CN115575432A - Method for measuring major and minor components in alunite ore by using X-ray fluorescence spectrum - Google Patents
Method for measuring major and minor components in alunite ore by using X-ray fluorescence spectrum Download PDFInfo
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- 229910052934 alunite Inorganic materials 0.000 title claims abstract description 47
- 239000010424 alunite Substances 0.000 title claims abstract description 47
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004876 x-ray fluorescence Methods 0.000 title claims description 32
- 238000001228 spectrum Methods 0.000 title claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 238000011088 calibration curve Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000004846 x-ray emission Methods 0.000 claims abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 65
- 229910052697 platinum Inorganic materials 0.000 claims description 33
- 239000011521 glass Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 13
- 238000001304 sample melting Methods 0.000 claims description 12
- 230000004907 flux Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000000156 glass melt Substances 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical class [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000010183 spectrum analysis Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 12
- 235000010755 mineral Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical group [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910052600 sulfate mineral Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Classifications
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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
- G01N23/223—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
-
- 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
-
- 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
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention relates to the technical field of spectral analysis, and particularly discloses a method for determining major and minor components in alunite ore by using X-ray fluorescence spectroscopy, which comprises the following steps of 1) treating a sample to be detected; 2) Preparing a standard sample; 3) Measuring a standard sample; 4) Establishing a standard curve; 5) Measuring a sample to be measured and calculating the content of the sample to be measured; selecting a proper reference reagent for mixing and compounding to prepare a series of calibration samples, establishing a calibration curve, and preparing samples by dewatering, roasting and remelting to eliminate the influence of crystal water and prevent the loss of sulfur at the same time, thereby realizing the accurate determination of 7 major and minor components in the alunite ore; the method has the advantages of good test precision, high accuracy, simple operation, rapid analysis speed, environmental protection, long-term use after the establishment of the method, shortened test period, reduced test labor and material cost, and reduced environmental pollution, and can complete simultaneous determination of 7 components by one-time sample preparation and loading.
Description
Technical Field
The invention relates to the technical field of spectral analysis, in particular to a method for determining major and minor components in alunite ore by using X-ray fluorescence spectrum.
Background
Alunite is a hydrous potassium-aluminum sulfate mineral, is an important non-metallic mineral resource, can be used for producing more than 40 chemical products, is mainly used for refining alum in industry, can also be used for producing products such as potassium sulfate, sulfuric acid, aluminum oxide and the like, and is widely used in the departments of food, printing, papermaking, tanning, paint, fertilizer and the like. The alunite mineral resources in China are rich, the reserves are third in the world, the reserves of the alunite are found to be more than 3 hundred million tons, and the development and utilization prospects are wide. The method can be used for rapidly and accurately measuring the major and minor components in the alunite ore, and has important significance for geological exploration, quality evaluation and development and utilization.
The alunite ore mainly contains Al 2 O 3 、SO 3 、K 2 O、Na 2 O、SiO 2 、Fe 2 O 3 、TiO 2 And the like, which are necessary indexes specified in the chemical industry standard alunite ore analysis method (HG/T2957-2004). In the alunite ore analysis method (HG/T2957-2004), after each component needs to be decomposed by different methods, the sample is independently measured by a chemical method or an instrument method (see figure 1 for details), the operation is very complicated, tedious, long in time consumption, low in efficiency, large in dosage of toxic chemical reagents such as acid and alkali, and waste liquid generated in experiments can pollute the environment. The literature data 'determination of 11 element contents in alunite ore by inductively coupled plasma atomic emission spectrometry' introduces that sodium carbonate and sodium tetraborate are used for melting and decomposing a sample, after hydrochloric acid leaching, the inductively coupled plasma atomic emission spectrometry is used for determining the 11 element contents in the alunite ore, but sodium and sulfur in alunite cannot be determined, high salt in solution easily blocks an atomizer, the background blank is high, and the determination precision and accuracy are influenced. Therefore, a method for measuring primary and secondary components in the alunite ore by using an X-ray fluorescence spectrum needs to be designed to solve the problems of single test index, complex operation, long time consumption, low efficiency and serious pollution of the existing alunite component measuring method.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a method for measuring main and secondary components in alunite ore by using X-ray fluorescence spectrum.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for measuring primary and secondary components in alunite ore by using X-ray fluorescence spectrum comprises the following steps:
