CN112179930A - Method for measuring contents of nine substances in high-sulfur bauxite by X-ray fluorescence spectrometry - Google Patents
Method for measuring contents of nine substances in high-sulfur bauxite by X-ray fluorescence spectrometry Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 127
- 239000011593 sulfur Substances 0.000 title claims abstract description 117
- 229910001570 bauxite Inorganic materials 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000000126 substance Substances 0.000 title claims abstract description 48
- 238000004846 x-ray emission Methods 0.000 title claims abstract description 27
- 230000004907 flux Effects 0.000 claims abstract description 74
- 239000011521 glass Substances 0.000 claims abstract description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 58
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims description 17
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical class [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 101710103839 Glucokinase-1 Proteins 0.000 claims description 5
- 101000921261 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Putative glucokinase-2 Proteins 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 28
- 239000000956 alloy Substances 0.000 abstract description 28
- 238000001514 detection method Methods 0.000 abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 12
- 238000001304 sample melting Methods 0.000 description 9
- 238000012795 verification Methods 0.000 description 9
- 238000009614 chemical analysis method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000590428 Panacea Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005464 sample preparation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000010200 validation analysis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 108010050062 mutacin GS-5 Proteins 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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Abstract
The invention relates to a method for measuring the content of nine substances in high-sulfur bauxite by X-ray fluorescence spectrometry, which comprises the steps of uniformly stirring a sulfur-containing mixed flux, a bauxite standard sample, lithium nitrate and a flux, and pre-oxidizing the mixture to prepare a standard sample glass sheet; sequentially measuring the fluorescence intensity of Al, Si, Fe, Ti, K, Na, Ca, Mg and S in the glass sheet in an X-ray fluorescence spectrometer, taking the fluorescence intensity as a vertical coordinate and taking the corresponding substance Al2O3、SiO2、Fe2O3、TiO2、K2O、Na2Establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as abscissa; uniformly stirring the high-sulfur bauxite, the flux and the lithium nitrate, and pre-oxidizing to prepare a glass sheet to be detected; and measuring the fluorescence intensity of the elements in the glass sheet to be detected, and calculating the content of the substances in the glass sheet to be detected according to the fluorescence intensity and the working curve. The invention can shorten the detection process of the high-sulfur bauxite mineral quality and reduceCorrosion of the platinum-yellow alloy crucible by elemental sulfur.
Description
Technical Field
The invention relates to the technical field of substance determination in high-sulfur bauxite, in particular to a method for determining the content of nine substances in the high-sulfur bauxite by using an X-ray fluorescence spectrometry method.
Background
The resources of the high-sulfur bauxite in China are rich, the development and the application of the high-sulfur bauxite are gradually promoted along with the shortage of the bauxite resources in recent years, and Al in the high-sulfur bauxite is inevitably required to be used in the application process of the bauxite2O3、SiO2、Fe2O3、TiO2、K2O、Na2And analyzing and detecting components such as O, CaO, MgO, S and the like. Many enterprises are currently using X-ray fluorescence spectroscopy to determine the components of bauxite, but it is common to determine the oxide content of bauxite. High sulfur bauxite is a special type of bauxite that contains, in addition to the oxides found in conventional bauxite, sulfur in a reduced valence state. The low-valence sulfur is volatile and corrodes a platinum-yellow alloy crucible in the melting process, even if only the oxide in the high-sulfur bauxite is measured, the low-valence sulfur cannot be directly measured by using a general X-ray fluorescence spectroscopy, if the platinum-yellow alloy crucible is seriously and irreversibly corroded by directly using the general X-ray fluorescence spectroscopy, so that the high-sulfur bauxite is firstly burnt at high temperature, the low-valence sulfur is burnt, and then the low-valence sulfur is measured according to the general X-ray fluorescence spectroscopy, only the oxide component in the high-sulfur bauxite can be measured, the sulfur content cannot be measured due to the large volatilization of the sulfur in the burning process, the burning step is added, the detection cost is increased, the detection flow is prolonged, the sulfur measurement needs to be separately measured by using a carbon-sulfur instrument, and an effective bauxite standard sample with high sulfur content is lack in China, so that the X-ray fluorescence spectrometry has great limitation in the detection of the high-sulfur bauxite.
