CN110514643B - Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry - Google Patents
Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry Download PDFInfo
- Publication number
- CN110514643B CN110514643B CN201910825841.9A CN201910825841A CN110514643B CN 110514643 B CN110514643 B CN 110514643B CN 201910825841 A CN201910825841 A CN 201910825841A CN 110514643 B CN110514643 B CN 110514643B
- Authority
- CN
- China
- Prior art keywords
- standard
- mug
- solution
- concentration
- coupled plasma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
Abstract
The invention discloses a method for measuring trace elements in high-purity magnesium-based oxide by using an inductively coupled plasma emission spectrometry. Simulating a high-purity series magnesium-based oxide matrix by utilizing the general rule of emission spectra of aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead, sulfur and silicon elements in inductively coupled plasma, and carrying out coexisting element and background emission spectrum research, medium determination, analysis spectral line screening, mutual interference elimination test and condition optimization between the matrix and a spectrum line containing miscellaneous elements, thereby establishing an optimal sample determination condition; the method adopts a standard addition method as a technical means to realize the determination of trace impurity elements in the high-purity series magnesium-based oxide samples.
Description
Technical Field
The invention relates to the technical field of analysis and detection in the chemical industry of salt lakes, in particular to a method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry.
Background
The salt lake resource is the advantage and the characteristic resource of the Qinghai region in China, the salt lake resource is deeply developed and utilized, the key technology for extracting magnesium from the salt lake makes a breakthrough, the yield and the quality of the western magnesium industry product reach five world I, and another new way is provided for the comprehensive development and utilization of the chloromagnesite waste resource of the Kaeer sweat salt lake which troubles the Qinghai for many years, and the magnesium damage is changed into 'magnesium treasure'. In order to solve the problem of 'magnesium harm' in the development and utilization of salt lake resources, high-purity series magnesium-based oxides have been developed in the industry in succession, wherein high-purity magnesite fills up the domestic blank, and the development of high-purity magnesium hydroxide with 10 million tons/year and downstream high-purity products with the magnesium hydroxide as a carrier is also actively carried out. However, the existing products do not bring significant benefits to enterprises, first because of the lack of detection methods and the inability to provide users, especially foreign users, with a miscellaneous indicator sufficient to prove product quality. The research on the spectral characteristics and the rules of the coexisting elements in the high-purity magnesium-based oxide in the inductively coupled plasma flame is an effective means for solving the defect.
The high-purity series magnesium-based oxides produced by Qinghai West magnesium industry Limited company mainly comprise magnesium oxide, magnesium hydroxide, developed magnesium carbonate and magnesium metal, the products (the main content is more than 99.9 percent) contain various hybrids, such as calcium, potassium, sodium, boron, iron, manganese, cadmium, lead, sulfur, silicon and the like, the content of the impurity elements can directly influence the performance, the use effect and the price of the products, and meanwhile, the content is very little, and the mass percentage content is usually 10-3-10-4Of order of magnitude and the matrix concentration of the sample is as high as 100-10-1%, these properties become the technical bottleneck for detecting the trace of the above elements. Proper dilution of the sample solution can reduce the influence of matrix effect in a certain range, but the dilution reduces the concentration of analysis elements, thereby limiting the application of the technical means.
The method for measuring the impurity elements in the high-purity metal oxide and the high-purity metal mainly comprises the following steps: spectrophotometry, atomic absorption, inductively coupled plasma emission spectroscopy, and the like. The spectrophotometry can only measure a small amount of elements such as iron and the like, can only measure a single element each time, and has low work efficiency and high cost; the atomic absorption method is only suitable for measuring most metal elements, but is difficult to measure non-metal elements such as boron, sulfur, silicon and the like, and the detection limit of part of trace metal elements is not high, so that the accuracy requirement is difficult to meet; the inductively coupled plasma emission spectrometry has the advantages of high sensitivity, low detection limit, good accuracy, wide linear range and capability of simultaneously measuring multiple elements in one sample.
