A method for preparing high-purity zirconium
Zirconium and yttrium were separated by cation exchange chromatography, and the difference in chelation intensity between zirconium and yttrium was used to solve the problems of severe tailing of zirconium peaks and low yields in the prior art, achieving efficient and simple separation of zirconium, which was suitable for the preparation of high-purity zirconium.
Patent Information
- Application Number
- CN202111288872.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-11-02
- Publication Date
- 2025-08-19
- Estimated Expiration
- 2041-11-02
AI Technical Summary
The prior art is difficult to efficiently separate and purify trace amounts of zirconium from high concentrations of yttrium, and the traditional methods have problems such as severe tailing of zirconium peaks, low yields and complex operations, which affects the preparation and application of Zr-89.
Using cation exchange chromatography, using specific leaching agents and cation exchange fillers as stationary phases, zirconium and yttrium are separated in a liquid chromatograph, and efficient separation is achieved by adjusting pH and temperature.
The separation of high-purity zirconium is achieved, with a yield of more than 93%, and a purity of up to 99.99%, which simplifies the operation process, improves the separation efficiency and automation level, and is suitable for different forms of yttrium zirconium mixtures.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of chemical separation of heavy metal elements, and in particular to a method for preparing high-purity zirconium. Background Art
[0002] Radionuclides can spontaneously emit high- or low-energy radiation, such as α, β, and γ, which can be used in nuclear medicine to diagnose diseases and treat cancer. Currently, the vast majority of nuclear medicines approved worldwide are diagnostic drugs, accounting for 80%-90% of the total nuclear medicine market. Diagnostic nuclear medicines use radionuclides as tracers and specific antibodies or small molecules as carriers to demonstrate changes at the cellular and subcellular levels in vivo through positron emission tomography (PET) or single-photon emission computed tomography (SPECT), allowing for qualitative and quantitative studies. Compared to classical medical imaging techniques, nuclear medicine imaging offers significant advantages such as early detection, strong specificity, and high resolution. Radioimmunoassays can be performed by labeling specific antibodies targeting tumor-associated antigens with radionuclides. However, large bioactive molecules, such as antibodies, have long retention times in target tissues, requiring long-half-life radionuclides to meet imaging requirements. Although F-18 has excellent molecular imaging properties and is the most commonly used PET imaging radionuclide, it has a short half-life (t 1 / 2 =109min), it has already decayed significantly before reaching the center of the tumor, making it unsuitable for tumor imaging. Zr-89 is a positron-emitting nuclide with a physical half-life of 78.41h and an average positron energy of 0.389MeV. It takes 2-4 days for the complete antibody to penetrate the tumor, making Zr-89 an ideal nuclide for tumor immuno-PET imaging, achieving an optimal distribution ratio between tumor and non-tumor areas. In addition, 89 Zr also has lower positron energy, shorter positron free travel distance, and is the most commonly used 18 Compared with F nuclide PET imaging, Zr-89 has higher resolution. In addition to being used for antibody labeling, Zr-89 has also been used to label the preparation of nanoparticles, nanotubes and microspheres, and has been widely used in preclinical research. For example, short-chain dextran nanoparticles (13 nm) based on cross-linking can be 89 Zr labeling has become a new macrophage-specific positron emission tomography imaging agent for quantifying the number of tumor-associated macrophages.
[0003] The common method for preparing the radioactive isotope zirconium-89 is to bombard yttrium-89 with protons or deuterons produced by a cyclotron. The two main nuclear reactions are 89 Y(p,n) 89 Zr or 89 Y(d,2n) 89The target material is high-purity yttrium metal or yttrium oxide. Since the amount of zirconium-89 produced is very small, it is necessary to separate and purify the trace amount of zirconium from a large amount of yttrium. Yttrium has only one stable isotope (Y-89), but side reactions, such as 89 Y(p,pn) 88 Y will introduce harmful impurities such as the long-half-life nuclide Y-88. At the same time, the copper or aluminum trays used in the target making process will bring in trace amounts of copper, iron, nickel and other elements. These impurities will have a negative impact on antibody labeling and human health. Therefore, only high-purity Zr-89 can meet the relevant medical standards.