The method for preparing the sulfur-containing mixed flux is adopted, the low-valence sulfur element is introduced into the standard sample preparation step, and the lithium nitrate is used for low-temperature pre-oxidation to convert the low-valence sulfur into the high-valence sulfur, so that the problems of volatilization and crucible corrosion of the low-valence sulfur element in the melting process are solved, and the sulfur and other oxide components in the high-sulfur alumina can be measured simultaneously. The method for preparing the sulfur-containing mixed flux and adding the sulfur standard reagent can reduce the weighing error of the sulfur element in the adding process, can ensure that the sulfur element is better and uniformly mixed with the flux and the bauxite standard sample, ensures that the subsequent pre-oxidation is more complete and thorough, and can simultaneously measure the sulfur and other oxides in the high-sulfur bauxite after the pre-oxidation.
Disclosure of Invention
Aiming at the technical problems encountered in the analysis and detection of the high-sulfur bauxite, the invention provides the method for measuring the content of nine substances in the high-sulfur bauxite by the X-ray fluorescence spectrometry, which can shorten the quality detection process and period of the high-sulfur bauxite minerals, improve the detection efficiency, reduce the corrosion of sulfur elements to a platinum-yellow alloy crucible and save the labor cost and the economic cost.
The invention adopts the following technical scheme:
the method for measuring the contents of nine substances in the high-sulfur bauxite by using the X-ray fluorescence spectrometry is characterized by comprising the following steps of:
(1) uniformly mixing the sulfur-containing standard substance with the flux to obtain a sulfur-containing mixed flux;
(2) uniformly stirring a sulfur-containing mixed flux, a bauxite standard sample, a pre-oxidant lithium nitrate and a flux to obtain a compound standard sample;
(3) adding a compound standard sample into release agent saturated lithium bromide, and heating for pre-oxidation;
(4) preparing a pre-oxidized compound standard sample into a standard sample glass sheet by adopting a melting method;
(5) sequentially measuring the fluorescence intensity of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S in a standard sample glass sheet in an X-ray fluorescence spectrometer, taking the fluorescence intensity of the nine elements in the standard sample glass sheet as a vertical coordinate, and taking nine substances Al corresponding to the nine elements in the standard sample glass sheet2O3、SiO2、Fe2O3、TiO2、K2O、Na2Establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as a horizontal coordinate, and correcting and verifying the accuracy of the working curve;
(6) uniformly stirring the high-sulfur bauxite, the flux and the pre-oxidizing agent lithium nitrate to obtain a mixture, dropwise adding the mixture into release agent saturated lithium bromide, and heating for pre-oxidizing;
(7) preparing the pre-oxidized mixture into a glass sheet to be detected by adopting a melting method;
(8) putting the glass sheet to be detected into an X-ray fluorescence spectrometer to measure the fluorescence intensity of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S, and calculating nine substances including Al, corresponding to the nine elements in the glass sheet to be detected according to the fluorescence intensity of the nine elements in the glass sheet to be detected and the working curve in the step (5)2O3、SiO2、Fe2O3、TiO2、K2O、Na2Contents of O, CaO, MgO, and S.
The method for determining the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the mass percentage of S in the high-sulfur bauxite is 0.7-9%.
The method for measuring the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the sulfur-containing standard substance in the step (1) is GBW 07267.
The method for measuring the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the flux in the step (1), the flux in the step (2) and the flux in the step (6) are mixed fluxes consisting of lithium tetraborate and lithium metaborate, and the mass ratio of the lithium tetraborate to the lithium metaborate in the mixed fluxes is 67: 33.
The method for measuring the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the mass ratio of the sulfur-containing standard substance to the flux in the step (1) is (5-10): 1.
The method for determining the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that in the step (2), the bauxite standard sample is a mixture consisting of five or more than five of GBW070036, GBW07177, GBW07178, GBW07179, GBW07180, GLK-1, GLK-2, GLK-4, GLK-6, GLK-7, GLK-8 and GLK-10.
The method for determining the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the mass ratio of the bauxite standard sample, the flux and the pre-oxidant lithium nitrate in the step (2) is 1: (7-14): (1-2); and (3) the weighed mass of the high-sulfur bauxite, the flux and the pre-oxidant lithium nitrate in the step (6) is the same as that of the standard bauxite sample, the flux and the pre-oxidant lithium nitrate in the step (2).
