CN113295760A - Method for simultaneously measuring low contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in furnace slag and mold powder - Google Patents
Method for simultaneously measuring low contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in furnace slag and mold powder Download PDFInfo
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- CN113295760A CN113295760A CN202110390873.8A CN202110390873A CN113295760A CN 113295760 A CN113295760 A CN 113295760A CN 202110390873 A CN202110390873 A CN 202110390873A CN 113295760 A CN113295760 A CN 113295760A
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- 239000002893 slag Substances 0.000 title claims abstract description 51
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 47
- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 47
- 229910052777 Praseodymium Inorganic materials 0.000 title claims abstract description 47
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 47
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 47
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 title claims abstract description 47
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 39
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims description 7
- 239000000523 sample Substances 0.000 claims abstract description 48
- 239000010948 rhodium Substances 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 239000012488 sample solution Substances 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 230000035945 sensitivity Effects 0.000 claims abstract description 7
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims abstract description 5
- 239000012086 standard solution Substances 0.000 claims description 48
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000007865 diluting Methods 0.000 claims description 13
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000012496 blank sample Substances 0.000 claims description 9
- 238000011088 calibration curve Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 239000012490 blank solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000000112 cooling gas Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 230000009191 jumping Effects 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 14
- 150000002910 rare earth metals Chemical class 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KSBBJJYULNAYMC-UHFFFAOYSA-N [Rh].[In] Chemical compound [Rh].[In] KSBBJJYULNAYMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for simultaneously measuring lanthanum, cerium, praseodymium, neodymium, samarium and barium in slag and protective slag, which comprises the steps of dissolving a sample by low-temperature acid, adding a rhodium internal standard on line under the condition of an optimized instrument, and measuring the lanthanum, cerium, praseodymium, neodymium and samarium in the slag by using a plasma mass spectrometer; and adding an indium internal standard on line, and measuring barium in the slag by using a plasma mass spectrometer. The invention aims to provide an analysis method for directly and simultaneously measuring low-content lanthanum, cerium, praseodymium, neodymium, samarium and barium in slag and protective slag sample solutions by ICP-MS, wherein the analysis method has the advantages of high sensitivity, high measurement speed, simple and convenient operation, small interference compared with other methods, good selectivity and capability of providing accurate data for low-temperature acid dissolution samples.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy analysis, in particular to a method for simultaneously measuring low contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in slag and covering slag.
Background
Lanthanum, cerium, praseodymium, neodymium and samarium are the main amount of rare earth elements in baotite, and meanwhile, the ore also contains different amounts of barium, and the elements usually enter slag in the processes of steelmaking, iron-making and slagging. In the modern smelting process, the casting powder containing a certain amount of barium is added during steel making to improve the properties of the casting powder, such as melting temperature, viscosity and the like; the covering slag can absorb rare earth oxides in molten steel and molten iron in the steel-making and iron-making processes, so that accurate determination of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the covering slag is very important.
The methods for measuring the rare earth so far are various, namely an oxalate gravimetric method, an azochlorophosphine-III photometric method and an EDTA volumetric method, and the methods can only measure the total amount of the rare earth but cannot carry out component detection; although inductively coupled plasma spectrometry can measure each component element of rare earth, the lower limit of detection is high, and the interference of spectral lines is serious. The inductively coupled plasma mass spectrometry can detect the rare earth component, has the characteristics of low detection limit, simple spectral line and capability of simultaneously determining multiple elements, and is widely applied to the determination of rare earth.
The method for measuring barium comprises an EDTA coordination titration method, a barium sulfate gravimetric method and an X-ray fluorescence spectrometry method, the methods are complicated in operation and high in labor intensity, and are mainly used for measuring barium with the mass fraction of more than 1%.