At present, the inductively coupled plasma emission spectrometry is used for measuring the trace elements in high-purity series magnesium-based oxides without national standards, local standards or national standards substances of the same matrix to implement quality control, and the methods with the most reference value are the national standard HG/T2573 for measuring magnesium oxide and the national standard HG/T3607 for measuring magnesium hydroxide. Unfortunately, the determination of other elements than calcium, iron, manganese (not in magnesia) is missing from both standards, and higher levels of calcium (minimum 10) are used-1Order of magnitude), the detection limit cannot reach 10-4The method has the advantages that the requirement of the order of magnitude content is met, meanwhile, the reproducibility and reproducibility indexes required by quality control are lacked in the two methods, and a laboratory lacks a reliability judgment basis for self detection results. At present, reports of measuring impurity elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry are not seen, in few similar researches, the content measurement of 17 elements such as cadmium, lead, nickel, aluminum, silicon, zirconium, manganese, beryllium, copper, iron, titanium, lead, silver, calcium, yttrium, lanthanum, cerium, neodymium and the like in magnesium and magnesium alloy is researched by adopting an interference coefficient method in the Taoyanjuan, the content measurement of silicon in magnesium and magnesium alloy is carried out by adopting a matrix matching method in the Meitan, and the mass percentage content of impurity elements in samples measured by the two methods is 10-2Of the order of magnitude, not suitable for a mass percentage of typically 10-4And (3) measuring impurity elements of the order of magnitude high-purity magnesium-based oxide.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method which has simple operation steps, simple and quick sample treatment, high measurement precision and can provide the sample with the mass percentage as low as 10 by utilizing the inductively coupled plasma emission spectrometry-4An analysis method of trace elements in high-purity magnesium-based oxide of orders of magnitude.
In order to solve the technical problem, the invention adopts the following technical scheme: a method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry is characterized by comprising the following steps: the test sample is pretreated, then the calcium, potassium, sodium, boron, iron, manganese, cadmium, lead, sulfur and aluminum multi-element standard solution or silicon element standard solution is added, hydrochloric acid is added for dilution, finally the series of standard solutions are measured by an inductively coupled plasma atomic emission spectrometer, the specific measuring steps are as follows,
1) preparing reagents: comprises hydrochloric acid, and multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum, and standard solution of silicon element;
2) preparing standard solution
A. Multielement standard mixed solution a 1: accurately transferring the multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum, diluting with water to scale, fixing the volume, and shaking up to obtain a multi-element standard mixed solution A1;
silicon element standard solution a 2: accurately transferring the silicon element standard solution, diluting with water to a scale, fixing the volume, and shaking up to obtain a silicon element standard solution A2;
B. multielement standard mixed solution B1: accurately transferring the multielement standard mixed solution A1, diluting with water to scale, fixing the volume, and shaking up to obtain multielement standard mixed solution B1 with the concentration of 10% of the multielement standard mixed solution A1;
silicon element standard solution B2: accurately transferring the silicon element standard solution A2, diluting with water to scale, diluting to constant volume, and shaking up to obtain a silicon element standard solution B2 with the concentration of 10% of the silicon element standard solution A2;
3) sample pretreatment: accurately weighing a sample, adding a little water for wetting, adding a small amount of hydrochloric acid (1+1) for many times under the continuous stirring of a glass rod until the sample is completely dissolved, cleaning the solution, washing the cup wall with a small amount of water, heating and slightly boiling the solution on a low-temperature electric heating plate for 2min, taking down the solution, cooling the solution, transferring the solution into a volumetric flask, adding (1+1) hydrochloric acid, fixing the volume with water, and shaking up the solution to obtain a sample solution;
4) preparation of working curve by standard addition method
Manufacturing a multi-element working curve: sequentially and accurately transferring a multi-element standard mixed solution B1: 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL, 5.00mL, in a 25mL volumetric flask, accurately adding 2.50mL of the pretreated sample solution in sequence, adding 0.5mL of hydrochloric acid, diluting with water to a scale, diluting to a constant volume, and shaking up; the concentrations of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum elements corresponding to the working curve are respectively 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL;
preparing a silicon element standard working solution: accurately transferring a silicon element standard solution B2: adding 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL and 5.00mL of the pretreated sample solution into a 25mL volumetric flask, diluting with water to a scale, fixing the volume, and shaking up; the concentrations of the working curve corresponding to the silicon element are respectively 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL;
5) and (3) determination: and (3) sequentially measuring the series of standard solutions by using an inductively coupled plasma atomic emission spectrometer, and drawing a standard curve of the standard addition method of each element by taking the concentrations of the standard solutions corresponding to each element, namely 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL, as abscissa and the corresponding emission spectrum intensity under each concentration as ordinate to obtain the concentration of the element to be measured in the sample, wherein the intersection point of the curve and the abscissa is the concentration of the element to be measured in the sample, and multiplying the concentration by the corresponding dilution multiple to obtain the content of the element to be measured in the sample.
Main instruments and working conditions:
inductively coupled plasma atomic emission spectrometer: iCAP 7000SERIES model, Sammer Feishel technologies, Inc. USA;
an electronic balance: ME204E model, sensory 0.0001g, Metlerthritods, Switzerland measurement technologies, Inc.;
thermo7400, RF frequency 27.12MHz, high efficiency concentric atomizer, plasma observation: vertical (diameter term), wavelength range 166-847nm, optical resolution (FHW) less than or equal to 0.007nm and 200 nm; 0.014nm, 400 nm; 0.021nm, 600 nm; the number of semiconductor refrigeration CID detectors is more than 290000.