The method for determining the element content in the high-sulfur bauxite by the X-ray fluorescence spectrometry is characterized in that the process conditions of the pre-oxidation in the step (3) and the process conditions of the pre-oxidation in the step (6) are both as follows: the pre-oxidation temperature is 500-650 ℃, and the pre-oxidation time is 10-20 min.
The invention has the beneficial technical effects that: the method can quickly and accurately measure the Al of the high-sulfur bauxite2O3、SiO2、Fe2O3、TiO2、K2O、Na2Contents of 9 substances such as O, CaO, MgO, and S. The invention is suitable for Al in the high-sulfur bauxite with 0.7 to 9 mass percent of S2O3、SiO2、Fe2O3、TiO2、K2O、Na2And (4) detecting the contents of 9 substances such as O, CaO, MgO, S and the like. The invention effectively solves the problem that the high-sulfur bauxite lacks effective standard samples in the X-ray fluorescence spectrum analysis; the method can simultaneously measure the sulfur and other conventional oxides of the high-sulfur bauxite only by using the X-ray fluorescence spectrometer, and the high-sulfur bauxite does not need to be measured after being burned at high temperature in the measuring process, and the carbon-sulfur instrument and the X-ray fluorescence spectrometer are not used for matching measurement, so that the material detection process and period of the high-sulfur bauxite are greatly shortened, and the detection efficiency is greatly improved; the invention solves the problem of serious corrosion of sulfur element to the platinum-yellow alloy crucible in the melting sample preparation process, and greatly prolongs the service life of the expensive vessel; the invention can be effectiveSaving labor cost and economic cost, and having important significance for accelerating the development and application of high-sulfur bauxite.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
Referring to fig. 1, the method for measuring the content of nine substances in the high-sulfur bauxite by using the X-ray fluorescence spectrometry comprises the following steps:
establishing a working curve:
(1) preparing a sulfur-containing mixed flux: putting the sulfur-containing standard substance and the flux into a tungsten carbide material pot, and grinding for 40-60 s by using a vibration mill to obtain a sulfur-containing mixed flux; the sulfur-containing standard substance is GBW 07267. The mass ratio of the sulfur-containing standard substance to the flux is (5-10): 1.
(2) Compounding a standard sample: determining proper flux weighing mass and sample weighing mass according to the volume of the crucible, sequentially weighing a certain amount of flux, a sulfur-containing mixed flux with the sulfur element content of 0.7-9% by mass, a bauxite standard sample with required mass and a pre-oxidizer lithium nitrate in a platinum-yellow alloy crucible, and uniformly stirring to obtain a compound standard sample; the mass ratio of the bauxite standard sample to the flux to the pre-oxidant lithium nitrate is 1: (7-14): (1-2). The bauxite standard sample is a mixture consisting of five or more than five of GBW070036, GBW07177, GBW07178, GBW07179, GBW07180, GLK-1, GLK-2, GLK-4, GLK-6, GLK-7, GLK-8 and GLK-10.
(3) Pre-oxidation: 5 drops of release agent saturated lithium bromide are dripped into the compound standard sample, and then the compound standard sample and the platinum-yellow alloy crucible are placed in a muffle furnace at 500-650 ℃ and are burnt for 10-20 min, so that the pre-oxidation of the compound standard sample is completed.
(4) Preparation of standard sample glass sheet: and putting the pre-oxidized compound standard sample and the platinum-yellow alloy crucible into a full-automatic sample melting machine, melting for 10-15 min at the temperature of 1065-1075 ℃, and pouring into uniform and transparent standard sample glass sheets for later use.
(5) Establishing a working curve: selecting proper measuring conditions for X-ray fluorescence spectrometerSequentially measuring the fluorescence intensities of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S in the standard sample glass sheet, taking the fluorescence intensities of the nine elements in the standard sample glass sheet as a vertical coordinate, and taking nine substances Al corresponding to the nine elements in the standard sample glass sheet2O3、SiO2、Fe2O3、TiO2、K2O、Na2And establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as the abscissa, and correcting and verifying the accuracy of the working curve.
Measuring a high-sulfur bauxite sample to be measured:
the mass percentage of S in the high-sulfur bauxite is 0.7-9%.