[0004] Even though we already know 89 Zr is of great significance as a nuclide, but currently there is no organization or manufacturer in China that can stably provide high-purity Zr. 89 Zr nuclide, quickly and easily obtain high purity 89 Zr and labeled products are crucial for clinical applications. Due to the radioactive decay properties of the materials, rapid separation is required, and the zirconium content is approximately one millionth of the yttrium, making separation of yttrium and zirconium technically challenging.
[0005] Currently, the methods that can be retrieved for purifying Zr-89 include extraction and ion exchange chromatography. Solvent extraction methods, such as using HDEHP and TPPO as organic phases to extract a mixture of zirconium and yttrium in the aqueous phase, extract the zirconium into the organic phase, and then use low-concentration oxalic acid to back-extract the zirconium in the organic phase into the aqueous phase. In solvent extraction technology, if high-purity zirconium is required, multiple extraction steps are required, which also leads to complicated processing operations. In general, the purity of zirconium prepared by the above liquid extraction technology is lower than that of chromatography. Ion exchange chromatography, such as using Dowex 21K anion resin, elutes and separates the mixture of Zr, Sr and Y based on inorganic acid and organic acid, but the zirconium ion peak in this report is severely tailing and the yield is very low (11-25%). Other literature uses Dowex-X8 anion exchange resin as the stationary phase, eluting yttrium and zirconium sequentially with varying concentrations of hydrochloric acid. Compared to using Dowex 21K resin, the yield increases to 60-80%, but remains relatively low, with significant tailing of the zirconium ion peak. Low zirconium-89 yields not only reduce production efficiency but also generate large amounts of nuclear waste requiring specialized treatment. Summary of the Invention
[0006] The present invention aims to overcome at least one of the shortcomings and deficiencies of the above-mentioned prior art and provides a method for preparing high-purity zirconium. The present invention is achieved based on the following technical solutions:
[0007] The present invention provides a method for preparing high-purity zirconium, comprising the following steps:
[0008] S1. Preparation of eluent: dissolving at least one of citric acid, malic acid, and tartaric acid in water, and then adding an alkaline reagent to adjust the pH to 1.0 to 6.0 to obtain an eluent;
[0009] S2. Separating the yttrium-zirconium mixed solution in a liquid chromatograph using a cation exchange filler as the stationary phase and the eluent obtained in step S1 as the mobile phase;
[0010] S3. Collect components flowing out of the liquid chromatograph according to the peak time of zirconium to obtain high-purity zirconium.
[0011] Based on chromatography, this method uses a cation exchange filler as the stationary phase of the chromatographic column and a specific eluent to separate zirconium and yttrium on a chromatograph. This method overcomes the problems of low yield, severe tailing of the zirconium peak, and low resolution in previous chromatographic separations. It offers simple, efficient operation and a high degree of automation. It has potential applications in the separation and preparation of zirconium and yttrium mixtures.
[0012] Preferably, step S0 is further included before step S1: dissolving the object containing yttrium and zirconium elements with a suitable solvent, then neutralizing it with ammonia water, and finally filtering to obtain a yttrium-zirconium mixed solution.
[0013] Preferably, the solvent in step S0 is at least one of water, hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid.
[0014] Preferably, the yttrium-zirconium mixture in step S0 is a mixture containing yttrium and zirconium elements formed by irradiating metallic yttrium or yttrium oxide.
[0015] Preferably, the concentration of the eluent in step S1 is 1-500 mM.
[0016] Preferably, the temperature of the chromatographic column of the liquid chromatograph in step S2 is 15-70°C.