Disclosure of Invention
The invention aims to provide a method for simultaneously measuring low-content lanthanum, cerium, praseodymium, neodymium, samarium and barium in slag and mold powder, which has the advantages of high sensitivity, high measuring speed, simple and convenient operation, small interference compared with other methods, good selectivity and capability of providing a low-temperature acid-soluble sample with accurate data, and ICP-MS directly and simultaneously measures the low-content lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and mold powder sample solution.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a method for simultaneously measuring low content of lanthanum, cerium, praseodymium, neodymium, samarium and barium in slag and covering slag, which comprises the following steps:
step 1: weighing 0.100g of sample, placing the sample in a polytetrafluoroethylene beaker which is acid-boiled and cleaned, adding 3mL of high-purity water to wet the sample, shaking the sample, and sequentially adding 10mL of hydrochloric acid and 5mL of hydrofluoric acid; adding 10mL of hydrochloric acid and 5mL of hydrofluoric acid into another acid-boiled and clean polytetrafluoroethylene beaker in sequence to prepare a blank sample, and then placing the polytetrafluoroethylene beaker filled with the slag sample and the blank sample on an electric heating plate for heating and dissolving;
step 2: adding 5mL of perchloric acid into the fuming solution until the volume is 2mL, and completely removing the residual hydrofluoric acid; taking down, and cooling to room temperature;
and step 3: adding 15mL of dilute aqua regia, heating on an electric heating plate to dissolve salts, taking down, cooling to room temperature, and transferring the solution into a 200mL volumetric flask;
and 4, step 4: determination of working parameters of the instrument: in the ICP-MS analysis process, high-frequency emission power, carrier gas flow and ion lens voltage directly influence the sensitivity and precision of instrument measurement, so that the instrument parameters are optimized by using tuning liquid during each measurement, and the sensitivity is as follows: in (115) greater than or equal to 200,000cps (10ug/L), signal-to-noise ratio 220 background value less than 30cps, oxide yield CeO/Ce less than 3.0%, and Ba++/Ba+< 3.0%, the operating parameters of the instrument were determined as follows:
and 5: preparing rhodium and indium internal standard solution: respectively sucking 5mL to 500mL of rhodium and indium single element standard solution into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and preparing 10 mu g/mL of rhodium and indium mixed standard solution with constant volume; sucking 2-1000 mL of mixed standard solution of rhodium and indium with the concentration of 10 mu g/mL into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and fixing the volume to prepare the mixed standard solution of rhodium and indium with the concentration of 20 mu g/L;
step 6: and (3) drawing a calibration curve: respectively absorbing 5mL to 500mL of lanthanum, cerium, praseodymium, neodymium, samarium and barium single element standard solution into a plastic volumetric flask according to the concentration of lanthanum, cerium, praseodymium, neodymium, samarium and barium in a sample to be detected, diluting the standard solution with 2% nitric acid aqueous solution, and preparing a mixed standard solution with a constant volume of 10 mu g/mL; sucking 10-100 mL of 10-mu g/mL mixed standard solution into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and preparing into 1-mu g/mL mixed standard solution with constant volume; respectively sucking 1 mu g/mL of mixed standard solution 0, 0.5, 2.0, 5.0, 10.0 and 20.0mL into 100mL of plastic capacity, using 2% nitric acid aqueous solution to fix the volume, and preparing a series of standard solutions 0ug/L, 5.0ug/L, 20.0ug/L, 50.0ug/L, 100.0ug/L and 200.0ug/L, wherein the matrix of the standard solution is consistent with that of the slag;
introducing standard solution into inductively coupled plasma mass spectrometer, and introducing Rh on line103、In115Internal standard elements inhibit matrix effect, and isotopes of the selected elements are respectively La139、Ce140、Pr141、Nd146、Sm147、Ba137Measuring the signal intensity of the ions to be measured, and drawing La by taking the concentration as an abscissa and the signal intensity of the ions as an ordinate139、Ce140、Pr141、Nd146、Sm147、Ba137Calibrating a curve;
under the selected optimal experimental conditions, the concentration of lanthanum, cerium, praseodymium, neodymium and samarium is in the range of 0.5-200 mu g/L, the calibration curve linearity is good, and the correlation coefficient r of lanthanum, cerium, praseodymium, neodymium and samarium is more than or equal to 0.999; measuring 50 mu g/L of lanthanum, cerium, praseodymium, neodymium and samarium standard solution for 11 times, and calculating the standard deviation, wherein the relative standard deviation is less than 5.0%; the 11 blank solutions were prepared according to the experimental method and measured in triplicate according to the detection limit formula C defined by IUPACL＝3Sb/k(SbBlank standard deviation, k is the corresponding slope of the calibration curve) to obtain the detection limits of 0.276 mug/L lanthanum, 0.308 mug/L cerium, 0.293 mug/L praseodymium, 0.624 mug/L neodymium, 0.501 mug/L samarium and 0.312 mug/L barium;