1) Treating a sample to be detected: accurately weighing m 0 Putting an alunite mineral sample with the weight into a porcelain crucible with constant weight, putting the crucible into a high-temperature furnace, gradually raising the temperature from low temperature and preserving the heat, taking out the crucible, and repeatedly operating until the constant weight is recorded as m 1 Weight, calculated loss on firing LOI = (m) 0 -m 1 )/m 0 Accurately weighing a weight of lithium tetraborate-lithium metaborate mixed flux, pouring the flux into a platinum yellow crucible, adding a roasted sample to be detected into the platinum yellow crucible, adding a solution, putting the platinum yellow crucible into an automatic sample melting machine, and casting to form a glass fuse piece to be detected;
2) Preparation of a series of standard samples: accurately weighing a plurality of parts of a parts by weight of lithium tetraborate-lithium metaborate mixed flux, respectively pouring the parts into different platinum yellow crucibles, respectively weighing a plurality of reference reagents in each platinum yellow crucible, adding the reference reagents into the platinum yellow crucible, stirring the reference reagents, adding a solution into the platinum yellow crucibles, and putting the platinum yellow crucibles into an automatic sample melting machine for casting into a series of standard glass fuse pieces;
3) Determination of the standard sample: measuring the standard glass fuse pieces of the standard sample by using an X-ray fluorescence spectrometer to obtain the X-ray fluorescence intensity of each component;
4) Establishing a standard curve: correcting matrix effect and spectral line overlapping interference, and drawing a calibration curve by taking the X-ray fluorescence intensity of each component as an abscissa and the content of each component as an ordinate;
5) And (3) determining a sample to be detected and calculating the content: measuring a glass fuse piece to be measured of a sample to be measured by adopting an X-ray fluorescence spectrometer, obtaining a direct measurement value of the X-ray fluorescence spectrometer according to the measured X-ray fluorescence intensity and a calibration curve equation, and then according to a formula:
w＝w i ×(1-LOI)
and converting into the content of each component in the sample to be detected.
Specifically, the alunite mineral sample in the step 1) is dried for 3 hours at 105 ℃, the crucible is placed into a high-temperature furnace, the temperature is gradually increased from low temperature to 600 ℃, the temperature is kept for 1 hour, the crucible is taken out and placed into a dryer to be cooled to room temperature, then weighing is carried out, and the operation is repeated until the weight is constant.
Specifically, the mass ratio of the lithium tetraborate-lithium metaborate mixed flux in step 2) was 67% by mass, and the platinum yellow crucible was 95% by mass, pt-5% by mass, au.
Specifically, the reference reagent in the step 2) is 0-0.300g of aluminum oxide, 0-0.300g of potassium sulfate, 0-0.300g of sodium sulfate, 0-0.500g of silicon dioxide, 0-0.100g of ferric oxide and 0-0.100g of titanium dioxide, the reference reagent is added and then uniformly stirred by using a plastic rod, the solution comprises a saturated lithium nitrate solution and a lithium bromide solution, a platinum yellow crucible is firstly pre-oxidized on an automatic sample melting machine at 700 ℃ for 15min, the temperature is increased to 1050 ℃ for sample melting for 10min, the crucible is shaken and fully and uniformly mixed at the same time, the melt is automatically poured into a casting mold for molding after the time, the glass melt is automatically separated from the casting mold after cooling, so that a standard glass melt of a standard sample is obtained, and the standard glass melt is placed into a dryer for sealed storage to be detected.
Specifically, the operating voltage of the X-ray fluorescence spectrometer in the step 3) is 55KV, and the operating current is 60mA.
Specifically, w in the report in the step 5) is the percentage content of each component in the sample to be detected; w is a i Is the percentage content of the direct measurement value of the X-ray fluorescence spectrometer; LOI is the percentage weight loss on firing.
The invention has the following beneficial effects:
the method for measuring the primary and secondary components in the alunite ore by using the X-ray fluorescence spectrum has the advantages that the X-ray fluorescence spectrum is used for measuring 7 primary and secondary components in the alunite, the precision is good, the accuracy is high, the operation is simple, the simultaneous measurement of 7 components can be completed by one-time sample preparation and machine, and the test items which can be completed by 6 or 7 methods in the industrial standard can be completed by one method; the analysis speed is high, the environment is protected, and the method can be used for a long time after being established; the detection period is shortened from 2-3 days to 1h, the used chemical reagent types are reduced from more than 50 (including sulfuric acid, hydrofluoric acid, perchloric acid, sodium peroxide, sodium fluoride, barium chloride and other dangerous chemicals) to 4, no waste liquid is discharged, and compared with an industrial standard method, the method shortens the detection period, reduces the cost of manpower and material resources for detection, and reduces the environmental pollution.
