- the concentration of the n-heptane solution of the quaternary ammonium salt ionic liquid extractant is 0.03 to 0.1 moH.
- the concentration of the rare earth nitrate aqueous solution is 7 to 9 x 1 (T 4 mol/L.
- the pH of the rare earth nitrate aqueous solution is controlled to be 1 to 4.
- the method further includes:
- the rare earth element extracted into n-heptane is back extracted with a nitric acid solution.
- the concentration of the nitric acid solution is 0.04 to 0.50 mol/L.
- the rare earth element is one or more of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
- the invention also provides a method for extracting and separating rare earth elements, comprising the following steps:
- the extraction temperature is 20 to 50 °C.
- a NaCl solution having a concentration of 0.2 to 1.5 mol/L is further included as a salting-out agent.
- the extracting the rare earth element in the rare earth chloride aqueous solution into the n-heptane is specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extractant, the salting-out agent and the rare earth chloride aqueous solution to form the rare earth chlorine
- the rare earth element in the aqueous solution of the compound is extracted into n-heptane, and the quaternary ammonium salt ionic liquid extracting agent is 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium or phosphonic acid di(2- Ethylhexyl) ester trialkyl decyl ammonium.
- the concentration of the n-heptane solution of the quaternary ammonium salt ionic liquid extractant is 0.01 to 0.08 mol/L.
- the concentration of the rare earth chloride aqueous solution is 7 to 11 X l (T 4 mol/L.
- the pH of the aqueous solution of the rare earth chloride is controlled to be 1 to 5.
- the method further includes:
- the rare earth element extracted into n-heptane is back-extracted with a hydrochloric acid solution.
- the concentration of the hydrochloric acid solution is 0.03 to 0.20 mol/L.
- the rare earth element is one or more of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
- the invention also provides a method for extracting and separating rare earth elements, comprising the following steps: using 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium as an extracting agent, and n-heptane as a dilute The rare earth element in the rare earth sulfate aqueous solution is extracted into n-heptane.
- the extraction temperature is 25 to 50 °C.
- the Na 2 SO 4 solution having a concentration of 0.1 to 1 mol/L is used as a salting-out agent.
- the extracting the rare earth element in the rare earth sulfate aqueous solution into the n-heptane is specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extracting agent, the salting-out agent and the rare earth sulfate aqueous solution, and the rare earth sulfuric acid
- the rare earth element in the brine solution is extracted into n-heptane, and the quaternary ammonium salt ionic liquid is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester trialkyl decyl ammonium.
- the concentration of the n-heptane solution of the quaternary ammonium salt ionic liquid extractant is
- the concentration of the rare earth sulfate aqueous solution is 7 ⁇ 9 x 10" 4 mol/L.
- the pH of the aqueous solution of the rare earth sulphate is controlled to be 1 to 7.
- the method further includes:
- the rare earth element extracted into n-heptane is subjected to back extraction using a sulfuric acid solution.
- the concentration of the sulfuric acid solution is 0.01 ⁇ 0. lmol / L.
- the rare earth element is one or more of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
- the invention provides a method for extracting and separating rare earth elements in a nitric acid system, comprising the following steps:
- 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium ([A336] [P507]) or phosphonic acid di(2-ethylhexyl) ester trialkyl decyl ammonium ([A336] [P204]) is an extractant, and the rare earth element in the rare earth nitrate aqueous solution is extracted into n-heptane.
- quaternary ammonium salt ionic liquid extractant is 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium and phosphonic acid di(2-ethylhexyl) ester triane
- the cations and anions in the guanidinium ammonium react with the rare earth ions to form a neutral complex molecule.
- the cations and anions in the quaternary ammonium salt ionic liquid extractant have internal synergistic effects and competitive effects in the process of extracting soil elements. , thereby increasing the separation factor for rare earth elements.
- the extraction and separation method provided by the invention has good interface phenomenon during the extraction process, no emulsification, no need to saponify the extractant, and has a high separation coefficient for rare earth elements, especially for heavy rare earths.
- this The method for extracting and separating rare earth elements provided by the invention has low extraction acidity, low stripping acidity and low acid consumption.
