CN116555600A

CN116555600A - Method for separating and purifying ytterbium and lutetium from ytterbium lutetium mixture

Info

Publication number: CN116555600A
Application number: CN202210101685.3A
Authority: CN
Inventors: 梁鑫淼; 程宇; 俞冬萍; 马雨; 于伟; 郭志谋; 魏阳
Original assignee: Ganjiang Traditional Chinese Medicine Innovation Center
Current assignee: Ganjiang Traditional Chinese Medicine Innovation Center
Priority date: 2022-01-27
Filing date: 2022-01-27
Publication date: 2023-08-08

Abstract

The invention relates to a method for separating and purifying ytterbium and lutetium from ytterbium and lutetium mixture, which uses one or more than two of silica gel or resin containing specific chelating groups as a stationary phase, and uses inorganic acid as flowing relative ytterbium ions and lutetium ion mixed solution for chromatographic separation and purification; collecting ytterbium-containing and lutetium-containing components flowing out of the chromatographic column according to different peak-off times of ytterbium and lutetium, respectively, so as to obtain ytterbium and lutetium respectively; the separation method of ytterbium and lutetium provided by the invention has high ytterbium and lutetium yield and purity.

Description

Method for separating and purifying ytterbium and lutetium from ytterbium lutetium mixture

Technical Field

The invention relates to the field of rare earth element separation, in particular to a method for separating ytterbium and lutetium mixtures to obtain high-purity ytterbium and high-purity lutetium respectively.

Background

Lutetium-177, which has a half-life of 6.7 days, decays to a stable isotope hafnium-177, emits beta particles with maximum energy of 498.3KeV, average energy of 134.2KeV, and maximum penetration distance in human tissue of only 2.2mm, and average penetration range of 0.67mm. Thus, lu-177 is a short-range beta particle emitter well suited for treating small volume or diffuse tumors, killing tumor cells with less radiation damage to adjacent normal tissue. In addition, lu-177 emits low energy gamma rays when attenuated, and the course of treatment can be monitored and guided by single photon emission tomography (SPECT). In 2017, 9 and 2018, 1, the European and United states food and drug administration respectively approve ¹⁷⁷ Lu-DOTA-TATE is used for treating gastrointestinal pancreatic neuroendocrine tumors (GEP-NETs, gastrointestinal pancreatic neuroendocrine tumors). Experiments show that compared with the control group of patients only receiving octreotide LAR treatment, ¹⁷⁷ the survival rate of patients in the Lu-DOTA-TATE and octreotide LAR combination group increased from 10.8% to 65.2%. In addition, the molecular probe of the PSMA marked by Lu-177 not only can find the focus of early prostate cancer, but also can effectively develop the radioactive targeting treatment; ¹⁷⁷ Lu-EDTMP can also be used for the palliative treatment of bone pain caused by bone metastasis. Thus, lutetium-177 is a "diagnostic-integrated" radioisotope of great interest in the current medical arts.

Lu-177 is generally prepared by neutron irradiation of a high purity ytterbium-176 target in a reactor. In this method, a high purity Yb-176 isotope target undergoes a (n, gamma) nuclear reaction to produce Yb-177, which is subsequently passed through beta ^- Decay (t- _1/2 =1.9h) is Lu-177. The Lu-177 nuclide prepared by reactor neutron radiation does not contain Lu-177m impurities, has no carrier and high specific activity, and is the most economical and effective method for preparing Lu-177. But the content of the ytterbium-176 after the reaction is still the main component of the target material because of the lower yield of the Lu-177, which is between 0.1 percent and 0.0001 percent. In addition, since the natural abundance of ytterbium-176 is only 12.9%, the natural ytterbium element can be used as a target material only after being isotopically enriched to obtain high-purity Yb-176 with the purity of more than 99.9%, and the price of Yb-176 is very expensive and is about 20-30 ten thousand/g. Thus, in the process of preparing Lu-177Not only is high-purity Lu-177 obtained by separation and purification, but also unreacted Yb-176 is fully recovered, so that the production cost of the Lu-177 can be controlled.