Thermoelectric ICP7400, power 950W, cooling gas 12L/min, auxiliary gas 0.5L/min, carrier gas 0.5L/min, and observation height 12 mm; integration time: long wave 5S and short wave 15S; pump speed: rinse 50rpm, analyze pump speed 50 rpm.
In step 5), each analytical element and corresponding wavelength are as follows: 167.079nm for Al, 249.773nm for B, 393.366nm for Ca, 228.802nm for Cd, 238.204nm for Fe, 766.490nm for K, 257.610nm for Mn, 589.592nm for Na, 220.353nm for Pb, 182.034nm for S and 251.611nm for Si.
In the step 3), the sample transfer amount is 5.0000g, the 1+1 hydrochloric acid addition amount is 30 ml, and a plurality of drops are added if necessary; heating on low temperature electric heating plate at 200 deg.C for 2min, cooling, transferring into 50ml volumetric flask, adding 5ml (1+1) hydrochloric acid, adding water to desired volume, and shaking.
The concentration of the silicon element standard solution is 1000 mu g/mL, the concentration of the multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum is 1000 mu g/mL, the concentration of the multi-element standard mixed solution A1 is 100 mu g/mL, the concentration of the silicon element standard solution A2 is 100 mu g/mL, the concentration of the multi-element standard mixed solution B1 is 10 mu g/mL, and the concentration of the silicon element standard solution B2 is 10 mu g/mL.
And (3) interference investigation of coexisting elements: the interference of the magnesium matrix to the element to be detected when the concentration of the magnesium matrix in the high-purity magnesium-based oxide is respectively 10mg/mL, 20mg/mL and 30mg/mL is examined, and the interference to the element to be detected is determined when the concentration of the magnesium matrix is not more than 20 mg/mL;
detection limit conditions: under the condition of the experimental instrument, 2% HCl is used as a blank for continuous measurement for 11 times, the standard deviation of 3 times of the measurement result is used as the detection limit of the method, and the standard deviation of 10 times of the measurement result is used as the measurement lower limit of the method;
detection limit: al: 0.0283 ug/mL; b: 0.0077 mu g/mL; ca: 0.00216 μ g/mL; cd: 0.0018 μ g/mL; fe: 0.0194. mu.g/mL; k: 0.0147 μ g/mL; mn: 0.0009 μ g/mL; na: 0.0250 μ g/mL; pb: 0.0120. mu.g/mL; si: 0.0175 mu g/mL; s: 0.0291 μ g/mL;
lower limit of measurement: al: 0.0942 μ g/mL; b: 0.0256 μ g/mL; ca: 0.0721 μ g/mL; cd: 0.0059 μ g/mL; fe: 0.0648 μ g/mL; k: 0.0490. mu.g/mL; mn: 0.0030. mu.g/mL; na: 0.0832 μ g/mL; pb: 0.0401. mu.g/mL; si: 0.0582 μ g/mL; s: 0.0971 μ g/mL.
Precision situation: after the electron coupled plasma atomic emission spectrometer is preheated for 30min, the measurement is repeated for 11 times by using a standard solution with the concentration of 1 mu g/mL, and the relative standard deviation is less than or equal to 1.5 percent.
Recovery rate experiment: a standard addition recovery experiment is carried out on a high-purity magnesium-based oxide sample, and the recovery rates of Al, B, Ca, Cd, Fe, K, Mn, Na, Pb, Si and S are 98.24-104.60%, 98.20-103.27%, 97.26-104.70%, 98.36-102.00%, 98.19-102.40%, 96.96-103.50%, 98.23-102.50%, 95.05-104.11%, 97.40-102.50%, 97.93-103.80% and 97.19-102.20%, so that the requirements of an analysis method are completely met.
Stability conditions: after an electron coupled plasma atomic emission spectrometer is preheated for 30min, aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead and sulfur multi-element standard mixed solution with the concentration of 1 mu g/mL and silicon element standard solution with the concentration of 1 mu g/mL are respectively used for measuring 1 time within 4h at an interval of 20min, the total time is 12 times, the relative standard deviation is less than or equal to 3 percent, and the linear correlation coefficient R of a working curve is more than or equal to 0.999.
The method comprises the steps of pretreating a sample, adding a potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum multi-element standard solution or a silicon element standard solution, adding hydrochloric acid, diluting, and finally measuring a series of standard solutions by using an inductively coupled plasma atomic emission spectrometer. Simulating a high-purity series magnesium-based oxide matrix by utilizing the general rule of emission spectra of magnesium, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead, sulfur and silicon elements in inductively coupled plasma, and carrying out coexistence element and background emission spectrum research, medium determination, analysis spectral line screening, mutual interference elimination test and condition optimization between the matrix and a spectrum line containing impurity elements, thereby establishing an optimal sample determination condition; the method has the advantages that the method takes a standard addition method as a technical means, realizes the simultaneous determination of trace impurity elements in high-purity series magnesium-based oxide samples, provides technical support for the high-end products of the dominant salt lake resources in China to enter the international market, improves the working efficiency, reduces the labor intensity of operators, and has remarkable social benefit.
