Method for rapidly determining types and contents of elements in molybdenum and vanadium tailings

Abstract

The invention discloses a method for rapidly determining types and contents of elements in molybdenum and vanadium tailings, which is specifically implemented according to the following steps: crushing and grinding the molybdenum and vanadium tailings to obtain a powdery material; dividing the powdery material to obtain a sample, and drying the sample to obtain a to-be-detected sample A; processing the to-be-tested sample A into a to-be-tested sample B for energy spectrum analysis; energy disperse spectroscopy analysis parameters are set, the to-be-tested sample B is analyzed through an energy disperse spectroscopy, and the types of main elements are determined; processing the to-be-detected sample A into a to-be-detected sample C for GDMS analysis; setting measurement parameters of the GDMS spectrometer, and measuring the sample C to be measured by the GDMS spectrometer. The method solves the problems of low accuracy and extremely high detection cost in determination of the types and contents of the elements in the molybdenum and vanadium tailings in the prior art.

Description

Technical Field

[0001] The invention belongs to the technical field of ore sample testing methods, and in particular relates to a method for quickly determining the types and contents of elements in molybdenum and vanadium tailings. Background Art

[0002] When analyzing the types and magnitude distribution of elements in molybdenum mine tailings and vanadium mine tailings, it is necessary to analyze and determine the content of precious metal elements. The content of precious metals (such as Au, Pt, Ir, Os, Rh, Ru, Pd, Ag, Ge) in molybdenum mine tailings, vanadium mine tailings and geological mines is only one billionth, which is a trace level (ppb level, one billionth). If conventional detection and analysis (ppm level, one millionth) is used, it is difficult to characterize. Therefore, it is necessary to establish a semi-quantitative analysis method for the detection of precious metal elements in tailings. The existing technology for the determination of element types and their contents in molybdenum and vanadium tailings has a long cycle, low accuracy, and extremely high detection costs.

[0003] GDMS (glow discharge mass spectrometer) technology is generally regarded as the ultimate tool for the determination of impurities in solid materials. It can analyze high-purity semiconductor materials, alloys (refractory metals such as Ni, Ti, Ta, Re, Nb), sputtering targets, advanced ceramic materials (TiB2, AlN, Al2O3, etc.), high-end metals and rare earth materials, optical / laser crystals, inorganic oxides, special coatings, and biomedical materials. Compared with other detection instruments such as ICP, ICP-MS, and AAS, GDMS is a solid injection, which can meet the analysis of rod-shaped or block-shaped solid samples of various sizes without the need to process the sample into a solution first. Using the GDMS detection method, the sample does not require a complex chemical reagent treatment process, which overcomes the limitations of traditional analysis methods and can directly perform solid injection analysis (including blocks, rods, chips, powders, particles, etc.), while also having the advantage of determining trace and micro impurities in conductors, semiconductors, and non-conductive materials. In addition, the glow discharge mass spectrometer uses built-in calibration parameters (RSF) to operate, thereby providing semi-quantitative measurement results (the ratio coefficient between the semi-quantitative results and the true value is approximately less than 2); the measurement process does not require reference materials or certified reference materials (CRMs) that strictly match the matrix. GDMS technology installs the sample to be tested as a cathode into the plasma discharge chamber, and uses the ions generated by the ionization of an inert gas (argon) to impact the sample surface to cause sputtering. The atoms sputtered from the sample surface are ionized and focused into an ion beam by the mass analyzer, and then collected and detected by the mass spectrometer. During quantitative analysis, the relative sensitivity factor is obtained by independently measuring the standard sample under the same analytical conditions, ion source structure and test conditions as the sample to be tested, and the mass fraction of each element is calculated using the relative sensitivity factor. The calculation of the GDMS relative sensitivity factor requires the prior knowledge of the main substance of the sample to be tested, so as to calculate the GDMS relative sensitivity factor based on the content of the main substance, and further calculate the content of each element in the sample to be tested. Therefore, determining the type of the main element of the sample to be tested becomes a key factor affecting the accurate determination of GDMS.