and 7: introducing the slag sample solution and the blank sample solution into an inductively coupled plasma mass spectrometer, and introducing Rh on line103、In115(20ug/L) internal standard element inhibits matrix effect, and La is measured139、Ce140、Pr141、Nd146、Sm147、Ba137Signal intensity of the ion to be measured, La according to known concentration139、Ce140、Pr141、Nd146、Sm147、Ba137Calibrating a standard solution calibration curve, and solving the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample solution;
the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample are calculated according to the following formula:
W％＝(Ci-C0)*V*f*100/m
in the formula: w represents the mass percentage of elements in the sample;
C0-the concentration of the element in the blank solution to be tested, ug/L;
Ci-the concentration of element in the sample to be tested, ug/L;
v-volume of solution to be measured, L;
f-dilution multiple;
m-weighing the mass of the sample, g.
Further, the dilute aqua regia is obtained by mixing water and aqua regia in equal volume.
Further, the detection range of the method is as follows: 0.0001 at-0.500 at%.
Compared with the prior art, the invention has the beneficial technical effects that:
the method is used for measuring lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the protective slag, and because the rare earth in the slag and the protective slag exists by simple electrostatic adsorption, the rare earth is easy to dissolve out, hydrofluoric acid is added to dissolve a silicon compound, a small amount of perchloric acid is added, and the residual hydrofluoric acid is completely removed by utilizing the characteristic of high boiling point of the perchloric acid and the rare earth fluoride is dissolved at the same time; the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag are detected by adopting an inductively coupled plasma mass spectrometer, and the invention has good application effect by detecting the slag sample for many times. The invention has the characteristics of small matrix interference, wide linear range, high sensitivity, simple and convenient operation and accurate and reliable analysis result.
By using the method to measure lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the protective slag, the measurement can be completed within 3 hours, the sample processing time is shortened, and the range of the analysis method can reach 0.0001-0.500%. In addition, the invention only uses 2mL nitric acid, 15mL hydrochloric acid and 5mL hydrofluoric acid to decompose the sample at low temperature, and then adds 5mL perchloric acid, which is beneficial to environmental protection.
Detailed Description
In this example, the reagents used are preferably:
nitric acid: the top grade is pure;
hydrofluoric acid: the top grade is pure;
hydrochloric acid: the top grade is pure;
aqua regia: hydrochloric acid to nitric acid volume ratio of 3: 1
Diluting aqua regia: equal volume mixing of water and aqua regia
Aqueous sulfuric acid solution: superior grade pure sulfuric acid: the water is mixed in equal volume and then 9 mol/L;
lanthanum, cerium, praseodymium, neodymium, samarium and barium single element standard solution: the concentration is 1000 mug/mL, and the product is from the national standard substance center;
lanthanum, cerium, praseodymium, neodymium, samarium and barium standard working solution: respectively sucking 5mL to 500mL of lanthanum, cerium, praseodymium, neodymium, samarium and barium single element standard solution (the concentration is 1000 mug/mL), diluting with 2% nitric acid aqueous solution, and fixing the volume to prepare 10 mug/mL mixed standard solution; sucking 10 mu g/mL to 100mL of mixed standard solution into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and preparing into 1 mu g/mL of mixed standard solution with constant volume;
rhodium and indium single element standard solution: the concentration is 1000 mug/mL, and the product is from the national standard substance center;
rhodium and indium working internal standard solution: sucking 5mL to 500mL of plastic volumetric flask of single element rhodium and indium standard solution (1000 mu g/mL), diluting with 2% nitric acid aqueous solution, and preparing 10 mu g/mL of rhodium and indium mixed standard solution with constant volume; sucking a 10 mu g/mL rhodium-indium mixed standard solution into a plastic volumetric flask with the volume of 2mL to 1000mL, diluting with a 2% nitric acid aqueous solution, and fixing the volume to prepare a 20 mu g/L rhodium-indium standard solution;
argon gas: the purity of argon is more than or equal to 99.996 percent.
