Chromatographic separation device

Abstract

The utility model belongs to the field of analytical chemistry and geochronology, and particularly relates to a chromatographic separation device. The chromatographic separation device comprises a tubular container, an ion exchange resin layer is arranged in the tubular container, the ion exchange resin layer is located on the lower middle portion of the tubular container, and quartz sand homogeneous layers are installed above and below the ion exchange resin layer. When the chromatographic separation device is used for separating beryllium (Be) elements, inclination or generation of pits on the upper surface of a resin layer caused by too high dropping speed or non-uniform dropping speed of eluent can be avoided, and meanwhile, the eluent or a sample solution can be prevented from being dried, so that the optimal elution efficiency of beryllium (Be) components in the chromatographic separation process is ensured, and the quality of the beryllium (Be) is ensured. And the purity of the separated beryllium (Be) component is improved.

Description

Technical Field

[0001] The utility model belongs to the fields of analytical chemistry and geochronology, and particularly relates to a chromatographic separation device. Background Art

[0002] The separation of cosmogenic nuclides in minerals is an important step in the cosmogenic nuclide geochronology method in the field of geochronology, and is the key to accurately determining the ages of geological bodies and landform surfaces. At present, the development of the cosmogenic nuclide geochronology method in China mainly focuses on the single mineral dating stage based on quartz, and the conventional nuclide separation and purification process is also established for quartz minerals. However, such conventional geochronology methods based on quartz often cannot be applied in special geological environments with high surface erosion rates and exposed bedrock. The reason is that in such geological environments, especially in bedrock areas dominated by ferromagnesian basic rocks, on the one hand, the distribution of surface sediments is extremely limited, and on the other hand, quartz minerals are rare in basic rocks, lacking suitable dating objects.

[0003] Similar to quartz, feldspar is also a common surface mineral. However, different from quartz minerals: (1) feldspar silicate minerals are widely present in basic bedrocks; (2) the contents of interfering components such as inherited stable cosmogenic nuclides and radioactivity reaction-derived nuclides in feldspar minerals are very low, which is conducive to carrying out 21 Ne exposure dating and 10 Be / 21 Ne nuclide pair burial dating research. Therefore, replacing quartz with feldspar minerals is an effective method for realizing surface dating and burial dating in bedrock areas and volcanic regions, and has important application value in the research of geological processes such as the determination of landform surface ages in basic bedrock areas, the calibration of surface process rates, the slip rates of bedrock faults, volcanic activities, and natural disasters.

[0004] At present, there is no complete and reliable sample preparation process for accelerator mass spectrometry 10 Be content determination for other minerals besides quartz. In the sample preparation process for accelerator mass spectrometry 10 Be content determination, high-purity beryllium components are the key to obtaining high-precision isotope contents and reducing the detection limit. The reason is that high-purity Be component samples help to improve the 9 Be 3+ beam current intensity during the testing process, thereby increasing the detection count, reducing the error of count statistics, and thus reducing the detection limit and improving the testing accuracy. Low-purity Be components, for example, the mixing of Al components or Ti components during the separation process, will reduce 9 Be 3+The beam intensity causes a decrease in the test accuracy.

[0005] Compared with quartz, feldspar minerals are characterized by high aluminum and potassium element contents and are minerals with a high metal ion content. Therefore, a method for preparing AMS test samples of beryllium elements in feldspar minerals that is suitable for efficient separation and purification of beryllium elements in a high-aluminum and potassium environment and has a high recovery rate is the basis and key for carrying out research on cosmogenic nuclide chronology methods and applications based on feldspar.

[0006] For example, the patent application with the patent application number 202111113231.X discloses an experimental method for separating beryllium elements in feldspar minerals and the chromatographic separation device used therein, which can efficiently separate and purify beryllium elements in a high-aluminum and potassium metal element environment, avoiding the problem of beryllium element loss or complete loss caused by the interference of high metal ion content. However, currently, the processing efficiency of this separation method is relatively limited, and the mass of feldspar that can be processed each time is 1 - 10 g. For low-altitude and low-latitude regions with a low cosmogenic nuclide production rate in surface feldspar minerals, multiple treatments are required to obtain a sufficient amount of beryllium elements for accelerator mass spectrometry analysis. Summary of the Invention

[0007] Based on the above technical background, the main purpose of the present utility model is to provide a chromatographic separation device. Using this device for beryllium element separation is not limited to feldspar minerals, and it is a method for separating beryllium elements from high-aluminum and potassium element minerals with high purity and high recovery efficiency for accelerator mass spectrometry analysis, so as to overcome the deficiencies in the prior art.