[0004] The energy spectrometer is a micro-area component analyzer (X-ray analysis) dedicated to electron microscopes. It is a new generation of silicon drift detector (SDD) equipped with large-area crystals and low-noise electronic components. The effective crystal area is 40mm 2 , the analysis speed and detection sensitivity have been greatly improved, and sufficient X-ray counts can be quickly collected to perform surface analysis on elements with a content as low as 0.1wt%; it can work under weaker electron beam conditions, greatly reducing sample damage and contamination; it can perform surface analysis under lower beam conditions and improve image quality. The spectrometer loads 8 to 12 samples on the sample stage at a time. Therefore, the spectrometer can quickly determine the main elements and their semi-quantitative values ​​in the sample to be tested.

[0005] Using a glow discharge mass spectrometer or an energy spectrometer alone cannot accurately measure the types and contents of elements in molybdenum and vanadium tailings. The error is large and it is impossible to accurately and quickly determine the types and contents of elements in molybdenum and vanadium tailings. Summary of the invention

[0006] The purpose of the present invention is to provide a method for quickly determining the types and contents of elements in molybdenum and vanadium tailings, thereby solving the problems of low accuracy and extremely high detection cost in the existing determination of the types and contents of elements in molybdenum and vanadium tailings.

[0007] The technical solution adopted by the present invention is a method for quickly determining the types and contents of elements in molybdenum and vanadium tailings, which is specifically implemented according to the following steps: Step 1, crushing and grinding molybdenum and vanadium tailings to obtain powdered materials; Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 6, setting the measurement parameters of the GDMS spectrometer, and measuring the sample C with the GDMS spectrometer.

[0008] The present invention is also characterized in that: Step 2 uses the cone quartering method to perform subdivision sampling. The sample is placed in a drying oven at a drying temperature of 105°C~110°C±5°C for 1h~2h. After drying, it is placed in a dryer to cool to room temperature to obtain sample A to be tested.

[0009] Step 3 is specifically as follows: Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0010] Step 4 is specifically as follows; The energy spectrometer analysis parameters are set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 20KeV~50KeV, beam current 100pA~500pA, working distance 7mm~10mm, magnification 10kx~20kx, count rate cps3500~4600, and acquisition time 20s~40s.

[0011] The spectrometer analyzes the sample B to be tested by breaking the vacuum; placing the sample B to be tested in the sample chamber; evacuating the chamber; turning on the SEM electron beam control, and after focusing, raising the sample stage to the working distance; and selecting the acceleration voltage and beam current for analysis.

[0012] Step 5 is specifically as follows; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high-purity carbon powder; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and maintain pressure to obtain a sample C to be tested; Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0013] Step 6 sets the measurement parameters including isotope, resolution, and integration time. The isotope, resolution, and integration time for molybdenum and vanadium tailings sample detection are determined through a large number of experiments.

[0014] Step 6 is specifically as follows: Step 6.1, firstly, pre-sputtering is performed, and the pre-sputtering time is 5min~15min; Step 6.2, adjust the sputtering conditions of the glow discharge ion source to the conditions required for analysis; adjust the instrument parameters until the medium resolution reaches 3000-4000 and the high resolution reaches 9000-10000; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; In step 6.4, the average of the three measurement data is taken as the measurement result, and the precision meets the requirements of the allowable relative deviation.

[0015] Step 5.6: The tablet press applies a pressure of 700-1200 MPa and the holding time is 20-90 s.

[0016] Step 1: crushing the molybdenum and vanadium tailings with a crusher and grinding them with a ball mill to obtain a powdery material, wherein the particle size of the powdery material is not greater than 100 μm.

