Phosphorite heavy metal detection method based on superfine sample and miniaturization experiment
Through ultra-fine samples and miniaturization experimental technology, the problem of high cost and long time for heavy metals in phosphate is solved, and low-cost and fast detection results are achieved.
Patent Information
- Application Number
- CN202510468753.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-07-11
AI Technical Summary
In the prior art, the detection method for heavy metals of phosphate ore has problems such as large sample size, large reagent usage, and long digestion time, resulting in high production costs and long detection time.
Ultrafine samples and miniaturization experimental technology are used to reduce the reagent dosage and digestion time by making phosphate ore into ultrafine powder samples and miniaturization detection using inductively coupled plasma spectroscopy and mass spectrometer.
It has achieved low-cost and short-term inspection of heavy metals for large-scale phosphate ore, reduced the amount of chemical reagents and pollutant treatment, and improved the detection efficiency and accuracy.
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Figure CN120293952A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of mineral analysis, and particularly to a method for detecting heavy metals in phosphate rock based on ultrafine samples and miniaturized experiments. Background Art
[0002] Phosphate rock is an important chemical raw material, widely used in industries such as phosphate fertilizers, medicine, food, ceramics, and national defense. With the development of the national economy, the demand for phosphate rock is increasing. To better utilize phosphate rock resources, it is imperative to accurately and rapidly determine the heavy metal content in phosphate rock.
[0003] In existing methods for detecting heavy metals in phosphate rock, the phosphate rock sample is preliminarily crushed and then dissolved in aqua regia, and then compared with the standard curves of various elements for determination. Although this traditional method can achieve the detection of heavy metals in phosphate rock, it has the disadvantages of large sample weighing, large reagent consumption, and long digestion time, resulting in high production costs and long detection time. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for detecting heavy metals in phosphate rock based on ultrafine samples and miniaturized experiments, which solves the problems of high production costs and long detection time in the traditional method for detecting heavy metal content in phosphate rock.
[0005] To achieve the above purpose, the present invention provides a method for detecting heavy metals in phosphate rock based on ultrafine samples and miniaturized experiments, including the following steps:
[0006] Make the phosphate rock into a sample, and take a certain amount to make an ultrafine powder sample;
[0007] Adopt miniaturized technology to completely digest the ultrafine powder sample;
[0008] After complete digestion, use an inductively coupled plasma spectrometer and mass spectrometer to determine the heavy metal content in the phosphate rock.
[0009] Among them, making the phosphate rock into a sample and taking a certain amount to make an ultrafine powder sample, the specific steps include:
[0010] Dry the phosphate rock at 105 °C for more than 2 hours to obtain a preliminary sample with a water content of less than 0.5%;
[0011] Gradually grind the preliminary sample through a jaw crusher, a pair-roll crusher, and a vibration mill to make a dry phosphate rock sample;
[0012] Adopt the quartering method to reduce the dry phosphate rock sample to 10 g to obtain a sample.
[0013] Among them, in gradually grinding the preliminary sample through a jaw crusher, a pair-roll crusher, and a vibration mill to make a dry phosphate rock sample, the particle size of the dry phosphate rock sample is 120 mesh.
[0014] Among them, the phosphate rock is made into a sample, and a certain amount is taken to make an ultrafine powder sample. The specific steps include:
[0015] Weigh 7.00 ± 0.02 g of the sample and put it into the grinding tray of a high-speed planetary ultrafine grinding machine. Among them, add 20 tungsten carbide balls of 5 mm and 30 tungsten carbide balls of 3 mm to each grinding tray in a tungsten carbide tank, tighten the tank lid, rotate at a speed of 1000 r / min for 4.0 min to obtain an ultrafine powder sample.
[0016] Among them, when the phosphate rock is made into a sample and a certain amount is taken to make an ultrafine powder sample:
[0017] The fineness of the ultrafine powder sample is on average below 10 μm.
[0018] Among them, using the miniaturization technology, the ultrafine powder sample is completely digested. The specific steps include:
[0019] Weigh 0.1 g of the ultrafine powder sample and put it into a 300 ml tall beaker, add 10 ml of water, 3 ml of hydrochloric acid and 1 ml of nitric acid, cover it with a watch glass, boil it on an electric furnace, then place it on a hot plate to keep it gently boiling for 10 min, take it off and transfer it to a 100 ml volumetric flask, and make the volume constant with primary distilled water. Then pour the liquid in the volumetric flask into a 50 ml beaker with a double-layer slow quantitative filter paper for filtration.
[0020] Among them, when using the miniaturization technology to completely digest the ultrafine powder sample:
[0021] The water is primary distilled water, the hydrochloric acid is GR grade concentrated hydrochloric acid, and the nitric acid is GR grade concentrated nitric acid.