The invention also has the following positive effects: (1) in the prior art, the inductively coupled plasma emission spectrometry is used for measuring the trace elements in high-purity series magnesium-based oxides without national standard, local standard or national standard substances of the same matrix to implement quality control, but the method of the invention utilizes the general rule of the emission spectrum of aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead, sulfur and silicon elements in inductively coupled plasma to simulate the high-purity series magnesium-based oxide matrix, carry out the research of coexisting elements and background emission spectrum, measure media, the screening of analysis spectral lines, the mutual interference elimination test and condition optimization between the matrix and the spectral lines containing the impurity elements, and establish the optimal sample measuring condition; the method adopts a standard addition method as a technical means to realize the determination of trace impurity elements in high-purity series magnesium-based oxide samples. (2) The method of the invention can simultaneously detect a plurality of trace elements in the high-purity magnesium-based oxide, and is suitable for detecting the trace elements with the mass percentage of 10-4The method can effectively relieve the detection pressure of enterprises, has important significance and is very necessary. The method provides technical support for detecting trace impurity elements in a sample of a high-purity series magnesium-based oxide produced by Qinghai West magnesium industry Co., Ltd, including magnesium oxide and magnesium hydroxide and a magnesium carbonate and magnesium metal product under development. (3) It is difficult to process high purity series of magnesium-based oxide samples using the existing methods, the method of the present invention throughThe sample is treated by hydrochloric acid to obtain a sample solution of high-purity series magnesium-based oxides, and the sample solution is measured by adopting a standard addition method, and the prior art does not relate to a similar method and does not have any suggestion.
Detailed Description
The following is further described in conjunction with the detailed description:
in the present embodiment, the first and second electrodes are,
1. main instruments and working conditions:
inductively coupled plasma atomic emission spectrometer: iCAP 7000SERIES model, Sammer Feishel technologies, Inc. USA;
an electronic balance: ME204E model, sensory 0.0001g, Metlerthritods, Switzerland measurement technologies, Inc.;
thermo7400, RF frequency 27.12MHz, high efficiency concentric atomizer, plasma observation: vertical (diameter term), wavelength range 166-847nm, optical resolution (FHW) less than or equal to 0.007nm and 200 nm; 0.014nm, 400 nm; 0.021nm, 600 nm; the number of semiconductor refrigeration CID detectors is more than 290000.
Thermoelectric ICP7400, power 950W, cooling gas 12L/min, auxiliary gas 0.5L/min, carrier gas 0.5L/min, and observation height 12 mm; integration time: long wave 5S and short wave 15S; pump speed: rinse 50rpm, analyze pump speed 50 rpm.
Analytical elements and corresponding measurement wavelengths:
2. principal agent
Hydrochloric acid: GR, Sichuan Kagaku GmbH;
potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum multi-element standard mixed solution: 1000. mu.g/mL, number: GNM-M104320-2013, national nonferrous metal and electronic material analysis and test center;
silicon element standard solution: 1000. mu.g/mL, number: GSB 04-1752-2004(a), national analysis and test center for nonferrous metals and electronic materials;
3. standard solution
Preparation of standard solution a:
multi-element Standard Mixed solution A1 (100. mu.g/mL): accurately transferring 10.00mL of multi-element standard mixed solution (10000 mug/mL) of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum into a 100mL volumetric flask, diluting with water to a scale, fixing the volume, and shaking up.
Elemental silicon standard solution A2 (100. mu.g/mL): accurately transferring 10.00mL of silicon standard solution (1000 mu g/mL) into a 100mL volumetric flask, diluting to the mark with water, fixing the volume and shaking up.
Preparation of standard solution B:
multi-element Standard Mixed solution B1 (10. mu.g/mL): accurately transferring 10.00mL of the multielement standard mixed solution A1 into a 100mL volumetric flask, diluting with water to a scale, fixing the volume, and shaking up.
Elemental silicon standard solution (10. mu.g/mL) B2: accurately transferring 10.00mL of the silicon element standard solution A2 into a 100mL volumetric flask, diluting with water to a scale, fixing the volume, and shaking up.