[0017] Preferably, the cation exchange filler in step S2 is a silica gel surface polar group bonded phase filler or a resin surface polar group bonded phase filler.
[0018] Preferably, the ion exchange functional group of the cation exchange filler is a sulfonic acid group.
[0019] Preferably, the pH value of the yttrium-zirconium mixed solution in step S2 is 0-5.0.
[0020] Preferably, the separation method in step S2 is isocratic elution or gradient elution.
[0021] The present invention can achieve at least one of the following beneficial effects:
[0022] The present invention establishes a simple separation method for yttrium-zirconium mixtures. This method utilizes cation exchange chromatography, using a cation exchange filler as the stationary phase of the chromatographic column and a specific eluent as the mobile phase to separate the yttrium and zirconium mixtures, achieving excellent separation results. The specific eluent used in the present invention exhibits different chelating strengths with zirconium and yttrium, exploiting this difference in chelating strength to achieve separation of the two elements.
[0023] The present invention can separate small amounts of zirconium from higher concentrations of yttrium, achieving a zirconium recovery rate exceeding 93%. Compared with traditional chromatographic separation methods, the present invention utilizes a more efficient stationary phase and a more suitable eluent, resulting in highly symmetrical chromatographic peaks and less pronounced tailing. The zirconium and yttrium peaks are highly separated on the chromatogram, ultimately yielding high-purity zirconium with a purity of up to 99.99%. Furthermore, the method exhibits excellent repeatability within the tolerance range. The chromatographic separation method in the embodiments of the present invention exhibits strong selectivity, high recovery rates, and a high degree of instrument automation, meeting radiation protection requirements. Furthermore, the method has a wide range of applicability and can separate various yttrium-zirconium mixtures of varying forms. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is a chromatogram of the separation of zirconium ions and yttrium ions in Example 1;
[0025] Figure 2 This is a chromatogram of the separation of zirconium ions and yttrium ions in Example 2;
[0026] Figure 3 This is the chromatogram for separation of zirconium ions and yttrium ions in Example 3 (injection volume is 10 μL);
[0027] Figure 4 This is the chromatogram for separation of zirconium ions and yttrium ions in Example 3 (injection volume 50 μL);
[0028] Figure 5 This is a chromatogram of the separation of zirconium ions and yttrium ions in Example 4;
[0029] Figure 6 This is a chromatogram of the separation of zirconium ions and yttrium ions in Example 5;
[0030] Figure 7 This is a chromatogram of the separation of zirconium ions and yttrium ions in Example 6;
[0031] Figure 8 This is the chromatogram for separating zirconium ions and yttrium ions in Example 7. DETAILED DESCRIPTION
[0032] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.
[0033] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention.
[0034] The embodiments of the present invention are based on the yttrium-zirconium mixture obtained in the accelerator method for preparing zirconium isotopes, and the zirconium isotopes are separated and purified from the mixture. In the process of preparing zirconium isotopes by the accelerator method, the conversion rate of zirconium is low, there are many impurities, and the preparation process is complicated. Therefore, how to achieve a simple and efficient separation and purification of zirconium from high concentrations of yttrium is a problem that needs to be solved urgently. The present invention adopts cation exchange chromatography, a specific eluent and a simple, low-cost separation method to separate and purify zirconium from a relatively high concentration of yttrium, and ultimately obtain high-purity zirconium.
[0035] In this embodiment, the yttrium-zirconium mixed solution is a mixture of yttrium and zirconium, such as a mixture of yttrium nitrate and zirconium nitrate, a mixture of yttrium oxide and zirconium oxide, a mixture of yttrium sulfate and zirconium sulfate, a mixture of yttrium chloride and zirconium chloride, or a mixture of zirconium oxychloride and yttrium nitrate.