Drawings
FIG. 1 is a chart of the primary and secondary quantity measurement standard analysis method in industry standard alunite ore.
FIG. 2 is SO 3 Standard curve chart.
FIG. 3 is K 2 O standard curve diagram.
FIG. 4 is Na 2 O standard curve diagram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely further described in detail below with reference to the accompanying drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in figures 1-4, the method for measuring the major and minor components in the alunite ore by using the X-ray fluorescence spectrum selects a proper reference reagent to mix and compound to prepare a series of calibration samples, establishes a calibration curve, adopts dehydration roasting and re-melting to prepare the samples, eliminates the influence of crystal water and prevents the loss of sulfur, and realizes the accurate measurement of 7 major and minor components in the alunite ore.
A method for measuring major and minor components in alunite ore by using X-ray fluorescence spectrum comprises the following specific steps:
(1) Preparation of Standard samples
8.000g of the lithium tetraborate-lithium metaborate (67% by mass) mixed flux was accurately weighed and poured into a platinum yellow crucible (95% Pt-5% Au). According to the weighing amount in Table 2, alumina, potassium sulfate, sodium sulfate, silica, ferric oxide and titanium dioxide reference reagents, such as standard sample No. S1, were respectively weighed into a platinum yellow crucible, and the 6 reference reagents were respectively added in amounts of dioxygen0.000g of silicon oxide, 0.300g of potassium sulfate, 0.300g of sodium sulfate, 0.000g of alumina, 0.100g of ferric oxide and 0.100g of titanium dioxide, and stirring the mixture uniformly by using a plastic rod. And then adding 1mL of saturated lithium nitrate solution and 1 drop of lithium bromide solution (1 g/mL), placing the platinum yellow crucible on an automatic sample melting machine, pre-oxidizing for 15min at 700 ℃, heating to 1050 ℃ for sample melting for 10min, fully shaking the platinum yellow crucible, automatically pouring the melt into a casting mold for molding after the time comes, automatically separating the glass fuse piece from the casting mold to obtain a standard glass fuse piece of the standard sample No. S1, and placing the standard glass fuse piece into a dryer for sealed storage to be tested. According to the steps, S2-S16 standard samples are weighed in sequence for melting to prepare standard glass melt sheets, and a group of 16 standard sample series with different content compositions is prepared. Al in standard sample series 2 O 3 、SO 3 、K 2 O、Na 2 O、SiO 2 、Fe 2 O 3 、TiO 2 The content ranges of the 7 components are shown in Table 4.
The method for preparing the standard sample series by mixing and compounding the reference reagent solves the problem of lack of alunite ore standard substances.
TABLE 2 formulation Scale for Standard samples
(2) Determination of the Standard sample and establishment of the Standard Curve
The instrument equipment comprises: the component determination adopts a ZSX Primus II type wavelength dispersion X-ray fluorescence spectrometer, a 4kW end window rhodium target X-ray tube (Nippon chemical company) and Chinese version ZSX analysis software; the automatic melting machine is a Lifumat-2.0-Ox type high-frequency melting machine (Germany Limanfei). Weighing with an analytical balance model ML204 (mettler-toledo); SX-8-10 type box electric resistance furnace (Tianjin Tester Co.); platinum yellow crucible (95% Pt +5% Au).
The instrument measurement conditions are as follows: the working voltage of the X-ray fluorescence spectrometer is 55KV, and the working current is 60mA. Other instrument conditions are shown in table 3.
TABLE 3 measurement conditions of the apparatus
According to the instrument conditions of table 3, the 16 standard sample glass fuse pieces prepared in step (1) were measured, and through correction of matrix effect and spectral line overlapping interference, a calibration curve was drawn with the fluorescence intensity of each component as abscissa and the content of each component as ordinate, and the standard curves and correlation coefficients of 7 components obtained by the experiment are shown in table 4.