(6) Pre-oxidation: the weighed mass of the high-sulfur bauxite, the flux and the pre-oxidant lithium nitrate is completely the same as that of the bauxite standard sample, the flux and the pre-oxidant lithium nitrate in the step (2). And (3) sequentially weighing the bauxite standard sample, the flux and the lithium nitrate serving as the preoxidant to be detected with equal mass according to the weighed mass of the bauxite standard sample, the flux and the lithium nitrate serving as the preoxidant in the step (2), placing the weighed samples into a platinum-yellow alloy crucible, uniformly stirring to obtain a mixture, dropwise adding 4-6 drops of release agent saturated lithium bromide into the mixture, placing the mixture dropwise added with the release agent into a muffle furnace at 500-650 ℃, and igniting for 10-20 min for preoxidation.
The flux in the step (1), the flux in the step (2) and the flux in the step (6) are mixed fluxes composed of lithium tetraborate and lithium metaborate, and the mass ratio of the lithium tetraborate to the lithium metaborate in the mixed fluxes is 67: 33.
(7) Preparing a glass sheet to be detected: and putting the pre-oxidized mixture sample and the platinum-yellow alloy crucible into a full-automatic sample melting machine, melting at 1065-1075 ℃ for 10-15 min, and pouring into a uniform and transparent glass sheet to be detected.
(8) Measurement: putting the glass sheet to be detected into an X-ray fluorescence spectrometer to measure the fluorescence intensity of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S, and calculating nine substances A corresponding to the nine elements in the glass sheet to be detected according to the fluorescence intensity of the nine elements in the glass sheet to be detected and the working curve in the step (5)l2O3、SiO2、Fe2O3、TiO2、K2O、Na2The contents of O, CaO, MgO and S are calculated according to the following formula:
Wi＝Di+Ei·I·M
in the formula:
Wi-mass concentration (%) of the test substance i;
Di-calibration curve intercept (%);
Ei-calibrating the slope of the curve;
i-the net fluorescence count rate (KCPS) of element I;
m is matrix correction coefficient.
The invention is further illustrated by the following examples.
Example 1
1. Establishing a measuring working curve:
(1) preparing a sulfur-containing mixed flux: selecting a flux (the flux is composed of anhydrous lithium tetraborate and lithium metaborate, wherein the mass ratio of the anhydrous lithium tetraborate to the lithium metaborate is 67:33) to GBW07267 is 10:1, accurately weighing 1.0000g (+ -0.0001 g) of sulfur-containing standard substance GBW07267 and 10.0000g (+ -0.0001 g) of flux in a weighing bottle, placing the weighing bottle in a tungsten carbide material bowl, grinding the tungsten carbide material bowl for 60s by using a vibration mill, and preparing the sulfur-containing mixed flux for later use. Wherein, the mass percentage of Fe in GBW07267 is 46.08%, the mass percentage of S is 52.72%, and each gram of the sulfur-containing mixed flux contains 0.0419g of Fe, 0.04792g S g of the sulfur-containing mixed flux, and 0.9091g of the anhydrous lithium tetraborate and lithium metaborate flux.
(2) Compounding a compound standard sample required for establishing a working curve: the sulfur-containing mixed flux is added into standard substances GBW070036, GBW07177, GBW07178, GBW07179, GBW07180, GLK-1, GLK-2, GLK-4, GLK-7 and GLK-10 respectively to obtain a compound standard sample required for establishing a working curve. According to the size of the platinum-yellow alloy crucible, the weight sample amount of anhydrous lithium tetraborate and lithium metaborate flux (mass ratio is 67:33) is 7g, the weight sample amount of bauxite standard sample is 0.7g, the weight sample amount of lithium nitrate is 0.7g, and the preparation mass fraction of S is 0.72-8.22%. The weighing quantities of the substances are shown in Table 1.
Table 1 weighing mass table for each substance in compound standard sample
(3) Pre-oxidation and glass sheet preparation: accurately weighing (+ -0.0001 g) the substances in a platinum-yellow alloy crucible according to the weighing amounts of the substances given in the table 1, uniformly stirring the weighed reagents and samples by using a glass rod, adding 5 drops of saturated lithium bromide solution, placing the compound standard sample and the platinum-yellow alloy crucible in a muffle furnace at 650 ℃ for preoxidation for 10min, then placing the preoxidized compound standard sample and the platinum-yellow alloy crucible in a full-automatic sample melting machine, melting the preoxidized compound standard sample at 1065-1075 ℃ for 13min, and pouring into uniform and transparent standard sample glass sheets for later use, wherein the substance content of each glass sheet is shown in the table 2.