[0022] Among them, after complete digestion, an inductively coupled plasma spectrometer and mass spectrometer are used to determine the heavy metal content in the phosphate rock. The specific steps are as follows:
[0023] Take the heavy metal element standard solution, and prepare solutions with concentrations of 0, 0.25, 2.5, and 5.0 mg / L respectively. Then, take 0, 1, 10, and 20 mL of the above solutions and place them in a 250 mL volumetric flask, and make the volume constant with 10% hydrochloric acid and distilled water to make the pH value of the solution 6.0. Prepare a standard series solution. Then put the standard series solution into the inductively coupled plasma spectrometer and mass spectrometer in turn to construct a heavy metal element standard curve; then detect the ultrafine powder sample, and calculate the content of heavy metal elements in the sample according to the detection results and the standard curve.
[0024] Compared with the prior art, the present invention has the following advantages: By superfine processing the phosphate rock sample and combining with microscale experimental techniques, the particle size of the phosphate rock is reduced (large particles disappear) and becomes more uniform, the specific surface area increases, the sample is more easily digested, the dosage of hazardous waste chemical reagents is greatly reduced, costs are saved, energy consumption is reduced, and the digestion time is shortened. While directly reducing the usage amount of chemical drugs, it also indirectly reduces the treatment amount of chemical experimental pollutants (three wastes), reduces the exposure amount of experimental personnel in a toxic chemical environment, achieves the purpose of obtaining a large amount of experimental data with extremely small amounts of reagents in microscale chemical experiments, enables a large number of experiments to be completed at low cost and in a short time. The development of superfine sample preparation and microscale analysis techniques is an important way for the analysis laboratory to save energy, reduce emissions (chemical pollutants), and achieve "environmental friendliness". It is applicable to phosphate rocks from different origins. A large number of statistical results show that there is no significant difference between the experimental results and the traditional method, and it has broad promotion and utilization value. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art.
[0026] Figure 1 It is a step diagram of the method for detecting heavy metals in phosphate rock based on superfine samples and microscale experiments of the present invention.
[0027] Figure 2 It is a flowchart of the method for detecting heavy metals in phosphate rock based on superfine samples and microscale experiments of the present invention.
[0028] Figure 3 It is the standard working curve graph of chromium element constructed in the embodiment. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0029] The following will describe in detail the embodiments of the present invention. The examples of the embodiments are shown in the drawings. The embodiments described below with reference to the drawings are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.
[0030] Please refer to Figure 1 and Figure 2 , wherein, Figure 1 It is a step diagram of the method for detecting heavy metals in phosphate rock based on superfine samples and microscale experiments of the present invention. Figure 2 It is a flowchart of the method for detecting heavy metals in phosphate rock based on superfine samples and microscale experiments of the present invention.
[0031] The present invention provides a method for detecting heavy metals in phosphate rock based on superfine samples and microscale experiments, including the following steps:
[0032] S101: Make the phosphate rock into a sample, and take a certain amount to make a superfine powder sample;
[0033] Specifically, the phosphate rock sample is dried at 105 °C for more than 2 hours to obtain a preliminary sample with a water content of less than 0.5%. Subsequently, it is ground step by step through a jaw crusher, a pair-roll crusher, and a vibrating mill to produce a dry phosphate rock sample that all passes through 120 mesh (125 um). Using the quartering method or a sample splitter, the dry phosphate rock sample is reduced to about 10 g, and then 7.00 ± 0.02 g of the sample is weighed and placed in the grinding tray of a high-speed planetary ultra-fine grinding machine (this model has multiple grinding trays). 20 tungsten carbide balls of 5 mm and 30 tungsten carbide balls of 3 mm are added to each grinding tray in a tungsten carbide tank (the steel balls and the tank are provided by the machine). The tank lid is tightened, the rotation speed is 1000 r / min, and the action time is 4.0 min to obtain an ultra-fine powder sample. At this moment, the fineness of the ultra-fine powder sample can reach below 10 um on average (about 800 mesh, laser particle size analyzer), and it is taken out and placed in a No. 5 self-sealing bag for standby.
[0034] S102: Using miniaturization technology, completely digest the ultra-fine powder sample;
[0035] Specifically, weigh 0.1000 g of the ultra-fine sample and put it into a 300 ml tall-form beaker. Add 10 ml of water (primary distilled water), 3 ml of hydrochloric acid (concentrated, GR grade), and 1 ml of nitric acid (concentrated, GR grade). Cover with a watch glass, boil on an electric furnace, and keep slightly boiling on a hot plate for 10 min. Then transfer it to a 100 ml volumetric flask and make up the volume (primary distilled water). The liquid in the volumetric flask is poured into a 50 ml beaker with a double-layer slow quantitative filter paper for dry filtration. When there is 30 to 40 ml of the filtrate in the beaker, it is measured by an inductively coupled plasma optical emission spectrometry and mass spectrometry (ICP-AES / MS). It realizes 1 / 10 of the traditional sample weighing amount, 1 / 5 of the traditional aqua regia usage amount, and 1 / 3 of the traditional digestion time.