[0008] To achieve the foregoing utility model purpose, the technical solutions adopted by the present utility model include:

[0009] The present utility model provides a chromatographic separation device, which includes a tubular container. An ion exchange resin layer is arranged inside the tubular container, and the ion exchange resin layer is located in the middle and lower part of the tubular container. A uniform layer is installed above and below the ion exchange resin layer;

[0010] The distance between the uniform layer above the ion exchange resin layer and the ion exchange resin layer (i.e., the separation layer) is 2 - 3 mm, and the uniform layer below the ion exchange resin layer is in contact with the ion exchange resin layer (i.e., the separation layer).

[0011] Preferably, the uniform layer is a quartz sand filter;

[0012] The quartz sand filter is provided with holes of uniform size and uniform distribution, and the diameter of the holes is The distance between adjacent holes is

[0013] The ion exchange resin layer is a cation resin or an anion resin.

[0014] More preferably, the diameter of the holes is

[0015] The distance between adjacent holes is

[0016] More preferably, the volume of the ion exchange resin layer is 2 - 4 mL.

[0017] Preferably, the distance between the homogeneous layer disposed above the ion exchange resin layer and the ion exchange resin layer is 2.5 mm.

[0018] Preferably, a liquid injection port is provided at the top of the tubular container. The liquid injection port is in a funnel shape, facilitating the injection of the liquid to be chromatographically separated into the tubular container. The part of the liquid injection port in contact with the tubular container has the same diameter as the tubular container, and the diameter gradually becomes larger as it is farther away from the tubular container.

[0019] The beneficial effects of the present utility model are as follows:

[0020] (1) The chromatographic separation device of the present utility model includes a homogeneous layer, a resin layer (i.e., a separation layer), and a homogeneous layer. The homogeneous layer and the resin layer (i.e., the separation layer) are both placed in a tubular container. By adding a homogeneous quartz sand filter layer on the upper part of the resin layer (i.e., the separation layer), when using this chromatographic separation device for separation, it is possible to avoid the upper surface of the resin bed layer from tilting or forming pits due to the too fast or uneven dropping speed of the eluent and the sample solution. If the upper surface of the resin bed layer tilts or pits are formed, it will cause different flow rates of the eluent or the sample solution at different positions of the resin bed layer, thereby affecting the separation effect of the elements to be separated, resulting in the inability to completely separate impurity elements such as aluminum (Al) and titanium (Ti) from the beryllium (Be) component, and the purity of the separated beryllium (Be) component is relatively low. In addition, this chromatographic separation device can also prevent the eluent or the sample solution from drying out, maintain the best elution efficiency during the chromatographic separation process, and obtain a beryllium (Be) component with higher purity.

[0021] (2) The method for separating the beryllium (Be) component from feldspar minerals of the present utility model is an effective method for realizing surface dating and buried dating in areas lacking conventional quartz dating minerals such as bedrock areas and volcanic rock areas. This utility model has important application value in the research of fields such as the bedrock fault slip rate and geomorphic evolution in basic bedrock areas.

[0022] (3) The method for separating beryllium elements from feldspar minerals provided by the present utility model is applicable to separating and purifying beryllium elements from feldspar minerals with a high aluminum content. At the same time, it has the excellent characteristic of high beryllium element separation efficiency. It can be used for the determination of exposure age, burial age, and surface erosion rate of cosmogenic nuclide chronology, and has important application value in geological processes such as surface process research, late Cenozoic climate change, volcanic activity, and natural disaster research.

[0023] (4) The method for separating beryllium (Be) components described in the present utility model is not limited to feldspar minerals. The present utility model can be widely applied to separating beryllium elements from minerals with high aluminum and potassium elements with high purity and high recovery efficiency for accelerator mass spectrometry analysis.

[0024] (5) The preparation method described in the present utility model is simple, has no special requirements for equipment, does not need to be carried out under high pressure, and the separation method is safe, pollution-free, and has a low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The structural schematic diagram of a chromatographic separation device showing a preferred embodiment of the present utility model is shown.

[0026] Figure 2 It is a method for separating and purifying beryllium (Be) elements from feldspar minerals provided by the present utility model. The flow chart shows the process of selecting and purifying feldspar mineral particles from rock samples, separating and purifying beryllium (Be) element components in feldspar minerals, and obtaining BeO for making accelerator mass spectrometry test targets.