[0017] The beneficial effects of the present invention are as follows: the present invention directly injects solid samples, satisfies the analysis of the types and contents of elements in molybdenum and vanadium tailings, and realizes the simultaneous determination of more than 70 types and contents of elements in one sample, and the detection lower limit can reach ppb level (10 -9), to analyze trace or ultra-trace valuable metals and precious metals in tailings, realize resource recycling, effectively reduce waste, and turn waste into treasure. The detection time for determining and detecting the same amount of elements is shortened from 3 to 5 days to 30 minutes, which greatly improves work efficiency, can quickly provide detection data, and provide a large amount of data for enterprises and scientific research. It has the advantages of simple operation, high efficiency, good effect, and low pollution. It can be used for the detection of element types and their contents in molybdenum and vanadium tailings, and realize the recovery and reuse of valuable metals. The present invention has broad application prospects and can meet the requirements of mining enterprises, scientific research and production for the determination of element types and content detection in molybdenum and vanadium tailings. DETAILED DESCRIPTION

[0018] The present invention is described in detail below in conjunction with specific implementation modes.

[0019] Example 1 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, crushing and grinding molybdenum and vanadium tailings to obtain powdered materials; Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 6, setting the measurement parameters of the GDMS spectrometer, and measuring the sample C with the GDMS spectrometer.

[0020] Example 2 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, crushing and grinding molybdenum and vanadium tailings to obtain powdered materials; The molybdenum and vanadium tailings are crushed by a crusher and ground by a ball mill to obtain a powder material, wherein the particle size of the powder material is not greater than 100 μm; Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; The cone quartering method is used for sampling. The sample is placed in a drying oven at a drying temperature of 105°C~110°C±5°C for 1h~2h. After drying, it is placed in a dryer and cooled to room temperature to obtain sample A to be tested. The moisture is removed by drying and the flotation agent residue in the mineral material is effectively removed, thereby effectively improving the measurement accuracy.

[0021] Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0022] Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high-purity carbon powder; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and maintain pressure to obtain a sample C to be tested; Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0023] Step 6, setting the measurement parameters of the GDMS spectrometer, the GDMS spectrometer measures the sample C to be measured; setting the measurement parameters including isotope, resolution, and integration time, and determining the isotope, resolution, and integration time for the detection of molybdenum and vanadium tailings samples through a large number of experiments.

[0024] Example 3 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, crushing and grinding molybdenum and vanadium tailings to obtain powdered materials; The molybdenum and vanadium tailings are crushed by a crusher and ground by a ball mill to obtain a powder material, wherein the particle size of the powder material is not greater than 100 μm; Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; The cone quartering method is used for sampling. The sample is placed in a drying oven at a drying temperature of 105°C~110°C±5°C for 1h~2h. After drying, it is placed in a dryer and cooled to room temperature to obtain sample A to be tested. The moisture is removed by drying and the flotation agent residue in the mineral material is effectively removed, thereby effectively improving the measurement accuracy.

[0025] Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0026] The conductivity of the sample A to be tested is poor, but it has no effect on the energy spectrum analysis. If the sample is plated, it will interfere with the energy spectrum analysis results, so that the types of elements contained in the sample A to be tested cannot be accurately determined and qualitative and semi-quantitative analysis cannot be performed on it. The present invention uses a conductive tape adhered to the aluminum sample stage to eliminate the interference caused by the coating process.

[0027] Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; The energy spectrometer analysis parameters are set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 20KeV~50KeV, beam current 100pA~500pA, working distance 7mm~10mm, magnification 10kx~20kx, count rate cps3500~4600, and acquisition time 20s~40s.

[0028] The energy spectrometer adopts EDS energy spectrometer, which analyzes the sample B to be tested by breaking the vacuum; placing the sample B to be tested into the sample chamber; evacuating the vacuum; turning on the SEM electron beam control, and after focusing, raising the sample stage to the working distance; and selecting the acceleration voltage and beam current for analysis.