Table 2 glass flake material content table
(4) Working curve creation
And (3) sequentially measuring the fluorescence intensities of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S in the standard sample glass sheet prepared in the step (3) in an X-ray fluorescence spectrometer, wherein the measurement conditions of the nine elements are shown in Table 3. The fluorescence intensity of nine elements in the glass sheet of the standard sample is taken as the ordinate, and nine substances Al corresponding to the nine elements in the glass sheet of the standard sample are taken2O3、SiO2、Fe2O3、TiO2、K2O、Na2And establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as the abscissa.
After the working curves are established, the working curves need to be corrected to reduce the absorption enhancement effect among elements, in example 1, superQ analysis software provided by panacea is used to correct the working curves, and the corrected working curves need to be subjected to accuracy verification of the method.
TABLE 3 measurement conditions
(5) Method accuracy verification
Preparing standard samples required by the accuracy of the verification method according to the weighing method shown in Table 4, accurately weighing the samples to +/-0.0001 g, uniformly stirring the weighed reagents and samples by using a glass rod, adding 5 drops of saturated lithium bromide solution, pre-oxidizing in a muffle furnace at 650 ℃ for 10min, then placing in an automatic sample melting machine, melting at 1070 +/-5 ℃ for 13min, and pouring into uniform and transparent glass sheets for later use. The glass sheets were measured using the established working curves, and the results of comparison of the measurement results of each element with the standard values are shown in Table 5. From the comparison result of the standard value and the measured value, the established working curve of each substance can meet the detection requirement in the relevant analysis standard, and therefore, the working curve can be used for measuring daily unknown samples.
Table 4 standard sample preparation method for validation
TABLE 5 working curve accuracy verification
2. Preparation and measurement of sample to be tested
(1) Sample weighing: 7.0000g (+ -0.0001 g) of anhydrous lithium tetraborate and lithium metaborate flux (the mass ratio of the anhydrous lithium tetraborate to the lithium metaborate is 67:33), 0.7000g (+ -0.0001 g) of lithium nitrate and 0.7g (+ -0.0001 g) of a high-sulfur bauxite sample to be detected are accurately weighed in a platinum-yellow alloy crucible, and are uniformly stirred by a glass rod to obtain a mixture.
(2) Pre-oxidation: and placing the mixture in a platinum-yellow alloy crucible, adding 5 drops of saturated lithium bromide solution serving as a release agent into the platinum-yellow alloy crucible, and then placing the mixture in a muffle furnace at 650 ℃ for burning for 10min to complete the pre-oxidation of the sample.
(3) Preparing a glass sheet to be detected: and putting the pre-oxidized mixture sample and the platinum-yellow alloy crucible into a full-automatic sample melting machine, melting for 13min at 1070 +/-5 ℃, and pouring into a uniform and transparent glass sheet to be detected.
(4) Measurement: placing the glass sheet to be detected in an X-ray fluorescence spectrometer to measure the fluorescence intensity of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S, and calculating nine substances including Al corresponding to the nine elements according to the fluorescence intensity of the nine elements in the glass sheet to be detected and the working curve after correction and accuracy verification2O3、SiO2、Fe2O3、TiO2、K2O、Na2Contents of O, CaO, MgO, and S.
Example 1 the precision of the method of example 1 was confirmed by taking a total of 4 unknown samples for measurement, of which sample GS-2 was melted into 11 glass pieces, and the measurement results are shown in table 6. The method of example 1 is accurate from 11 measurements and standard deviations. The results of the measurements of the 4 unknown samples using the method of example 1 are compared with the results of the chemical analysis method using a carbon sulfur analyzer, as shown in Table 7. From the comparison results between the chemical analysis method and the method of example 1, the detection result of the method of example 1 and the detection result of the chemical analysis method are better matched. The method of the embodiment 1 effectively solves the problems of volatilization of sulfur element and corrosion to the platinum-yellow alloy crucible in the sample melting preparation process, can simultaneously measure sulfur and other conventional oxide components of the high-sulfur bauxite by only using the X-ray fluorescence spectrometer, does not need to burn the high-sulfur bauxite at high temperature and then measure the high-sulfur bauxite, and does not need to use two instruments of a carbon-sulfur instrument and the X-ray fluorescence spectrometer for measurement, thereby greatly prolonging the service life of the platinum-yellow alloy crucible, shortening the detection flow, saving the detection cost for enterprises and improving the detection rate.