4. Sample pretreatment
5.0000g of sample is accurately weighed, a little water is added for wetting, a small amount of hydrochloric acid (1+1) is added for a plurality of times under the continuous stirring of a glass rod until the sample is completely dissolved, the solution is clear, (the theoretical addition amount of the 1+1 hydrochloric acid is 30 mL, and a plurality of drops are added if necessary), the cup wall is flushed with a small amount of water, the cup is heated and slightly boiled for 2min on a low-temperature electric heating plate (200 ℃), the cup is taken down, cooled, transferred into a 50mL volumetric flask, 5mL of (1+1) hydrochloric acid is added, the volume is fixed by water, and the cup is shaken uniformly.
And (3) making a working curve by a standard addition method:
manufacturing a multi-element working curve: sequentially and accurately transferring a multi-element standard mixed solution B1(10 mu g/mL) of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum: 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL, 5.00mL, in a 25mL volumetric flask, accurately adding 2.50mL of the pretreated sample solution, adding 0.5mL of hydrochloric acid, diluting with water to a certain volume, and shaking up. The concentrations of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum elements corresponding to the working curve are respectively 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL.
Preparing a silicon element standard working solution: accurately removing silicon element standard solution B2(10 mu g/mL): 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL, 5.00mL, in a 25mL volumetric flask, exactly add 2.50mL of the pretreated sample solution, dilute to the mark with water, fix the volume, shake. The concentrations of Si element in the working curve are 0. mu.g/mL, 0.10. mu.g/mL, 0.20. mu.g/mL, 0.50. mu.g/mL, 1.00. mu.g/mL, and 2.00. mu.g/mL, respectively.
And (3) sequentially measuring the series of standard solutions by ICP-OES according to the optimized working conditions of the instrument and the wavelength of the element to be measured, and drawing by taking the concentrations of the standard solutions corresponding to the elements as 0 mu g/mL, 0.10 mu g/mL, 0.20 mu g/mL, 0.50 mu g/mL, 1.00 mu g/mL and 2.00 mu g/mL as abscissa and the corresponding emission spectrum intensities at the concentrations as ordinate to obtain a standard curve of the standard addition method of the elements. And the intersection point of the curve and the abscissa axis is the concentration of the element to be detected in the sample, and the concentration is multiplied by the corresponding dilution multiple, (5.0000g of the sample is subjected to pretreatment, the volume is fixed in a 50mL volumetric flask, and 2.50mL of the sample is transferred and fixed in a 25mL volumetric flask), so that the content of the element to be detected in the sample is obtained.
5. And (3) determination: and sequentially measuring the series of standard solutions by using an inductively coupled plasma atomic emission spectrometer, and drawing by taking the concentrations of the standard solutions corresponding to the elements as 0 mu g/mL, 0.10 mu g/mL, 0.20 mu g/mL, 0.50 mu g/mL, 1.00 mu g/mL and 2.00 mu g/mL as abscissa and the corresponding emission spectrum intensities under the concentrations as ordinate to obtain a standard curve of the standard addition method of the elements, wherein the intersection point of the curve and the abscissa axis is the concentration of the element to be measured in the sample and is multiplied by the corresponding dilution factor to obtain the content of the element to be measured in the sample.
In step 5, each analytical element and the corresponding wavelength are as follows: 167.079nm for Al, 249.773nm for B, 393.366nm for Ca, 228.802nm for Cd, 238.204nm for Fe, 766.490nm for K, 257.610nm for Mn, 589.592nm for Na, 220.353nm for Pb, 182.034nm for S and 251.611nm for Si.
In the step 4, the sample transfer amount is 5.0000g, the 1+1 hydrochloric acid addition amount is 30 ml, and a plurality of drops are added if necessary; heating on low temperature electric heating plate at 200 deg.C for 2min, cooling, transferring into 50ml volumetric flask, adding 5ml (1+1) hydrochloric acid, adding water to desired volume, and shaking.
The concentration of the silicon element standard solution is 1000 mu g/mL, the concentration of the multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum is 1000 mu g/mL, the concentration of the multi-element standard mixed solution A1 is 100 mu g/mL, the concentration of the silicon element standard solution A2 is 100 mu g/mL, the concentration of the multi-element standard mixed solution B1 is 10 mu g/mL, and the concentration of the silicon element standard solution B2 is 10 mu g/mL.
Coexistence element interference investigation
The interference of the magnesium matrix to the element to be detected when the concentration of the magnesium matrix in the high-purity magnesium-based oxide is respectively 10mg/mL, 20mg/mL and 30mg/mL is examined, and the interference to the element to be detected is determined when the concentration of the magnesium matrix is not more than 20 mg/mL.
