CN115029566A - Method for separating zirconium in yttrium sample by using TEVA-UTEVA resin - Google Patents

Abstract

The invention discloses a method for separating zirconium in a yttrium sample by using TEVA-UTEVA resin. The yttrium sample contains zirconium, and the method includes the following steps in sequence: S1: adding an acid solution and a stabilizer to the yttrium sample, dissolving the yttrium zirconium and stabilizing the zirconium No hydrolysis; S2: Use TEVA resin to separate yttrium and zirconium, and elute zirconium through the eluent; S3: Absorb zirconium through the dissolving solution, and the dissolving solution is a hydrochloric acid solution; S4: The dissolving solution is then passed through the UTEVA resin to further purify the zirconium. The invention overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art, the overall process of the method is relatively simple and stable, easy to operate and control, and the separation efficiency of zirconium separated from the yttrium sample is high, the recovery rate is high, and the separation purity is high. it is good.

Description

A method of separating zirconium in yttrium samples using TEVA-UTEVA resin

technical field

The invention relates to the field of chemistry, in particular, to a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin.

Background technique

The metal zirconium is widely used, but the radioisotope zirconium is rarely used. The half-life of ⁸⁹ Zr is 78.41(12)h, and it decays into beta particle emission with a decay probability of 22.74(24)% and a maximum decay energy of 900keV. The other 77.26(24)% of the decay probability occurs through electron capture. The radionuclide has a short half-life, and ^89Zr is considered a promising radionuclide for nuclear medicine: such as labeling of monoclonal antibodies, biodistribution studies, and immunopositron emission tomography (PET). Among them, the specificity and affinity of antibodies make them attractive as cancer therapy and drug delivery agents. One of the most fundamental principles for constructing effective antibody-based radionuclide imaging agents is to match the physical half-life of the radioisotope with the pharmacokinetic half-life of the immunoglobulin. In general, intact antibodies have relatively slow pharmacokinetics, often taking days to reach their optimal biodistribution in the body. On the other hand, ^89Zr has good physical properties, half-life and relatively low positron energy, making it more suitable for antibody imaging, safer to handle, cheaper to produce, and more stable in vivo.

The separation and purification of ⁸⁹ Zr has always been a very important research topic. For the existing conventional method, ^89Zr is produced by the reaction of 89Y(p,n)89Zr and 89Y(d,2n)89Zr on a cyclotron. After yttrium irradiation, dibutyl phosphate, trifluoroacetone, 4, 4,4-Trifluoro-1-(2-thiosulfinyl)-1,3-butanedione or bis(2-ethylhexyl)phosphoric acid (HDEHP) solvent extraction to ^isolate89Zr . It is also possible to separate zirconium with Dowex 50w-x8, 2-x8, 1-x8 cation and anion exchange resins, and the separation of zirconium can reach 80%, and the recovery rate of zirconium is also expected to be higher. In recent years, ⁸⁹ Zr is most commonly separated by hydroxyester resin. Hydroxylate selectively binds zirconium from hydrochloric acid, but Zr has a strong residue on the hydroxamic acid resin. Therefore, a stronger complexing agent will be selected. Elution, generally 0.1-0.5M oxalic acid solution is used for elution, but the eluate needs to be further purified from oxalate, because oxalic acid is harmful to humans in the human body, in addition, oxalic acid will also prevent zirconium and markers Combination of zirconium, the separation process of zirconium is complicated, which is not conducive to improving the efficiency.

SUMMARY OF THE INVENTION

In order to solve the problems that the existing zirconium separation process is complicated and the recovery rate is low, the present invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin.

A method for separating zirconium in yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and comprises the following steps successively:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, and elute zirconium through the eluent;

S3: Absorb zirconium through a dissolving solution, which is a hydrochloric acid solution;

S4: further purify the zirconium by passing the dissolving solution through UTEVA resin. The method has the advantages of simple operation, easy control, low cost and high separation rate of zirconium, which solves the problems of low recovery rate of zirconium and complicated separation process in the prior art.

In some embodiments, TEVA resin is used for the separation of yttrium and zirconium, and after the yttrium sample is loaded on the column, an acidic solution is used for washing, which is beneficial to improve the separation rate of zirconium.

In some embodiments, in step S4, before the UTEVA resin further purifies the zirconium, the concentration of the dissolved solution is adjusted to 9 mol/L, which is beneficial to improve the separation rate of zirconium. When the concentration of the dissolving solution, that is, the hydrochloric acid solution, is 9 mol/L, the zirconium content of the yttrium sample with the same quality is the largest, and the recovery rate of zirconium is improved.

In some embodiments, the acidic solution is a hydrochloric acid solution.

In some embodiments, the concentration of the acidic solution is 1-9 mol/L.

In some embodiments, the stabilizer is amine citrate, which stabilizes Zr so that it does not generate clusters and cause precipitation.