The preferred inductively coupled plasma mass spectrometer model is PE company ELAN 9000; the working parameters of the instrument are as follows:
| parameter name | Numerical value |
| RF power (W) | 1300 |
| Flow of cooling gas | 15 |
| Auxiliary gas flow | 1.2 |
| Flow rate of atomized gas | 0.97 |
| Detector voltage (V) | -2200 |
| Sample introduction mode | Peristaltic pump feed |
| Sampling mode | Peak jumping mode |
| Number of repetitions | 3 |
| Lens voltage (V) | 7.50 |
| Sample introduction speed | 1.0 |
Sample analysis
0.100g of a sample is weighed, placed in a beaker of acid-boiled and cleaned polytetrafluoroethylene, 3mL of high-purity water is added to wet the sample and the sample is shaken off, and 10mL of hydrochloric acid and 5mL of hydrofluoric acid are added in sequence. And (3) putting high-purity iron into a polytetrafluoroethylene beaker cleaned by acid boiling, sequentially adding 10mL of hydrochloric acid and 5mL of hydrofluoric acid to prepare a blank sample, and then putting the polytetrafluoroethylene beaker filled with the slag sample and the blank sample on an electric hot plate for heating and dissolving. 5mL of perchloric acid is added, fuming is carried out until 2mL of perchloric acid is left, and the residual hydrofluoric acid is completely removed. Taking down, and cooling to room temperature. Adding 15mL of dilute aqua regia (aqua regia 1:1) to an electric heating plate, heating to dissolve salts, taking down, cooling to room temperature, and transferring the solution into a 200mL volumetric flask to fix the volume.
When the mass fraction of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample is more than 0.05%, transferring 25mL of sample solution into a 250mL plastic volumetric flask for constant volume to obtain a sample of the slag to be measured and a blank solution; when the mass fraction of lanthanum, cerium, praseodymium, neodymium and samarium in the sample is less than or equal to 0.05 percent, liquid separation is not needed.
Respectively sucking 1 mug/mL of mixed standard solution 0, 0.5, 2.0, 5.0, 10.0 and 20.0mL into 100mL of plastic capacity, and preparing a series of standard solutions of 0ug/L, 5.0ug/L, 20.0ug/L, 50.0ug/L, 100.0ug/L and 200.0ug/L after constant volume by using 2% nitric acid aqueous solution. The matrix of the standard solution is consistent with the slag matrix. On-line introduction of Rh103、In115(20ug/L) internal standard element, wherein the isotope of each selected element is La139、Ce140、Pr141、Nd146、Sm147、Ba137Measuring the signal intensity of the ions to be measured, and drawing La by taking the concentration as an abscissa and the signal intensity of the ions as an ordinate139、Ce140、Pr141、Nd146、Sm147、Ba137Calibration curves.
Introducing the sample solution and the blank sample solution into an inductively coupled plasma mass spectrometer, and introducing Rh on line103、In115(20ug/L) internal standard element inhibits matrix effect, and La is measured139、Ce140、Pr141、Nd146、Sm147、Ba137Signal intensity of the ion to be measured, La according to known concentration139、Ce140、Pr141、Nd146、Sm147、Ba137And (5) calibrating a curve of the standard solution, and calculating the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample solution.
The contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample are calculated according to the following formula:
W％＝(Ci-C0)*V*f*100/m
in the formula: w represents the mass percentage of elements in the slag;
C0-the concentration of the element in the blank solution to be tested, ug/L;
Ci-the sample concentration of the element in the slag to be measured, ug/L;
v-volume of solution to be measured, L;
f-dilution multiple;
m-weighing the mass of the sample, g;
the detection range of the method is as follows: 0.0001 at-0.500 at%.