TABLE 6 method precision test
TABLE 7 comparison of the results of measurements of unknown samples using the method of example 1 with the results of measurements of chemical analysis methods
Example 2
1. Establishing a measuring working curve:
(1) preparing a sulfur-containing mixed flux: selecting a flux (the flux is composed of anhydrous lithium tetraborate and lithium metaborate, wherein the mass ratio of the anhydrous lithium tetraborate to the lithium metaborate is 67:33) to GBW07267 is 5:1, accurately weighing 1.0000g (+ -0.0001 g) of flux of sulfur-containing standard substances GBW07267 and 5.0000g (+ -0.0001 g) in a weighing bottle, placing the flux in a tungsten carbide material pot, and grinding the flux for 60s by using a vibration mill to prepare a sulfur-containing mixed flux for later use. Wherein, the percentage content of Fe in GBW07267 is 46.08%, the percentage content of S is 52.72%, and each gram of the sulfur-containing mixed flux contains 0.0768g of Fe, 0.08787g S and 0.8333g of flux.
(2) Compounding a compound standard sample required for establishing a working curve: the sulfur-containing mixed flux is added into standard substances GBW070036, GBW07177, GBW07178, GBW07179, GBW07180, GLK-1, GLK-2, GLK-4, GLK-7 and GLK-10 respectively to obtain a compound standard sample required for establishing a working curve. According to the size of the platinum-yellow alloy crucible, the weight sample amount of anhydrous lithium tetraborate and lithium metaborate flux (mass ratio is 67:33) is 7g, the weight sample amount of bauxite standard sample is 0.7g, the weight sample amount of lithium nitrate is 1.4g, and the preparation mass fraction of S is 0.79-8.79%. The weighing amounts of the substances are shown in Table 8.
Table 8 weighing mass table for each substance in the compound standard sample
(3) Pre-oxidation and glass sheet preparation: accurately weighing (+ -0.0001) the substances in a platinum-yellow alloy crucible according to the weighing amounts of the substances given in the table 8, uniformly stirring the weighed reagents and samples by using a glass rod, adding 5 drops of saturated lithium bromide solution, placing the compound standard sample and the platinum-yellow alloy crucible in a muffle furnace for pre-oxidation at 500 ℃ for 20min, placing the pre-oxidized compound standard sample in an automatic sample melting machine, melting for 13min at 1070 +/-5 ℃, and pouring into uniform and transparent standard sample glass sheets for later use, wherein the element content of each glass sheet is shown in the table 9.
Table 9 preparation of glass flake element content table
(4) Working curve creation
The prepared standard sample glass sheet is placed in an X-ray fluorescence spectrometer to sequentially measure the fluorescence intensity of nine elements of Al, Si, Fe, Ti, K, Na, Ca, Mg and S in the standard sample glass sheet, and the measurement conditions of the nine elements are shown in Table 3. The fluorescence intensity of nine elements in the glass sheet of the standard sample is taken as the ordinate, and nine substances Al corresponding to the nine elements in the glass sheet of the standard sample are taken2O3、SiO2、Fe2O3、TiO2、K2O、Na2And establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as the abscissa.
After the working curves are established, the working curves need to be corrected to reduce the absorption enhancement effect among elements, in example 2, superQ analysis software provided by panacea is used to correct the working curves, and the corrected working curves need to be subjected to accuracy verification of the method.
(5) Method accuracy verification
Standard samples required for the accuracy of the verification method were prepared by the weighing method shown in Table 10, and the weighing results were accurate to. + -. 0.0001 g. And (3) uniformly stirring the weighed reagents and samples by using a glass rod, adding 5 drops of saturated lithium bromide solution, pre-oxidizing in a muffle furnace at 650 ℃ for 10min, then placing in an automatic melting machine, melting at 1070 +/-5 ℃ for 13min, and pouring into uniform and transparent glass sheets for later use. The glass sheet was measured using the established working curve, and the results of comparison of the measurement results of each element with the standard values are shown in Table 11. From the comparison result of the standard value and the measured value, the established working curve of each substance can meet the detection requirement in the relevant analysis standard, and therefore, the working curve can be used for measuring daily unknown samples.