[0027] DESCRIPTION OF THE REFERENCE NUMERALS IN THE DRAWINGS

[0028] 1 - homogeneous layer;

[0029] 2 - ion exchange resin layer (i.e., separation layer);

[0030] 3 - liquid injection port;

[0031] 4 - tubular container. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0032] The present utility model will be described in detail below, and the features and advantages of the present utility model will become clearer and more definite with these descriptions.

[0033] The first aspect of the present utility model lies in providing a chromatographic separation device. The chromatographic separation device includes a tubular container 4. An ion exchange resin layer 2 is arranged inside the tubular container 4. The ion exchange resin layer 2 is located in the middle and lower part of the tubular container 4. Homogeneous layers 1 are installed above and below the ion exchange resin layer 2, as Figure 1 shown.

[0034] The distance between the homogeneous layer 1 above the ion exchange resin layer 2 and the ion exchange resin layer (i.e., the separation layer) 2 is 2 - 3 mm. The homogeneous layer 1 below the ion exchange resin layer 2 is in contact with the ion exchange resin layer (i.e., the separation layer) 2.

[0035] Preferably, the distance between the homogeneous layer 1 above the ion exchange resin layer 2 and the ion exchange resin layer 2 is 2.5 mm.

[0036] The ion exchange resin layer 2 is a cation resin or an anion resin.

[0037] The volume of the ion exchange resin layer 2 is 2 - 4 mL. Preferably, the volume of the ion exchange resin layer 2 is 2 mL.

[0038] According to a preferred embodiment of the present utility model, a liquid injection port 3 is provided at the top of the tubular container 4. The liquid injection port 3 is in a funnel shape, which is convenient for injecting the liquid to be chromatographically separated into the tubular container. The part of the liquid injection port 3 in contact with the tubular container has the same diameter as the tubular container, and the diameter gradually becomes larger as it is farther away from the tubular container.

[0039] The homogeneous layer 1 is a filter disc, preferably a quartz sand filter disc.

[0040] The filter disc is provided with holes of uniform size and uniform distribution. The diameter of the holes is Preferably, the diameter of the holes is

[0041] The distance between adjacent holes is Preferably, the distance between adjacent holes is

[0042] By adding a homogeneous layer 1 on the ion exchange resin layer, it can be avoided that the upper part of the anion / cation resin directly contacts the eluent or the sample solution. When using a polypropylene ion exchange column with a large column bed volume, the cross-sectional area of the anion / cation resin is large. During the process of dripping the eluent and the sample solution, if the dripping speed is too fast or locally uneven, it will cause the surface of the resin bed layer to tilt or form a tunnel, resulting in inconsistent elution efficiency of the beryllium (Be) component: for example, in the place with a tunnel, the beryllium (Be) component is eluted first; in the place without a tunnel, the beryllium (Be) component is eluted later; when the beryllium (Be) component in the place without a tunnel is completely eluted, impurity components such as aluminum (Al) and titanium (Ti) have been eluted in the place with a tunnel, thus affecting the purity of the beryllium (Be) component. This causes the impurities in the beryllium (Be) component to reduce the ionization efficiency of the beryllium (Be) element during subsequent accelerator mass spectrometry analysis, weaken the beam intensity, reduce the count, and ultimately lead to a decrease in the test accuracy of the beryllium (Be) element.

[0043] The second aspect of the present utility model lies in providing a method for separating beryllium (Be) element from feldspar minerals for accelerator mass spectrometry analysis, characterized in that the method includes the step of separating feldspar minerals by using the chromatographic separation device described in the first aspect of the present utility model to obtain the component beryllium (Be). The method flow is shown in Figure 2 as follows.

[0044] Preferably, the method includes the following steps:

[0045] Step 1: Crush the rock minerals, remove magnetic minerals by magnetic separation, and subject the non-magnetic minerals to etching, heavy liquid separation, washing, and drying in sequence to obtain pure feldspar minerals;

[0046] Step 2: Add a Be(NO3)2 standard solution to the pure feldspar minerals, then place them in a hydrofluoric acid solution to completely dissolve. After cooling and centrifuging, wash the precipitated sediment, then combine the sediment and the supernatant obtained by centrifugation, and finally evaporate to dryness to obtain a solid;

[0047] Step 3: Add hydrochloric acid to the solid obtained in Step 2 to obtain a sample solution, then rinse the anion resin with hydrochloric acid. Subsequently, add the sample solution to the anion resin, elute the anion resin with hydrochloric acid to obtain an eluate, and finally evaporate the eluate to dryness to obtain a solid substance;