Example 1
The rare earth-rich blast furnace slag standard sample R-713(RExOy has an approved value of 11.32 percent and mainly contains rare earth elements of lanthanum, cerium, praseodymium, neodymium and samarium) and the rare earth-rich blast furnace slag standard sample R-711(RExOy has an approved value of 5.32 percent and mainly contains rare earth elements of lanthanum, cerium, praseodymium, neodymium and samarium) are respectively measured by adopting the alkali fusion-ICP-AES and the method, and the results are shown in Table 1.
TABLE 1 measurement results of standard samples
Description of the implementation: the rare earth-rich blast furnace slag standard sample RExOy > 1.0%, so that 0.100g of the sample is weighed, and 2mL of the liquid is separated into 250mL plastic volumetric flasks.
Example 2
Slag standard samples are weighed, barium is measured by the method respectively, and the results are shown in table 2.
TABLE 2 results of sample measurement
Example 3
The slag samples were weighed and measured by alkali fusion-ICP-AES and the above method, respectively, and the results are shown in Table 3.
TABLE 3 results of sample measurement
Description of the implementation: the lower limit of detection of ICP-AES is 0.010%.
Example 4
Recovery by adding a label
Weighing a refining slag standard sample GBW (E)010213 not containing lanthanum, cerium, praseodymium, neodymium and samarium and a plurality of parts of YSBC28852-98 of blast furnace slag, adding a standard solution of lanthanum, cerium, praseodymium, neodymium and samarium to ensure that the contents of lanthanum, cerium, praseodymium, neodymium and samarium are respectively 0.0010%, 0.0100%, 0.100% and 0.500%, and determining by the method, wherein the results are shown in Table 4.
TABLE 4 Standard sample addition recovery assay results
The data in the table can be calculated, the standard recovery rates of lanthanum, cerium, praseodymium, neodymium, samarium and barium are all 96-106%, the measurement result is accurate, and the requirements of measuring lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the protective slag are met.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (3)
1. A method for simultaneously measuring low content of lanthanum, cerium, praseodymium, neodymium, samarium and barium in furnace slag and mold powder is characterized in that: the method comprises the following steps:
step 1: weighing 0.100g of sample, placing the sample in a polytetrafluoroethylene beaker which is acid-boiled and cleaned, adding 3mL of high-purity water to wet the sample, shaking the sample, and sequentially adding 10mL of hydrochloric acid and 5mL of hydrofluoric acid; adding 10mL of hydrochloric acid and 5mL of hydrofluoric acid into another acid-boiled and clean polytetrafluoroethylene beaker in sequence to prepare a blank sample, and then placing the polytetrafluoroethylene beaker filled with the slag sample and the blank sample on an electric heating plate for heating and dissolving;
step 2: adding 5mL of perchloric acid into the fuming solution until the volume is 2mL, and completely removing the residual hydrofluoric acid; taking down, and cooling to room temperature;
and step 3: adding 15mL of dilute aqua regia, heating on an electric heating plate to dissolve salts, taking down, cooling to room temperature, and transferring the solution into a 200mL volumetric flask;
and 4, step 4: determination of working parameters of the instrument: in the ICP-MS analysis process, high-frequency emission power, carrier gas flow and ion lens voltage directly influence the sensitivity and precision of instrument measurement, so that the instrument parameters are optimized by using tuning liquid during each measurement, and the sensitivity is as follows: in (115) greater than or equal to 200,000cps (10ug/L), signal-to-noise ratio 220 background value less than 30cps, oxide yield CeO/Ce less than 3.0%, and Ba++/Ba+< 3.0%, the operating parameters of the instrument were determined as follows:
And 5: preparing rhodium and indium internal standard solution: respectively sucking 5mL to 500mL of rhodium and indium single element standard solution into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and preparing 10 mu g/mL of rhodium and indium mixed standard solution with constant volume; sucking 2-1000 mL of mixed standard solution of rhodium and indium with the concentration of 10 mu g/mL into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and fixing the volume to prepare the mixed standard solution of rhodium and indium with the concentration of 20 mu g/L;