[0036] S103: After complete digestion, use an inductively coupled plasma optical emission spectrometry and mass spectrometry to measure the heavy metal content in the phosphate rock.
[0037] Specifically, when using an inductively coupled plasma optical emission spectrometry and mass spectrometry (ICP-AES / MS), a mixed standard solution is prepared by proportioning with a heavy metal national standard substance (liquid). For example, when measuring the content of 9 heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) in phosphate rock, it is measured according to the instrument operation procedures, and the values of 9 heavy metal elements in the phosphate rock can be obtained within 3 min. The selection of the standard substance is shown in Table 1.
[0038] Table 1 Selection of Standard Substances
[0039] Reference Material (Element) Reference Material Source Arsenic 1 mg / ml GSB 04-1714-2004 National Institute of Nonferrous Metals and Electronic Materials Lead 1 mg / ml GBW(E)3779 Beijing North Weiye Metrology Technology Research Institute Chromium 1 mg / ml GSB 04-1728-2004 National Institute of Nonferrous Metals and Electronic Materials Cadmium 1 mg / ml GBW(E)083788 Beijing North Weiye Metrology Technology Research Institute Zinc 1 mg / ml GSB 04-1761-2004 National Institute of Nonferrous Metals and Electronic Materials Mercury 1 mg / ml GSB 04-1729-2004 National Institute of Nonferrous Metals and Electronic Materials Copper 1 mg / ml GSB 04-1725-2004 National Institute of Nonferrous Metals and Electronic Materials Nickel 1 mg / ml GBW(E)080536 Beijing North Weiye Metrology Technology Research Institute Cobalt 1 mg / ml GSB 04-1722-2004 National Institute of Nonferrous Metals and Electronic Materials
[0040] The preparation method of the heavy metal standard series solution is shown in Table 2
[0041] Table 2. Preparation method of heavy metal standard series solutions
[0042]
[0043] For example, for chromium (GSB 04-1728-2004), solutions with concentrations of 0, 0.25, 2.5, and 5.0 mg / L were prepared respectively. Then, 0, 1, 10, and 20 mL of the above solutions were respectively taken and placed in a 250 mL volumetric flask, and made up to the mark with 10% hydrochloric acid and distilled water to make the pH value of the solution 6.0, thus preparing the standard series solutions. The standard series solutions were successively put into an inductively coupled plasma spectrometer and mass spectrometer to construct the standard curve of heavy metal elements; then the ultrafine powder sample was detected, and the content of heavy metal elements in the sample was calculated according to the detection results and the standard curve.
[0044] Comparative example:
[0045] Traditional phosphorus ore heavy metal analysis technology: The phosphorus ore sample was dried at 105°C for more than 2 hours to obtain a sample with a water content of less than 0.5%. Subsequently, the sample was ground step by step through a jaw crusher, a pair-roll crusher, and a vibration mill to make a dry phosphorus ore sample that all passed through 120 mesh (125 um). Weigh 1.000 - 5.000 g of the dry phosphorus ore sample and put it into a 500 ml tall-form beaker, add 30 ml of water, 15 ml of hydrochloric acid and 5 ml of nitric acid, cover with a watch glass, boil on an electric furnace, then place it on a hot plate to keep slightly boiling for 30 min, let it stand and cool slightly (near room temperature), redissolve, and then place it on the hot plate to keep slightly boiling for 10 min and then take it off, transfer it to a 100 ml volumetric flask and make up to the mark (with primary distilled water). The liquid in the volumetric flask was poured into a 50 ml beaker with a double-layer slow quantitative filter paper for filtration. When there was 30 - 40 ml of filtrate in the beaker, the heavy metal content was determined by inductively coupled plasma spectroscopy (ICP-AES), mass spectrometer (ICP-MS), and atomic absorption spectrometer.
[0046] Example 1: An experiment was carried out using the colloidal phosphate rock stored in a certain place in Yunnan as the raw ore, and the experimental indicators are shown in Table 1.
[0047] Table 1 Precision and accuracy experiments of this method for colloidal phosphate rock in a certain place in Yunnan
[0048]
[0049]
[0050] As can be seen from Table 1, taking the phosphorus ore in a certain place in Yunnan as the experimental object, the ultrafine sample processing miniaturization experiment was used to detect the heavy metal elements in the phosphorus ore sample. The results and the values of the traditional method were all within the allowable error range, with good accuracy and meeting the analysis requirements. The relative deviation statistics (RSD, 7 times for each element), and the RSD were all less than 5%, proving that the precision of this method was good.
[0051] Example 2: Experiments were carried out using the phosphate rock stored in a certain place in Guizhou as the raw ore. The various indexes of the experiments are shown in Table 2.
[0052] Table 2 Precision and accuracy experiments of this method for phosphate rock in a certain place in Guizhou
[0053]
[0054] It can be seen from Table 2 that taking the phosphate rock in a certain place in Guizhou as the experimental object, the ultrafine sample processing miniaturization experiment was used to detect the heavy metal elements in the phosphate rock sample. The results and the values of the traditional method are within the allowable error range, with good accuracy, meeting the analysis requirements. The relative deviation statistics (RSD, 7 times for each element), and the RSD are all less than 5%, proving that the precision of this method is good.
[0055] Example 3: Experiments were carried out using the collophanite stored in a certain place in Hubei as the raw ore. The various indexes of the experiments are shown in Table 3.
[0056] Table 3 Precision and accuracy experiments of this method for phosphate rock in a certain place in Hubei
[0057]
[0058]
[0059] It can be seen from Table 1, Table 2 and Table 3 that taking the phosphate rock in a certain place in Hubei as the experimental object, the ultrafine sample processing miniaturization experiment was used to detect the heavy metal elements in the phosphate rock sample. The results and the values of the traditional method are within the allowable error range, with good accuracy, meeting the analysis requirements. The relative deviation statistics (RSD, 7 times for each element), and the RSD are all less than 5%, proving that the precision of this method is good, and at the same time indicating that this method has a wide application range.
[0060] What is disclosed above is only one or more preferred embodiments of the present application, and the scope of rights of the present application cannot be limited thereby. Those of ordinary skill in the art can understand all or part of the processes of implementing the above embodiments, and the equivalent changes made according to the claims of the present application still fall within the scope covered by the present application.
Claims
1. A method for detecting heavy metals in phosphate rock based on ultra-fine samples and miniaturized experiments, characterized in that, It includes the following steps: S101. Make the phosphate rock into a sample, and take a certain amount to make an ultrafine powder sample; S102. Adopt miniaturization technology to completely digest the ultrafine powder sample; S103. After complete digestion, use an inductively coupled plasma spectrometry and mass spectrometer to determine the heavy metal content in the phosphate rock.
2. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 1, wherein The specific steps for making the phosphate rock into a sample in S101 include: Dry the phosphate rock at 105 °C for more than 2 hours to obtain a preliminary sample with a water content of less than 0.5%; Gradually grind the preliminary sample through a jaw crusher, a pair-roll crusher, and a vibration mill to make a dry phosphate rock sample; Use the quartering method to reduce the dry phosphate rock sample to 10 g to obtain a sample.
3. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 2, wherein, The particle size of the dry phosphate rock sample is 120 mesh.
4. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 2, wherein The specific steps for making the ultrafine powder sample in S101 include: Weigh 7.00 ± 0.02 g of the sample and put it into the grinding tray of a high-speed planetary ultra-fine grinding mill. Among them, add 20 5-mm and 30 3-mm tungsten carbide balls to each grinding tray in a tungsten carbide tank, tighten the tank lid, rotate at a speed of 1000 r / min for 4.0 min to obtain an ultrafine powder sample.
5. The method for detecting heavy metals in phosphate rock based on ultrafine samples and miniaturized experiments according to claim 4, characterized in that, The fineness of the ultrafine powder sample is on average below 10 μm.
6. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 1, characterized in that, The specific steps of S102 include: Weigh 0.1 g of the ultrafine powder sample and put it into a 300-ml tall-form beaker, add 10 ml of water, 3 ml of hydrochloric acid, and 1 ml of nitric acid, cover with a watch glass, boil on an electric furnace, then place it on a hot plate to keep slightly boiling for 10 min, take it off and transfer it to a 100-ml volumetric flask, and make up the volume with primary distilled water. Then pour the liquid in the volumetric flask into a 50-ml beaker with a double-layer slow quantitative filter paper for filtration.
7. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 6, characterized in that, The water is primary distilled water, the hydrochloric acid is GR grade concentrated hydrochloric acid, and the nitric acid is GR grade concentrated nitric acid.
8. The heavy metal detection method for phosphate rock based on ultrafine samples and miniaturized experiments according to claim 1, wherein, The specific steps of S103 are: Take standard solutions of heavy metal elements, and prepare solutions with concentrations of 0, 0.25, 2.5, and 5.0 mg / L respectively. Then, draw 0, 1, 10, and 20 mL of the above solutions and place them in a 250-ml volumetric flask, and make up the volume with 10% hydrochloric acid and distilled water to make the pH value of the solution 6.0 to prepare a standard series of solutions. Put the standard series of solutions into an inductively coupled plasma spectrometry and mass spectrometer in turn to construct a standard curve of heavy metal elements; then detect the ultrafine powder sample, and calculate the content of heavy metal elements in the sample according to the detection results and the standard curve.