Detecting limit conditions
Under the condition of the experimental instrument, 2% HCl is used as a blank for continuous measurement for 11 times, the standard deviation which is 3 times of the measurement result is used as a detection limit, and the standard deviation which is 10 times of the standard deviation is used as the lower limit of the measurement of the method;
detection limit: al: 0.0283 ug/mL; b: 0.0077 mu g/mL; ca: 0.00216 μ g/mL; cd: 0.0018 μ g/mL; fe: 0.0194. mu.g/mL; k: 0.0147 μ g/mL; mn: 0.0009 μ g/mL; na: 0.0250 μ g/mL; pb: 0.0120. mu.g/mL; si: 0.0175 mu g/mL; s: 0.0291 μ g/mL;
lower limit of measurement: al: 0.0942 μ g/mL; b: 0.0256 μ g/mL; ca: 0.0721 μ g/mL; cd: 0.0059 μ g/mL; fe: 0.0648 μ g/mL; k: 0.0490 mu g/mL; mn: 0.0030. mu.g/mL; na: 0.0832 μ g/mL; pb: 0.0401. mu.g/mL; si: 0.0582 μ g/mL; s: 0.0971 μ g/mL.
Precision situation
After the electron coupled plasma atomic emission spectrometer is preheated for 30min, the measurement is repeated 11 times by using a standard solution with the concentration of 1 mu g/mL, and the relative standard deviation is less than or equal to 1.5 percent.
Recovery rate experiment
Performing a labeling recovery experiment on a high-purity magnesium-based oxide sample to obtain that the recovery rates of Al, B, Ca, Cd, Fe, K, Mn, Na, Pb, Si and S are respectively 98.24-104.60%, 98.20-103.27%, 97.26-104.70%, 98.36-102.00%, 98.19-102.40%, 96.96-103.50%, 98.23-102.50%, 95.05-104.11%, 97.40-102.50%, 97.93-103.80% and 97.19-102.20%, and the recovery rates completely meet the requirements of an analysis method;
after preheating for 30min by an electron coupled plasma atomic emission spectrometer, respectively measuring 1 time at intervals of 20min within 4h by using a multi-element standard mixed solution of aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead and sulfur with the concentration of 1 mu g/mL and a silicon element standard solution with the concentration of 1 mu g/mL for 12 times, wherein the relative standard deviation is less than or equal to 3%, the linear correlation coefficient R of a working curve is more than or equal to 0.999, the precision test result is shown in table 1, the detection limit and the measurement lower limit measurement result is shown in table 2, and the recovery rate measurement result is shown in table 3.
TABLE 1 precision test results (%)
TABLE 2 detection and lower determination limits (. mu.g/mL) for the method of the invention
Table 3 standard recovery test (%)
While the invention has been described in detail in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (8)
1. A method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry is characterized by comprising the following steps: the test sample is pretreated, then multi-element standard mixed solution of aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead and sulfur or standard solution of silicon element is added, hydrochloric acid is added for dilution, finally an inductively coupled plasma atomic emission spectrometer is used for measuring the series of standard solution, the specific measuring steps are as follows,
1) preparing a reagent: comprises hydrochloric acid, and potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum multi-element standard mixed solution and silicon element standard solution;
2) preparing standard solution
A. Multielement standard mixed solution a 1: accurately transferring the multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum, diluting with water to a scale, fixing the volume, and shaking up to obtain the multi-element standard mixed solution A1;
silicon element standard solution a 2: accurately transferring the silicon element standard solution, diluting with water to a scale, fixing the volume, and shaking up to obtain a silicon element standard solution A2;
B. multielement standard mixed solution B1: accurately transferring the multielement standard solution A1, diluting with water to a scale, fixing the volume, and shaking up to obtain multielement standard mixed solution B1 with the concentration of 10% of the multielement standard solution A1;
silicon element standard solution B2: accurately transferring the silicon element standard solution A2, diluting with water to scale, diluting to constant volume, and shaking up to obtain a silicon standard solution B2 with the concentration of 10% of the silicon standard solution A2;
3) sample pretreatment: accurately weighing a sample, adding a little water for wetting, adding 1+1 hydrochloric acid for a few times under the continuous stirring of a glass rod until the sample is completely dissolved, cleaning the solution, washing the cup wall with a little water, heating and slightly boiling on a low-temperature electric heating plate for 2min, taking down, cooling, transferring into a volumetric flask, adding 1+1 hydrochloric acid, fixing the volume with water, and shaking up to obtain a sample solution;
4) preparation of working curve by standard addition method
Manufacturing a multi-element working curve: sequentially and respectively and accurately transferring a multielement standard solution B1: 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL and 5.00mL, sequentially and accurately adding 2.50mL of the pretreated sample solution and 0.5mL of hydrochloric acid into a set of 25mL volumetric flasks, diluting with water to a scale, fixing the volume and shaking up; the concentrations of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum elements corresponding to the working curve are respectively 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL;
preparing a silicon element standard working solution: accurately transferring a silicon element standard solution B2: 0mL, 0.25mL, 0.50mL, 1.25mL, 2.50mL, 5.00mL, in a set of 25mL volumetric flasks, accurately adding 2.50mL of the pretreated sample solution, diluting with water to a scale, diluting to a constant volume, shaking up; the concentration of the silicon element corresponding to the working curve is 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL respectively;
5) and (3) determination: and (3) sequentially measuring the series of standard solutions by using an inductively coupled plasma atomic emission spectrometer, and drawing a standard curve of the standard addition method of each element by taking the concentrations of the standard solutions corresponding to each element, namely 0 mug/mL, 0.10 mug/mL, 0.20 mug/mL, 0.50 mug/mL, 1.00 mug/mL and 2.00 mug/mL, as abscissa and the corresponding emission spectrum intensity under each concentration as ordinate to obtain the concentration of the element to be measured in the sample, wherein the intersection point of the curve and the abscissa is the concentration of the element to be measured in the sample, and multiplying the concentration by the corresponding dilution multiple to obtain the content of the element to be measured in the sample.
2. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: in step 5), each analytical element and the corresponding wavelength are as follows: 167.079nm for Al, 249.773nm for B, 393.366nm for Ca, 228.802nm for Cd, 238.204nm for Fe, 766.490nm for K, 257.610nm for Mn, 589.592nm for Na, 220.353nm for Pb, 182.034nm for S and 251.611nm for Si.
3. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: in the step 3), the sample transfer amount is 5.0000g, the 1+1 hydrochloric acid addition amount is 30 ml, and a plurality of drops are added if necessary; heating on low temperature electric heating plate at 200 deg.C for 2min, cooling, transferring into 50ml volumetric flask, adding 1+1 hydrochloric acid 5ml, adding water to desired volume, and shaking.
4. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: the concentration of the silicon element standard solution is 1000 mu g/mL, the concentration of the multi-element standard mixed solution of potassium, sodium, calcium, sulfur, boron, lead, iron, cadmium, manganese and aluminum is 1000 mu g/mL, the concentration of the multi-element standard mixed solution A1 is 100 mu g/mL, the concentration of the silicon element standard solution A2 is 100 mu g/mL, the concentration of the multi-element standard mixed solution B1 is 10 mu g/mL, and the concentration of the silicon element standard solution B2 is 10 mu g/mL.
5. The method of inductively coupled plasma emission spectrometry for the determination of trace elements in high purity magnesium based oxides as claimed in claim 1, wherein: continuously measuring 11 times by using 2% HCl as a blank, taking 3 times of standard deviation of the measurement result as a detection limit of the method, and taking 10 times of the standard deviation as a measurement lower limit of the method;
detection limit: al: 0.0283. mu.g/mL; b: 0.0077 mu g/mL; ca: 0.00216 μ g/mL; cd: 0.0018. mu.g/mL; fe: 0.0194. mu.g/mL; k: 0.0147 μ g/mL; mn: 0.0009 μ g/mL; na: 0.0250 μ g/mL; pb: 0.0120. mu.g/mL; si: 0.0175 mu g/mL; s: 0.0291 μ g/mL;
lower limit of measurement: al: 0.0942 μ g/mL; b: 0.0256 μ g/mL; ca: 0.0721 μ g/mL; cd: 0.0059 μ g/mL; fe: 0.0648 μ g/mL; k: 0.0490. mu.g/mL; mn: 0.0030. mu.g/mL; na: 0.0832 μ g/mL; pb: 0.0401. mu.g/mL; si: 0.0582 μ g/mL; s: 0.0971 μ g/mL.
6. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: after preheating the inductively coupled plasma atomic emission spectrometer for 30min, the measurement is repeated 11 times by using a standard solution with the concentration of 1 mug/mL, so that the relative standard deviation is less than or equal to 1.5 percent.
7. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: a labeling recovery experiment is carried out on a high-purity magnesium-based oxide sample, and the recovery rates of Al, B, Ca, Cd, Fe, K, Mn, Na, Pb, Si and S are 98.24-104.60%, 98.20-103.27%, 97.26-104.70%, 98.36-102.00%, 98.19-102.40%, 96.96-103.50%, 98.23-102.50%, 95.05-104.11%, 97.40-102.50%, 97.93-103.80% and 97.19-102.20% respectively, so that the requirement of an analysis method is met.