TABLE 4 calibration curves for each component
| Composition (I) | Content range/%) | Equation of calibration curve | Correlation coefficient |
| Al 2 O 3 | 0.00～37.50 | y＝0.44920x-0.029542 | 0.9962 |
| K 2 O | 0.00～20.27 | y＝0.055628x-0.033324 | 0.9998 |
| Na 2 O | 0.00～16.36 | y＝2.6274x-0.11574 | 0.9998 |
| SO 3 | 0.00～38.37 | y＝0.90348x+0.037911 | 0.9983 |
| SiO 2 | 0.00～62.50 | y＝0.43045x-2.2949 | 0.9962 |
| Fe 2 O 3 | 0.00～12.50 | y＝0.063560x-0.00296419 | 0.9998 |
| TiO 2 | 0.00～12.50 | y＝0.077955x-0.0099133 | 0.9998 |
(3) Pretreatment of sample to be tested
Accurately weigh 1.000g (denoted as m) 0 ) Drying alunite mineral sample for 3h at 105 ℃, putting the alunite mineral sample into a platinum yellow crucible with constant weight, putting the platinum yellow crucible into a high-temperature furnace, gradually increasing the temperature from low temperature to 600 ℃, preserving the heat for 1h, taking out the platinum yellow crucible, putting the platinum yellow crucible into a drier, cooling to room temperature, weighing, and repeatedly operating until the weight is constant (marked as m) 1 ) Meter for measuringWeight loss by roasting
LOI＝(m 0 -m 1 )/m 0 。
8.000g of the lithium tetraborate-lithium metaborate (67% by mass: 33) mixed flux was accurately weighed and poured into a platinum yellow crucible (95% pt-5% au). Weighing and adding 0.800g of roasted sample to be detected, and uniformly stirring by using a plastic rod. And then adding 1mL of saturated lithium nitrate solution and 1 drop of lithium bromide solution (1 g/mL), placing the platinum yellow crucible on an automatic sample melting machine, pre-oxidizing for 15min at 700 ℃, heating to 1050 ℃ for sample melting for 10min, fully shaking the platinum yellow crucible, automatically pouring the melt into a casting mold for molding after the time comes, automatically separating the glass fuse piece from the casting mold after cooling to obtain a glass fuse piece to be detected of the sample to be detected, and placing the glass fuse piece to be detected in a dryer for sealed storage.
(4) Determination and content calculation of sample to be detected
And (3) according to the instrument conditions in the table 1, measuring the glass fuse piece to be measured of the sample to be measured prepared in the step (3), and obtaining the direct measurement value of the instrument measurement according to the measured X-ray fluorescence intensity and the calibration curve equation. And then converting the content into the content of each component in the sample to be detected according to the following formula (1).
w＝w i ×(1-LOI) (1)
In the formula: w is the percentage content of each component in the sample to be detected; w is a i The percentage content of the measured value is directly measured by an instrument; LOI is the percentage weight loss on firing.
The method of the invention uses reference reagents of alumina, potassium sulfate, sodium sulfate, silicon dioxide, ferric oxide and titanium dioxide to mix and compound according to specific proportion to prepare calibration sample series with different content compositions. The method solves the problem of lacking alunite standard substance.
According to the method, the dehydration roasting temperature of the sample is 600 ℃, the crystal water in the sample can be removed, but the sulfur in the sample cannot be volatilized. The method eliminates the influence of the crystallization water on the measurement, and avoids the loss of sulfur in the roasting process.
In the method, the mixed flux is lithium tetraborate and lithium metaborate; the ratio of the two is 67. The oxidant is lithium nitrate; the release agent used was lithium bromide. The sample melting procedure is to pre-oxidize at 700 deg.C for 15min, and then heat up to 1050 deg.C to melt the sample for 10min. The method avoids the volatilization loss of sulfur in the melting process by adding an oxidant and increasing a pre-oxidation step.
In order to verify the scientificity and effectiveness of the method for determining 7 main and secondary components in alunite, the method carries out the following work:
(1) Determination of similar Standard substances
The rock standard substances GBW07104, GBW07105 and GBW07122 which have similarities in content and composition with alunite ore were determined by the method, and the results are shown in Table 5. The result shows that the measured values of the components of the standard substance basically accord with the set values, and the method has higher measurement accuracy.
TABLE 5 Standard substance determination (%)
(2) Compared with the test result of the current standard method
The results of the method and the chemical industry standard alunite ore analysis method (HG/T2957-2004) are shown in Table 6, wherein the actual samples of 13 alunite ores to be detected are respectively measured. The results show that the method is applied to Al 2 O 3 、SO 3 、K 2 O、Na 2 O、SiO 2 、Fe 2 O 3 、TiO 2 The measured values of the 7 components basically accord with the measured values of the industrial standard method, which proves that the method has accurate and reliable pre-treatment and measured results of the sample, and also proves that the method can reach the accuracy level of the industrial standard method and can meet the analysis requirement of the alunite mine.