In some embodiments, the eluent is a hydrochloric acid solution.

In some embodiments, the solubility of the eluent is 4-9 mol/L.

In some embodiments, an acidic solution is used as a rinse during further purification of zirconium by UTEVA resin.

In some embodiments, the concentration of the dissolving solution in step S3 is 1-4 mol/L.

Compared with the prior art, the beneficial effects are as follows: the present invention provides a method for separating zirconium in a yttrium sample by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of existing zirconium and complicated separation process, and the overall process of the method. It is relatively simple, stable, easy to operate and control, and the separation efficiency of zirconium from yttrium samples is high, the recovery rate is high, and the separation purity is good.

Description of drawings

Fig. 1 provides the flow chart of the method for separating zirconium in yttrium sample using TEVA-UTEVA resin for the embodiment of the application;

FIG. 2 is a diagram of the separation equilibrium coefficient of yttrium and zirconium provided by the embodiment of the present application.

Detailed ways

In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The described embodiments are some, but not all, embodiments of the present invention.

Accordingly, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1:

The present embodiment provides a method for separating zirconium in a yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and the following steps are included in sequence:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, after the yttrium sample is loaded on the column, use an acidic solution for rinsing, elute zirconium through the eluent, and the elution solution flowing out of the TEVA resin contains zirconium;

S3: Absorb zirconium through the dissolving solution, which is a hydrochloric acid solution; the dissolving solution cannot be replaced with other acidic solutions, otherwise the recovery rate of the final zirconium will be greatly reduced.

S4: further purify the zirconium by passing the dissolving solution through the UTEVA resin, and adjust the concentration of the dissolving solution to 9 mol/L before further purifying the zirconium by the UTEVA resin. During the further purification of zirconium by UTEVA resin, an acidic solution is used for rinsing.

The acidic solution is a hydrochloric acid solution, and the concentration of the acidic solution is 1 mol/L.

The stabilizer is citrate amine, the concentration of citrate amine is 100mmol/L, and the pH is 2.5-4.

The eluent is a hydrochloric acid solution, and the solubility of the eluent is 4 mol/L.

The dissolving solution in step S3 is a hydrochloric acid solution, and the concentration of the dissolving solution in step S3 is 1 mol/L.

The yttrium content in the yttrium sample is as high as 10 ⁷ times that of zirconium. After the TEVA chromatography column, the resin adsorbs yttrium, and the eluent elutes the zirconium, that is, the elution solution flowing out of the TEVA resin contains most of the zirconium and a small amount of yttrium. Afterwards, the residual trace yttrium is further removed through the UTEVA chromatography column. The dissolved solution passes through the UTEVA, and the yttrium is adsorbed on the UTEVA chromatography column, and the zirconium is separated to obtain the separated zirconium.

The invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art. The separation efficiency of zirconium from the sample is high, the recovery rate is high, and the separation purity is good.

Example 2:

The present embodiment provides a method for separating zirconium in a yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and the following steps are included in sequence:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, after the yttrium sample is loaded on the column, use an acidic solution for rinsing, elute zirconium through the eluent, and the elution solution flowing out of the TEVA resin contains zirconium;

S3: Absorb zirconium through the dissolving solution, which is a hydrochloric acid solution; the dissolving solution cannot be replaced with other acidic solutions, otherwise the recovery rate of the final zirconium will be greatly reduced.

S4: further purify the zirconium by passing the dissolving solution through the UTEVA resin, and adjust the concentration of the dissolving solution to 9 mol/L before further purifying the zirconium by the UTEVA resin. During the further purification of zirconium by UTEVA resin, an acidic solution is used for rinsing.

The acidic solution is a hydrochloric acid solution, and the concentration of the acidic solution is 9 mol/L.

The stabilizer is citrate amine, the concentration of citrate amine is 100mmol/L, and the pH is 2.5-4.

The eluent is a hydrochloric acid solution, and the solubility of the eluent is 9 mol/L.

The dissolving solution in step S3 is a hydrochloric acid solution, and the concentration of the dissolving solution in step S3 is 4 mol/L.

The yttrium content in the yttrium sample is as high as 10 ⁷ times that of zirconium. After the TEVA chromatography column, the resin adsorbs yttrium, and the eluent elutes the zirconium, that is, the elution solution flowing out of the TEVA resin contains most of the zirconium and a small amount of yttrium. Afterwards, the residual trace yttrium is further removed through the UTEVA chromatography column. The dissolved solution passes through the UTEVA, and the yttrium is adsorbed on the UTEVA chromatography column, and the zirconium is separated to obtain the separated zirconium.

The invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art. The separation efficiency of zirconium from the sample is high, the recovery rate is high, and the separation purity is good.

Example 3:

The present embodiment provides a method for separating zirconium in a yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and the following steps are included in sequence:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, after the yttrium sample is loaded on the column, use an acidic solution for rinsing, elute zirconium through the eluent, and the elution solution flowing out of the TEVA resin contains zirconium;

S3: Absorb zirconium through the dissolving solution, which is a hydrochloric acid solution; the dissolving solution cannot be replaced with other acidic solutions, otherwise the recovery rate of the final zirconium will be greatly reduced.

S4: further purify the zirconium by passing the dissolving solution through the UTEVA resin, and adjust the concentration of the dissolving solution to 9 mol/L before further purifying the zirconium by the UTEVA resin. During the further purification of zirconium by UTEVA resin, an acidic solution is used for rinsing.

The acidic solution is a hydrochloric acid solution, and the concentration of the acidic solution is 5 mol/L.

The stabilizer is citrate amine, the concentration of citrate amine is 100mmol/L, and the pH is 3.5.

The eluent is a hydrochloric acid solution, and the solubility of the eluent is 6 mol/L.

The dissolving solution in step S3 is a hydrochloric acid solution, and the concentration of the dissolving solution in step S3 is 2 mol/L.

The yttrium content in the yttrium sample is as high as 10 ⁷ times that of zirconium. After the TEVA chromatography column, the resin adsorbs yttrium, and the eluent elutes the zirconium, that is, the elution solution flowing out of the TEVA resin contains most of the zirconium and a small amount of yttrium. Afterwards, the residual trace yttrium is further removed through the UTEVA chromatography column. The dissolved solution passes through the UTEVA, and the yttrium is adsorbed on the UTEVA chromatography column, and the zirconium is separated to obtain the separated zirconium.

The invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art. The separation efficiency of zirconium from the sample is high, the recovery rate is high, and the separation purity is good.

Example 4:

The present embodiment provides a method for separating zirconium in a yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and the following steps are included in sequence:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, after the yttrium sample is loaded on the column, use an acidic solution for rinsing, elute zirconium through the eluent, and the elution solution flowing out of the TEVA resin contains zirconium;

S3: Absorb zirconium through the dissolving solution, which is a hydrochloric acid solution; the dissolving solution cannot be replaced with other acidic solutions, otherwise the recovery rate of the final zirconium will be greatly reduced.

S4: further purify the zirconium by passing the dissolving solution through the UTEVA resin, and adjust the concentration of the dissolving solution to 9 mol/L before further purifying the zirconium by the UTEVA resin. During the further purification of zirconium by UTEVA resin, an acidic solution is used for rinsing.

The acidic solution is a hydrochloric acid solution, and the concentration of the acidic solution is 8 mol/L.

The stabilizer is citrate amine, the concentration of citrate amine is 100mmol/L, and the pH is 3.3.

The eluent is a hydrochloric acid solution, and the solubility of the eluent is 7 mol/L.

The dissolving solution in step S3 is a hydrochloric acid solution, and the concentration of the dissolving solution in step S3 is 3 mol/L.

The yttrium content in the yttrium sample is as high as 10 ⁷ times that of zirconium. After the TEVA chromatography column, the resin adsorbs yttrium, and the eluent elutes the zirconium, that is, the elution solution flowing out of the TEVA resin contains most of the zirconium and a small amount of yttrium. Afterwards, the residual trace yttrium is further removed through the UTEVA chromatography column. The dissolved solution passes through the UTEVA, and the yttrium is adsorbed on the UTEVA chromatography column, and the zirconium is separated to obtain the separated zirconium.

The invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art. The separation efficiency of zirconium from the sample is high, the recovery rate is high, and the separation purity is good.

Example 5:

The present embodiment provides a method for separating zirconium in a yttrium sample using TEVA-UTEVA resin, the yttrium sample contains zirconium, and the following steps are included in sequence:

S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis;

S2: use TEVA resin to separate yttrium and zirconium, after the yttrium sample is loaded on the column, use an acidic solution for rinsing, elute zirconium through the eluent, and the elution solution flowing out of the TEVA resin contains zirconium;

S3: Absorb zirconium through the dissolving solution, which is a hydrochloric acid solution; the dissolving solution cannot be replaced with other acidic solutions, otherwise the recovery rate of the final zirconium will be greatly reduced.

S4: further purify the zirconium by passing the dissolving solution through the UTEVA resin, and adjust the concentration of the dissolving solution to 9 mol/L before further purifying the zirconium by the UTEVA resin. During the further purification of zirconium by UTEVA resin, an acidic solution is used for rinsing.

The acidic solution is a hydrochloric acid solution, and the concentration of the acidic solution is 7 mol/L.

The stabilizer is citrate amine, the concentration of citrate amine is 100mmol/L, and the pH is 3.3.

The eluent is a hydrochloric acid solution, and the solubility of the eluent is 8 mol/L.

The dissolving solution in step S3 is a hydrochloric acid solution, and the concentration of the dissolving solution in step S3 is 4 mol/L.

The yttrium content in the yttrium sample is as high as 10 ⁷ times that of zirconium. After the TEVA chromatography column, the resin adsorbs yttrium, and the eluent elutes the zirconium, that is, the elution solution flowing out of the TEVA resin contains most of the zirconium and a small amount of yttrium. Afterwards, the residual trace yttrium is further removed through the UTEVA chromatography column. The dissolved solution passes through the UTEVA, and the yttrium is adsorbed on the UTEVA chromatography column, and the zirconium is separated to obtain the separated zirconium.

The invention provides a method for separating zirconium in yttrium samples by using TEVA-UTEVA resin, which overcomes the problems of low recovery rate of zirconium and complicated separation process in the prior art. The separation efficiency of zirconium from the sample is high, the recovery rate is high, and the separation purity is good.

The invention adopts the combination of TEVA and UTEVA resin to separate zirconium in yttrium, utilizes the extraction characteristics of TEVA and UTEVA to Zr(IV), greatly simplifies operation steps and saves operation time.

The present invention adopts citrate amine to stabilize Zr, so that it does not produce clusters and cause precipitation. The acidic solution, the eluent and the dissolving solution are all hydrochloric acid solutions, and hydrochloric acid can also be used for the leaching acidic solution, that is, the whole system adopts the hydrochloric acid system, which increases the number of ions and makes the separation simple, and finally the Zr-containing solution is cleaner. .

Referring to accompanying drawing 2, in the hydrochloric acid leaching process, the amount of yttrium basically did not change, the content of zirconium changed greatly, first increased and then decreased, when the concentration of hydrochloric acid reached 9mol/L, the amount of zirconium was the largest. Therefore, before UTEVA resin further purifies zirconium, adjusting the concentration of the dissolved solution to 9 mol/L can effectively improve the separation rate of zirconium.

Since the chromatographic column of TEVA and UTEVA resins have a relatively large distribution of Zr, even a small amount of upper column can separate more zirconium. There is no need to increase the column volume during operation, so TEVA and UTEVA color columns with small column volumes can be used. Therefore, the amount of rinsing and eluent can be correspondingly reduced, the time required for separation is reduced, the separation efficiency is effectively improved, and the amount of waste liquid is effectively controlled.

The TEVA and UTEVA resin chromatography columns in the present invention can be small-sized columns, which are suitable for operation through a glove box, improve the safety of operation, and at the same time can prevent the solution from being polluted during the operation, which is suitable for batch analysis of zirconium in yttrium samples. separation.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention.

The above descriptions are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still understand the above-mentioned embodiments. The recorded technical solutions are modified, or some technical features thereof are equivalently replaced. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of this implementation are included in the protection scope of the present invention.

Claims (10)

1. a method for separating zirconium in yttrium sample using TEVA-UTEVA resin, is characterized in that: contain zirconium in the yttrium sample, comprise the following steps successively: S1: Add an acidic solution and a stabilizer to the yttrium sample to dissolve the yttrium zirconium and stabilize the zirconium from hydrolysis; S2: use TEVA resin to separate yttrium and zirconium, and elute zirconium through the eluent; S3: Absorb zirconium through a dissolving solution, which is a hydrochloric acid solution; S4: further purify the zirconium by passing the dissolving solution through UTEVA resin. 2. a kind of method that uses TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, it is characterized in that: utilize TEVA resin to carry out the separation of yttrium, zirconium, after yttrium sample goes up the column, use acidic solution to carry out shower wash. 3. a kind of method that uses TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, is characterized in that: in step S4, before UTEVA resin further purifies zirconium, the concentration of adjusting solution is to 9mol/L. 4. a kind of method using TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, is characterized in that: described acid solution is hydrochloric acid solution. 5 . A method for separating zirconium in a yttrium sample using TEVA-UTEVA resin according to claim 4 , wherein the acid solution has a concentration of 1 to 9 mol/L. 6 . 6. a kind of method using TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, is characterized in that: described stabilizer is citrate amine. 7. a kind of method that uses TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, is characterized in that: described eluent is hydrochloric acid solution. 8 . The method for separating zirconium in a yttrium sample using TEVA-UTEVA resin according to claim 5 , wherein the solubility of the eluent is 4 to 9 mol/L. 9 . 9. a kind of method that uses TEVA-UTEVA resin to separate zirconium in yttrium sample according to claim 1, it is characterized in that: in further purifying zirconium process by UTEVA resin, use acid solution to carry out leaching. 10 . A method for separating zirconium in yttrium samples using TEVA-UTEVA resin according to claim 9 , wherein the concentration of the solution in step S3 is 1 to 4 mol/L. 11 .

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