- the invention provides a method for extracting and separating rare earth elements in a hydrochloric acid system, comprising the following steps:
- 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium ([A336] [P507]) or phosphonic acid di(2-ethylhexyl) ester trialkyl decyl ammonium ([A336] [P204]) is an extractant, and the rare earth element in the rare earth chloride aqueous solution is extracted into n-heptane.
- quaternary ammonium salt ionic liquid extractant is 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium and phosphonic acid di(2-ethylhexyl) ester triane
- the cations and anions in the guanidinium ammonium react with the rare earth ions to form a neutral complex molecule, and the cations and anions in the quaternary ammonium salt ionic liquid extractant have an internal synergistic effect in the process of extracting the soil element, thereby improving the The separation factor for rare earth elements.
- the extraction and separation method provided by the invention has good interface phenomenon during the extraction process, no emulsification, no need to saponify the extractant, and has a high separation coefficient for rare earth elements, especially for several light rare earth elements.
- the extraction and separation method of the rare earth element provided by the invention has low extraction acidity, low strip acidity and low acid consumption.
- the invention provides a method for extracting and separating rare earth elements in a sulfuric acid system, comprising the following steps: extracting 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkylsulfonium ammonium ([A336][P507]) The rare earth element in the rare earth sulfate aqueous solution is extracted into n-heptane.
- the cations and anions in the quaternary ammonium salt ionic liquid extractant react with the rare earth ions to form a neutral
- the complex molecules and the cations and anions in the quaternary ammonium salt ionic liquid extractant have an internal synergistic effect in the process of extracting rare earth elements. Thereby increasing the separation factor for rare earth elements. Therefore, the extraction separation method provided by the invention has good interface phenomenon during the extraction process, no emulsification, and no saponification of the extractant.
- the extraction and separation method of the rare earth element provided by the invention has low extraction acidity, low strip acidity and low acid consumption.
- Fig. 1 is a dot diagram showing the solution equilibrium H value and the rare earth ion extraction distribution ratio when [A336][P507] provided as an extractant in Examples 13 to 27 of the present invention;
- Figure 3 is a graph showing the concentration of a salting-out agent and a rare earth extraction rate when [A336][P507] as an extractant according to Examples 43 to 45 of the present invention
- Figure 4 is a graphene concentration of [A336][P204] as an extractant according to Examples 46 to 48 of the present invention. And the rare earth extraction rate curve;
- FIG. 6 is a graph showing the concentration of HN0 3 solution and the stripping rate of supported rare earth ions when [A336][P204] provided as an extractant according to Examples 52 to 54 of the present invention;
- Figure 8 is a dot diagram of the solution equilibrium pH value and the rare earth ion extraction distribution ratio of [A336][P204] as an extractant according to Examples 113 to 127 of the present invention
- Figure 9 is a graph showing the concentration of a salting-out agent and a rare earth distribution ratio when [A336][P507] provided as an extractant according to Examples 128 to 130 of the present invention.
- Figure 10 is a graph showing the concentration of a salting-out agent and a rare earth distribution ratio when [A336][P204] as an extractant according to Examples 131 to 133 of the present invention.
- Figure 11 is a graph showing the concentration of HC1 solution and the stripping rate of supported rare earth ions when [A336][P507] provided as an extractant according to Examples 134 to 137 of the present invention
- Figure 12 is a graph showing the concentration of HC1 solution and the stripping rate of supported rare earth ions when [A336][P204] provided as an extractant according to Examples 138 to 141 of the present invention
- Figure 13 is a graph showing the effect of NaCl concentration on the extraction rate provided in Example 143 of the present invention.
- Figure 14 is a graph showing the relationship between the equilibrium pH value of the solution and the rare earth ion extraction distribution ratio when [A336][P507] provided as an extractant according to Examples 146 to 160 of the present invention;
- Figure 15 is a graph showing the concentration of a salting-out agent Na 2 SO 4 and a rare earth ion extraction rate when [A336] [P507] provided as an extractant according to Examples 161 to 164 of the present invention;
- Figure 16 is a graph showing the NaCl concentration of the salting-out agent and the rare earth ion extraction rate when [A336][P507] as an extractant according to Example 165 of the present invention.
- Figure 17 is a graph showing the concentration of H 2 SO 4 solution and the stripping rate of supported rare earth ions when [A336] [P507] provided as an extractant according to Examples 166 to 168 of the present invention.
- the invention provides a method for extracting and separating rare earth elements, using 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium or phosphonic acid di(2-ethylhexyl) ester trialkyl hydrazine
- the ammonium is an extractant for extracting rare earth elements in hydrochloric acid, nitric acid and sulfuric acid systems.
- the invention discloses a method for extracting and separating rare earth elements, comprising the following steps: 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium or phosphonic acid di(2-ethylhexyl) ester
- the trialkyl decyl ammonium is an extractant, and the rare earth element in the rare earth nitrate aqueous solution is extracted into n-heptane using n-heptane as a dilute agent.
- the present invention uses a quaternary ammonium salt ionic liquid extractant, 2-ethylhexylphosphine S, 2-ethylhexyl ester, trialkyl decyl ammonium or phosphonic acid di(2-ethylhexyl).
- the ester trialkyl decyl ammonium is an extractant, and the cations and anions in the extractants [A336] [P507] and [A336] [P204] react with the rare earth ions to form a neutral complex molecule.
- the cations and anions in the extractant [A336][P507] or [A336][P204] have internal synergistic effects and competitive effects in the process of extracting different rare earth ions. Due to the internal synergy and competition of anions and cations, Thereby, the separation coefficient of the rare earth element is increased, especially the separation coefficient of the heavy rare earth is increased.
- the preparation method of the quaternary ammonium salt ionic liquid extractant of the present invention is not particularly limited, and can be produced by a method well known to those skilled in the art.
- the present invention separately synthesizes 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium ([A336][P507]) and the technical scheme provided in Chinese Patent Application No. 200910217922.7 and Di(2-ethylhexyl) phosphotium trialkyl decyl ammonium ([A336][P204]).
- 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium ([A336][P507]) is preferably prepared as follows: Weigh 112.36 g of quaternary ammonium chloride 336 dissolved in 500 mL of distilled In the isopropanol, completely dissolve it; add 6.39 g of sodium metal in a plastic bottle, add 125 mL of distilled isopropanol, and react at room temperature for 3 hours to prepare sodium alkoxide; mix the above solution at 50 After stirring for 4 hours at °C, [A336][OR] was prepared; the obtained solution was centrifuged at 8000 rpm for 10 minutes to remove the sodium chloride precipitate; 500 ml of deionized water was added to the filtrate, and shaken for 30 minutes to prepare for hydrolysis [ A336][OH]; Take 172 mL of [A336][OH] solution at a concentration of
- the preparation method of di(2-ethylhexyl) phosphotium trialkyl decyl ammonium ([A336][P204]) is specifically as follows: After preparing [A336][OH] according to the above method, the concentration is 0.111. 192 mL of [A336][OH] solution of mol/L, adding 8.057g of P204 (the molar ratio of [A336][OH] to P204 is 1.1:1), and the solution was stirred under reflux at 50 ° C for 12 hours. After the solution was allowed to stand for phase separation, the lower phase was discarded, and the upper phase was spun out of isopropanol and water at 80 ° C, 20 mbar to obtain [A336] [P204].
- the rare earth element in the rare earth nitrate aqueous solution is extracted into n-heptane, specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extractant, the salting-out agent and the rare earth nitrate aqueous solution to
- the rare earth element in the aqueous nitrate solution is extracted into n-heptane
- the quaternary ammonium salt ionic liquid extracting agent is 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium or phosphonic acid di(2) -ethylhexyl) ester trialkyl decyl ammonium.
- the n-heptane solution, the salting-out agent and the rare earth nitrate aqueous solution of the quaternary ammonium salt ionic liquid extracting agent preferably further comprise: oscillating at a constant temperature of 25' e , preferably shaking for 1 hour, determining the aqueous phase The concentration of the rare earth element in the middle, and then the extraction rate and distribution ratio of the rare earth element are calculated.
- the present invention preferably further comprises a NaN0 3 solution having a concentration of 0.2 to 1.5 mol/L as a salting-out agent, and the concentration of the NaNO ⁇ solution is preferably 0.5 to 1.2 mol/L, more preferably 0.6 to 1.0. Mol/L.
