Preparation method of N235 levextrel resin and application of N235 levextrel resin in rhenium separation

Abstract

The invention relates to the technical field of rhenium (Re) separation and enrichment, and discloses a preparation method of N235 extraction-elution resin and application of the N235 extraction-elution resin in rhenium separation.The N235 extraction-elution resin is prepared by loading tri-octyldecyl tertiary amine to a polystyrene type macroporous polymer carrier, the N235 extraction-elution resin has special adsorption performance on Re, Re is adsorbed in a 0.1-0.5 mol / L HNO3 solution, and the Re is separated from the HNO3 solution. According to the method, rhenium can be completely eluted, other ions cannot be adsorbed, and the rhenium can be completely eluted by a high-concentration HNO3 solution, so that the N235 extraction resin can be used as special-effect resin for separating and enriching Re, and has the advantage of high Re recovery rate.

Description

Technical Field:

[0001] The present invention relates to the technical field of rhenium (Re) separation and enrichment, and particularly relates to a preparation method and application of N235 extraction resin. Background Art:

[0002] Rhenium (Re) is a typical rare and dispersed metal element and one of the elements with the lowest abundance on the earth. The content of Re in most geological and environmental samples is extremely low, and it mainly exists in molybdenite. In production and life applications, metal Re and its alloys can be used to make fountain pen nibs and high-temperature thermocouples; it is used as a catalyst in chemical industries such as alcohol dehydrogenation and ammonia synthesis; alloys containing Re can withstand high temperatures. In addition, Re is a very important redox-sensitive element. Under oxidizing conditions, the highly soluble perrhenate ion ReO4- is the main form of Re; in a reducing environment, Re tends to precipitate and combine with organic matter or sulfide to be enriched in sediments. The redox property of its solubility enables it to trace the redox reaction of the chemical weathering process and reconstruct the redox cycle process of marine sediments. In addition, Re isotopes fractionate under redox or weathering conditions, so the Re isotope composition has the potential to infer changes in the redox of the seafloor and the intensity of global weathering. Therefore, Re has important research value and significance not only in industry but also in earth and environmental sciences.

[0003] Since the content of Re in geological and environmental samples is very low, it is difficult to accurately determine its content by conventional trace element testing methods, and it needs to be pre-enriched before testing. Summary of the Invention:

[0004] The purpose of the present invention is to provide a preparation method of N235 extraction resin and its application in separating rhenium.

[0005] The present invention is achieved through the following technical solutions:

[0006] A preparation method of N235 extraction resin includes the following steps: Mix polystyrene macroporous resin, dilute hydrochloric acid and an organic solvent, and then add the active ingredient trioctyldecyl tertiary amine thereto. The volume ratio of the trioctyldecyl tertiary amine to the polystyrene macroporous resin is 1:5, and shake well to obtain the N235 extraction resin. The polystyrene macroporous resin is of the CHP20 / P120 type.

[0007] Preferably, the organic solvent is ethanol.

[0008] The concentration of the dilute hydrochloric acid is preferably 0.1 - 0.5 mol / L.

[0009] The particle size of the CHP20 / P120 type polystyrene macroporous resin is preferably 75 μm, and the pore diameter is preferably The particle size and pore size of the CHP20 / P120 polystyrene macroporous resin can affect the flow rate and adsorption capacity of the subsequent column separation process. If the flow rate is too fast, Re will flow away before it can be adsorbed onto the resin. If the flow rate is too slow, the separation efficiency will be affected. The present invention selects a CHP20 / P120 polystyrene macroporous resin with a particle size of 75 μm and a pore size of which can balance the flow rate and adsorption capacity.

[0010] For the shaking and mixing, after each shaking, let it stand for 2 hours. If some resin floats on the surface, add a small amount of ethanol and shake and mix again. Repeat this operation until the resin is completely immersed and precipitated; during the shaking process, the trioctyl decyl group is loaded onto the polystyrene macroporous resin.