8. The method for determining trace elements in high purity magnesium based oxide by inductively coupled plasma emission spectrometry as claimed in claim 1, wherein: after an inductively coupled plasma atomic emission spectrometer is preheated for 30min, aluminum, calcium, potassium, sodium, boron, iron, manganese, cadmium, lead and sulfur multi-element standard mixed solution with the concentration of 1 mu g/mL and silicon element standard solution with the concentration of 1 mu g/mL are respectively used for measuring 1 time within 4h at an interval of 20min, the total measurement time is 12 times, the relative standard deviation is less than or equal to 3 percent, and the linear correlation coefficient R of a working curve is more than or equal to 0.999.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825841.9A CN110514643B (en) | 2019-09-03 | 2019-09-03 | Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825841.9A CN110514643B (en) | 2019-09-03 | 2019-09-03 | Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110514643A CN110514643A (en) | 2019-11-29 |
| CN110514643B true CN110514643B (en) | 2022-07-15 |
Family
ID=68629409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910825841.9A Active CN110514643B (en) | 2019-09-03 | 2019-09-03 | Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110514643B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111929353A (en) * | 2020-05-11 | 2020-11-13 | 承德华勘五一四地矿测试研究有限公司 | Method for combined determination of multiple elements of phosphorus, vanadium, chromium, nickel, zinc, potassium, manganese, cobalt, copper, molybdenum, cadmium, lead and selenium in soil |
| CN111896607A (en) * | 2020-06-12 | 2020-11-06 | 国标（北京）检验认证有限公司 | Method for detecting content of trace impurity rare earth elements in high-purity terbium and compound |
| CN112147130A (en) * | 2020-09-29 | 2020-12-29 | 浙江巨化技术中心有限公司 | Method for determining content of metal elements in polyvinylidene fluoride resin |
| CN115616135A (en) * | 2022-11-22 | 2023-01-17 | 江苏正力新能电池技术有限公司 | Method for detecting sulfate ion content in electrolyte for lithium ion battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102721582B (en) * | 2012-05-18 | 2015-04-15 | 中国航空工业集团公司北京航空材料研究院 | A method for determining contents of potassium element, sodium element, calcium element, silicon element, and magnesium element in nickel oxide |
| CN109781713A (en) * | 2019-02-13 | 2019-05-21 | 西部矿业股份有限公司 | The method that inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously |
-
2019
- 2019-09-03 CN CN201910825841.9A patent/CN110514643B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110514643A (en) | 2019-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110514643B (en) | Method for measuring trace elements in high-purity magnesium-based oxide by inductively coupled plasma emission spectrometry | |
| CN101644677B (en) | Method for detecting element content in alloy or ore by utilizing ICP emission spectrometer | |
| CN102033101A (en) | Method for measuring metal impurities in high-purity MgO film material by using inductively coupled plasma mass spectrometer | |
| CN103604800A (en) | Analysis method for determining titanium, vanadium, tungsten, manganese and silicon in K25 chromium-base high temperature alloy | |
| CN111443079A (en) | Method for simultaneously detecting contents of trace As, Pb, Cd, Zn, Cr, Co and V elements in ferric trichloride | |
| CN111024665A (en) | Method for measuring content of organic selenium in selenium-enriched rice or product prepared from selenium-enriched rice | |
| CN110361441B (en) | Method for detecting trace impurity elements in tungsten carbide powder | |
| CN113295676A (en) | Method for measuring calcium, aluminum and barium in deoxidizer | |
| CN107632011A (en) | The assay method of impurity content in a kind of high purity bismuth | |
| CN106153603A (en) | Measure the method for copper ferrum magnesium nickel manganese in Cast aluminium alloy gold simultaneously | |
| CN111257097A (en) | Vanadium carbide sample to be tested manufacturing method and impurity content analysis method thereof | |
| CN110018155A (en) | A kind of method of tin amount in aes determination electronic waste smelting ash | |
| CN104677883A (en) | Analytical method for measuring impurity content in tin sample | |
| CN112683611B (en) | Digestion solution and method for determining element content in refined aluminum ingot for remelting | |
| CN112129744B (en) | Chemical phase analysis method for lithium in ore | |
| CN108362685B (en) | Analysis method for determining silicon element in high-purity aluminum | |
| CN114354579B (en) | Method for simultaneously detecting silver and palladium elements in silver and palladium mixture | |
| CN111964990A (en) | Method for analyzing selenium/tellurium content in complex copper-based multi-metal solid waste metallurgical slag | |
| CN108680563A (en) | A kind of solid organic fertilizer element silicon detection method and application | |
| CN117214153A (en) | Method for rapidly detecting contents of titanium, aluminum and silicon in ferrotitanium alloy | |
| CN106370608A (en) | Measuring method of silicon in silicon/carbon anode material | |
| CN117250184A (en) | Method for rapidly determining nickel and copper content in sulfuric acid | |
| CN114324305A (en) | Method for measuring content of valuable metals in different reclaimed materials of waste circuit board | |
| CN115165816A (en) | Method for simultaneously determining contents of multiple elements in lead brass | |
| CN112730289A (en) | Analysis method for determining palladium content in waste residues |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |