CN117849028A - Method for measuring calcium fluoride and silicon dioxide in fluorite - Google Patents
Method for measuring calcium fluoride and silicon dioxide in fluorite Download PDFInfo
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 27
- 239000010436 fluorite Substances 0.000 title claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011575 calcium Substances 0.000 claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000523 sample Substances 0.000 claims abstract description 27
- 238000004458 analytical method Methods 0.000 claims abstract description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 20
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000012488 sample solution Substances 0.000 claims abstract description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 230000004907 flux Effects 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 6
- HXOLFXRMWWHLMH-UHFFFAOYSA-L disodium boric acid carbonate Chemical compound [Na+].[Na+].OB(O)O.[O-]C([O-])=O HXOLFXRMWWHLMH-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- 239000012086 standard solution Substances 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 238000011088 calibration curve Methods 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000009616 inductively coupled plasma Methods 0.000 claims description 4
- 238000010813 internal standard method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012496 blank sample Substances 0.000 claims description 3
- 239000012490 blank solution Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004380 ashing Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000005259 measurement Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 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 3
- 230000000694 effects Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000007590 Calpain Human genes 0.000 description 1
- 108010032088 Calpain Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AMUJFVCOMQMFIE-UHFFFAOYSA-N dilithium boric acid hydrogen borate Chemical compound [Li+].[Li+].OB(O)O.OB(O)O.OB(O)O.OB([O-])[O-] AMUJFVCOMQMFIE-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000013582 standard series solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for measuring calcium fluoride and silicon dioxide in fluorite, which is characterized in that a calcium-containing acetic acid solution is adopted to dissolve a sample, the sample is filtered, sodium fluoride solution is used for washing to separate calcium carbonate from calcium fluoride, sodium carbonate-boric acid mixed flux is adopted to treat residues, after hydrochloric acid is used for leaching frit, yttrium internal standard is added to improve the accuracy of measuring the calcium fluoride, and meanwhile, the calcium fluoride and the silicon dioxide in the sample solution are measured. The invention has the characteristics of wide linear range, high sensitivity, simple and convenient operation, high analysis speed and accurate and reliable analysis result, and provides reliable data for the detection of calcium fluoride and silicon dioxide in fluorite.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy analysis, in particular to a method for measuring calcium fluoride and silicon dioxide in fluorite.
Background
The fluorite comprises main components of calcium fluoride and silicon dioxide, and the determination of silicon, aluminum, iron, potassium, magnesium and titanium in the fluorite currently has national standard GB/T5195.6-2017. There is a national standard method for determining calcium fluoride in fluorite, which adopts an EDTA volumetric method.
The related literature reports that 11 elements in fluorite are measured by an inductively coupled plasma atomic emission spectrometry, a sample is dissolved by using perchloric acid-nitric acid, silicate in the sample cannot be completely dissolved according to the method, and residues exist after the dissolution; the method adopts dilute acetic acid to dissolve and separate calcium carbonate from calcium fluoride, and the EDTA capacity method is used for measuring the calcium fluoride, so that the method is complex and has long analysis time; the method comprises the steps of measuring the content of calcium fluoride in fluorite balls by an instrumental analysis method, measuring the content of calcium fluoride and calcium carbonate by adopting lithium tetraborate-lithium metaborate as a composite flux and adopting an X-fluorescence spectrometry method, converting the measured total carbon value into calcium carbonate, obtaining the content of calcium fluoride after subtraction, and having lower accuracy of analysis results during detection.
Disclosure of Invention
The invention aims to provide a method for measuring calcium fluoride and silicon dioxide in fluorite, which comprises the steps of dissolving fluorite samples by using a calcium-containing acetic acid solution, filtering, washing, separating calcium carbonate from calcium fluoride, treating residues by using a sodium carbonate-boric acid mixed flux, leaching frit by hydrochloric acid, adding an internal standard, and directly measuring the calcium fluoride and the silicon dioxide in the sample solution by using ICP-OES.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a method for measuring calcium fluoride and silicon dioxide in fluorite, which comprises the steps of dissolving a sample by adopting a calcium-containing acetic acid solution, filtering, washing by adopting a sodium fluoride solution to separate calcium carbonate from calcium fluoride, treating residues by adopting a sodium carbonate-boric acid mixed flux, leaching a frit by hydrochloric acid, adding an yttrium internal standard to improve the accuracy of measuring the calcium fluoride, and simultaneously measuring the calcium fluoride and the silicon dioxide in the sample solution.
Further, the method specifically comprises the following steps:
step 1: weighing 0.1000g of sample into a 150mL polytetrafluoroethylene beaker, dripping 10 drops of absolute ethyl alcohol for wetting, accurately adding 10.00mL of calcium-containing acetic acid solution, and dissolving at room temperature for 20min; performing three reagent blank tests;
step 2: filtering the sample solution with slow quantitative filter paper in a 250mL polytetrafluoroethylene volumetric flask, washing a beaker with a fluorine-containing washing liquid (10 ug/mL) for 3 times, washing residues for 2 times, placing the residues in a platinum crucible together with the filter paper, ashing at 850 ℃ and burning for 30min, taking out, cooling to room temperature, adding 1.5g of mixed flux, melting at 1000 ℃ for 10min, taking out, and cooling to room temperature;
step 3, placing the platinum crucible in a 300mL beaker, adding 100mL of hot water (about 80 ℃) and 10mL of hydrochloric acid into the beaker, heating the crucible by a low-temperature electric heating plate, leaching the frit, cooling the crucible to room temperature, transferring the crucible to a 250mL polytetrafluoroethylene volumetric flask, and fixing the volume of the crucible; this solution was used to determine calcium fluoride, silica;
step 4: 50mL of a sample is dispensed into a 250mL volumetric flask, 5.00mL (50 mug/mL) of yttrium internal standard is accurately added, high-purity water is diluted to a scale, and the sample is waited for being put on a machine;
step 5: preparation of standard calibration Curve solution
Standard solutions of silicon, calcium, yttrium single element: the concentration is 1000 mug/mL, and is derived from the national standard substance center;
standard solution of silicon unit element: the concentration is 100 mug/mL, and the standard solution of the silicon unit element with the concentration of 1000 mug/mL is taken for dilution by 10 times;
standard solution of calcium unit element: the concentration is 100 mug/mL, and the standard solution of the calcium unit element with the concentration of 1000 mug/mL is taken for dilution by 10 times;
yttrium single element standard solution: taking yttrium single element standard with the concentration of 1000 mug/mL for stepwise dilution, wherein the concentration is 50 mug/mL;
adding 6 parts of (1+1) hydrochloric acid 10mL into a 250mL polytetrafluoroethylene volumetric flask, adding silicon and calcium standard solutions to prepare solutions containing silicon dioxide 0, 0.100%, 0.500%, 2.50%, 5.00% and 10.00% respectively, calcium fluoride 0, 0.100%, 1.00%, 5.00%, 10.00% and 20.00% respectively, accurately adding yttrium internal standard 5.00mL (50 mug/mL), diluting to scale with high-purity water, and shaking uniformly; the solution is used for preparing a standard curve;
step 6: method for establishing analysis
Determining Ca317.956 nm as an analysis line, Y371.056 nm as an analysis line, and Si251.625nm as an analysis line;
si and Ca are analysis elements, Y is an internal standard element of calcium, and calcium is an internal standard method;
step 7, introducing a standard solution into an inductively coupled plasma spectrometer, and drawing each calibration curve by taking the mass concentration as an abscissa and the signal intensity of an element as an ordinate;
step 8: introducing the sample filtrate, the filter residue sample solution and the blank sample solution into an inductive coupling plasma spectrometer to obtain the contents of calcium fluoride and silicon dioxide in the sample solution;
SiO 2 ％＝(W i -W 0 )×f
wherein: w (W) 0 SiO in blank solution 2 ,％；
W i Sample SiO 2 Content,%;
f-dilution factor;
CaF 2 ％＝(W i -W 0 )×f×78÷40
wherein: w (W) 0 -Ca,%;
W i sample Ca content,%;
f-dilution factor;
the detection range of the method is as follows: siO (SiO) 2 0.10～50.00％；CaF 2 5.00～99.00％。
Further, in the step (2), the mixed flux comprises sodium carbonate and boric acid, and the mass ratio is 2:1.
Further, in the step (6), the measurement instrument is Optima 5300DV of PE company in the united states.
Further, the observation mode is vertical observation.
Further, the detection range: siO (SiO) 2 0.10～50.00％；CaF 2 5.00～99.00％。
Compared with the prior art, the invention has the beneficial technical effects that:
1. according to the invention, only 1.0g of mixed flux, 10mL of hydrochloric acid, trace sodium fluoride, calcium carbonate and acetic acid are used, so that less chemical reagent is used, the materials are saved, and the environment protection is facilitated; the method is simple to operate, and the calcium fluoride and the silicon dioxide are measured in 3 hours at the same time, so that the operation flow and the measuring time are shortened relative to an EDTA capacity method, an atomic absorption method and a silicon dioxide weight method, and the aim of measuring the calcium fluoride and the silicon dioxide at the same time is fulfilled.
2. The signal intensity of calcium, yttrium and silicon is reduced by adopting a vertical observation mode, so that the measurement range is enlarged, the measurement stability is improved, and the measurement result has high sensitivity and more accurate result.
3. The internal standard method eliminates errors caused by instrument drift to a certain extent by measuring the relative values of the calcium element and the yttrium internal standard, so that the accuracy and precision of the measurement result are high, the measurement stability is improved, and the sensitivity of the measurement result is high.
4. The method adopts calcium-containing acetic acid to pretreat the sample, and the sodium fluoride dilute solution is used for washing the residue to avoid the dissolution of calcium fluoride, so that the calcium carbonate in the sample is separated from the calcium fluoride, and the internal standard-ICP-OES method is used for respectively measuring the calcium carbonate and the calcium fluoride, so that the method is more advanced and has more popularization value.
Scope of the method SiO 2 0.10～50.00％；CaF 2 5.00-99.00%. The invention has good application effect through multiple times of inspection on fluorite samples. The invention has the characteristics of wide linear range, high sensitivity, simple and convenient operation, high analysis speed and accurate and reliable analysis result, and provides reliable data for the detection of calcium fluoride and silicon dioxide in fluorite.
Detailed Description
In the examples of the present invention, the reagents used are preferably:
inductively coupled plasma emission spectrometer (ICP-OES) Optima 5300DV (american PE company); the observation mode is vertical observation; ca317.956 nm is determined as an analysis line, Y371.056 nm is an analysis line, si251.625nm is determined as an analysis line (Si, ca are analysis elements, Y is an internal standard element of calcium, and calcium is an internal standard method). A muffle furnace; 250mL polytetrafluoroethylene volumetric flask; a polytetrafluoroethylene beaker; argon: argon purity is more than or equal to 99.9%; compressed air.
Sodium fluoride: high purity; a calcium carbonate reference; acetic acid; hydrochloric acid: high-grade purity; sodium carbonate: high-grade purity; boric acid: high-grade purity.
Standard solutions of silicon, calcium, yttrium single element: the concentration is 1000 mug/mL, which is from the national center for standard substance.
Standard solution of silicon unit element: the concentration was 100. Mu.g/mL, and the standard solution of silicon single element with the concentration of 1000. Mu.g/mL was diluted 10 times.
Standard solution of calcium unit element: the concentration was 100. Mu.g/mL, and the standard solution of calpain at a concentration of 1000. Mu.g/mL was diluted 10-fold.
Yttrium single element standard solution: the yttrium single unit element standard with the concentration of 1000 mug/mL is diluted step by step with the concentration of 50 mug/mL.
Calcium-containing acetic acid solution: 0.1500g of calcium carbonate was weighed into a 400mL beaker, 50mL of acetic acid (1+9) was added, heated to boiling for 3min to remove carbon dioxide, cooled to room temperature, and diluted to 1000mL with acetic acid (5+95). This solution was 60ug/mL.
Fluorine-containing washing solution (250 ug/mL), 0.5528g of sodium fluoride (high purity) was weighed and dissolved in water, transferred into a 1000mL plastic volumetric flask, diluted to scale with water, and shaken well.
The fluorine-containing washing solution (10 ug/mL) was diluted to 1000mL with 40mL of the fluorine-containing washing solution (250 ug/mL), and prepared.
1. Sample analysis
0.1000g of the sample is weighed into a 150mL polytetrafluoroethylene beaker, 10 drops of absolute ethyl alcohol are dripped into the beaker to be wetted, 10.00mL of calcium-containing acetic acid solution is accurately added, and the solution is dissolved for 20min at room temperature. The sample solution was filtered with a slow quantitative filter paper in a 250mL polytetrafluoroethylene volumetric flask, the beaker was washed 3 times with a fluorine-containing washing solution (10 ug/mL), the residue was washed 2 times, the residue was ashed and burned with the filter paper in a platinum crucible at 850 ℃ for 30min, and after cooling to room temperature, 1.5g of a mixed flux (sodium carbonate: boric acid=2:1) was added and melted at 1000 ℃ for 10min. Taking out, and cooling to room temperature. The platinum crucible is placed in a 300mL beaker, 100mL hot water (about 80 ℃) and 10mL hydrochloric acid are added, after the frit is heated and leached by a low-temperature electric hot plate, the temperature is cooled to room temperature, and the mixture is transferred and fixed in a 250mL polytetrafluoroethylene volumetric flask. This solution was used for the determination of calcium fluoride, silica. Three reagent blank tests were performed concomitantly.
50mL of the sample was dispensed into a 250mL volumetric flask, 5.00mL (50. Mu.g/mL) of yttrium internal standard was accurately added, and high purity water was diluted to a scale and the flask was waited for machine-on.
Preparation of standard calibration Curve solution
6 parts of (1+1) hydrochloric acid (10 mL) are taken in a 250mL polytetrafluoroethylene volumetric flask, silicon and calcium standard solutions are added to prepare solutions respectively containing 0, 0.100%, 0.500%, 2.50%, 5.00% and 10.00% of silicon dioxide, 0, 0.100%, 1.00%, 5.00% and 10.00% of calcium fluoride, 5.00mL (50 mug/mL) of yttrium internal standard is accurately added, the solutions are diluted to scale by high-purity water, and shaking is carried out uniformly. The solution was used to make a standard curve.
And (3) measuring:
and introducing the standard series solution into an inductively coupled plasma spectrometer, and drawing each calibration curve by taking the mass concentration as an abscissa and the signal intensity of the element as an ordinate. And introducing the sample solution and the blank sample solution into an inductive coupling plasma spectrometer to obtain the contents of calcium fluoride and silicon dioxide in the sample solution.
SiO 2 ％＝(W i -W 0 )×f
Wherein: w (W) 0 SiO in blank solution 2 ,％；
W i Sample SiO 2 Content,%;
f-dilution factor;
CaF 2 ％＝(W i -W 0 )×f×78÷40
wherein: w (W) 0 -Ca,%;
W i sample Ca content,%;
f-dilution factor;
the detection range of the method is as follows: siO (SiO) 2 0.10～50.00％；CaF 2 5.00～99.00％。
Example 1
Working curves are made according to the method, curve correlation coefficients r of silicon dioxide and calcium fluoride are all larger than 0.9990, and the method detects limit SiO 2 0.01%, caF 2 0.05%.
Example 2
Accuracy test
Standard substances GBW07252, YSB14792-02, YSB14796-02, YSB14794-02, BH0121-14W, GBW07254a were measured by the method, and the results are shown in the following table.
Standard sample measurement results
Example 3
Precision of the method
Under the selected experimental method, weighing fluorite samples No. 1, no. 2 and No. 3, preparing 8 sample solutions in parallel, and performing precision investigation. The Relative Standard Deviation (RSD) of each component measurement was calculated as shown in the following table.
Results of precision test
Thus, it can be seen from the verification of the above examples that the method for detecting silicon dioxide and calcium fluoride in fluorite according to the present invention has a detection range of SiO 2 0.10～50.00％；CaF 2 5.00-99.00%. Through multiple tests on fluorite samples, the application effect is good. The invention has the characteristics of wide linear range, high sensitivity, simple and convenient operation, high analysis speed and accurate and reliable analysis result, and provides reliable data for detecting silicon dioxide and calcium fluoride in fluorite.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (6)
1. A method for measuring calcium fluoride and silicon dioxide in fluorite is characterized in that a calcium-containing acetic acid solution is adopted to dissolve a sample, the sample is filtered, the sodium fluoride solution is used for washing, calcium carbonate and calcium fluoride are separated, a sodium carbonate-boric acid mixed flux is adopted to treat residues, after hydrochloric acid is used for leaching frit, yttrium internal standard is added to improve the accuracy of measuring the calcium fluoride, and meanwhile, the calcium fluoride and the silicon dioxide in the sample solution are measured.
2. The method for measuring calcium fluoride and silicon dioxide in fluorite according to claim 1, comprising the following steps:
step 1: weighing 0.1000g of sample into a 150mL polytetrafluoroethylene beaker, dripping 10 drops of absolute ethyl alcohol for wetting, accurately adding 10.00mL of calcium-containing acetic acid solution, and dissolving at room temperature for 20min; performing three reagent blank tests;
step 2: filtering the sample solution with slow quantitative filter paper in a 250mL polytetrafluoroethylene volumetric flask, washing a beaker with a fluorine-containing washing liquid (10 ug/mL) for 3 times, washing residues for 2 times, placing the residues in a platinum crucible together with the filter paper, ashing at 850 ℃ and burning for 30min, taking out, cooling to room temperature, adding 1.5g of mixed flux, melting at 1000 ℃ for 10min, taking out, and cooling to room temperature;
step 3, placing the platinum crucible in a 300mL beaker, adding 100mL of hot water (about 80 ℃) and 10mL of hydrochloric acid into the beaker, heating the crucible by a low-temperature electric heating plate, leaching the frit, cooling the crucible to room temperature, transferring the crucible to a 250mL polytetrafluoroethylene volumetric flask, and fixing the volume of the crucible; this solution was used to determine calcium fluoride, silica;
step 4: 50mL of a sample is dispensed into a 250mL volumetric flask, 5.00mL (50 mug/mL) of yttrium internal standard is accurately added, high-purity water is diluted to a scale, and the sample is waited for being put on a machine;
step 5: preparation of standard calibration Curve solution
Standard solutions of silicon, calcium, yttrium single element: the concentration is 1000 mug/mL, and is derived from the national standard substance center;
standard solution of silicon unit element: the concentration is 100 mug/mL, and the standard solution of the silicon unit element with the concentration of 1000 mug/mL is taken for dilution by 10 times;
standard solution of calcium unit element: the concentration is 100 mug/mL, and the standard solution of the calcium unit element with the concentration of 1000 mug/mL is taken for dilution by 10 times;
yttrium single element standard solution: taking yttrium single element standard with the concentration of 1000 mug/mL for stepwise dilution, wherein the concentration is 50 mug/mL;
adding 6 parts of (1+1) hydrochloric acid 10mL into a 250mL polytetrafluoroethylene volumetric flask, adding silicon and calcium standard solutions to prepare solutions containing silicon dioxide 0, 0.100%, 0.500%, 2.50%, 5.00% and 10.00% respectively, calcium fluoride 0, 0.100%, 1.00%, 5.00%, 10.00% and 20.00% respectively, accurately adding yttrium internal standard 5.00mL (50 mug/mL), diluting to scale with high-purity water, and shaking uniformly; the solution is used for preparing a standard curve;
step 6: method for establishing analysis
Determining Ca317.956 nm as an analysis line, Y371.056 nm as an analysis line, and Si251.625nm as an analysis line;
si and Ca are analysis elements, Y is an internal standard element of calcium, and calcium is an internal standard method;
step 7, introducing a standard solution into an inductively coupled plasma spectrometer, and drawing each calibration curve by taking the mass concentration as an abscissa and the signal intensity of an element as an ordinate;
step 8: introducing the sample filtrate, the filter residue sample solution and the blank sample solution into an inductive coupling plasma spectrometer to obtain the contents of calcium fluoride and silicon dioxide in the sample solution;
SiO 2 ％＝(W i -W 0 )×f
wherein: w (W) 0 SiO in blank solution 2 ,％；
W i Sample SiO 2 Content,%;
f-dilution factor;
CaF 2 ％＝(W i -W 0 )×f×78÷40
wherein: w (W) 0 -Ca,%;
W i sample Ca content,%;
f-dilution factor;
the detection range of the method is as follows: siO (SiO) 2 0.10～50.00％；CaF 2 5.00～99.00％。
3. The method for measuring calcium fluoride and silica in fluorite according to claim 2, wherein in the step (2), the mixed flux comprises sodium carbonate and boric acid in a mass ratio of 2:1.
4. The method according to claim 1, wherein in the step (6), the measuring instrument is Optima 5300DV of PE company in America.
5. The method for measuring calcium fluoride and silica in fluorite according to claim 4, wherein the observation mode is vertical observation.
6. The method for measuring calcium fluoride and silica in fluorite according to claim 2, wherein the detection range is: siO (SiO) 2 0.10～50.00％；CaF 2 5.00～99.00％。
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