[0029] The EDS spectrometer is used in conjunction with a scanning electron microscope or a transmission electron microscope. The electron beam is used to bombard the sample surface in a vacuum chamber to excite the material to emit characteristic x-rays. According to the wavelength of the characteristic x-rays, the elements of BU in the periodic table are qualitatively and semi-quantitatively analyzed. The EDS spectrometer provides qualitative or semi-quantitative component element analysis of the micro-area of ​​the sample surface, as well as Point&ID, Line Scan, and Mapping analysis of specific areas. The present invention selects the Point&ID point scanning analysis method through experiments, which is more suitable for the detection and analysis of molybdenum and vanadium tailings samples. The parameter determination is obtained through a large number of single-factor optimization experiments.

[0030] Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; the purity of ultra-high purity carbon powder is 99.9995%~99.9999%; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high purity carbon powder; the high-purity tantalum sheet mold is a high-purity tantalum sheet with a purity greater than or equal to 99.99%; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and pressure holding to obtain the sample C to be tested; the pressure applied by the tablet press is 700 MPa to 1200 MPa, and the pressure holding time is 20 s to 90 s.

[0031] Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0032] The use of tantalum sheets as auxiliary conductive materials effectively solves the conductivity problem of molybdenum and vanadium tailings during GDMS detection, further improving the accuracy and stability of GDMS analysis and detection.

[0033] Step 6, setting the measurement parameters of the GDMS spectrometer, the GDMS spectrometer measures the sample C to be measured; setting the measurement parameters including isotope, resolution, and integration time, and determining the isotope, resolution, and integration time for the detection of molybdenum and vanadium tailings samples through a large number of experiments.

[0034] Set the measurement isotope and resolution as shown in Table 1; Table 1 shows the isotope and resolution of the determination

[0035] Set the integration time as shown in Table 2.

[0036] Table 2 shows the integration time

[0037] Step 6.1, first pre-sputtering is performed, and the pre-sputtering time is 5min~15min; pre-sputtering effectively reduces the interference of surface residues on detection and analysis, and reduces inaccurate measurement results caused by contamination.

[0038] Step 6.2, adjust the sputtering conditions of the glow discharge ion source to the conditions required for analysis; adjust the instrument parameters until the medium resolution reaches 3000-4000 and the high resolution reaches 9000-10000; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; In step 6.4, the average of the three measurement data is taken as the measurement result, and the precision meets the requirements of the allowable relative deviation.

[0039] Example 4 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, select 2 batches of molybdenum tailings (molybdenum tailings 1# and molybdenum tailings 2#), crush them with a crusher, and grind them with a ball mill to obtain a powder material with a particle size of 75 μm.

[0040] Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; The cone quartering method is used to reduce the sample to 50g. The sample is placed in a drying oven at a drying temperature of 105℃±5℃ for 1h. After drying, it is placed in a desiccator to cool to room temperature to obtain sample A to be tested.

[0041] Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0042] Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; The energy spectrometer analysis parameters were set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 20KeV, beam current 500pA, working distance 10mm, magnification 10kx, count rate cps3500, and acquisition time 20s.

[0043] The spectrometer used was Oxford ULTIM MAX40 spectrometer. The Oxford ULTIM MAX40 spectrometer analyzed the sample B by breaking the vacuum; placing the sample B in the sample chamber; evacuating the chamber; turning on the SEM electron beam control, and after focusing, raising the sample stage to the working distance; selecting the acceleration voltage and beam current to analyze the sample B. The test results are shown in Table 3.

[0044] Table 3 is the energy spectrum test results of molybdenum tailings obtained in Example 4 of the present invention

[0045] The main element determined by the energy spectrum of the detection results of Example 4 is: Si, and the other main elements are O, Mg, Al, K, Fe, and Te.

[0046] Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; the purity of the ultra-high purity carbon powder is 99.9995%; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high purity carbon powder; the high-purity tantalum sheet mold is a high-purity tantalum sheet with a purity of 99.9995%; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and hold pressure to obtain the sample C to be tested; the pressure applied by the tablet press is 700 MPa, and the holding time is 20 s.

[0047] Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0048] Step 6, setting the measurement parameters of the GDMS spectrometer, the GDMS spectrometer measures the sample C to be measured; setting the measurement parameters including isotope, resolution, and integration time, and determining the isotope, resolution, and integration time for the molybdenum tailings sample detection through a large number of experiments.

[0049] Step 6.1, firstly, pre-sputtering is performed, and the pre-sputtering time is 5 minutes; Step 6.2, adjust the glow discharge ion source sputtering conditions to the conditions required for analysis; adjust the instrument parameters until the medium resolution reaches 3000 and the high resolution reaches 9000; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; In step 6.4, the average of the three measurement data is taken as the measurement result, and the precision meets the requirement that the relative deviation RSD is less than or equal to 10%.

[0050] The results of element types and contents in molybdenum tailings are shown in Table 4.

[0051] Table 4 shows the results of determination of element types and contents in molybdenum tailings

[0052] Example 5 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, select 2 batches of vanadium tailings (vanadium tailings 1# and vanadium tailings 2#), crush them with a crusher, and grind them with a ball mill to obtain a powder material with a particle size of 100 μm.

[0053] Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; The cone quartering method is used to reduce the sample to 80g. The sample is placed in a drying oven at a drying temperature of 110℃±5℃ for 1.5h. After drying, it is placed in a desiccator to cool to room temperature to obtain sample A to be tested.

[0054] Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0055] Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; The energy spectrometer analysis parameters were set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 50KeV, beam current 100pA, working distance 7mm, magnification 20kx, count rate cps4600, and acquisition time 40s.

[0056] The spectrometer uses Oxford ULTIM MAX40 spectrometer. Oxford ULTIM MAX40 spectrometer analyzes the sample B to be tested by breaking the vacuum; placing the sample B to be tested in the sample chamber; evacuating the vacuum; turning on the SEM electron beam control, after focusing, raising the sample stage to the working distance; selecting the acceleration voltage and beam current to analyze the sample B to be tested. The test results are shown in Table 5. Table 5 is the energy spectrum test results of vanadium tailings obtained in Example 5 of the present invention

[0057] In Example 5, the main element is determined to be Si, and the other main elements are Ba, Ca, Al, S, K, and V. Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; the purity of the ultra-high purity carbon powder is 99.9995%; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high purity carbon powder; the high-purity tantalum sheet mold is a high-purity tantalum sheet with a purity greater than or equal to 99.9995%; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and pressure holding to obtain the sample C to be tested; the pressure applied by the tablet press is 1200 MPa, and the pressure holding time is 90 s.

[0058] Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0059] Step 6, setting the measurement parameters of the GDMS spectrometer, and the GDMS spectrometer measures the sample C to be measured; setting the measurement parameters including isotope, resolution, and integration time, and determining the isotope, resolution, and integration time for the detection of vanadium tailings samples through a large number of experiments.

[0060] Step 6.1, firstly pre-sputtering is performed, and the pre-sputtering time is 15 minutes; Step 6.2, adjust the sputtering conditions of the glow discharge ion source to the conditions required for analysis; adjust the instrument parameters until the medium resolution reaches 4000 and the high resolution reaches 10000; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; Step 6.4, take the average of the three measurement data as the measurement result, the precision meets the requirement that the relative deviation RSD is less than or equal to 10%. The determination results of the element types and their contents in the vanadium tailings are shown in Table 6.

[0061] Table 6 shows the results of element types and contents in vanadium tailings

[0062] Example 6 The method for rapidly determining the content of trace elements in molybdenum and vanadium tailings provided by the present invention is specifically implemented according to the following steps: Step 1, select 2 batches of vanadium tailings (vanadium tailings 3# and vanadium tailings 4#), crush them with a crusher, and grind them with a ball mill to obtain a powder material with a particle size of 85 μm.