[0048] Step 4: Add the solid substance obtained in Step 3 to a sulfuric acid solution and hydrogen peroxide, heat to dissolve, then evaporate to dryness. Add the sulfuric acid solution and hydrogen peroxide again, heat to dissolve, then evaporate to dryness. Add the sulfuric acid solution and hydrogen peroxide again, heat to dissolve and evaporate to dryness until the solid after evaporation is colorless or amber transparent;

[0049] Step 5: Add hydrochloric acid solution and sulfuric acid solution to the chromatographic separation device in sequence to rinse the cation resin. Dissolve the colorless transparent solid prepared in Step 4 in hydrochloric acid to obtain a sample solution, then add the sample solution to the chromatographic separation device. Subsequently, add sulfuric acid solution to elute the titanium (Ti) component and hydrochloric acid to elute the beryllium (Be) component to the chromatographic separation device in sequence. Add nitric acid to dilute the beryllium (Be) component eluate, and measure the contents of beryllium (Be) and aluminum (Al) elements. When the contents of beryllium (Be) and aluminum (Al) components are less than 3:1, repeat the above cation exchange separation process until the ratio of beryllium (Be) and aluminum (Al) components is greater than 3 to obtain the beryllium (Be) element component;

[0050] Step 6: Add an alkali solution to the beryllium (Be) element component to adjust the pH value until the beryllium component is completely precipitated in the form of hydroxide. After centrifugation, discard the supernatant. Disperse and wash the precipitate in the alkali solution to remove impurities; after centrifugation again, discard the supernatant, dry the precipitate, and finally perform high-temperature heating to obtain BeO.

[0051] The above steps are described in detail below.

[0052] In Step 1, after crushing the rock minerals, the rock components of 250 - 500 μm are screened.

[0053] The non - magnetic minerals are etched in a hydrofluoric acid and nitric acid solution, where the mass percentages of both hydrofluoric acid and nitric acid are 1 - 3%, and then heavy - liquid separation is carried out in methylene iodide.

[0054] Preferably, the non - magnetic minerals are etched in a hydrofluoric acid and nitric acid solution, where the mass percentages of both hydrofluoric acid and nitric acid are 2%, and then heavy - liquid separation is carried out in methylene iodide.

[0055] Take pure feldspar minerals, place them in a mixed solution and heat to complete dissolution of the minerals at 100 - 130°C. The mixed solution is obtained by mixing hydrofluoric acid with a mass percentage of 20 - 40% and concentrated nitric acid with a mass fraction of 30 - 63% in a volume ratio of (4 - 6):1. Place the solid obtained after evaporating the solvent in nitric acid with a mass fraction of 5%. Perform inductively coupled plasma - atomic emission spectrometry test to measure the main element content.

[0056] Preferably, take pure feldspar minerals, place them in a mixed solution and heat to complete dissolution of the minerals at 120°C. The mixed solution is obtained by mixing hydrofluoric acid with a mass percentage of 40% and concentrated nitric acid with a mass fraction of 63% in a volume ratio of 5:1. Place the solid obtained after evaporating the solvent in nitric acid with a mass fraction of 5%.

[0057] In Step 2, take pure feldspar minerals, place them in a hydrofluoric acid solution with a mass concentration of 20 - 40%, and heat to dissolve the sample at 100 - 130°C. Preferably, place them in a hydrofluoric acid solution with a mass concentration of 40% and heat to dissolve the sample at 120°C.

[0058] Wash the precipitated sediment with deionized water 2 - 3 times.

[0059] In Step 3, the anion resin is AG - 1X8 anion resin with a mesh size of 200 - 400, and the anion resin is dispersed in 1.2 mol / L hydrochloric acid.

[0060] Add 5 - 7 mol / L hydrochloric acid to the solid obtained in Step 2, and then rinse the anion resin with 5 - 7 mol / L hydrochloric acid. Preferably, add 6 mol / L hydrochloric acid to the solid obtained in Step 2, and then rinse the anion resin with 6 mol / L hydrochloric acid.

[0061] Elute the anion resin with 5 - 7 mol / L hydrochloric acid. Preferably, elute the anion resin with 6 mol / L hydrochloric acid.

[0062] In Step 4, into the solid substance obtained in Step 3, add a sulfuric acid solution with a concentration of 0.03 - 0.04 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution, heat and dissolve at 90 - 120 °C. After evaporation to dryness, add again a sulfuric acid solution with a concentration of 0.03 - 0.04 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution, heat and dissolve at 90 - 120 °C, and then evaporate to dryness. The above steps usually need to be repeated 3 - 6 times until the solid after evaporation to dryness is colorless or light amber transparent.

[0063] Preferably, into the solid substance obtained in Step 3, add a sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution, heat and dissolve at 100 °C. After evaporation to dryness, add again a sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution, heat and dissolve at 100 °C, and then evaporate to dryness. The above steps usually need to be repeated 3 - 6 times until the solid after evaporation to dryness is colorless or light amber transparent.

[0064] In Step 5, the cation resin is AG 50W - X8H+ type cation resin with a mesh size of 200 - 400, and disperse the cation resin in 1.2 mol / L hydrochloric acid.

[0065] Add high - purity water containing a trace amount of sulfuric acid solution with a concentration of 0.03 - 0.04 M and 2% hydrogen peroxide into the colorless or light amber transparent solid prepared in Step 4 to completely dissolve the solid and obtain a sample solution. Preferably, place the colorless or light amber transparent solid prepared in Step 4 in a sulfuric acid solution with a concentration of 0.0368 M and 1 - 2 drops of a 2% (volume percentage concentration) hydrogen peroxide solution for dissolution.

[0066] Rinse the resin successively with a 3 - 5 mol / L hydrochloric acid solution, a 1 - 1.5 mol / L hydrochloric acid solution, and a 0.1 - 0.3 mol / L sulfuric acid solution. After rinsing, add the sample solution, and then elute the titanium component with a 0.4 - 0.6 mol / L sulfuric acid solution and elute the beryllium (Be) component with a 1 - 1.5 mol / L hydrochloric acid solution.

[0067] Preferably, rinse the resin successively with a 4 mol / L hydrochloric acid solution, a 1.2 mol / L hydrochloric acid solution, and a 0.2 mol / L sulfuric acid solution. After rinsing, add the sample solution, and then use a 0.5 mol / L sulfuric acid solution to elute the titanium component. After the eluate runs dry, use a 1.2 mol / L hydrochloric acid solution to elute the beryllium (Be) component.

[0068] In Step 6, ammonia water is added to the beryllium (Be) element component to adjust the pH to between 8 and 8.5. At this time, the beryllium (Be) element precipitates in the form of beryllium hydroxide (Be(OH)2). After centrifugation, the supernatant is discarded, and the precipitate is dispersed in ammonia water and then washed 2 to 3 times.

[0069] The washed precipitate is dried at 60 - 80 °C and then subjected to high-temperature heating at 800 - 900 °C to oxidize Be(OH)2 to form BeO.

[0070] Preferably, the washed precipitate is dried at 70 °C and then subjected to high-temperature heating at 900 °C to obtain BeO.

[0071] Examples

[0072] The present utility model will be further described below through specific examples. These examples are only for illustrating the present utility model and are not used to limit the scope of the present utility model. The raw materials used in the examples of the present utility model are all commercially available.

[0073] Example 1

[0074] A chromatographic separation device, which includes a tubular container 4, a homogeneous layer 1, and an ion exchange resin layer (i.e., separation layer) 2. The ion exchange resin layer 2 is arranged inside the tubular container 4. The ion exchange resin layer 2 is located in the middle and lower part of the tubular container 4. Homogeneous layers 1 are installed above and below the ion exchange resin layer 2. The distance between the homogeneous layer 1 above the ion exchange resin layer 2 and the ion exchange resin layer (i.e., separation layer) 2 is 2.5 mm. The homogeneous layer 1 below the ion exchange resin layer 2 is in contact with the ion exchange resin layer (i.e., separation layer) 2, as Figure 1 shown.

[0075] The ion exchange resin layer (i.e., separation layer) 2 is a cation resin or an anion resin. The volume of the ion exchange resin layer (i.e., separation layer) 2 is 2 mL. A liquid injection port 3 is provided at the top of the tubular container. The liquid injection port 3 is in a funnel shape. The part of the liquid injection port 3 in contact with the tubular container has the same diameter as the tubular container, and the diameter gradually becomes larger as it is farther away from the tubular container.

[0076] The homogeneous layer 1 is a quartz sand filter. The homogeneous layer 1 is provided with holes of uniform size and uniform distribution. The diameter of the holes is The distance between adjacent holes is

[0077] Example 2

[0078] After crushing the granite rock sample (sample name: HLL12), the rock components with a size of 250 - 500 μm were screened, and magnetic minerals were removed by magnetic separation. The non-magnetic mineral components were etched 2 - 3 times in a solution of dilute hydrofluoric acid and nitric acid (the mass percentages of HF and HNO3 in the solution were both 2%) to disperse the multi-mineral adhesion particles, and then heavy liquid separation was carried out in methylene iodide to obtain the feldspar component. After washing and drying, pure feldspar minerals were obtained.

[0079] Take 1 g of pure feldspar minerals and dissolve them by heating in a mixed solution of hydrofluoric acid (HF) with a mass percentage of 40% and concentrated nitric acid with a mass percentage of 63% at a volume ratio of 5:1 at 120 °C. After the minerals were completely dissolved, the solvent was evaporated to dryness. The solid was dissolved in 5% (mass percentage) nitric acid, and inductively coupled plasma - optical emission spectrometer (ICP - OES) tests were carried out to obtain the main element contents in the solution.

[0080] Take 10 g of pure feldspar minerals and add a Be(NO3)2 standard solution (where 9 the Be concentration is 1000 μg / mL), 9 The Be standard solution is a national standard beryllium solution produced by the National Center for Iron and Steel Materials Testing, National Iron and Steel Research Institute (NCS) of China, with the label GSBG 62002 - 90. Dissolve the sample by heating in a 40% hydrofluoric acid (HF) solution at 120 °C. After the sample was completely dissolved, it was cooled to room temperature. During the cooling process of the solution, a large amount of precipitate was precipitated. Centrifuge, and the supernatant was collected in a beaker; the precipitate was washed 2 - 3 times with a small amount of deionized water (18 MΩ), and the supernatants were combined into the beaker and evaporated to dryness.

[0081] Load 2 ml of AG - 1X8 anion resin with a mesh size of 200 - 400 (dispersed in 0.1 mol / L hydrochloric acid) into the chromatographic separation device described in Example 1 with a volume of 10 ml as the resin layer of the chromatographic separation device. Add a 6.0 mol / L hydrochloric acid solution to the above-mentioned solid evaporated to dryness to dissolve the solid substances and obtain a sample solution. Use a 6 mol / L hydrochloric acid solution to rinse the anion resin. After the rinsing solution drained completely, add the sample solution. Use a 6 mol / L hydrochloric acid solution as the eluent to elute the beryllium (Be), aluminum (Al), and part of the titanium (Ti) components, and evaporate the eluent to dryness to obtain solid substances.

[0082] A sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution were added to the solid substance obtained by evaporating the stripping solution. Under the heating condition of 100 °C, the solid was dissolved; then it was evaporated to dryness again. The sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution were repeatedly added, and under the heating condition of 100 °C, after dissolving the solid, it was evaporated to dryness. For the third time, a small amount of sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution were added. After dissolving the solid again, it was evaporated to dryness. The above steps were repeated 4 times, and the solid after evaporation was light amber and transparent.

[0083] 2 ml of AG 50W - X8H+ type cation resin with a mesh size of 200 - 400 (dispersed in 1.2 mol / L hydrochloric acid) was loaded into the chromatographic separation device described in Example 1, serving as the resin layer of the chromatographic separation device. The light amber transparent solid was dissolved in a sulfuric acid solution with a concentration of 0.0368 M and 1 - 2 drops of a 2% (volume percentage concentration) hydrogen peroxide solution to obtain a sample solution. The cation resin was rinsed successively with 4 mol / L, 1.2 mol / L hydrochloric acid solutions and 0.2 mol / L sulfuric acid solution. After the rinsing solution had drained completely, the sample solution was added. A 0.5 mol / L sulfuric acid solution was used to elute the titanium component. After the eluate had drained completely, a 1.2 mol / L hydrochloric acid solution was used to elute the beryllium (Be) component. After repeating the above cation exchange separation process 4 times, a small amount of the beryllium (Be) component eluate was taken, diluted with 5% nitric acid, and tested by an inductively coupled plasma - optical emission spectrometer (ICP - OES) to determine the contents of beryllium (Be) and aluminum (Al) components. The test results are listed in Table 2, and the ratio of the contents of beryllium (Be) and aluminum (Al) components is ~6 (HLL12). At this time, the beryllium (Be) element component was obtained.

[0084] Ammonia water was added to the beryllium (Be) element component to adjust the pH to between 8 - 8.5. The beryllium (Be) element still precipitated in the form of beryllium hydroxide (Be(OH)2). After centrifugation, the supernatant was discarded. After the precipitate was dispersed in ammonia water, it was washed repeatedly 2 - 3 times to remove trace impurities such as aluminum (Al) element. The precipitate was dried at 70 °C. The dried precipitate was transferred to a quartz crucible and placed in a muffle furnace. It was heated at a high temperature of 900 °C to oxidize Be(OH)2 to form BeO, which was used to prepare a sample target for accelerator mass spectrometry testing.