TABLE 6 comparison of analytical results of actual alunite ore samples (%)
TABLE 6 actual alunite ore sample analysis results comparison (%) continuation
TABLE 6 actual alunite ore sample analysis results comparison (%) continuation
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the scope of the present invention, which is similar or similar to the technical solutions of the present invention.
The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (6)
1. A method for measuring primary and secondary components in alunite ore by using X-ray fluorescence spectrum is characterized by comprising the following steps:
1) Treating a sample to be detected: accurately weighing m 0 Putting an alunite mineral sample with the weight into a porcelain crucible with constant weight, putting the crucible into a high-temperature furnace, gradually raising the temperature from low temperature and preserving the heat, taking out the crucible, and repeatedly operating until the constant weight is recorded as m 1 Weight, calculated weight loss on firing LOI = (m) 0 -m 1 )/m 0 Accurately weighing a weight of lithium tetraborate-lithium metaborate mixed flux, pouring the mixed flux into a platinum yellow crucible, adding a roasted sample to be tested into the platinum yellow crucible, adding a solution, and putting the platinum yellow crucible into an automatic sample melting machine to be molded into a glass fuse piece to be tested;
2) Preparation of a series of standard samples: accurately weighing a plurality of parts of a weight of lithium tetraborate-lithium metaborate mixed flux, respectively pouring the weighed parts into different platinum yellow crucibles, respectively weighing a plurality of reference reagents in each platinum yellow crucible, adding the reference reagents into the platinum yellow crucible, stirring the reference reagents, then adding the solution into the platinum yellow crucible, and putting the platinum yellow crucible into an automatic sample melting machine to mold the platinum yellow crucible into a series of standard glass fuse pieces;
3) Determination of the standard sample: measuring the standard glass fuse pieces of the standard sample by using an X-ray fluorescence spectrometer to obtain the X-ray fluorescence intensity of each component;
4) Establishment of a standard curve: correcting matrix effect and spectral line overlapping interference, and drawing a calibration curve by taking the X-ray fluorescence intensity of each component as an abscissa and the content of each component as an ordinate;
5) And (3) measuring and calculating the content of the sample to be measured: measuring a glass fuse piece to be measured of a sample to be measured by adopting an X-ray fluorescence spectrometer, obtaining a direct measurement value of the X-ray fluorescence spectrometer according to the measured X-ray fluorescence intensity and a calibration curve equation, and then according to a formula:
w＝w i ×(1-LOI)
and converting into the content of each component in the sample to be detected.
2. The method for measuring the major and minor components in the alunite ore by using the X-ray fluorescence spectrum as claimed in claim 1, wherein the alunite mineral sample in the step 1) is dried at 105 ℃ for 3h, the crucible is placed into a high temperature furnace to gradually increase the temperature from low temperature to 600 ℃ and is kept warm for 1h, the crucible is taken out and is placed into a drier to be cooled to room temperature, then the weighing is carried out, and the operation is repeated until the weight is constant.
3. The method for measuring major and minor components in alunite ore according to claim 1, wherein the mass ratio of the lithium tetraborate-lithium metaborate mixed flux in step 2) is 67% to 33, and the platinum-yellow crucible is 95% to pt-5% to au.
4. The method for determining major and minor components in alunite ore by using X-ray fluorescence spectroscopy as claimed in claim 1, wherein the reference reagents in step 2) are 0-0.300g of alumina, 0-0.300g of potassium sulfate, 0-0.300g of sodium sulfate, 0-0.500g of silica, 0-0.100g of ferric oxide and 0-0.100g of titanium dioxide, the reference reagents are uniformly stirred by a plastic rod after being added, the solution comprises a saturated lithium nitrate solution and a lithium bromide solution, a platinum yellow crucible is pre-oxidized on an automatic sample melting machine for 15min at 700 ℃, the temperature is increased to 1050 ℃ for melting for 10min, the crucible is shaken to be fully and uniformly mixed, the melt is automatically poured into a casting mold for molding after time, the glass melt is automatically separated from the casting mold after cooling to obtain a standard glass melt of a standard sample, and the standard glass melt is placed into a dryer for sealed storage.
5. The method for measuring major and minor components in alunite ore according to claim 1, wherein the operating voltage of the X-ray fluorescence spectrometer in step 3) is 55KV and the operating current is 60mA.
6. The method for determining the primary and secondary components in the alunite ore by using the X-ray fluorescence spectrum according to claim 1, wherein w in the indication in the step 5) is the percentage content of each component in the sample to be determined; w is a i Is the percentage content of the direct measurement value of the X-ray fluorescence spectrometer; LOI is the percentage weight loss on firing.
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