[0063] Step 2, reducing the powdered material to obtain 100 g of sample, and drying the sample to obtain sample A to be tested; The cone quartering method is used for sampling. The sample is placed in a drying oven at a drying temperature of 108°C ± 5°C for 2 hours. After drying, it is placed in a desiccator to cool to room temperature to obtain sample A to be tested.

[0064] Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

[0065] Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; The energy spectrometer analysis parameters were set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 30KeV, beam current 300pA, working distance 9mm, magnification 15kx, count rate cps4100, and acquisition time 30s.

[0066] The spectrometer used was Oxford ULTIM MAX40 spectrometer. The Oxford ULTIM MAX40 spectrometer analyzed the sample B by breaking the vacuum; placing the sample B in the sample chamber; evacuating the chamber; turning on the SEM electron beam control, and after focusing, raising the sample stage to the working distance; selecting the acceleration voltage and beam current to analyze the sample B. The test results are shown in Table 7.

[0067] Table 7 is the energy spectrum test results of vanadium tailings obtained in Example 6 of the present invention

[0068] In Example 6, the main element is determined to be Si, and the other main elements are O, Na, Mg, Al, K, Ca, V, and Fe.

[0069] Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; the purity of the ultra-high purity carbon powder is 99.9999%; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high purity carbon powder; the high-purity tantalum sheet mold is a high-purity tantalum sheet with a purity of 99.995%; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and pressure holding to obtain the sample C to be tested; the pressure applied by the tablet press is 900 MPa, and the pressure holding time is 60 s.

[0070] Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

[0071] Step 6, setting the measurement parameters of the GDMS spectrometer, and the GDMS spectrometer measures the sample C to be measured; setting the measurement parameters including isotope, resolution, and integration time, and determining the isotope, resolution, and integration time for the detection of vanadium tailings samples through a large number of experiments.

[0072] Step 6.1, firstly, pre-sputtering is performed, and the pre-sputtering time is 10 min; Step 6.2, adjust the glow discharge ion source sputtering conditions to the conditions required for analysis; adjust the instrument parameters until the medium resolution reaches 3500 and the high resolution reaches 9500; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; In step 6.4, the average of the three measurement data is taken as the measurement result, and the precision meets the requirement that the relative deviation RSD is less than or equal to 10%.

[0073] The results of determination of element types and contents in vanadium tailings are shown in Table 8.

[0074] Table 8 is the results of determination of element types and contents in vanadium tailings

[0075] The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings of the present invention can rapidly determine the contents of more than 70 elements within 30 minutes, with a simple process flow and low detection cost. The present invention directly uses solid sampling, and there is no need to first process the sample into a solution. The sample processing will not generate waste gas and waste liquid, and is environmentally friendly; almost no chemical reagents are used, which greatly reduces the environmental pollution caused by the use of chemical reagents and the cost of treating hazardous waste liquids. The energy spectrum and GDMS spectrometer are used in combination to achieve rapid determination of the types of main elements in molybdenum and vanadium tailings, thereby accurately setting the parameters of the GDMS spectrum detection method, and further achieving rapid determination of the types and contents of elements in molybdenum and vanadium tailings, providing accurate values ​​for the calculation and analysis of the GDMS relative sensitivity factor, thereby rapidly determining the types and contents of elements in molybdenum and vanadium tailings, and solving the problems of long determination cycle, low accuracy, and extremely high detection cost for the types and contents of elements in molybdenum and vanadium tailings. The detection lower limit of the present invention reaches the ppb level (10 -9 ), the determination range reaches 0.000001%~1%, and the trace or ultra-trace valuable metals and precious metals in molybdenum and vanadium tailings are analyzed. The method of the present invention. The precision of the determination result of the method of the present invention can reach RSD less than 10%, which fully meets the analysis requirements and realizes the requirements of large-scale detection and analysis.