[0085] Example 3

[0086] The separation of beryllium (Be) component was carried out in a similar manner to Example 2, with the only difference being that the granite rock sample (sample name: HLL23) was crushed, and the remaining steps were exactly the same as in Step 2.

[0087] Example 4

[0088] After crushing the basalt rock sample (sample name: BP20), the rock components with a size of 125 - 250 μm were screened, and magnetic minerals were removed by magnetic separation. The non-magnetic mineral components were etched 4 - 5 times in a dilute hydrofluoric acid and nitric acid solution (the mass percentages of HF and HNO3 in the solution were both 5%) to disperse the multi-mineral adhesion particles, and then heavy liquid separation was carried out in methylene iodide to obtain the feldspar component. After washing and drying, pure feldspar minerals were obtained.

[0089] Take 1 g of pure feldspar minerals and dissolve them by heating in a 40% (mass percentage) hydrofluoric acid (HF) solution at 120°C. After the minerals were completely dissolved, the solvent was evaporated to dryness. The solid was dissolved in 5% (mass percentage) nitric acid, and inductively coupled plasma - optical emission spectrometer (ICP - OES) tests were carried out to obtain the main element contents in the solution.

[0090] Take 10 g of pure feldspar minerals and add a Be(NO3)2 standard solution (where 9 the Be concentration was 1000 μg / mL). 9 The Be standard solution was a national standard beryllium solution produced by the National Center for Iron and Steel Materials Testing, National Iron and Steel Research Institute of China (NCS), with the label GSBG 62002 - 90. The sample was dissolved by heating in a 40% hydrofluoric acid (HF) solution at 120°C. After the sample was completely dissolved, it was cooled to room temperature. During the cooling process of the solution, a large amount of precipitation was separated out. Centrifuge, and the supernatant was collected in a beaker; the precipitate was washed 4 - 5 times with a small amount of deionized water (18 MΩ), and the supernatants were combined into the beaker and evaporated to dryness.

[0091] Load 2 ml of AG - 1X8 anion resin with a mesh size of 200 - 400 (dispersed in 0.1 mol / L hydrochloric acid) into the chromatographic separation device described in Example 1 with a volume of 10 ml as the resin layer of the chromatographic separation device. Add a 6.0 mol / L hydrochloric acid solution to the above-mentioned solid evaporated to dryness to dissolve the solid substance and obtain a sample solution. The anion resin was rinsed with a 6 mol / L hydrochloric acid solution. After the rinsing solution drained completely, the sample solution was added. Using a 6 mol / L hydrochloric acid solution as the eluent, beryllium, aluminum, and part of the titanium components were eluted, and the eluent was evaporated to dryness to obtain a solid substance.

[0092] A sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of a 2% (volume percentage concentration) hydrogen peroxide solution were added to the solid material obtained by evaporating the washing solution to dryness. Under the heating condition of 120 °C, the solid was dissolved; then it was evaporated to dryness again. The addition of the sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of the 2% (volume percentage concentration) hydrogen peroxide solution was repeated, and under the heating condition of 120 °C, after dissolving the solid, it was evaporated to dryness. For the third time, the sulfuric acid solution with a concentration of 0.0368 M and 5 - 6 drops of the 2% (volume percentage concentration) hydrogen peroxide solution were added. After dissolving the solid again, it was evaporated to dryness. The above steps were repeated 6 times, and the solid after evaporation was light amber and transparent.

[0093] 2 ml of AG 50W - X8H+ type cation resin with a mesh size of 200 - 400 (dispersed in 1.2 mol / L hydrochloric acid) was loaded into the 10 - ml chromatographic separation device described in Example 1 as the resin layer of the chromatographic separation device. The light amber transparent solid was dissolved in a sulfuric acid solution with a concentration of 0.0368 M and 1 - 2 drops of a 2% (volume percentage concentration) hydrogen peroxide solution to obtain a sample solution. The cation resin was rinsed successively with 4 mol / L, 1.2 mol / L hydrochloric acid solutions and 0.2 mol / L sulfuric acid solution. After the rinsing solution had drained, the sample solution was added. A 0.5 mol / L sulfuric acid solution was used to elute the titanium component. After the eluate had drained, a 1.2 mol / L hydrochloric acid solution was used to elute the beryllium (Be) component. After repeating the above cation exchange separation process 7 times, a small amount of the beryllium (Be) component eluate was taken, diluted with 5% nitric acid, and tested with an inductively coupled plasma - atomic emission spectrometer (ICP - OES) to determine the contents of beryllium (Be) and aluminum (Al) components. The test results are listed in Table 2, and the content ratio of beryllium (Be) and aluminum (Al) components was ~18. At this time, the beryllium (Be) element component was obtained.

[0094] Ammonia water was added to the beryllium (Be) element component to adjust the pH to between 8 - 8.5. The beryllium element still precipitated in the form of beryllium hydroxide (Be(OH)2). After centrifugation, the supernatant was discarded. After the precipitate was dispersed in ammonia water, it was washed repeatedly 2 - 3 times to remove trace impurities such as aluminum (Al) element. The precipitate was dried at 70 °C. The dried precipitate was transferred to a quartz crucible and placed in a muffle furnace. It was heated at a high temperature of 900 °C to oxidize Be(OH)2 to form BeO, which was used to prepare a sample target for accelerator mass spectrometry testing.

[0095] Experimental Example

[0096] ICP - OES Test in Experimental Example 1

[0097] The main element contents in the feldspar used in Example 2, Example 3, and Example 4 were tested respectively, and the test results (wt%) are shown in Table 1. Among them, granite sample HLL12 is the result of Example 2, granite sample HLL23 is the result of Example 3, and basalt sample BP20 is the test result of Example 4.

[0098] Table 1

[0099]

[0100]

[0101] The element contents in the beryllium (Be) component eluate after 4 cation exchange separation processes in Example 2, the beryllium (Be) component eluate after 4 cation exchange separation processes in Example 3, and the beryllium (Be) component eluate after 7 cation exchange separation processes in Example 4 were tested respectively, and the test results (μg) are shown in Table 2. Among them, granite sample HLL12 is the result of Example 2, granite sample HLL23 is the result of Example 3, and basalt sample BP20 is the test result of Example 4.

[0102] Table 2

[0103] sample rock type feldspar type Al Be Fe Ti Mg HLL12 granite orthoclase 15 176 0 0 26 HLL23 granite orthoclase 30 195 0 0 30 BP20 basalt plagioclase 8 153 0 0 72

[0104] By comparing Table 1 and Table 2, it can be seen that after separation and purification, the contents of iron (Fe) and titanium (Ti) elements in the beryllium component are reduced below the detection limit, and the contents of aluminum (Al) and magnesium (Mg) elements are greatly reduced. At the same time, by comparing the contents of beryllium (Be) element and aluminum (Al) element in Table 2, it can be seen that after separation and purification, the ratio of the content of beryllium (Be) component to the content of aluminum (Al) component is much greater than 3, meeting the requirements for the purity of beryllium (Be) component in accelerator mass spectrometry analysis, indicating that the method of the present invention can separate beryllium element from minerals with high purity and high recovery efficiency.

[0105] The present invention has been described in detail above in combination with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent substitutions, modifications, or improvements can be made to the technical solutions and their implementation manners of the present invention, and these all fall within the scope of the present invention. The protection scope of the present invention is subject to the appended claims.

Claims

1. A chromatographic separation device, characterized in that: The chromatographic separation device comprises a tubular container, an ion exchange resin layer is arranged in the tubular container, the ion exchange resin layer is located in the middle and lower part of the tubular container, and a uniform layer is installed above and below the ion exchange resin layer; The distance between the uniform layer arranged above the ion exchange resin layer and the ion exchange resin layer is 2-3 mm, and the uniform layer arranged below the ion exchange resin layer is in contact with the ion exchange resin layer.

2. The chromatographic separation device according to claim 1, characterized in that: The uniform layer is a quartz sand filter; The quartz sand filter is provided with holes of uniform size and uniform distribution, and the diameter of the holes is The distance between adjacent holes is The ion exchange resin layer is a cation resin or anion resin.

3. The chromatographic separation device according to claim 2, characterized in that: The diameter of the hole is The distance between adjacent holes is 4. The chromatographic separation device according to claim 2, characterized in that: The volume of the ion exchange resin layer is 2 to 4 mL.

5. The chromatographic separation device according to claim 1, characterized in that: The distance between the uniform layer disposed above the ion exchange resin layer and the ion exchange resin layer was 2.5 mm.

6. The chromatographic separation device according to claim 1, characterized in that: A liquid injection port is arranged at the top of the tubular container, and the liquid injection port is funnel-shaped, so as to facilitate the injection of the liquid to be chromatographically separated into the tubular container. The portion where the liquid injection port contacts the tubular container has the same diameter as the tubular container, and the diameter gradually increases as it is farther from the tubular container.

Images