TABLE 10 Standard sample preparation method for validation
TABLE 11 working Curve accuracy verification conditions
2. Preparation and measurement of sample to be tested
(1) Sample weighing: 7.0000g (+ -0.0001) g of anhydrous lithium tetraborate and lithium metaborate flux (the mass ratio of the anhydrous lithium tetraborate to the lithium metaborate is 67:33), 1.4000g (+ -0.0001) of lithium nitrate and 0.7000g (+ -0.0001) of a to-be-detected high-sulfur bauxite sample are weighed in a platinum-yellow alloy crucible, and are uniformly stirred by a glass rod to obtain a mixture.
(2) Pre-oxidation: and (3) placing the mixture into a platinum-yellow alloy crucible, adding 5 drops of saturated lithium bromide solution serving as a release agent, placing the mixture into a muffle furnace at 500 ℃, and burning for 20min to complete the pre-oxidation of the sample.
(3) Preparing a glass sheet to be detected: and putting the preoxidized sample and the platinum-yellow alloy crucible into a full-automatic sample melting machine, melting for 13min at 1070 +/-5 ℃, and pouring into a uniform and transparent glass sheet to be detected.
(4) Measurement: placing the glass sheet to be measured in an X-ray fluorescence spectrometer to measure the fluorescence of nine elements of Al, Si, Fe, Ti, K, Na, Ca, Mg and SCalculating nine substances Al corresponding to the nine elements in the glass sheet to be detected according to the corrected and accuracy-verified working curve of the fluorescence intensity of the nine elements in the glass sheet to be detected2O3、SiO2、Fe2O3、TiO2、K2O、Na2Contents of O, CaO, MgO, and S.
Example 2 the precision of the method of example 2 was confirmed by selecting a total of 4 unknown samples for measurement, of which sample GS-5 was melted into 11 glass pieces, and the measurement results are shown in table 12, and the precision of the method of example 2 was good in terms of the standard deviation of 11 measurement data. The results of the measurements of the 4 unknown samples using the method of example 2 are compared with the results of the chemical analysis method using a carbon sulfur analyzer, as shown in Table 13. From the comparison results between the chemical analysis method and the method of example 2, the detection result of the method of example 2 can be matched well with the detection result of the chemical analysis method. The method of the embodiment 2 effectively solves the problems of volatilization of sulfur element and corrosion to the platinum-yellow alloy crucible in the sample melting preparation process, can simultaneously measure sulfur and other conventional oxide components of the high-sulfur bauxite by only using the X-ray fluorescence spectrometer, does not need to burn the high-sulfur bauxite at high temperature and then measure the high-sulfur bauxite, and does not need to use two instruments of a carbon-sulfur instrument and the X-ray fluorescence spectrometer for measurement, thereby greatly prolonging the service life of the platinum-yellow alloy crucible, shortening the detection flow, saving the detection cost for enterprises and improving the detection rate.
TABLE 12 results of precision test
TABLE 13 comparison of the results of measurements of unknown samples using the method of example 2 with the results of measurements of chemical analysis methods
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (8)
- The method for measuring the content of nine substances in the high-sulfur bauxite by using the X-ray fluorescence spectrometry is characterized by comprising the following steps of:(1) uniformly mixing the sulfur-containing standard substance with the flux to obtain a sulfur-containing mixed flux;(2) uniformly stirring a sulfur-containing mixed flux, a bauxite standard sample, a pre-oxidant lithium nitrate and a flux to obtain a compound standard sample;(3) adding a compound standard sample into release agent saturated lithium bromide, and heating for pre-oxidation;(4) preparing a pre-oxidized compound standard sample into a standard sample glass sheet by adopting a melting method;(5) sequentially measuring the fluorescence intensity of nine elements including Al, Si, Fe, Ti, K, Na, Ca, Mg and S in a standard sample glass sheet in an X-ray fluorescence spectrometer, taking the fluorescence intensity of the nine elements in the standard sample glass sheet as a vertical coordinate, and taking nine substances Al corresponding to the nine elements in the standard sample glass sheet2O3、SiO2、Fe2O3、TiO2、K2O、Na2Establishing a working curve by taking the mass concentrations of O, CaO, MgO and S as a horizontal coordinate, and correcting and verifying the accuracy of the working curve;(6) uniformly stirring the high-sulfur bauxite, the flux and the pre-oxidizing agent lithium nitrate to obtain a mixture, dropwise adding the mixture into release agent saturated lithium bromide, and heating for pre-oxidizing;(7) preparing the pre-oxidized mixture into a glass sheet to be detected by adopting a melting method;(8) putting the glass sheet to be measured into an X-ray fluorescence spectrometer for measuring Al, Si, Fe, Ti, K, Na and Ca. Fluorescence intensities of nine elements including Mg and S, and calculating nine substances Al corresponding to the nine elements in the glass sheet to be detected according to the fluorescence intensities of the nine elements in the glass sheet to be detected by the working curve in the step (5)2O3、SiO2、Fe2O3、TiO2、K2O、Na2Contents of O, CaO, MgO, and S.