Claims

1. A method for quickly determining the types and contents of elements in molybdenum and vanadium tailings, characterized in that: Follow the steps below to implement it: Step 1, crushing and grinding molybdenum and vanadium tailings to obtain powdered materials; Step 2, reducing the powdered material to obtain a sample, and drying the sample to obtain a sample A to be tested; Step 3, processing the sample A to be tested into the sample B to be tested for energy spectrum analysis; Step 4, setting the energy spectrometer analysis parameters, using the energy spectrometer to analyze the sample B to be tested, and determining the main element types; Step 5, processing the sample A to be tested into the sample C to be tested for GDMS analysis; Step 6, setting the measurement parameters of the GDMS spectrometer, and measuring the sample C with the GDMS spectrometer.

2. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 1, characterized in that: Step 2 uses the cone quartering method to perform subdivision sampling. The sample is placed in a drying oven at a drying temperature of 105°C~110°C±5°C for 1h~2h. After drying, it is placed in a dryer to cool to room temperature to obtain sample A to be tested.

3. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 2, characterized in that: Step 3 is specifically as follows: Step 3.1, take the sample A to be tested and stick it on the conductive tape on the aluminum sample table; Step 3.2, press lightly with a sample spoon; Step 3.3, use compressed air to blow off the surface of the sample A to be tested, and obtain the sample B to be tested for energy spectrum analysis.

4. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 3, characterized in that: Step 4 is specifically as follows; The energy spectrometer analysis parameters are set as follows: select ET detector, select point scanning analysis mode, acceleration voltage 20KeV~50KeV, beam current 100pA~500pA, working distance 7mm~10mm, magnification 10kx~20kx, count rate cps3500~4600, and acquisition time 20s~40s.

5. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 4, characterized in that: The energy spectrometer analyzes the sample B to be tested by breaking the vacuum; placing the sample B to be tested into the sample chamber; and evacuating the chamber; Turn on the SEM electron beam control, focus, and raise the sample stage to the working distance; select the accelerating voltage and beam current for analysis.

6. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 5, characterized in that: Step 5 is specifically as follows; Step 5.1, placing weighing paper at the bottom of the tablet press mold; Step 5.2, take ultra-high purity carbon powder and spread it on the bottom of the tablet press mold; Step 5.3, placing a high-purity tantalum sheet mold on the ultra-high-purity carbon powder; Step 5.4, taking the sample A to be tested and placing it in a high-purity tantalum sheet mold; Step 5.5, place weighing paper on the tablet press mold; Step 5.6, the tablet press applies pressure to perform compression and maintain pressure to obtain a sample C to be tested; Step 5.7, take out the pressed sample C, remove the weighing papers on both sides, and place it in a pollution-free environment for later use.

7. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 6, characterized in that: Step 6 sets the measurement parameters including isotope, resolution, and integration time. The isotope, resolution, and integration time for molybdenum and vanadium tailings sample detection are determined through a large number of experiments.

8. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 7, characterized in that: Step 6 is specifically as follows: Step 6.1, firstly, pre-sputtering is performed, and the pre-sputtering time is 5min~15min; Step 6.2, adjusting the sputtering conditions of the glow discharge ion source to the conditions required for analysis; Adjust the instrument parameters until the medium resolution reaches 3000-4000 and the high resolution reaches 9000-10000; Step 6.3, GDMS determines that the sample C to be tested is three measurement data collected continuously at the same sputtering point; In step 6.4, the average of the three measurement data is taken as the measurement result, and the precision meets the requirements of the allowable relative deviation.

9. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 8, characterized in that: Step 5.6: The tablet press applies a pressure of 700-1200 MPa and the holding time is 20-90 s.

10. The method for rapidly determining the types and contents of elements in molybdenum and vanadium tailings according to claim 9, characterized in that: Step 1: crushing the molybdenum and vanadium tailings with a crusher and grinding them with a ball mill to obtain a powdery material, wherein the particle size of the powdery material is not greater than 100 μm.

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