[0036] In an embodiment of the present invention, a metal yttrium target containing zirconium can also be directly used as the object to be purified, and then dissolved by nitric acid, hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, etc., and after the pH of the system is adjusted with ammonia water, it is diluted with pure water and filtered to obtain a yttrium-zirconium mixed solution, and the pH value of the yttrium-zirconium mixed solution is 0 to 5.0.
[0037] In this embodiment, a cation exchange chromatography can be used to separate the yttrium-zirconium mixed solution, specifically including:
[0038] S1. Preparation of eluent: dissolving at least one of citric acid, malic acid, and tartaric acid in water, and then adding an alkaline reagent to adjust the pH to 1.0 to 6.0 to obtain an eluent;
[0039] S2. Separating the yttrium-zirconium mixed solution in a liquid chromatograph using a cation exchange filler as the stationary phase and the eluent obtained in step S1 as the mobile phase;
[0040] S3. Collect components flowing out of the liquid chromatograph according to the peak time of zirconium to obtain high-purity zirconium.
[0041] The cation exchange filler is a silica gel surface polar group bonded phase filler or a resin surface polar group bonded phase filler, the filler particle size is 2 to 300 μm, the pore size is The specific surface area is 50~1000m 2 / g. The ion exchange functional group of the cation exchange filler is a sulfonic acid group.
[0042] During the elution process, isocratic elution or gradient elution is performed using the eluent as the mobile phase, and the column temperature during the elution process is 15-70°C. The concentration of the eluent in the mobile phase is 1-500mM. The pH of the mobile phase is adjusted by an alkaline reagent, which preferably includes at least one of ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide, and an organic amine, and the organic amine includes ethylamine, diethylamine, triethylamine, etc. However, the alkaline reagent is not limited to this, as long as it is an alkaline chemical substance that can be used to adjust the pH of the solution. Preferably, the alkaline reagent is ammonia water, ethylamine, sodium hydroxide, and potassium hydroxide.
[0043] During the elution process of the cation exchange chromatography in this embodiment, the eluent has different chelation strengths with zirconium and yttrium. Based on the difference in their chelation strengths, the peak elution times of zirconium ions and yttrium ions are significantly different, with zirconium ions appearing earlier than yttrium ions. Therefore, the solution exiting the detector of the ion exchange chromatograph is collected according to the peak elution time of zirconium to obtain high-purity zirconium.
[0044] The present invention can separate small amounts of zirconium from higher concentrations of yttrium, achieving a zirconium recovery rate exceeding 93%. Compared to traditional chromatographic separation methods, the present invention utilizes a more efficient stationary phase and a more suitable eluent, resulting in highly symmetrical chromatographic peaks and less pronounced tailing. The zirconium and yttrium peaks are highly resolved on the chromatogram, ultimately yielding high-purity zirconium with a purity of up to 99.99%. Furthermore, the method exhibits excellent repeatability within the tolerance range. The chromatographic separation in the embodiments of the present invention exhibits strong selectivity, high recovery rates, and a high degree of instrument automation, making it easier to meet radiation protection requirements.
[0045] The content of the present invention and the beneficial effects brought about by the present invention will be described below with specific implementation methods.
[0046] Example 1
[0047] A method for preparing high-purity zirconium comprises the following steps:
[0048] S1. Preparation of zirconium and yttrium standard solutions
[0049] Standard solutions of yttrium and zirconium were prepared with concentrations of 100 mg / L and 10 mg / L, respectively, at a ratio of 10:1 and a pH of 2.8. The mixed solution was filtered through a 0.22 μm filter membrane for separation and purification on a chromatographic system; the injection volume was 10 μL.
[0050] S2. Preparation of eluent
[0051] Weigh 19.2 g of citric acid into a beaker and dissolve it in water. Once dissolved, adjust the solution to pH 3.3 with concentrated ammonia. Pour the solution into a 500 mL volumetric flask and dilute to the mark with water. The final eluent has a citric acid concentration of 200 mM and a pH of 3.3.
[0052] S3, Packing column
[0053] Weighing a sulfonic acid type cationic silica gel separation filler, filling the filler into a chromatographic separation column (size: 4.6×250 mm) using a high-pressure homogenization method, and then installing the chromatographic separation column in a chromatographic instrument pipeline for separation of a mixed solution of yttrium and zirconium;
[0054] S4. Liquid chromatography separation and purification of zirconium
[0055] After passing through the degassing system, the eluent was delivered to the separation system of the ion exchange chromatograph by an infusion pump at a flow rate of 1 mL / min. The eluent was used as the mobile phase, and the yttrium and zirconium standard solutions were introduced into the chromatographic separation column for gradient elution (elution condition a). The column temperature was 30°C.
[0056] Elution condition a:
[0057]
[0058] The zirconium or yttrium ions exiting the chromatographic column can react with the derivatization reagent to form a corresponding colored complex; then, the components exiting the detector are collected based on the zirconium peak time. Since the yttrium and zirconium ions react with the derivatization reagent (i.e., the developer) to form a complex that can be detected by the UV-visible detector, a post-column derivatization device needs to be installed between the separation column and the detector. The derivatization reagent consists of 0.15 mM arsenazo, 3 mM urea, and 3 M nitric acid. The infusion pump delivers the derivatization reagent at a flow rate of 0.5 mL / min, where it mixes with the eluent through a tee and flows into the reaction tube, and finally into the detector.
[0059] Figure 1 The chromatogram of the separation of zirconium ions and yttrium ions in Example 1 was obtained with an injection volume of 10 μL. Figure 1As can be seen from the figure, the peak time of zirconium ion is about 2.3 minutes, the peak time of yttrium ion is about 14.2 minutes, and the selectivity factor is 7.84. The selectivity factor α represents the degree of separation of the two separated components. The larger the α value, the better the separation effect. Therefore, in this embodiment, the separation degree of zirconium ion and yttrium ion is very large, and the separation efficiency is high. The sample solution exiting the detector was collected according to the time period when the zirconium ion peak appeared. The concentrations of zirconium ion and yttrium ion in the sample solution were tested and analyzed. The calculated zirconium element yield was 93%, and the purity was greater than 99.99%.
[0060] Example 2
[0061] The composition of the standard mixed solution was changed, and the other steps were the same as in Example 1.
[0062] Standard solutions of yttrium ions and zirconium ions were prepared with concentrations of 235.0 mg / L and 13.8 mg / L, respectively, at a pH of approximately 2.8. After filtration through a 0.22 μm filter membrane, separation and purification were performed on a chromatographic system using elution condition b. The injection volume was 100 μL. Compared to Example 1, both the ion concentration and injection volume in the sample were significantly increased.
[0063] Elution condition b:
[0064]
[0065] The separation chromatogram of zirconium ions and yttrium ions in this embodiment is as follows: Figure 2 As shown. When the composition of the standard solution is changed and the injection volume is 100μL, Figure 2 As can be seen from the figure, the peak elution time of zirconium ions is about 2.5 minutes, the peak elution time of yttrium ions is about 9.8 minutes, and the selectivity factor is 12.4. Therefore, in this embodiment, increasing the yttrium concentration and increasing the sample volume to 100 μL, the separation degree of yttrium ions and zirconium ions is very large, and the separation efficiency is high. The components emitted from the detector are collected according to the peak elution time of zirconium ions. Elemental analysis confirms that even with a significant increase in the sample load, the recovery rate of zirconium element does not decrease, being approximately 94%, and the purity is approximately 99.99%.
[0066] Example 3
[0067] The composition of the standard solution was changed, and the other steps were the same as in Example 1.
[0068] Prepare standard solutions of yttrium and zirconium with concentrations of 1000 mg / L and 1 μg / L respectively, with a concentration ratio of yttrium to zirconium of 10. 6:1, the mixed solution was filtered through a 0.22 μm filter membrane and then chromatographed using the same gradient elution separation conditions (elution condition b) as in Example 2, while a more sensitive inductively coupled plasma-mass spectrometry (ICP-MS) was used as the detector, with injection volumes of 10 μL and 50 μL, respectively.
[0069] The separation spectrum of zirconium ions and yttrium ions in this embodiment is as follows Figure 3 and Figure 4 As shown. Change the composition of the standard mixed solution so that the concentration of yttrium ions is 10 of that of zirconium ions. 6 , the injection volume was 10 μL ( Figure 3 ) and 50 μL ( Figure 4 ), the peak time of zirconium is about 1.8 minutes, and the peak time of yttrium is about 11.3 minutes. Mass spectrometry analysis confirmed that zirconium and yttrium were completely baseline separated, with a zirconium element yield of 93% and a purity of zirconium ion close to 100%. Therefore, this example demonstrates that even if the concentration of yttrium is increased to one million times that of zirconium ion, zirconium ion and yttrium ion have good separation, and the entire separation process does not exceed 20 minutes.
[0070] Example 4
[0071] In the actual separation process, the raw material is the irradiated metal yttrium target, not the standard solution of zirconium and yttrium, so the actual separation process involves hydrochloric acid target dissolution, so we prepared a simulated target material dissolving solution. After weighing an appropriate amount of zirconium oxychloride and yttrium nitrate, 1.5mL of hydrochloric acid was added as the target dissolving condition, followed by adding an appropriate amount of ammonia water to adjust the pH to 0.8. In this embodiment, a simulated target material dissolving solution with a concentration of yttrium and zirconium of 470.0mg / L and 13.8mg / L was prepared, and after filtering through a 0.22μm filter membrane, the same gradient elution separation condition (elution condition b) as in Example 2 was used for separation and purification in liquid chromatography, and the injection volume was 100μL. The rest is the same as in Example 2.
[0072] The separation chromatogram of zirconium ion and yttrium ion in the embodiment is as follows Figure 5 As shown. Figure 5 As can be seen from the figure, the peak elution time for zirconium ions is approximately 2.5 minutes, and the peak elution time for yttrium ions is approximately 9.7 minutes, with a selectivity factor of 5.1. The zirconium yield is 95%, and the purity is greater than 99.9%. Therefore, this method achieves the same separation effect on the simulated solution of the irradiated target, maintaining the same zirconium peak shape, purity, and yield.
[0073] Example 5
[0074] The standard solution composition and eluent type were modified, and all other steps were the same as in Example 1. Standard solutions with yttrium and zirconium ion concentrations of 25.0 mg / L and 100.0 mg / L, respectively, were prepared. The pH was adjusted to 4.0, filtered through a 0.22 μm filter membrane, and separated and purified on a chromatographic system using elution condition c. The injection volume was 10 μL.
[0075] Elution condition c: eluent: 20 mM malic acid, pH = 5.0, isocratic elution.
[0076] The separation chromatogram of zirconium ion and yttrium ion in the embodiment is as follows Figure 6 As shown. Figure 6 As can be seen from the results, the peak time of zirconium ion is about 2.3 minutes, the peak time of yttrium ion is about 16.0 minutes, and the selectivity factor is 8.4. The yield of zirconium element is 94.5%, and the purity is greater than 99.99%.
[0077] Example 6
[0078] The composition of the standard solution and the type of eluent were changed, the sulfonic acid type ion separation filler was changed to silica gel, and the other steps were the same as in Example 1.
[0079] Prepare standard solutions of yttrium ion and zirconium ion concentrations of 10.5 mg / L and 101.2 mg / L, respectively, with a pH of approximately 3.0. After filtering through a 0.22 μm filter membrane, separate and purify the solution on a chromatographic system using elution condition c. The injection volume is 10 μL.
[0080] Elution condition d: the eluent was 50 mM citric acid + 50 mM tartaric acid, pH = 4.3, isocratic elution.
[0081] The separation chromatogram of zirconium ion and yttrium ion in the embodiment is as follows Figure 7 As shown. Figure 7 As can be seen, the peak elution time for zirconium ions is approximately 2.3 minutes, and that for yttrium ions is approximately 5.5 minutes, with a selectivity factor of 2.7. The zirconium yield is 93% and the purity is 99.99%. When the eluent pH is higher and the concentration is higher, its elution capacity is enhanced, thus shortening the separation time, but the resolution is reduced. If the yttrium concentration in the sample solution is not very high, this method can be used for rapid zirconium and yttrium chromatographic separation.
[0082] Example 7
[0083] The composition of the standard solution and the type of eluent were changed, the sulfonic acid type ion separation filler was changed to silica gel, and the other steps were the same as in Example 1.
[0084] A mixed solution of yttrium ions and zirconium ions with concentrations of 25.0 mg / L and 100.0 mg / L, respectively, was prepared. The pH was adjusted to 4.0, filtered through a 0.22 μm filter membrane, and separated and purified on a chromatographic system using elution condition e. The injection volume was 10 μL.
[0085] Elution conditions:
[0086]
[0087] The separation chromatogram of zirconium ion and yttrium ion in the embodiment is as follows Figure 8 As shown. Figure 8 As can be seen from the results, the peak time of zirconium ion is about 2.3 minutes, the peak time of yttrium ion is about 11.4 minutes, and the selectivity factor is 6.01. The yield of zirconium element is 93.7%, and the purity is greater than 99.99%.
[0088] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A method for preparing high-purity zirconium, characterized in that: The following steps are involved: S0, dissolving the object containing yttrium and zirconium elements with a suitable solvent, and then neutralizing it with ammonia water to obtain a yttrium-zirconium mixed solution; S1. Preparation of eluent: dissolving at least one of citric acid, malic acid, and tartaric acid in water, and then adding an alkaline reagent to adjust the pH value to obtain an eluent; S2. Separating the yttrium-zirconium mixed solution in a liquid chromatograph using a cation exchange filler as a stationary phase and the eluent obtained in step S1 as a mobile phase, wherein the cation exchange filler is a silica gel surface polar group bonded phase filler, and the ion exchange functional group of the cation exchange filler is a sulfonic acid group; The elution conditions in the liquid chromatograph using the eluent obtained in step S1 as the mobile phase are one of the following: Elution condition a ; or elution condition b ; Or elution condition c: eluent is 20mM malic acid, pH=5.0, isocratic elution; or elution condition d: eluent is 50mM citric acid + 50mM tartaric acid, pH=4.3, isocratic elution; or elution condition e ; S3. The eluent has different chelating effects with zirconium and yttrium, and the peak time of zirconium ions is earlier than that of yttrium ions. The components flowing out of the liquid chromatograph are collected according to the peak time of zirconium to obtain high-purity zirconium. The detector for detecting the components is: under elution condition a, the detector is an inductively coupled plasma-mass spectrometer or an ultraviolet-visible light detector, and under other elution conditions, it is an ultraviolet-visible light detector.
2. A method for preparing high-purity zirconium according to claim 1, characterized in that: The solvent in step S0 is at least one of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid.
3. The method for preparing high-purity zirconium according to claim 1, wherein: The object containing yttrium and zirconium elements in step S0 is a mixture of yttrium and zirconium elements formed by irradiating metallic yttrium.
4. The method for preparing high-purity zirconium according to claim 1, wherein: The temperature of the chromatographic column of the liquid chromatograph in step S2 is 15-70°C.
5. The method for preparing high-purity zirconium according to claim 1, wherein: The pH value of the yttrium-zirconium mixed solution in step S2 is 0-5.0.
Citation Information
Patent Citations
Method and apparatus for purifying zirconium
JP2019163182A