- 2. The method for determining the element content in the high-sulfur bauxite by using the X-ray fluorescence spectrometry as claimed in claim 1, wherein the mass percentage of S in the high-sulfur bauxite is 0.7-9%.
- 3. The method for measuring the content of elements in the high-sulfur bauxite by using the X-ray fluorescence spectrometry according to claim 2, wherein the sulfur-containing standard substance in the step (1) is GBW 07267.
- 4. The method for determining the element content in the high-sulfur bauxite by using the X-ray fluorescence spectrometry according to claim 3, characterized in that the flux in the step (1), the flux in the step (2), and the flux in the step (6) are mixed fluxes composed of lithium tetraborate and lithium metaborate, and the mass ratio of the lithium tetraborate to the lithium metaborate in the mixed fluxes is 67: 33.
- 5. The method for measuring the element content in the high-sulfur bauxite by using the X-ray fluorescence spectrometry as claimed in claim 4, wherein the mass ratio of the sulfur-containing standard substance to the flux in the step (1) is (5-10): 1.
- 6. The method for determining the content of elements in high-sulfur bauxite by X-ray fluorescence spectrometry as claimed in claim 3, wherein the bauxite standard sample in the step (2) is a mixture consisting of five or more of GBW070036, GBW07177, GBW07178, GBW07179, GBW07180, GLK-1, GLK-2, GLK-4, GLK-6, GLK-7, GLK-8 and GLK-10.
- 7. The method for determining the element content in the high-sulfur bauxite by using the X-ray fluorescence spectrometry as claimed in claim 6, wherein the mass ratio of the bauxite standard sample, the flux and the pre-oxidant lithium nitrate in the step (2) is 1: (7-14): (1-2); and (3) the weighed mass of the high-sulfur bauxite, the flux and the pre-oxidant lithium nitrate in the step (6) is the same as that of the standard bauxite sample, the flux and the pre-oxidant lithium nitrate in the step (2).
- 8. The method for determining the element content in the high-sulfur bauxite by using the X-ray fluorescence spectrometry according to claim 1, wherein the process conditions of the pre-oxidation in the step (3) and the process conditions of the pre-oxidation in the step (6) are both as follows: the pre-oxidation temperature is 500-650 ℃, and the pre-oxidation time is 10-20 min.
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| CN113092510A (en) * | 2021-03-18 | 2021-07-09 | 成都中光电科技有限公司 | X-fluorescence determination method for potassium nitrate as high-alumina glass raw material |
| CN114486970A (en) * | 2022-01-24 | 2022-05-13 | 清远南玻节能新材料有限公司 | X-ray fluorescence determination method for content of metal elements in toughened salt |
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| CN113092510A (en) * | 2021-03-18 | 2021-07-09 | 成都中光电科技有限公司 | X-fluorescence determination method for potassium nitrate as high-alumina glass raw material |
| CN114486970A (en) * | 2022-01-24 | 2022-05-13 | 清远南玻节能新材料有限公司 | X-ray fluorescence determination method for content of metal elements in toughened salt |
| CN114486970B (en) * | 2022-01-24 | 2023-06-06 | 清远南玻节能新材料有限公司 | X-ray fluorescence determination method for metal element content in tempered salt |
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