[0011] The N235 extraction resin is preferably stored sealed in a mixed solution of dilute hydrochloric acid and ethanol, which can prevent the resin from oxidation and at the same time has the function of soaking and cleaning the resin.

[0012] The present invention also protects the N235 extraction resin obtained by the above preparation method, which includes trioctyl decyl tertiary amine and polystyrene macroporous resin, and the trioctyl decyl tertiary amine is loaded on the surface of the polystyrene macroporous resin.

[0013] The N235 extraction resin prepared by the present invention has a special adsorption property for Re. In a 0.1 - 0.5 mol / L HNO3 solution, Re is adsorbed, while other metal ions (including alkali metals, alkaline earth metals, rare earth elements (REE), elements in the third, fourth, and fifth main groups of the periodic table, and transition metal elements such as scandium, titanium, vanadium, chromium, nickel, cobalt, iron, copper, zinc, zirconium, niobium, molybdenum, tungsten, cadmium, etc.) are not adsorbed. A high - concentration HNO3 solution (such as 3 - 6 mol / L HNO3) can completely elute rhenium. Therefore, the N235 extraction resin can be used as a special resin for separating and enriching Re and has the advantage of high Re recovery rate. Thus, the present invention also protects the application of the N235 extraction resin obtained by the above preparation method in separating and enriching rhenium, and the application includes the following steps:

[0014] After packing the N235 extraction resin into a column, perform pre - washing, column equilibration, sample loading, elution, and elution in sequence;

[0015] The solvent for pre - washing is a 3 - 6 mol / L HNO3 solution;

[0016] The solvent for column equilibration is a 0.1 - 0.5 mol / L HNO3 solution;

[0017] The sample loading solution is a 0.1 - 0.5 mol / L HNO3 solution containing Re;

[0018] The elution uses a 0.1 - 0.5 mol / L HNO3 solution;

[0019] The eluent solvent is a 3 - 6 mol / L HNO3 solution, more preferably a 4 mol / L HNO3 solution.

[0020] It is preferred to use a polystyrene centrifuge column for column packing. The packing volume of the polystyrene centrifuge column is preferably 0.5 mL (corresponding to a dry weight of 0.25 g of N235 extraction resin), and the column height is preferably 1 cm.

[0021] The sample loading solution is preferably prepared by a method including the following steps: dissolving the sample to be tested and then evaporating the solvent to dryness to obtain a residue;

[0022] After driving away concentrated HCl and concentrated HF solutions from the residue with concentrated HNO3 solution, it is extracted with a 0.1 - 0.5 mol / L HNO3 solution to obtain the sample loading solution.

[0023] The sample to be tested is preferably a geological sample, the geological sample includes rock powder and seawater, the particle size of the rock powder is preferably 200 mesh, and the rock powder includes rock powders such as basalt, granite, and peridotite.

[0024] The solvent for dissolving the sample to be tested is preferably a mixed acid of concentrated HF and concentrated HNO3, and the volume ratio of concentrated HF to concentrated HNO3 in the mixed acid is preferably 2:1; the concentration of concentrated HF is preferably 22 mol / L, and the concentration of concentrated HNO3 is preferably 14 mol / L. When the geological sample contains more organic matter, the dissolving solvent is preferably a mixed acid of concentrated HF, concentrated HCl, and concentrated HNO3. Using a mixed acid containing concentrated HCl can increase the dissolving ability for organic matter.

[0025] The dosage ratio of the mixed acid of concentrated HF and concentrated HNO3 to the sample to be tested is preferably 4 mL:0.1 g; the dosage ratio of the mixed acid of concentrated HF, concentrated HCl, and concentrated HNO3 to the sample to be tested is preferably 4 mL:0.1 g.

[0026] The temperature of the dissolution is preferably 120 - 140 °C, more preferably 130 °C.

[0027] The beneficial effects of the present invention are as follows:

[0028] The present invention loads trioctyl decyl tertiary amine onto a macroporous polystyrene polymer support to prepare N235 extraction resin. This N235 extraction resin has a specific adsorption property for Re. In a 0.1 - 0.5 mol / L HNO3 solution, Re is adsorbed, while other metal ions (including alkali metals, alkaline earth metals, rare earth elements, elements in the third, fourth, and fifth main groups of the periodic table, and transition metal elements such as scandium, titanium, vanadium, chromium, nickel, cobalt, iron, copper, zinc, zirconium, niobium, molybdenum, tungsten, cadmium, etc.) are not adsorbed. A high - concentration HNO3 solution (such as 3 - 6 mol / L HNO3) can elute rhenium completely. Therefore, the N235 extraction resin can be used as a specific resin for separating and enriching Re, and has the advantage of a high recovery rate of Re. Compared with the traditional anion resin AG1 - X8 for separating Re, which requires the simultaneous use of a relatively high - concentration HNO3, the N235 extraction resin only needs to use a lower - concentration HNO3 solution to quickly separate and purify Re. When using a 0.1 - 0.5 mol / L HNO3 solution medium loaded onto the N235 extraction resin, most of the matrix elements are quickly eluted, while Re can be strongly adsorbed on the resin. Finally, Re is eluted and collected with a 3 - 6 mol / L HNO3 solution. The high selectivity of the N235 extraction resin for Re significantly improves the efficiency of separating and enriching Re. The prepared N235 extraction resin has the characteristics of separating and enriching Re and the advantage of a high recovery rate of Re. Applying the N235 extraction resin prepared by the present invention to separate and enrich Re, after packing the column and using different pre - washing, column - equilibration, sample - loading, elution, and stripping solvents, the separation of Re from other elements is achieved. The operation is simple, and the recovery rate of Re is high, greater than 98%. Description of the Drawings:

[0029] Figure 1 It is the elution curve of the N235 extraction resin prepared in Example 1 for separating Re. Detailed Embodiments:

[0030] The following is a further description of the present invention, rather than a limitation of the present invention.

[0031] Example 1: Preparation of N235 Extraction Resin

[0032] First, the particle size is 75 μm and the pore size is The CHP20 / P120 type macroporous polystyrene resin (purchased from Mitsubishi Chemical Corporation, Japan) was soaked in a mixed solution of 0.1 mol / L dilute hydrochloric acid and ethanol, shaken evenly at room temperature (25 °C) and allowed to stand. After the macroporous polystyrene resin precipitated, the active ingredient trioctyl decyl tertiary amine was added, and the volume ratio of the added trioctyl decyl to the macroporous polystyrene resin was 1:5. It was shaken evenly at room temperature (25 °C) and allowed to stand for 2 hours. If part of the N235 extraction resin floated on the surface layer, a small amount of ethanol was added again and shaken and mixed evenly. This operation was repeated until the N235 extraction resin was completely soaked and precipitated. During the shaking process, the trioctyl decyl was loaded onto the macroporous polystyrene resin to obtain the N235 extraction resin.

[0033] Application Example 1 Method for Separating Re by Column Using N235 Extraction Resin

[0034] The N235 extraction resin prepared in Example 1 was packed into a polypropylene centrifuge column with a column height of 1 cm and a volume of 0.5 mL. First, the resin column was pre-washed with 6 mL of 4 mol / L HNO3 solution, and then column equilibration was carried out with 2 mL of 0.5 mol / L HNO3 solution. Weigh about 200 mg of rock geological sample, completely dissolve it with concentrated HF-HCl-HNO3 mixed acid (where the volume ratio of concentrated HF: concentrated HCl: concentrated HNO3 is 2:2:1, the concentration of concentrated HF is 22 mol / L, the concentration of concentrated HCl is 10 mol / L, and the concentration of concentrated HNO3 is 14 mol / L) at 130 °C, evaporate to dryness, add 14 mol / L concentrated nitric acid to drive off the acid and evaporate to dryness again, extract with 6 ml of 0.5 mol / L HNO3 and separate on the N235 extraction resin. Use 10 ml of 0.5 mol / L HNO3 solution to wash impurities and interfering ions, and finally elute the Re adsorbed on the resin with 11 mL of 4 mol / L HNO3 solution. The specific separation process is shown in Table 1, and 2 mL is received each time, and the metal ion concentration in the solution is measured by ICP-MS. Figure 1 It is the elution curve for separating Re using the N235 extraction resin prepared in Example 1.

[0035] Table 1 Separation Process of N235 Extraction Resin Column

[0036] Process Reagent Volume (mL) Pre-washing <![CDATA[4mol / L HNO3]]> 6 Column equilibration <![CDATA[0.5mol / L HNO3]]> 2 Loading <![CDATA[0.5mol / L HNO3]]> 4～10 Washing <![CDATA[0.5mol / L HNO3]]> 10 Elution <![CDATA[4mol / L HNO3]]> 12

[0037] From Figure 1From the elution curve, it can be seen that the present invention uses N235 extraction resin to separate and enrich Re, and has good separation effect and high selectivity for the separation of Re from other metal ions (titanium, iron, zinc, gallium, germanium, zirconium, niobium, molybdenum, silver, cadmium, rare earth elements (REE), tungsten, lead). The recovery rate of Re is above 98%, greatly improving the separation and enrichment efficiency of Re in geological and environmental samples, and will become a special resin separation method for analyzing Re elements and isotopes in laboratories.

[0038] Application Example 2

[0039] Taking the basalt reference sample BCR-2 as the analysis object, its Re content was determined.

[0040] Weighed 0.1264g, 0.1259g, and 0.1262g of three BCR-2 samples as parallel samples, denoted as BCR-2-1, BCR-2-2, and BCR-2-3 respectively. Completely dissolved with a concentrated HF-HNO3 mixed acid (volume ratio of concentrated HF to concentrated HNO3 is 2:1, concentration of concentrated HF is 22mol / L, concentration of concentrated HNO3 is 14mol / L) at 130°C, evaporated to dryness, then redissolved with aqua regia (concentrated HCL:concentrated HNO3 is 1:1), evaporated to dryness, added 0.5ml of concentrated HNO3 for acid removal, evaporated to dryness again, extracted with 0.5mol / L HNO3 solution and then separated by an N235 extraction resin column filled with the N235 extraction resin prepared in Example 1. The amount of N235 extraction resin used is 0.5mL (column height is about 1cm), and the separation process of the N235 extraction resin column is the same as that in Table 1. The measurement of Re content uses inductively coupled plasma mass spectrometry (ICP-MS), and a 2ng·g -1 Re standard solution is used as the external standard, and iridium (Ir) is added as the internal standard element to monitor the drift of the instrument sensitivity.

[0041] The measured Re content of the finally obtained BCR-2 is shown in Table 2. The recovery rates of Re for the three parallel samples of BCR-2 are 99.0%, 98.5%, and 98.8% respectively.

[0042] Table 2 Measurement results of the content of rock reference sample BCR-2 in Application Example 2

[0043] Sample Re Content (ng / g) BCR-2-1 11.93 BCR-2-2 11.87 BCR-2-3 11.90 Average value 11.90 Reference value 12.05

[0044] Application Example 3

[0045] Taking seawater as the analysis object, its Re content was determined.

[0046] Three 250 mL seawater samples were taken separately as parallel samples and directly separated on an N235 extraction resin column filled with the N235 extraction resin prepared in Example 1. The amount of N235 extraction resin used was 0.5 mL, and the separation process of the N235 extraction resin column was the same as that in Table 1. The measurement of Re content was carried out by inductively coupled plasma mass spectrometry (ICP-MS), and a Re standard solution of 2 ng·g -1 was used as the external standard, and iridium (Ir) was added as an internal standard element to monitor the drift of the instrument sensitivity.

[0047] The Re content of the finally obtained seawater is shown in Table 3. The Re content in seawater is in the range of 6.8 - 7.7 pg·g -1 and the average recovery rate of the measured rhenium is 98.6%.

[0048] Table 3 Measurement results of rhenium content in seawater in Application Example 3

[0049] Sample Re Content (pg / g) Seawater 20m-1 7.17 Seawater 20m-2 7.05 Seawater 20m-3 7.14 Average value 7.12 Reference value 6.8～7.7

[0050] In Application Examples 2 and 3, whether it is a rock or seawater sample, the present invention can efficiently separate and enrich Re and accurately determine it. The recovery rate of Re is greater than 98%. Therefore, the N235 extraction resin of the present invention can be used as a special resin for separating and enriching Re.

[0051] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, not all embodiments. People can also obtain other embodiments according to the embodiments of the present invention without creative labor, and these embodiments all belong to the protection scope of the present invention.

Claims

1. A method for preparing N235 leaching resin, characterized in that: The method comprises the following steps: after uniformly mixing polystyrene macroporous resin, dilute hydrochloric acid and an organic solvent, adding an effective ingredient trioctyldecyl tertiary amine thereto, wherein the volume ratio of the trioctyldecyl tertiary amine to the polystyrene macroporous resin is 1:5, and shaking and mixing to obtain the N235 leaching resin; the polystyrene macroporous resin is CHP20 / P120 type.

2. The preparation method according to claim 1, characterized in that: The organic solvent is ethanol.

3. The preparation method according to claim 1, characterized in that: The concentration of the dilute hydrochloric acid is 0.1-0.5 mol / L.

4. The preparation method according to claim 1, characterized in that: The particle size of CHP20 / P120 polystyrene macroporous resin is 75 μm and the pore size is 5. The use of the N235 leaching resin obtained by the preparation method according to claim 1 in separation and enrichment of rhenium, characterized in that: The application comprises the following steps: after the N235 leaching resin is loaded into a column, pre-washing, column balancing, sample loading, elution and washing are sequentially performed; the pre-washing solvent is a 3-6 mol / L HNO3 solution; the column balancing solvent is a 0.1-0.5 mol / L HNO3 solution; the loading solution is a 0.1-0.5 mol / L HNO3 solution containing Re; the elution is performed with a 0.1-0.5 mol / L HNO3 solution; and the elution solvent is a 3-6 mol / L HNO3 solution.

6. The use according to claim 5, characterized in that: The elution solvent was 4 mol / L HNO3 solution.

7. The use according to claim 5, characterized in that: A polystyrene centrifugal column was used for column packing. The packing volume of the polystyrene centrifugal column was 0.5 mL and the column height was 1 cm.

8. The use according to claim 5, characterized in that: The sample solution is prepared by a method comprising the following steps: dissolving a sample to be tested and then evaporating the solvent to obtain a residue; using a concentrated HNO3 solution to drive away concentrated HCL and concentrated HF solutions from the residue, and then extracting with a 0.1-0.5 mol / L HNO3 solution to obtain the sample solution.

9. The use according to claim 8, characterized in that: The sample to be tested is a geological sample, which includes rock powder and seawater. The rock powder has a particle size of 200 meshes, and the rock powder includes basalt, granite, and peridotite.

10. The use according to claim 8, characterized in that: The solvent for dissolving the sample to be tested is a mixed acid of concentrated HF and concentrated HNO3 or a mixed acid of concentrated HF, concentrated HCl and concentrated HNO3, the volume ratio of concentrated HF and concentrated HNO3 in the mixed acid is 2:1; the concentration of the concentrated HF is 22 mol / L, and the concentration of the concentrated HNO3 is 14 mol / L; the dissolution temperature is 120-140°C.

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