Ytterbium and lutetium are the heaviest two lanthanoids, their chemical properties are very close due to lanthanide shrinkage, and the Yb/Lu mass ratio in the irradiated target reaches thousands to hundreds of thousands times, so ytterbium and lutetium separation is a challenging task. Ytterbium and lutetium are generally separated by cascade extraction, electrochemical method, chromatography and other methods. The chromatographic separation has the advantages of simple equipment, low capital investment, strong separation capability, high product purity and high separation efficiency, and has remarkable advantages in small-scale rare earth element separation and purification. Techniques have been reported for separating ytterbium and lutetium using sulfonate cation exchange chromatography columns in combination with organic carboxylic acids as the eluent, but organic acids cannot be injected into the body and require further treatment to remove the organic acid and convert it to a lutetium salt solution, after which the process increases the operator radiation exposure risk and also causes a loss of radioactive dose.

According to the invention, on the basis of chromatography, silica gel or resin containing specific ion chelating functional groups is adopted as a stationary phase, and inorganic acid is adopted as a leaching agent to separate and purify ytterbium and lutetium mixed solution, so that the whole chromatographic separation process is simple and convenient to operate, the degree of automation is high, and the method has a good application prospect in separation and purification of ytterbium and lutetium.

Disclosure of Invention

A method of separating and purifying ytterbium and lutetium comprising:

silica gel or resin containing specific ion chelating groups is used as a stationary phase, and inorganic acid is used as flowing phase to separate and purify the mixed solution containing ytterbium ions and lutetium ions;

the solution flowing out of the chromatographic column is collected according to the peak-off times of ytterbium and lutetium to obtain high purity ytterbium and high purity lutetium.

Further, in the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture, the functional group of the silica gel or the resin filler is aminotriacetic acid.

Further, the ytterbium lutetium mixtureThe method for separating and purifying ytterbium and lutetium, wherein the particle size of the stationary phase filler is 2-300 mu m, and the pore size isThe specific surface area is 50-1000 m ² /g。

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture comprises the step of separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture, wherein the specification of the chromatographic column is phi 4-20 mm.

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture comprises the step of loading the chromatographic column with one tenth to one ppm of sample.

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture comprises the step of separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture, wherein the mobile phase is an inorganic acid solution.

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture comprises the step of separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture, wherein the inorganic acid is at least one of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture comprises the step of separating and purifying ytterbium and lutetium from the ytterbium lutetium mixture, wherein the concentration of inorganic acid in the mobile phase is 10-200 mM.

Further, the method for separating and purifying ytterbium and lutetium from the ytterbium and lutetium mixture comprises the step of enabling the flow rate of the mobile phase to be 0.20-40 mL/min.

Further, the above method for separating and purifying ytterbium and lutetium from ytterbium lutetium mixture, wherein the separation is performed at a temperature of 20-75 ℃.

Technical advantages are that:

1. the method for separating and purifying ytterbium and lutetium provided by the invention is not only suitable for preparing radioactive lutetium-177, but also suitable for separating and purifying general ytterbium and lutetium.

2. The separation method of ytterbium and lutetium provided by the invention has high ytterbium and lutetium yield and purity, wherein the ytterbium yield is higher than 98%, the lutetium yield is higher than 95%, and the purity can reach 99.99%.

3. The invention uses inorganic acid as mobile phase, has low production cost and little pollution, and is beneficial to expanding production.

4. The invention uses inorganic acid as eluent, and the post-treatment of the prepared lutetium-177 is simple, thereby reducing the radiation exposure risk of production personnel and reducing the loss of radioactive dose.

Drawings

FIG. 1 is a chromatogram of ytterbium and lutetium separation in example 1;

FIG. 2 is a chromatogram of ytterbium and lutetium separation in example 2;

FIG. 3 is a chromatogram of ytterbium and lutetium separation in example 3;

FIG. 4 is a chromatogram of ytterbium and lutetium separation in example 4;

FIG. 5 is a chromatogram after separation of the lutetium-containing component obtained after separation of the secondary sample in example 4;

FIG. 6 is a chromatogram of ytterbium and lutetium separation in example 5;

FIG. 7 is a chromatogram of ytterbium and lutetium separation in example 6;

FIG. 8 is a chromatogram of ytterbium and lutetium separation in example 7;

FIG. 9 is a chromatogram of ytterbium and lutetium separation in example 8;

FIG. 10 is a chromatogram of ytterbium and lutetium separation in example 9.

FIG. 11 is a chromatogram of ytterbium and lutetium separation in example 10.