step 6: and (3) drawing a calibration curve: respectively absorbing 5mL to 500mL of lanthanum, cerium, praseodymium, neodymium, samarium and barium single element standard solution into a plastic volumetric flask according to the concentration of lanthanum, cerium, praseodymium, neodymium, samarium and barium in a sample to be detected, diluting the standard solution with 2% nitric acid aqueous solution, and preparing a mixed standard solution with a constant volume of 10 mu g/mL; sucking 10-100 mL of 10-mu g/mL mixed standard solution into a plastic volumetric flask, diluting with 2% nitric acid aqueous solution, and preparing into 1-mu g/mL mixed standard solution with constant volume; respectively sucking 1 mu g/mL of mixed standard solution 0, 0.5, 2.0, 5.0, 10.0 and 20.0mL into 100mL of plastic capacity, using 2% nitric acid aqueous solution to fix the volume, and preparing a series of standard solutions 0ug/L, 5.0ug/L, 20.0ug/L, 50.0ug/L, 100.0ug/L and 200.0ug/L, wherein the matrix of the standard solution is consistent with that of the slag;
introducing standard solution into inductively coupled plasma mass spectrometer, and introducing Rh on line103、In115Internal standard elements inhibit matrix effect, and isotopes of the selected elements are respectively La139、Ce140、Pr141、Nd146、Sm147、Ba137Measuring the signal intensity of the ions to be measured, and drawing La by taking the concentration as an abscissa and the signal intensity of the ions as an ordinate139、Ce140、Pr141、Nd146、Sm147、Ba137Calibrating a curve;
under the selected optimal experimental conditions, the concentration of lanthanum, cerium, praseodymium, neodymium and samarium is in the range of 0.5-200 mu g/L, the calibration curve linearity is good, and the correlation coefficient r of lanthanum, cerium, praseodymium, neodymium and samarium is more than or equal to 0.999; measuring 50 mu g/L of lanthanum, cerium, praseodymium, neodymium and samarium standard solution for 11 times, and calculating the standard deviation, wherein the relative standard deviation is less than 5.0%; the 11 blank solutions were prepared according to the experimental method and measured in triplicate according to the detection limit formula C defined by IUPACL＝3Sb/k(SbBlank standard deviation, k is the corresponding slope of the calibration curve) to obtain the detection limits of 0.276 mug/L lanthanum, 0.308 mug/L cerium, 0.293 mug/L praseodymium, 0.624 mug/L neodymium, 0.501 mug/L samarium and 0.312 mug/L barium;
and 7: introducing the slag sample solution and the blank sample solution into an inductively coupled plasma mass spectrometer, and introducing Rh on line103、In115(20ug/L) internal standard element inhibits matrix effect, and La is measured139、Ce140、Pr141、Nd146、Sm147、Ba137Signal intensity of the ion to be measured, La according to known concentration139、Ce140、Pr141、Nd146、Sm147、Ba137Calibrating a standard solution calibration curve, and solving the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample solution;
the contents of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the sample are calculated according to the following formula:
W％＝(Ci-C0)*V*f*100/m
in the formula: w represents the mass percentage of elements in the sample;
C0-the concentration of the element in the blank solution to be tested, ug/L;
Ci-the concentration of element in the sample to be tested, ug/L;
v-volume of solution to be measured, L;
f-dilution multiple;
m-weighing the mass of the sample, g.
2. The method for simultaneously determining the low content of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the covering slag according to claim 1, which is characterized in that: the dilute aqua regia is obtained by mixing water and aqua regia in equal volume.
3. The method for simultaneously determining the low content of lanthanum, cerium, praseodymium, neodymium, samarium and barium in the slag and the covering slag according to claim 1, which is characterized in that: the detection range of the method is as follows: 0.0001 at-0.500 at%.
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