- concentration is less than 0.2 mol/L, the extraction rate of rare earth ions is very low, which is difficult to detect and calculate.
- concentration is more than 1.5 mol/L, the rare earth ions are completely extracted, which is also difficult to detect and calculate.
- the extraction temperature will have a certain effect on the extraction and separation results of rare earth elements. The extraction temperature is too high or too low, which is not conducive to the extraction and separation of rare earth elements.
- the extraction temperature employed in the present invention is preferably 20 to 50 ° C, more preferably 20 to 30 ° C.
- concentration of the n-heptane solution of the above quaternary ammonium salt ionic liquid extractant is preferably 0.03 to 0.1 mol/L, more preferably 0.03 to 0.08 mol/L, still more preferably 0.05 mol/L.
- the rare earth element in the rare earth nitrate aqueous solution of the present invention is not particularly limited, and may be a single rare earth element or a plurality of rare earth elements well known to those skilled in the art.
- the rare earth element is La, Ce, Pr, One or more of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
- the concentration of the rare earth nitrate aqueous solution is preferably 7 to 9 x 1 (T 4 mol/L, more preferably 7 to 8 x 1 (T 4 mo l/L, most preferably 7.5 x 1 (T 4 mo l/L).
- the present invention preferably further comprises: back-extracting the rare earth element extracted into n-heptane using a nitric acid solution.
- the concentration of the nitric acid solution is from 0.04 to 0.50 mol/L, more preferably from 0.1 to 0.3 mol/L. When the concentration is less than 0.04 mol/L, some are thin The soil ion stripping rate is relatively low and difficult to detect and calculate.
- the rare earth element in the raffinate or stripping solution obtained by the present invention is preferably determined by arsenazo(III) colorimetry.
- the calculation formula of the extraction ratio distribution ratio CD) and the separation factor is as follows:
- V org is the volume of the aqueous and organic phases, respectively.
- the present invention uses [A336][P507] or [A336][P204] as an extractant, and n-heptane is used as a dilute agent for the separation of rare earths in a nitric acid system, and has the following characteristics: low extraction acidity, The stripping acidity is low, the acid consumption is low; the interface phenomenon is good without emulsification; the extracting agent does not need to be saponified, no need to add other auxiliaries, cost saving and high separation coefficient for rare earth, especially for heavy rare earth.
- the invention provides a method for extracting and separating rare earth elements in a hydrochloric acid system, comprising the following steps: 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium or phosphonic acid di(2-ethyl
- the hexyl) ester trialkyl decyl ammonium is an extractant, and the rare earth element in the rare earth chloride aqueous solution is extracted into n-heptane using n-heptane as a diluent.
- the present invention uses a quaternary ammonium salt ionic liquid extracting agent, 2-ethylhexylphosphine.
- Acid mono 2-ethylhexyl trialkyl decyl ammonium ( [A336] [P507] ) or phosphonic acid di(2-ethylhexyl) ester trialkyl decyl ammonium ( [A336] [P204] ) for extraction
- the separation of a single rare earth in a hydrochloric acid system can avoid the saponification process and the compositional changes of long-term operation.
- the process has low acidity and high separation factor for rare earth elements.
- the inventors have found that the extraction and separation of rare earth ions by the extractant is affected by the anion of the system. ( ⁇ , C ⁇ or S0 4 2 — ) Because these anions form different extracts between the rare earth ions and the extractant during the extraction process, and because of the different anions, the optimum pH for the combination of the rare earth ions and the extractant occurs. Variety.
- the [A336][P507] has the structure shown in Formula I;
- [A336][P204] has the structure shown in Formula II
- the present invention separately synthesizes 2-ethylhexylphosphonic acid mono 2-ethylhexyl ester trialkyl decyl ammonium and phosphonic acid di(2-ethylhexyl) ester according to the technical scheme provided in Chinese Patent Application No. 201210120559.9 Trialkyl decyl ammonium.
- 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkylsulfonium ammonium [A336][P507]
- the preparation method of di(2-ethylhexyl) phosphinate trialkyl decyl ammonium ([A336][P204]) is specifically: after preparing [A336][OH] according to the above method, 0.08 mol of P204 Joined 0. lmol[A336][OH], stirred at room temperature for 1 hour, the upper ionic liquid organic phase was taken, washed three times with deionized water, and then the solvent ethanol was distilled off under reduced pressure, and the product was vacuum dried to obtain [ ⁇ 336][ ⁇ 204] .
- the rare earth element in the rare earth chloride aqueous solution is extracted into n-heptane, specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extractant, the salting-out agent and the rare earth chloride aqueous solution to
- the rare earth element in the aqueous chloride solution is extracted into n-heptane
- the quaternary ammonium salt ionic liquid extracting agent is 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium or phosphonic acid di(2) -ethylhexyl) ester trialkyl decyl ammonium.
- the method further comprises: oscillating at a constant temperature of 25 ° C, preferably shaking for 1 hour, determining the aqueous phase The concentration of the rare earth element in the middle, and then the extraction rate and distribution ratio of the rare earth element are calculated.
- the present invention preferably further comprises a salting-out agent having a concentration of 0.2 to 1.5 mol/L, and the concentration of the NaCl is preferably 0.5 to 1.2 mol/L, more preferably 0.6 to 1.0 mol/L.
- concentration is less than 0.2 mol/L, the extraction rate of rare earth ions is very low, which is difficult to detect and calculate.
- concentration is more than 1.5 mol/L, the rare earth ions are completely extracted, which is also difficult to detect and calculate.
- the extraction temperature will have a certain effect on the extraction and separation of rare earth elements. The extraction temperature is too high or too low, which is not conducive to the extraction and separation of rare earth elements.
- the extraction temperature employed in the present invention is preferably 20 to 50 ° C, more preferably 20 to 30 ° C.
- concentration of the n-heptane solution of the above quaternary ammonium salt ionic liquid extractant is preferably 0.01 to 0.08 mol/L, more preferably 0.03 to 0.06 mol/L, still more preferably 0.05 mol/L.
- the rare earth element in the aqueous solution of the rare earth chloride is not particularly limited, and may be a single rare earth element or a plurality of rare earth elements well known to those skilled in the art.
- the rare earth element is La, Ce, Pr, One or more of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
- the concentration of the rare earth chloride aqueous solution is preferably 7 to 11 x 1 (T 4 mol/L, more preferably 7 to 8 x 1 (T 4 mo l/L, most preferably 7.5 x 1 (T 4 mo l/L).
- the present invention preferably further comprises: back-extracting the rare earth element extracted into n-heptane using a hydrochloric acid solution.
- the hydrochloric acid solution has a concentration of 0.03 to 0.20 mol/L, more preferably 0.1 to 0.2 mol/L. When the concentration is less than 0.03 mol/L, some rare earth ions have a low stripping rate and are difficult to detect and calculate.
- the rare earth element in the raffinate or stripping solution obtained by the present invention is preferably determined by arsenazo(III) colorimetry. Calculation formula of extraction ratio distribution ratio CD) and separation coefficient as follows:
- V org is the volume of the aqueous and organic phases, respectively.
- the invention adopts [A336][P507] or [A336][P204] as an extracting agent, and n-heptane as a diluent, which is applied to the separation of rare earth in a hydrochloric acid system, and has the following characteristics: low extraction acidity, consumption Less acid; good interface phenomenon without emulsification; extractant does not need to be saponified, no need to add other additives, cost saving and high separation factor for rare earth.
- the invention provides a method for extracting and separating rare earth elements in a sulfuric acid system, comprising the steps of: 2-ethylhexylphosphonic acid mono 2-ethylhexyl trialkyl ammonium sulfonate, n-heptane as a diluent, The rare earth element in the rare earth sulfate aqueous solution is extracted into n-heptane.
- the present invention uses a quaternary ammonium salt ionic liquid extractant, 2-ethylhexylphosphonic acid.
- 2-Ethylhexyl trialkyl decyl ammonium [A336][P507] is an extractant, which has low acidity in the sulfuric acid system and a high separation factor for rare earth elements.
- the [A336][P507] has the structure shown in Formula I;
- 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium it is preferred to prepare 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium by itself.
- 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkylsulfonium ammonium ([A336][P507] ) is preferably prepared as follows:
- the rare earth element in the rare earth sulfate aqueous solution is extracted into n-heptane, specifically: mixing the n-heptane solution of the quaternary ammonium salt ionic liquid extracting agent, the salting-out agent and the rare earth sulfate aqueous solution to
- the rare earth element in the aqueous solution of the sulphate is extracted into n-heptane, which is 2-ethylhexylphosphonic acid mono-2-ethylhexyl trialkyl decyl ammonium.
- the n-heptane solution, the salting-out agent and the rare earth sulfate aqueous solution of the quaternary ammonium salt ionic liquid extracting agent preferably further comprise: oscillating at a constant temperature of 25 ° C, preferably shaking for 1 hour, determining the aqueous phase The concentration of the rare earth element in the middle, and then the extraction rate and distribution ratio of the rare earth element are calculated.
- the present invention further preferably comprises a concentration of 0.1 ⁇ lmol / L of Na 2 S0 4 as the salting-out agent, the concentration of the Na 2 S0 4 is preferably 0.3 ⁇ 0.9mol / L, more preferably 0.5 ⁇ 0.7 Mol/L.
- concentration is less than 0.1 mol/L, the rare earth ion extraction rate is very low, which is difficult to detect and calculate.
- concentration is greater than 1.0 mol/L, the rare earth ions are completely extracted, which is also difficult to detect and calculate.
- the extraction temperature will have a certain effect on the extraction and separation results of rare earth elements. The extraction temperature is too high or too low, which is not conducive to the extraction and separation of rare earth elements.
- the extraction temperature employed in the present invention is preferably 25 to 50 ° C, more preferably 25 to 30 ° C.
- concentration of the n-heptane solution of the above quaternary ammonium salt ionic liquid extractant is preferably 0.02 to 0.08 mol/L, more preferably 0.03 to 0.06 mol/L, still more preferably 0.05 mol/L.
- the rare earth element in the salt solution of the rare earth salt is not particularly limited, and may be a single rare earth element or a plurality of rare earth elements well known to those skilled in the art, and the rare earth element is La, Ce, One or more of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. Further, the concentration of the rare earth sulphate aqueous solution is preferably 7 to 9 x 1 (T 4 mol/L, more preferably 7 to 8 x 1 (T 4 mo l/L, most preferably 7.5 x 1 (T 4 mo l /L.
- the present invention preferably further comprises: back-extracting the rare earth element extracted into n-heptane using a sulfuric acid solution.
- the concentration of the sulfuric acid solution is 0.01 to 0.1 mol/L, more preferably 0.05 to 0.1 mol/L. When the concentration is less than 0.01 mol/L, some rare earth ions have a low stripping rate and are difficult to detect and calculate.
- the rare earth element in the raffinate or stripping solution obtained by the present invention is preferably determined by arsenazo(III) colorimetry.
- the calculation formula of the extraction ratio distribution ratio CD) and the separation factor is as follows:
- c aq , 0 and c are the initial concentration and equilibrium concentration of the aqueous phase rare earth ions, respectively
- v aq and v org are the volume of the aqueous phase and the organic phase, respectively.
- the invention adopts [A336][P507] as an extracting agent and n-heptane as a diluent, and is applied to the separation of rare earth in a sulfuric acid system, and has the following characteristics: low extraction acidity and low acid consumption; good interface phenomenon Emulsification produces; the extractant does not need to be saponified, no need to add other additives, cost saving and high separation factor for rare earth.
- the reaction was carried out for 3 hours to prepare sodium alkoxide; the above solution was mixed and stirred at 50 ° C for 4 hours to prepare [A336] [OR]; the obtained solution was centrifuged at 8000 rpm for 10 minutes to remove sodium chloride precipitate; Add 500 ml of deionized water, shake for 30 minutes, prepare for hydrolysis [A336][OH]; take 192mL of [A336][OH] solution with a concentration of 0.111mol/L, add 8.057g P204 ([A336][OH] and The molar ratio of P204 is 1.1: 1), the solution is stirred under reflux at 50 ° C for 12 hours, the resulting solution is allowed to stand for phase separation, the lower phase is discarded, and the upper phase is rotated at 80 ° C, 20 mbar. Isopropyl alcohol and water were obtained, and [A336][P204] was obtained.
- Table 1 shows the separation factor between rare earth ions when [ ⁇ 336] [ ⁇ 507] is used as the extractant.
- Tm 4.31 4.61 As can be seen from Table 1, the partition coefficient between the heavy rare earth ions is large, and therefore, the extraction separation method provided by the present invention has a high separation coefficient for heavy rare earths.
- the extraction separation method provided by the present invention has a high separation coefficient for heavy rare earths.
- the aqueous solution of La(III) is mixed, wherein the concentration of NaN0 3 in the aqueous solution is 1.0 mol/L, the concentration of La(III) is 7.5 ⁇ 10′ 4 mol/L, and the temperature is tempered at a constant temperature of 25 ° C for 1 h, respectively.
- the aqueous phase balances the pH value and the corresponding La(III) concentration in the aqueous phase. Calculates the extraction ratio. When the solution balance pH is different, The extraction distribution ratio will change.
- Fig. 1 is a dot plot of the solution equilibrium pH value and the rare earth ion extraction distribution ratio when [A336][P507] is used as an extractant. It can be seen from the figure that the equilibrium ratio of rare earth ions increases as the equilibrium pH increases. By measuring the equilibrium pH value, the equilibrium pH is in the range of 1 to 4, and the different rare earth ions can complete the extraction process, and the extraction acidity of the extractant is low.
- Figure 2 is a dot plot of the solution equilibrium pH value and the rare earth ion extraction distribution ratio when [A336][P204] is used as an extractant. It can be seen from the figure that the equilibrium ratio of rare earth ions increases as the equilibrium pH increases. At the same time, by measuring the equilibrium pH value, the equilibrium pH value is in the range of 1 to 3. The different rare earth ions can complete the extraction process, and the extraction acidity of the extractant is low.
- the aqueous solution of La(III) is mixed, wherein the concentration of NaN0 3 in the aqueous solution is 0.2 ⁇ 1.5 mol/L, and the concentration of La(III) is 7.5xl (T 4 mol/L, shaking at a constant temperature of 25' e for 1 h, respectively)
- the concentration of La(III) in the aqueous phase after shaking at different concentrations of the salting-out agent.
- the concentration of the salting-out agent is different, the extraction rate will change.
- Extractant [A336] Separation factor for ruthenium ( ⁇ ) and other rare earth ions.
- Extractant [ ⁇ 336] [ ⁇ 204] Separation coefficient of mixed heavy rare earth.
- Tm(III), Yb(III), Lu (III) are respectively l.lxlO" 4 mol/L, 7.2x1 (T 4 mol/L and 1.3 xl (T 4 mol/L, after shaking for 1 h at a constant temperature of 25 °, the aqueous phase Tm(III) is determined.
- the aqueous solution of La(III) is mixed, wherein the concentration of NaCl in the aqueous solution is 1.0 mol/L, the concentration of La(III) is 7.5 ⁇ 10 -4 mol/L, and the water phase is measured after shaking at a constant temperature of 25 ° C for 1 h.
- the La(III) concentration is calculated, and the extraction ratio and distribution ratio of La(III) are calculated.
- the extraction separation method provided by the present invention has a high separation coefficient for light rare earth.
- the extraction ratio of Lu(III) and ⁇ ( ⁇ ) is the distribution ratio of different rare earth ions at different pH values.
- Fig. 7 is a dot diagram of the solution equilibrium pH value and the rare earth ion extraction distribution ratio of [ ⁇ 336][ ⁇ 507] as an extractant. It can be seen from the figure that the equilibrium ratio of rare earth ions increases as the equilibrium pH increases. By measuring the equilibrium pH value, the equilibrium pH value is in the range of 1 to 5, and the different rare earth ions can complete the extraction process, and the extraction acidity of the extractant is low.
- the aqueous solution of La(III) was mixed, wherein the concentration of NaCl in the aqueous solution was 1.0 mol/L, the concentration of La(III) was 7.5 ⁇ 10′ 4 mol/L, and the temperature was tempered at a constant temperature of 25 ° C for 1 h.
- the phase equilibrium pH value and the corresponding La(III) concentration in the aqueous phase Calculate the extraction distribution ratio. When the solution equilibrium pH value is different, the extraction distribution ratio will change.
- Figure 8 is a dot plot of the solution equilibrium pH value and the rare earth ion extraction distribution ratio when [A336][P204] is used as an extractant. It can be seen from the figure that the equilibrium ratio of rare earth ions increases as the equilibrium pH increases. At the same time, by measuring the equilibrium pH value, the equilibrium pH value is in the range of 1 to 5, and the different rare earth ions can complete the extraction process, and the extraction acidity of the extractant is low.
- the aqueous solution of La(III) is mixed, wherein the concentration of NaCl in the aqueous solution is 0.2 ⁇ 1.5 mol/L, the concentration of La(III) is 7.5 ⁇ 10′ 4 mol/L, and the temperature is 25 ° C for 1 h, and the salt is determined separately.
- the concentration of La(III) in the aqueous phase after shaking at different concentrations of the extractant. Calculating the distribution ratio When the concentration of the salting-out agent is different, the distribution ratio changes.
- Extractant [A336] [P507] Separation coefficient for mixed rare earths.
- a mixed solution containing La(III), Ce(III), Pr(III) and Nd(III) is prepared.
- 1.0 mL of 0.05 mol/L [A336][P507]-heptane solution and 5.0 mL of mixed solution were mixed, and the NaCl concentration in the mixed solution was 1.0 mol/L, La(III), Ce(III), Pr( III), Nd(III) is 2.5x 10 -4 mol/L, 4.5 lO" 4 mol/L, 1.7 10" 4 mol/L ⁇ 2.1 10" 4 mol/L, respectively, at a constant temperature of 25 ° C
- the concentrations of La(III), Ce(III), Pr(III) and Nd(III) in the aqueous phase were measured, and the extraction ratio and the separation coefficient ( ) between different rare earth ions were calculated.
- Table 7 As can be seen from Table 7, in the mixed system, the separation coefficients
- the extractant [A336][P507] is extracted from the mixed rare earth.
- a sulfate mixed solution containing La(III), Ce(III), Pr(III), Nd(III), Y(III), Gd(III) and Yb(III) is disposed.
- Potassium hydroxide (8.4g, 0.15mol) was dissolved in 42ml of ethanol, added dropwise to [C 25 H 54 N][C1] (40g, O.lmol), stirred at room temperature for 1 hour, and filtered to remove potassium chloride. Clarify [C 25 H 54 N] [OH] ionic liquid.
- the aqueous solution of La(III) is mixed, wherein the concentration of Na 2 SO 4 in the aqueous solution is 1.0 mol/L, and the concentration of La(III) is 7.5xl0" 4 mol/L, oscillate for 0.5 h at a constant temperature of 25 ° C, and determine the equilibrium pH of the aqueous phase after shaking and the La(III) concentration in the corresponding aqueous phase. Calculate the extraction ratio. When the values are different, the extraction distribution ratio changes.
- the extraction ratio of Y(III) is the distribution ratio of different rare earth ions at different pH values.
- Figure 14 is a dot plot of the solution equilibrium pH value and the rare earth ion extraction distribution ratio when [A336][P507] is used as an extractant. It can be seen from the figure that the equilibrium ratio of rare earth ions increases as the equilibrium pH increases. By measuring the equilibrium pH value, the equilibrium pH is in the range of 1 to 7, and the different rare earth ions can complete the extraction process, and the extraction acidity of the extractant is low. The average separation coefficient of the rare earth element was calculated to be 1.36.
- the aqueous solution of Pr(III) is mixed, wherein the concentration of Na 2 SO 4 in the aqueous solution is 0.1 to 1 mol/L, and the concentration of Pr (III) is 7.5 x 1 (T 4 mol/L, and the temperature is oscillated at a constant temperature of 25 ° C 0.5 h, Determine the concentration of Pr(III) in the aqueous phase after shaking at different concentrations of the salting-out agent. Calculate the extraction rate. When the concentration of the salting-out agent is different, the extraction rate will change.
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CN114574697A (zh) * | 2022-03-11 | 2022-06-03 | 郑州中科新兴产业技术研究院 | 一种磷酸酯类离子液体萃取分离稀土钕的方法 |
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