Detailed Description

The following detailed description of the present invention will provide further understanding of the objects, features and advantages of the present invention by way of example. Several embodiments of the invention are presented in the examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

The embodiment of the invention is based on the problem that the separation and purification of the heaviest two lanthanoids, ytterbium and lutetium are difficult, and particularly, for the ytterbium target containing trace lutetium obtained by preparing medical isotope lutetium-177 through a reactor, a chelate ion chromatography method is adopted, and a simple and low-cost separation method is adopted, so that the high-purity lutetium and the high-purity ytterbium are finally obtained.

In the embodiment, ytterbium lutetium mixed solution with different concentration ratios prepared from ytterbium nitrate and lutetium nitrate is used as a solution to be separated and purified, and chelating ion exchange chromatography is adopted to separate the solution to be purified.

Wherein the particle size of the silica gel or resin filler is 2-300 mu m, and the pore size isThe specific surface area is 50-1000 m ² /g。

Wherein, the specification of the chromatographic column used for separation is phi 4-20 mm, and the sample loading amount is one tenth to one part per million.

In the elution process, inorganic acid is used as a mobile phase for elution, the concentration of the inorganic acid is 10-200 mM, the flow rate is 0.20-40 mL/min, and the column temperature is 20-75 ℃.

The inorganic acid is at least one of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.

In the chromatographic separation process of this embodiment, the peak times of ytterbium ions and lutetium ions are significantly different, and ytterbium ions are earlier than lutetium ions, so that the solution flowing out of the chromatographic column is collected according to the peak times of ytterbium ions and lutetium ions to obtain high-purity lutetium and high-purity ytterbium.

In the embodiment, the filler bonded by the ion chelating group is used as a chromatographic column stationary phase, the inorganic acid solution is used as a mobile phase, the mixed solution of ytterbium and lutetium in ten thousandth can be separated, the recovery rate of the final ytterbium is not lower than 98%, the purity is higher than 99.99%, the yield of the lutetium is not lower than 95%, and the purity can reach more than 99.99%. The chromatographic separation process in the embodiment of the invention is simple, strong in operability, good in repeatability within the allowable error range, low in running cost and small in pollution. This method requires less post-treatment for preparing the medical nuclide lutetium-177.

The following description will explain the content of the present invention and the positive effects brought by the present invention in the form of specific embodiments.

Example 1

A method for separating and purifying ytterbium and lutetium, comprising the steps of:

preparation of S1, ytterbium and lutetium mixed solution

2.595mg ytterbium nitrate and 2.680mg lutetium nitrate were weighed into a beaker, dissolved by adding 40mL of pure water, then poured into a 100mL volumetric flask, the beaker was washed 3 times with pure water (10 mL each time), and the solution was poured entirely into the volumetric flask, finally diluted with pure water to 100mL of the scale mark. The ytterbium and lutetium concentrations in the target material simulated liquid prepared above are 10mg/L respectively, and the mixed liquid is filtered by a filter membrane of 0.22 mu m so as to be separated and purified on ion chromatography or liquid chromatography, and the sample injection amount is 5 mu L.

S2, preparation of stationary phase

Into a 250mL flask was charged 10g of silica gel having a particle diameter of 3.5 μm and a pore diameter ofSpecific surface area of 330m ² /g; then, 100mL of 25wt% hydrochloric acid solution was added, heated under reflux, stirred for 5 hours, filtered, washed with water to ph=6.5, and the resulting solid was dried in a dry oven at 160 ℃ for 24 hours to give an acidified silica gel.

10g of acidified silica gel, 10mL of 3- (2, 3-glycidoxy) propyl trimethoxysilane and 100mL of 8.2g/L sodium bicarbonate aqueous solution are added into a 250mL flask, reacted for 24 hours at 30 ℃, filtered, washed with water, methanol, water and methanol in sequence, and the obtained solid is dried in vacuum for 24 hours at 80 ℃ in a drying oven to obtain a 3- (2, 3-glycidoxy) propyl silica gel intermediate, the structure of which is confirmed by infrared spectrum, elemental analysis and nuclear magnetic carbon spectrum, wherein gray solid spheres in the formula represent silica gel, and X is oxygen atoms.

3- (2, 3-epoxypropoxy) propyl silica gel intermediate

10g of the epoxy silica gel and 40mL of water are added into a flask and stirred uniformly, 3.93g of N, N-bis (carboxymethyl) -L-lysine is dissolved by 30mL of water and added into the flask, 3.78g of sodium bicarbonate is added into 50mL of water and dissolved, then sodium bicarbonate aqueous solution is added into the flask, the pH of the reaction solution is 8-9, and the reaction is carried out for 24 hours at 70 ℃.

After the completion of the reaction, the mixture was suction-filtered, washed with 100mL of water and 50mL of methanol, and then stirred in 100mL of 100mM sodium acetate for 30min, washed with 100mL of water and 50mL of methanol in this order, heated with 100mL of water at 65℃for 2 hours, and then dried, and washed with 100mL of water and 50mL of methanol.

The sample is evenly spread at the bottom of a beaker, the filler is dried in an oven at 80 ℃ for 16 hours, and the required chelating silica gel with the amino triacetic acid functional group is finally obtained, and the structure is confirmed to be as follows through infrared spectrum, elemental analysis and nuclear magnetic carbon spectrum, wherein the gray solid sphere in the formula represents the silica gel, and each gram of the silica gel contains 0.05mmol of amino triacetic acid.

S3, packing column

Weighing 3.8g of the chelating silica gel, filling a filler into a chromatographic separation column (specification: inner diameter and height: 4.6X1250 mm) by adopting a high-pressure homogenization method, and then installing the chromatographic column in a chromatographic instrument pipeline for separating ytterbium and lutetium mixed solution;

s4, chromatographic separation and purification

Injecting the ytterbium and lutetium mixed solution prepared by adopting a Siemens Dionex AS-AP automatic sample injection system into a sample ring, switching a pipeline of a sample in the sample ring, and then passing through 75mM HNO ₃ The leacheate is carried into a chromatographic column for separation at a flow rate of 1mL/min, and the column temperature is 65 ℃; the ytterbium-containing and lutetium-containing components are collected separately to obtain high purity ytterbium and lutetium, respectively.

By chromatography-mass spectrometry, sensitive inductively coupled plasma-mass spectrometry (ICP-MS) can be used as a detector to detect elements flowing from a chromatographic column; the chromatographic instrument used was a Waters Arc model. The model of ICP-MS is NexION 2000. The chromatography and ICP-MS can also be connected by a tee joint, one part enters an ICP-MS detector, and the other part respectively collects components of lutetium and ytterbium flowing out of the chromatographic column according to the peak-off time of lutetium and ytterbium (primary separation and purification). And (3) adopting the same elution condition, and carrying out secondary separation and purification on the components which are separated and purified once and collected to obtain lutetium, wherein the conditions are the same. And the deflection voltage (RPa value) of the mass spectrum quadrupole is adjusted to electronically dilute a specific mass spectrum signal, so that the damage of the high-abundance element signal to the detector is reduced. In this example, each of Yb-174 and Lu=175 has a Rpa value of 0.014.

FIG. 1 is a chromatogram of the chelate silica gel of example 1 for separating ytterbium ions from lutetium ions, wherein the ytterbium has a peak time of 17.619min, the lutetium has a peak time of 21.241min, and the selectivity factor α is 1.24. The selectivity factor alpha represents the degree of separation of the two components, and the greater the alpha value, the better the separation effect. In this example, the separation degree of ytterbium ion and lutetium ion is larger, and the elemental analysis results of the two components confirm that the purity of ytterbium is greater than 99.99%, the yield is 69.83%, the purity of lutetium is 69.87%, the yield is 96.90%, the purity of lutetium after secondary purification is 99.99%, the yield is 94.53%, the comprehensive yield of ytterbium (the yield of the sum of the primary and secondary purified products) is 99.95%, and the purity of ytterbium is greater than 99.99%.

Example 2

The elution conditions were changed, and the other steps and conditions were the same as those of example 1. The differences from example 1 are as follows:

ytterbium and lutetium were separated and purified on a chromatographic system by reducing the concentration of the eluent nitric acid to 60 mM. In this example, each of Yb-174 and Lu=175 has a Rpa value of 0.014.

The separation pattern of ytterbium ions and lutetium ions in this example is shown in fig. 2. As the concentration of the eluent was reduced, the peak time of ytterbium increased to 35.360min, the peak time of lutetium increased to 44.367min, and the separation factor increased to 1.27. The elemental analysis of the two components confirmed that the purity of ytterbium purified once was greater than 99.99%, the yield was 80.34%, the purity of lutetium was 80.35%, and the yield was 97.78%.

The purity of lutetium after secondary purification is 99.99%, the yield is 95.34%, the comprehensive yield of ytterbium is 99.99%, and the purity of ytterbium is more than 99.99%. Lower elution strength increases the separation efficiency of ytterbium and lutetium, but increases the time required for separation.

Example 3

The elution conditions and temperatures were changed, and the other steps and conditions were the same as in example 1. The differences from example 1 are as follows:

70mM HNO was used to change the column temperature to 55℃and to change the column temperature to 55 ℃ ₃ Isocratic elution. The mobile phase concentration and column temperature used for separation were reduced compared to example 1. In this example, each of Yb-174 and Lu=175 has a Rpa value of 0.014.

FIG. 3 is a chromatogram of this example ytterbium and lutetium separation with a ytterbium ion peak time of 18.226min, a lutetium ion peak time of 22.402min, and a selectivity factor of 1.27. The purity of the once purified ytterbium is more than 99.99 percent, the yield is 71.86 percent, the purity of lutetium is 71.89 percent, and the yield is 97.53 percent.

The purity of lutetium after secondary purification is 99.99%, the yield is 95.10%, the comprehensive yield of ytterbium is 99.97%, and the purity of ytterbium is more than 99.99%. Thus, this example demonstrates that optimizing column temperature and elution strength, ytterbium ions and lutetium ions can maintain greater separation selectivity with shorter peak times.

Example 4

The ytterbium lutetium concentration ratio in the sample solution was changed, and the other steps and conditions were the same as in example 3. The differences from example 3 are as follows:

25.95mg ytterbium nitrate and 0.026mg lutetium nitrate were weighed into a beaker, dissolved by adding 40mL of pure water, then poured into a 100mL volumetric flask, the beaker was washed 3 times with pure water (10 mL each time), and the solution was poured entirely into the volumetric flask, and finally diluted with pure water to 100mL on the scale mark. The concentrations of ytterbium and lutetium in the target material simulated liquid prepared in the above way are 100mg/L and 0.1mg/L respectively, and the mass concentration ratio of ytterbium to lutetium is 1000:1. Where Yb-174, lu=175 have Rpa values of 0.014.

Yb ³⁺ And Lu ³⁺ The separation spectrum of (2) is shown in FIG. 4, the ytterbium has a peak time of 18.330min and lutetium of 22.824min. Through between chromatographic column and ICP-MSTee joint, collect the component of ytterbium and lutetium flowing out from chromatographic column according to the peak time of lutetium and ytterbium separately. As a result of elemental analysis of these two components, it was confirmed that the purity of ytterbium in the ytterbium component was more than 99.99% and the yield was 95.80%, but the purity of lutetium in the lutetium component was insufficient, the purity was only 42.40% and the yield was 98.56%.

Lutetium fractions were separated again (secondary separation and purification) where Yb-174, lu=175 each had a Rpa value of 0.014. Elemental analysis proves that ytterbium ions and lutetium ions are completely separated after secondary separation, and the purity of lutetium is higher than 99.99%. After two separations, the comprehensive yield of ytterbium is 99.99%, the purity of ytterbium is more than 99.99%, and the comprehensive yield of lutetium is 96.10%. Therefore, this example demonstrates that even though the mass concentration of ytterbium is one thousand times that of lutetium, separation and purification of ytterbium and lutetium can be achieved by using this method through two separations, and purity and yield of ytterbium and lutetium are high.

Example 5

The ytterbium lutetium concentration ratio and the sample injection amount were changed, and other steps and conditions were the same as in example 3. The differences from example 3 are as follows:

25.95mg ytterbium nitrate and 0.0026mg lutetium nitrate were weighed into a beaker, dissolved by adding 40mL pure water, then poured into a 100mL volumetric flask, the beaker was washed 3 times with pure water (10 mL each time), and the solution was poured entirely into the volumetric flask, finally diluted with pure water to 100mL on the scale mark. The concentrations of ytterbium and lutetium in the target material simulation liquid prepared in the above way are 100mg/L and 0.01mg/L respectively, and the mass concentration ratio of ytterbium to lutetium is 10000:1. The sample loading was 10 μl, where Yb-174, lu=175 have Rpa values of 0, 0.014, respectively.

Yb ³⁺ And Lu ³⁺ As shown in FIG. 6, the ytterbium has a peak time of 18.358min and lutetium has a peak time of 22.753min. The components of ytterbium and lutetium flowing out of the chromatographic column are respectively collected according to the peak-out time of lutetium and ytterbium through a tee joint between the chromatographic column and the ICP-MS. The two components are subjected to elemental analysis, the purity of ytterbium in the ytterbium component is more than 99.99%, the ytterbium yield can reach 99.99%, and the purity of lutetium in the lutetium component is lower, the purity is only 8.10%, and the yield is 97.43%.

Lutetium components were separated by reinjection, where each of Yb-174, lu=175, had a Rpa value of 0. Elemental analysis proves that the ytterbium ions and the lutetium ions are completely separated after secondary separation, the purity of the lutetium reaches 99.99 percent, the comprehensive yield of ytterbium is 99.99 percent after the secondary separation, the purity of ytterbium is more than 99.99 percent, and the comprehensive yield of lutetium is 95.00 percent. Therefore, this example demonstrates that even if the mass concentration of ytterbium is ten thousand times that of lutetium, separation and purification of ytterbium and lutetium can be achieved by using this method through two separations, and purity and yield of ytterbium and lutetium are high.

Example 6

The type, concentration, flow rate and column temperature of the eluent were varied, and the other steps and conditions were the same as those of example 3. The differences from example 3 are as follows:

the column temperature was 20℃and the elution was isocratic using 10mM sulfuric acid at a flow rate of 2 mL/min. Where Yb-174, lu=175 have Rpa values of 0.014. The chromatogram of the ytterbium and lutetium separation in this example is shown in FIG. 7, with a peak time of 21.663min for ytterbium ions, 26.174min for lutetium ions, and a selectivity factor of 1.24. The elemental analysis results prove that the purity of the ytterbium purified once is more than 99.99 percent, the yield is 71.19 percent, the purity of lutetium is 71.20 percent, and the yield is 96.30 percent.

The purity of lutetium after secondary purification is 99.99%, the yield is 93.94%, the comprehensive yield of ytterbium is 99.99%, and the purity of ytterbium is more than 99.99%.

Example 7

The column temperature was 75℃and elution was performed isocratically with 200mM phosphoric acid at a flow rate of 0.5mL/min, and the other steps and conditions were the same as in example 3, wherein Yb-174 and Lu=175 had Rpa values of 0.014. As shown in FIG. 8, the separation chromatogram of ytterbium and lutetium shows that the peak time of ytterbium ion is about 13.842min, the peak time of lutetium ion is about 16.247min, and the selectivity factor is 1.21. The elemental analysis of these two components demonstrated that the purity of ytterbium was greater than 99.99%, the yield was 70.61%, the purity of lutetium was 70.63%, and the yield was 97.28% for the first purification.

The purity of lutetium after secondary purification is 99.99%, the yield is 94.80%, the comprehensive yield of ytterbium is 99.97%, and the purity of ytterbium is more than 99.99%.

Example 8

The column temperature was 35℃and the elution was performed at an isocratic rate of 1.0mL/min using 50mM hydrochloric acid, and the other steps and conditions were the same as in example 3. Where Yb-174, lu=175 have Rpa values of 0.014.

As shown in FIG. 9, the separation chromatogram of ytterbium and lutetium shows that the peak time of ytterbium ion is 17.619min, the peak time of lutetium ion is 21.241min, and the selectivity factor is 1.23. The elemental analysis results prove that the purity of the ytterbium purified once is more than 99.99 percent, the yield is 65.40 percent, the purity of lutetium is 65.41 percent, and the yield is 97.80 percent.

The purity of lutetium after secondary purification is 99.99%, the yield is 95.36%, the comprehensive yield of ytterbium is 99.98%, and the purity of ytterbium is more than 99.99%.

Example 9

The eluting procedure was the same as in example 3 except that the eluting conditions and the species of the eluting solution were changed. The differences from example 3 are as follows:

separation and purification were performed on a chromatographic system using 100mM hydrochloric acid isocratic elution as separation conditions. Where Yb-174, lu=175 has a Rpa value of 0.014, 0.01.

The separation chromatograms of ytterbium and lutetium in the examples are shown in fig. 10. As can be seen from fig. 10, the peak time of ytterbium ion was 8.639min, the peak time of lutetium ion was 9.687min, and the selectivity factor was 1.17. The elemental analysis results prove that the purity of ytterbium in the ytterbium component purified once is more than 99.98%, the yield is 34.71%, the purity of lutetium is 34.80%, and the yield is 97.90%.

The purity of lutetium after secondary purification is more than 99.99%, the yield is 95.46%, the comprehensive yield of ytterbium is 99.90%, and the purity of ytterbium is more than 99.99%. When the elution condition is 100mM hydrochloric acid isocratic elution, the elution capacity is enhanced, the retention time is reduced, the separation degree is reduced, but the method can be applied to separation and purification of ytterbium and lutetium.

Example 10

The procedure was the same as in example 3 except that the silica gel was changed. The differences from example 3 are as follows:

the particle size of the silica gel is 10 mu m, and the specific surface area is 300m ² And/g. In this example, each of Yb-174 and Lu=175 has a Rpa value of 0.014。

The separation chromatograms of ytterbium and lutetium in the examples are shown in fig. 11. As can be seen from fig. 11, the peak time of ytterbium ion was 11.796min, the peak time of lutetium ion was 13.682min, and the selectivity factor was 1.202. The elemental analysis results prove that the purity of the ytterbium purified once is more than 99.99 percent, the yield is 53.20 percent, the purity of lutetium is 53.26 percent, and the yield is 96.56 percent.

The purity of lutetium after secondary purification is more than 99.99%, the yield is 94.15%, the comprehensive yield of ytterbium is 99.93%, and the purity of ytterbium is more than 99.99%. The silica gel used in this example had an increased particle size and decreased column efficiency as compared with the silica gel of example 3. Thus, the retention time of this example is reduced and the degree of separation is reduced under the same elution conditions as it was, but it can be applied to separation and purification of ytterbium and lutetium.

Example 11

The other steps were the same as in example 3 except that the functional carbon chain length was changed. The differences from example 3 are as follows:

and taking m and n in the silica gel structure as the maximum value of 10, wherein the specific structure is shown in the following formula, and the middle gray solid sphere in the formula represents silica gel. In this example, each of Yb-174 and Lu=175 has a Rpa value of 0.014.

Experimental results show that the separation effect of Yb and Lu by changing the carbon chain length of the functional group is the same as in example 3. The elemental analysis results prove that the purity of the ytterbium purified once is more than 99.99 percent, the yield is 70.40 percent, the purity of lutetium is 70.43 percent, and the yield is 97.68 percent.

The purity of lutetium after secondary purification is 99.99%, the yield is 95.24%, the comprehensive yield of ytterbium is 99.97%, and the purity of ytterbium is more than 99.99%.

Example 12

The stationary phase functional structure was changed and the other steps were the same as in example 3. The differences from example 3 are as follows:

the stationary phase functional structure is changed, and the specific structure is shown in the following formula, wherein the middle gray solid sphere represents silica gel, and in the example, the Rpa values of Yb-174 and lu=175 are all 0.014.

Experimental results show that by changing the structure of the stationary phase functional groups, the baseline separation of the chromatographic peaks of the two components Yb and Lu can not be realized by adopting the same elution conditions as in example 3. The complete separation of Yb and Lu still cannot be achieved by changing the elution conditions.

Example 13

Example 14

The type of stationary phase was changed, and the other steps were the same as in example 3, except that the following were made in example 3:

the type of stationary phase was changed to resin, and the specific preparation procedure is shown below, with Yb-174 and Rpa values of lu=175 in this example of 0.014.

The particle diameter of the intermediate epoxy resin is 50 mu m, and the aperture isThe specific surface area is 300m ² Per g, consisting of divinylbenzene and allyl glycidyl ether monomers, by infrared spectroscopy, elemental separationThe structural formula of the nuclear magnetic resonance spectroscopy is shown in the specification, wherein gray solid spheres in the formula represent resin particles, and X represents oxygen atoms.

3- (2, 3-epoxypropoxy) propyl resin intermediate

10g of the epoxy resin, 3.93g of N, N-bis (carboxymethyl) -L-lysine and 100mL of water are added into a 500mL flask, the mixture is stirred uniformly, 4.00g of sodium hydroxide is added into 100mL of water for dissolution, and then an aqueous solution of sodium hydroxide is added into the flask for reaction for 24 hours at 70 ℃. After the reaction, the reaction is filtered by suction, washed and dried by 200mL of water, 200mL of water and 100mL of methanol, stirred in 400mL of water for 1h, then dried by suction, washed by 200mL of water and 100mL of methanol, and the obtained resin is dried in vacuum for 24 hours at 60 ℃ in a drying box to obtain the required chelating resin with the aminotriacetic acid functional group, the structure of the chelating resin is shown as follows through infrared spectrum, elemental analysis and nuclear magnetic resonance spectroscopy, wherein the gray solid spheres in the formula represent resin particles, and each gram of silica gel contains 0.028mmol of aminotriacetic acid.

The experimental results showed that the separation effect of the two components Yb and Lu was the same as in example 3 by changing the type of stationary phase and using the same elution conditions as in example 3. The elemental analysis results prove that the purity of the ytterbium purified once is more than 99.99 percent, the yield is 71.24 percent, the purity of lutetium is 71.26 percent, and the yield is 97.42 percent.

The purity of lutetium after secondary purification is 99.99%, the yield is 94.99%, the comprehensive yield of ytterbium is 99.98%, and the purity of ytterbium is more than 99.99%.

Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.

Claims

1. A method for separating and purifying ytterbium and lutetium from a mixture of ytterbium and lutetium, comprising:

taking one or more than two of silica gel or resin containing specific chelating groups as a stationary phase, and taking an inorganic acid solution as a flowing ytterbium ion and lutetium ion mixed solution for chromatographic separation and purification;

collecting ytterbium-containing and lutetium-containing components flowing out of the chromatographic column according to different peak-off times of ytterbium and lutetium, respectively, so as to obtain ytterbium and lutetium respectively;

the chelating functional group on the silica gel and/or resin is an aminotriacetic acid group, the specific structural schematic formula is shown in the following formula,

wherein: wherein the gray solid spheres represent silica gel and/or resin particles; n=an integer of 0 to 10 (preferably 1 to 10), m=an integer of 0 to 10 (preferably m=4 to 10), and X is one or both of an oxygen atom and a carbon atom.

2. The method according to claim 1, wherein the particle size of the bare spheres of the stationary phase (silica gel and/or resin particles before modification) is 2 to 300 μm (preferably 3 to 50 μm) and the pore size is(preferably->) The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area is 50-1000 m ² /g (preferably 200-650 m) ² /g)。

3. A method according to claim 1 or 2, characterized in that: the specification of the chromatographic column is that the inner diameter phi is 2.1-120 mm (preferably 3-5 mm), and the filling height of the stationary phase filler is 50-800mm (preferably 150-300 mm).

4. The method of claim 1, wherein: the loading amount of the chromatographic column is one tenth to one ppm; the unit loading is the ratio of the sample mass to the filler mass;

respectively collecting ytterbium-containing and lutetium-containing components flowing out of the chromatographic column according to different peak-off times of ytterbium and lutetium to respectively obtain once separated and purified ytterbium and lutetium; re-sampling the components which are separated and purified once to obtain lutetium, and carrying out secondary separation and purification to obtain separated and purified ytterbium and lutetium;

the resin is one or more than two of epoxy resin, phenolic resin and amino resin.

5. The method of claim 1, wherein the mobile phase is an aqueous mineral acid solution;

the inorganic acid is at least one or more than two of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.

6. The method of claim 1 or 5, wherein the concentration of mineral acid in the mobile phase is between 10 and 200mM.

7. The method of claim 1 or 2 or 3 or 5 or 6, wherein: the flow rate of the mobile phase is 0.20-40 mL/min.

8. A method according to claim 1 or 2 or 3 or 5 or 6, wherein the separation is carried out at a temperature of 20 to 75 ℃ (preferably 30 to 60 ℃).

9. A process according to claim 1 or 2 or 3 or 5 or 6, wherein said silica gel and/or resin contains 0.01-0.5mmoL (preferably 0.01-0.24 mmoL) aminotriacetic acid per gram of silica gel and/or resin.

10. The method of claim 1 or 2 or 3 or 5 or 6, wherein the ytterbium lutetium mixture comprises at least one or more of ytterbium and lutetium chloride, nitrate, sulfate.